Adhesive resin composition

Abstract

To provide a resin composition that enables superior thermal and melt adhesion to a resin having a polar group and allows development of sufficient tensile fracture strain.SOLUTION: A resin composition comprises (A) a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, (B) a polyester elastomer, (C) a crystalline polyester, and (D) an ethylene-unsaturated carboxylic acid copolymer, the resin composition optionally further containing (E) a non-aromatic rubber softener. The component (A) may have structural units derived from β-farnesene. The component (B) may include a polybutylene terephthalate-based elastomer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an adhesive resin composition. [Background technology]

[0002] Traditionally, flexible elastomers have been bonded or laminated to the surfaces of structural components, such as automobiles, buildings, furniture, and home appliances, for the purposes of shock absorption and breakage prevention, or for fastening, bonding, adhering, or sealing other structural components. Hydrogenated block copolymers of aromatic vinyl compounds and conjugated diene compounds are often used as elastomer materials for these applications due to their flexibility, tensile properties, and moldability, as well as their excellent thermal and melt adhesion to polyolefins such as polypropylene. However, while polar-group-containing resins such as acrylonitrile-butadiene-styrene copolymers (ABS resins) and aromatic polycarbonates (PC resins) are often used as materials for these structural components, hydrogenated block copolymers of aromatic vinyl compounds and conjugated diene compounds have the disadvantage of poor thermal and melt adhesion to these polar-group-containing resins. Therefore, as a technique for imparting thermal adhesion and melt adhesion to a resin having a polar group to a resin composition containing a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, techniques such as those disclosed in Patent Documents 1 and 2 have been proposed. However, these techniques have the disadvantage that the tensile breaking strain is low, which limits the types and shapes of parts to which they can be applied. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2018-024776 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-249373 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a resin composition which has excellent thermal adhesion and melt adhesion to resins having polar groups and which exhibits a sufficient tensile breaking strain. [Means for solving the problem]

[0005] As a result of extensive research, the present inventors have found that the above object can be achieved by using a specific resin composition.

[0006] That is, the various aspects of the present invention are as follows. