JP2018150525A - Polyester-based thermoplastic elastomer composition and molded article of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester-based thermoplastic elastomer composition having excellent moldability, oil resistance and abrasion resistance and having a soft texture, and a molded product thereof. 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 type rubber polymer, a silicone-based core-shell rubber copolymer, and a butadiene / acrylonitrile copolymer rubber polymer. Rubber polymer component (C): Ester compound [selection diagram] None

Description

  The present invention relates to a polyester-based thermoplastic elastomer having a soft texture and excellent moldability, oil resistance, and wear resistance, and a molded body thereof.

  Polyester-based thermoplastic elastomers are excellent in mechanical properties such as strength, impact resistance, elastic recovery, flexibility, low temperature and constant temperature characteristics, oil resistance, and wear resistance. Since it can be heat-sealed with a hard resin such as acrylonitrile-butadiene copolymer resin (ABS resin), it is widely used in fields such as automobiles, electric / electronic parts, and consumer goods.

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

  Patent Document 1 discloses a polyester thermoplastic elastomer composition that can be heat-sealed to a polyolefin resin by blending a polyester elastomer with a styrene thermoplastic elastomer.

  In Patent Document 2, 0.1 to 5.0 parts by mass of an ester plasticizer is blended with 100 parts by mass of a polyester elastomer. The Duro D hardness is 47 to 50, and the elasticity is high. A polyester elastomer resin composition excellent in bending fatigue is disclosed.

Japanese Patent Laid-Open No. 9-12487 JP2015-168815A

  According to detailed examinations by the present inventors, it has been found that the conventional technique has the following problems.

  Since the polyester-based thermoplastic elastomer composition described in Patent Document 1 uses a styrene-based thermoplastic elastomer to achieve softening, the oil resistance is poor, nonpolar oil such as machine oil, sweat, etc. When it comes into contact with the oil component, there is a problem that the oil component is absorbed to swell and deform. In addition, the polyester elastomer resin composition described in Patent Document 2 is not provided with sufficient flexibility due to a small amount of plasticizer, and is flexible for grips and packings of cameras, electric tools, bicycles, and the like. Is not suitable for use in a required member. It is easily considered that sufficient flexibility can be imparted by increasing the blending amount of the plasticizer, which has been clarified by the present inventors. I know it will get worse.

  An object of the present invention is to provide a polyester-based thermoplastic elastomer composition that is excellent in moldability, oil resistance, and wear resistance, and can provide a molded article having a soft texture in view of the above-described problems of the prior art. And providing a molded body thereof.

As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by blending a specific rubbery polymer and an ester compound in a polyester elastomer, and further, by adding a carbodiimide compound. It discovered that abrasion resistance could be improved more by mix | blending.
That is, the gist of the present invention resides 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 type rubbery polymer, a silicone type core-shell type rubbery copolymer, and a butadiene / acrylonitrile copolymer rubbery polymer Rubbery polymer component (C): ester compound

[2] 10 to 400 parts by mass of the rubber polymer of the component (B) and 6 to 100 parts by mass of the ester compound of the component (C) with respect to 100 parts by mass of the polyester elastomer of the component (A). The polyester-based thermoplastic elastomer composition as described in [1].

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

[4] The polyester-based thermoplastic elastomer composition according to any one of [1] to [3], wherein the component (A) includes 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], comprising a polyalkylene glycol component of component (A), wherein the content of the polyalkylene glycol component is 60% by mass or more. .

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

[7] The polyester thermoplastic elastomer composition according to any one of [1] to [6], wherein 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 body made from the polyester thermoplastic elastomer composition according to any one of [1] to [9].

  According to the present invention, by molding a specific rubbery polymer and an ester compound, preferably a carbodiimide compound, into a polyester elastomer, a molded article having a soft texture and excellent in oil resistance and wear resistance is obtained. It can be provided under good moldability.

  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 implemented without departing from the gist of the present invention. In addition, in this specification, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

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

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

  Examples of the polyester elastomer include a cyclic polyester (in the present invention, “cyclic polyester” means a dicarboxylic acid or alkyl ester thereof containing dicarboxylic acid having a cyclic structure or an alkyl ester thereof). A block copolymer (hereinafter referred to as “polyalkylene glycol unit”) having a hard segment (hereinafter also referred to as “cyclic polyester unit”) and a soft segment composed of polyalkylene glycol (hereinafter referred to as “polyalkylene glycol unit”). , Sometimes referred to as “cyclic polyester-polyalkylene glycol block copolymer”), and a hard segment comprising a cyclic polyester and a chain aliphatic polyester (in the present invention, “chain aliphatic polyester” is a raw material) A soft segment composed of a dicarboxylic acid or an alkyl ester thereof having only a chain structure (hereinafter, referred to as a “chain aliphatic polyester unit”). And the like (hereinafter, sometimes referred to as “cyclic polyester-chain aliphatic polyester block copolymer”) and the like. Among these, a cyclic polyester-polyalkylene glycol block copolymer is preferable because it is easily available.

  As the cyclic polyester-polyalkylene glycol block copolymer, for example, a hard segment (hereinafter sometimes referred to as “aromatic polyester unit”) made of an aromatic polyester and a copolymer having a polyalkylene glycol unit (hereinafter referred to as “aromatic polyester unit”). , Sometimes referred to as “aromatic polyester-polyalkylene glycol block copolymer”) and a hard segment composed of alicyclic polyester (hereinafter sometimes referred to as “alicyclic polyester unit”) and polyalkylene. And a block copolymer having a glycol unit (hereinafter, sometimes referred to as “alicyclic polyester-polyalkylene glycol block copolymer”). Among these, an aromatic polyester-polyalkylene glycol block copolymer is preferable from the viewpoint of heat resistance.

  The aromatic polyester-polyalkylene glycol block copolymer is a known thermoplastic elastomer as described in JP-A-10-130451, etc., and if it is a polymer containing a polyalkylene glycol unit, The block may be a single polymer or a copolymer.

  Although the raw material of an aromatic polyester unit is explained in full detail below, it is preferable that polybutylene terephthalate is included as a hard segment. On the other hand, the raw material of the polyalkylene glycol unit is also described in detail below, but preferably includes a soft segment (hereinafter sometimes referred to as “polytetramethylene glycol unit”) made of polytetramethylene ether glycol. .

  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.

  Examples of the alicyclic polyester-polyalkylene glycol block copolymer include alicyclic dicarboxylic acids (in the present specification, “alicyclic dicarboxylic acid” refers to a cyclic aliphatic hydrocarbon in which two carboxyl groups are directly formed. And a compound obtained by using alicyclic diol and polyalkylene glycol as raw materials.

  If it is a polymer containing a polyalkylene glycol unit, each block may be a single polymer or a copolymer. The alicyclic polyester unit preferably includes a hard segment obtained using cyclohexanedicarboxylic acid and cyclohexanedimethanol as raw materials. The polyalkylene glycol unit of the alicyclic polyester-polyalkylene glycol block copolymer preferably includes a soft segment (polytetramethylene glycol unit) obtained using 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 an aromatic polyester and a soft segment made of a chain aliphatic polyester (hereinafter referred to as “aromatic polyester-chain-like”). And a block copolymer having a hard segment composed of an alicyclic polyester and a soft segment composed of a chain aliphatic polyester (hereinafter referred to as “alicyclic polyester-”). May be referred to as "chain aliphatic polyester block copolymer").

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

  As the soft segment having flexibility, 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 the group ether, a single polymer or copolymer of an alicyclic ether such as a condensate of cyclohexanediol and a condensate of cyclohexanedimethanol can be used. Further, a random copolymer in these ether units may be used. 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 900 to 2 , 100 is more preferable. Here, the number average molecular weight of the polyalkylene glycol unit refers to a value in terms of polystyrene measured by gel permeation chromatography (GPC).

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

  There is no restriction | limiting in particular as a manufacturing method of a polyester elastomer, For example, among cyclic polyester-polyalkylene glycol block copolymers, the aromatic polyester-polyalkylene glycol block copolymer using aromatic polyester and polyalkylene ether glycol is used. Then, using 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 as raw materials, an esterification reaction or a transesterification reaction It can be obtained by condensing the obtained oligomer.

As said C1-C12 chain | strand-shaped aliphatic and / or alicyclic diol, what is normally used as a raw material of 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, and 1,6-hexene glycol. Of these, 1,4-butylene glycol is preferred.
Examples of the alicyclic diol include 1,4-cyclohexene glycol and 1,4-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol is preferable.
These C2-C12 chain aliphatic and / or alicyclic diols may be used alone or in a mixture of two or more.

As the aromatic dicarboxylic acid or alkyl ester thereof, those generally used as raw materials for polyesters can be used. For example, terephthalic acid and its lower (in this specification, “lower” means 4 or less carbon atoms) .) Alkyl esters, isophthalic acid, phthalic acid, 2,5-norbornene dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and their lower alkyl esters Is mentioned. Among these, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is more preferable.
These aromatic dicarboxylic acids or alkyl esters thereof may be used alone or in combination of two or more.

Examples of the polyalkylene ether glycol include linear chains such as polymethylene glycol, polyethylene glycol, poly (1,2- and 1,3-) propylene glycol, polytetramethylene glycol and polyhexanemethylene glycol, as described above. In addition to the branched aliphatic ether glycol, a single polymer or copolymer of an alicyclic ether such as a condensate of cyclohexanediol and a condensate of cyclohexanedimethanol is exemplified.
Moreover, the random copolymer in these ether units may be sufficient.
Among 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 preferred. More preferred are polymethylene glycol, polyethylene glycol, poly (1,2- and 1,3-) propylene glycol and polytetramethylene glycol, and particularly preferred is polytetramethylene glycol.
These may be used alone or in combination of two or more.

  Moreover, when manufacturing an alicyclic polyester-polyalkylene glycol block copolymer, the aromatic dicarboxylic acid used as a raw material in the case of manufacturing said aromatic polyester-polyalkylene glycol block copolymer, or its alkyl ester Instead of alicyclic dicarboxylic acid or its alkyl ester, it may be used.

  That is, it is obtained by esterification reaction or 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. The obtained oligomer can be obtained by polycondensation.

  As the alicyclic dicarboxylic acid or its alkyl ester, those generally used as raw materials for polyesters can be used, for example, cyclohexane dicarboxylic acid and its lower alkyl ester, cyclopentane dicarboxylic acid and its lower alkyl ester, etc. Can be mentioned. Among these, cyclohexanedicarboxylic acid and its lower alkyl ester are preferable, and cyclohexanedicarboxylic acid is particularly preferable. One of these alicyclic dicarboxylic acids may be used alone, or two or more thereof may be used in combination.

  The content of each of the cyclic polyester unit and the polyalkylene glycol unit in the cyclic polyester-polyalkylene glycol block copolymer is not limited. However, from the balance of crystallinity of the hard segment and flexibility of the soft segment, it is usually as follows. 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. Moreover, the upper limit of content of a cyclic polyester unit is 95 mass% or less normally, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, Most preferably, it is 40 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. 60% by mass or more. Moreover, the upper limit of content of a polyalkylene glycol unit is 90 mass% or less normally, Preferably it is 80 mass% or less.

  In addition, 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 the content using nuclear magnetic resonance spectroscopy (NMR). it can. Similarly, the content of the polyalkylene glycol unit in the block copolymer having the polyalkylene glycol unit is calculated based on the chemical shift of the hydrogen atom and the 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 the crystallization speed is particularly fast and the moldability is excellent. 2-12 are preferable, as for carbon number of an alkylene group, 2-8 are more preferable, 2-5 are still more preferable, and 4 is especially preferable.

  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 a trifunctional alcohol and tricarboxylic acid and / or its component. One kind or two or more kinds of 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.

  Said cyclic polyester-polyalkylene glycol block copolymer can also be obtained as a commercial item. Examples of such commercially available products include “KEYFLEX (registered trademark)” (manufactured by LG Chemical Co., Ltd.), “Primalloy (registered trademark)” (manufactured by Mitsubishi Chemical Corporation), and “Perprene (registered trademark)” (Toyo Spinner). And "Hytrel (registered trademark)" (manufactured by DuPont).

  Polyester thermoplastic elastomers such as cyclic polyester-polyalkylene glycol block copolymers may be used alone or in combination of two or more.

[Component (B)]
In the present invention, as the rubbery copolymer of component (B), an acrylic core-shell rubbery polymer such as an acrylate / styrene / acrylonitrile copolymer (ASA resin), an acrylate / methyl methacrylate copolymer; silicone / acrylate / Silicone core-shell type rubbery polymer such as methyl methacrylate copolymer, silicone / acrylate / acrylonitrile / styrene copolymer; butadiene / acrylonitrile copolymer rubbery polymer (NBR) is used. In the present invention, oil resistance can be enhanced because of the high polarity by using these limited specific rubbery polymers as the rubbery polymer of the component (B).
In addition, these rubbery polymers may use only 1 type, and may use 2 or more types together.

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

  In the polyester-based thermoplastic elastomer composition of the present invention, the blending amount of the rubber polymer of the component (B) is preferably 10 to 400 parts by weight with respect to 100 parts by weight of the polyester elastomer of the component (A). Preferably it is 20-200 mass parts, More preferably, it is 40-125 mass parts. If the amount of 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 upper limit, oil resistance and wear resistance tend to be insufficient. .

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

  Component (C) functions as a plasticizer, and examples thereof include dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, and diisononyl phthalate. Phthalate compounds; Phosphate 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 Fatty acid ester compounds such as ruadipate, diisobutyl adipate, dibutyl adipate, diisodecyl adipate, dibutyl diglycol adipate, di-2-ethylhexyl azelate, dioctyl sebacate, methylacetyl ricinolate; pyromellitic acid such as pyromellitic octyl ester Acid ester compounds; epoxidized soybean oil, epoxidized linseed oil, epoxidized ester compounds such as epoxidized fatty acid alkyl ester; and polyether ester compounds such as adipic acid ether ester and polyether ester; diethylene glycol dibenzoate, polypropylene Glycol dibenzoate, tripropylene glycol dibenzoate, dipropylene glycol dibenzoate, propylene glycol dibenzoate Benzoate ester compounds such as benzoate, dibutylene glycol dibenzoate, neopentyl glycol dibenzoate, glycerin tribenzoate, pentaerythritol tetrabenzoate, triethylene glycol dibenzoate, polyethylene glycol dibenzoate, trimethylolethane tribenzoate; and mineral oil And hydrocarbon softeners such as synthetic resin softeners and synthetic resin softeners. Among these, trimellitic acid ester compounds are preferred because of their high affinity with the component (A) polyester elastomer. Particularly preferred is tri-2-ethylhexyl trimellitic acid.

  In this invention, only 1 type of these ester compounds may be used, and 2 or more types may be used in arbitrary combinations and ratios.

  In the polyester thermoplastic elastomer composition of the present invention, the compounding amount of the ester compound of component (C) is preferably 6 to 100 parts by mass with respect to 100 parts by mass of the polyester elastomer of component (A). Preferably it is 10-80 mass parts, More preferably, it is 15-50 mass parts. If the amount of 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 components (A), (B) and (C).
By including a component (D), abrasion resistance can be improved without impairing the softness | flexibility, oil resistance, and moldability of a polyester-type thermoplastic elastomer composition.

  Examples of the carbodiimide compound include compounds having one or more carbodiimide groups in the molecule (including polycarbodiimide compounds). Specifically, as the monocarbodiimide compound, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, Examples include dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N, N′-di-2,6-diisopropylphenylcarbodiimide and the like. As the polycarbodiimide compound, those having a degree of polymerization of usually 2 or more, preferably 4 or more and an upper limit of usually 40 or less, preferably 30 or less are used. US Pat. No. 2,941,956, JP 47-33279, J. Pat. Org. Chem. 28, p2069-2075 (1963), and Chemical Review 1981, 81, No. 4, p. And those produced by the method described in 619-621 and the like.

  Examples of the organic diisocyanate that is a raw material for producing the polycarbodiimide compound include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and mixtures thereof. Specifically, 1,5-naphthalene diisocyanate, 4 , 4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4 A mixture of tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate And 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropylbenzene-2,4-diisocyanate, etc. .

  Specific examples of carbodiimide compounds that can be industrially obtained include Carbodilite HMV-8CA (manufactured by Nisshinbo Chemical Co., Ltd.), Carbodilite LA-1 (manufactured by Nisshinbo Chemical Co., Ltd.), Starbakusol P (manufactured by Rhein Chemie), Starbactol P100 (manufactured by Rhein Chemie) And the like.

  These carbodiimide compounds may be used alone or in combination of two or more.

  In the polyester-based thermoplastic elastomer composition of the present invention, the amount of the component (D) carbodiimide compound is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A) polyester elastomer. More preferably, it is 1-3 mass parts. If the amount of 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 production cost increases, which is not realistic.

[Other ingredients]
In the polyester-based thermoplastic elastomer composition of the present invention, other components other than the above components (A) to (D), for example, various additives and fillings, as long as the object of the present invention is not impaired. A material etc. can be mix | blended suitably.

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

  As filler, talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, glass cut fiber, Glass milled fiber, glass flake, glass powder, silicon carbide, silicon nitride, gypsum, gypsum whisker, calcined kaolin, carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, metal powder, ceramic Inorganic fillers such as whisker, potassium titanate, boron nitride, graphite, carbon fiber; organic fillers such as starch, cellulose fine particles, wood flour, okara, fir shell, bran, natural polymers and their modified products etc And the like. 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, based on all components.

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

  The polyester-based thermoplastic elastomer composition of the present invention is obtained by impregnating a rubber polymer of component (B) with an ester compound of component (C), which is a plasticizer, to form a composite, and then component (A), component (D) Other components to be blended as necessary are mechanically mixed by a known method such as a Henschel mixer, V blender, tumbler blender, etc., and then mechanically melt-kneaded by a known method. Can also be manufactured. Also in this case, a general melt-kneader such as a Banbury mixer, various kneaders, a single-screw or twin-screw extruder can be used for mechanical melt-kneading.

  When the rubber compound of component (B) is impregnated with the ester compound of component (C), the compounding 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. When the amount of the ester compound exceeds 66 parts by mass, the rubber polymer may not be impregnated with the total amount of the compounded ester compound.

[Physical properties 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 min or less, more preferably 90 g / 10 min or less, and still more preferably 80 g / 10 min. If the MFR exceeds the above upper limit, it is considered that burrs are generated during injection molding and a molded product cannot be obtained.

  Since the polyester-based thermoplastic elastomer composition of the present invention is required to have a soft tactile sensation from the viewpoint of the application to which it is applied, the Duro A hardness is preferably 40 to 90, more preferably 50 to 80. Preferably, it is 60-70.

  Further, the polyester-based thermoplastic elastomer composition of the present invention is easily expected to come into contact with oil components such as human fat components and machine oils from the viewpoint of the application to which the polyester-based thermoplastic elastomer composition is applied. Therefore, the mass increase rate and the volume increase rate after being immersed in a liquid resistance test oil “IRM903” of vulcanized rubber or thermoplastic rubber for 24 hours at room temperature are preferably 9% or less. % Or less is more preferable, and 5% or less is further preferable.

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

  In addition, about the evaluation method of said duro A hardness, oil resistance, and abrasion resistance, it describes in the item of an Example concretely.

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

  Since the polyester-based thermoplastic elastomer composition of the present invention is excellent in moldability by using a specific rubber polymer, it can be molded by various molding methods such as injection molding, extrusion molding and blow molding. Yes, it can also be applied to a molding method combining a plurality of molding techniques such as injection blow molding combining injection molding and blow molding.

  The molded body produced from the polyester-based thermoplastic elastomer composition of the present invention has a soft texture and is excellent in oil resistance, wear resistance and the like. For this reason, stationery; toys; sports equipment; covers for mobile phones and smartphones; parts such as grips; school teaching materials, home appliances, repair parts for OA equipment, various parts such as automobiles, motorcycles, and bicycles; It can use suitably for various uses, such as a member.

  Hereinafter, the content of the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist. The values of various production conditions and evaluation results in the following examples have meanings as preferred values of the upper limit or lower limit in the embodiments of the present invention, and the preferred ranges are the upper limit or lower limit values described above, and It may be a range defined by a combination of values of the examples or values between the examples.

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

<Component (B)>
B-1: Kaneace (registered trademark) FM-40 manufactured by Kaneka Corporation
Butyl acrylate / methyl methacrylate copolymer B-2: Metablene (registered trademark) W-450 manufactured by Mitsubishi Rayon Co., Ltd.
Alkyl methacrylate / alkyl acrylate copolymer B-3: Metablene (registered trademark) S-2001 manufactured by Mitsubishi Rayon Co., Ltd.
Alkyl methacrylate / alkyl acrylate / dimethylsiloxane copolymer B-4: Nipol (registered trademark) 1411 manufactured by Nippon Zeon Co., Ltd.
Acrylonitrile / butadiene copolymer B-5: Chemnova (registered trademark) P-83 manufactured by Omninova
Acrylonitrile / butadiene copolymer B-6: METABRENE (registered trademark) S-2501 manufactured by Mitsubishi Rayon Co., Ltd.
Alkyl methacrylate / alkyl acrylate / dimethylsiloxane copolymer B-7: Clayton (registered trademark) G1641HU manufactured by Clayton
Styrene-ethylene / butylene-styrene block copolymer <component (C)>
C-1: TOPLUS (registered trademark) manufactured by J-Plus
Trimellitic acid tri-2-ethylhexyl C-2: Process oil (registered trademark) PW-90 manufactured by Idemitsu Kosan Co., Ltd.
Petroleum hydrocarbon (mineral oil)

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

[Examples 1-13, Comparative Examples 1-3]
[Production of polyester-based thermoplastic elastomer composition]
Each component described in the composition of Table-1 and Table-2 was melt-kneaded (cylinder temperature 200) with a twin-screw kneader to produce a polyester thermoplastic elastomer composition pellet.

[Creation of molded product for physical property evaluation]
The above polyester thermoplastic elastomer composition pellets are injected at a mold temperature of 40 ° C. and a cylinder temperature of 200 to 230 ° C. using an injection molding machine (“J110AD” manufactured by Nippon Steel Works, mold clamping force 110T). Molding was performed to obtain a molded body of 100 mm × 100 mm and a thickness of 2 mm.
Hereinafter, they will be referred to as “molded bodies for evaluating physical properties”, respectively.

〔Evaluation method〕
The results of evaluating the pellets of the polyester 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 evaluating physical properties by the following methods are shown in Tables 1 and It is shown in 2.

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

<Moldability>
The ease with which the molded product was removed from the mold in injection molding was evaluated according to the following criteria.
+: When taking out the molded body from the mold, it is necessary to pull with a strong force using human power.
++: When taking out the molded body from the mold, it is necessary to pull it with light force using human power.
+++: It is not necessary to use human power when taking out the molded body from the mold.

<Duro A hardness>
About the molded object for physical property evaluation created above, Duro A hardness was measured based on ISO 7619-1.

<Oil resistance>
The molded product for physical property evaluation prepared above is immersed in a liquid resistance test oil “IRM903” of vulcanized rubber or thermoplastic rubber specified by JIS K6258 and ASTM D47 for 24 hours at a temperature 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>
About the compact | molding | casting for the physical property evaluation produced above, the Toyo Seiki Co., Ltd. Taber type | mold abrasion tester was used, and the mass reduction amount before and behind an abrasion test and an abrasion trace external appearance were evaluated. Using “CS-17” as a wear ring, a load of 9.8 N was applied and the wheel was rotated 1000 times. Regarding the amount of mass reduction, it is preferable that the amount of mass reduction before and after the wear test is small, and the appearance of wear marks is relatively evaluated by “+”, “++”, and “++++”, and the more “+” is more preferable.

[Discussion]
As shown in Table 2, Comparative Examples 1 and 2 use only a polyester elastomer and an ester compound and do not use a rubbery polymer, and are excellent in oil resistance and wear resistance. Inferior.

  Comparative Example 3 uses a styrene thermoplastic elastomer as a rubbery polymer and paraffin oil as an ester compound, and it is found that although the moldability is not inferior, it is inferior in oil resistance and wear resistance. It was.

  In contrast, in Examples 1 to 13, the rubbery polymer is an acrylic core-shell type rubbery polymer such as an acrylate / methyl methacrylate copolymer, a silicone / acrylate / methyl methacrylate copolymer rubbery polymer, a silicone / Trimellitic acid tri-ester which is an ester compound using a rubbery polymer selected from silicone-based core-shell type rubbery copolymer such as acrylate / acrylonitrile / styrene copolymer resin, butadiene / acrylonitrile copolymer rubbery polymer, etc. It uses 2-ethylhexyl and is excellent in balance in flexibility, oil resistance, wear resistance, and moldability as compared with Comparative Examples 1 to 3. In particular, in Example 6, the wear resistance was dramatically improved by using a carbodiimide compound.

  From Tables 1 and 2, according to the present invention, by blending a specific rubbery polymer and an ester compound into a polyester elastomer, the polyester elastomer has a soft texture, oil resistance, wear resistance and molding. It can be seen that a polyester-based thermoplastic elastomer composition having excellent properties can be provided. Furthermore, it turns out that abrasion resistance can further be improved by mix | blending a carbodiimide compound.

  According to the present invention, by providing a specific elastomeric polymer and an ester compound, preferably a carbodiimide compound, to a polyester elastomer, a molded article having a soft texture and excellent in oil resistance and wear resistance is provided. can do. The molded article produced according to the present invention is a stationery; a toy; a sports article; a cover for a mobile phone or a smartphone; a part such as a grip; a school teaching material, a home appliance, a repair part for OA equipment, or a variety of parts such as an automobile, a motorcycle, or a bicycle. It can be suitably used for applications such as building materials.

Claims (10)

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 type rubbery polymer, a silicone type core-shell type rubbery copolymer, and a butadiene / acrylonitrile copolymer rubbery polymer Rubbery polymer component (C): ester compound   10 to 400 parts by mass of the rubber polymer of the component (B) and 6 to 100 parts by mass of the ester compound of the component (C) with respect to 100 parts by mass of the polyester elastomer of the component (A) The polyester-based thermoplastic elastomer composition according to claim 1.   Furthermore, the polyester-type thermoplastic elastomer composition of Claim 1 or 2 which contains 0.01-10 mass parts of carbodiimide compounds as a component (D) with respect to 100 mass parts of polyester elastomers of the said component (A).   The polyester-based thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the component (A) includes a polyalkylene glycol component, and the polyalkylene glycol is polytetramethylene glycol.   The polyester-based thermoplastic elastomer composition according to any one of claims 1 to 4, comprising a polyalkylene glycol component of component (A), wherein the content of the polyalkylene glycol component is 60% by mass or more.   The polyester-based thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the component (B) includes a unit derived from an alkyl methacrylate compound.   The polyester-based thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the component (C) is tri-2-ethylhexyl trimellitic acid.   The polyester-based thermoplastic elastomer composition according to any one of claims 1 to 7, wherein the component (D) is a carbodiimide-modified isocyanate.   The polyester-based thermoplastic elastomer composition according to any one of claims 1 to 8, which is a polyester-based thermoplastic elastomer composition for grips.   The molded object which uses the polyester-type thermoplastic elastomer composition of any one of Claims 1 thru | or 9 as a raw material.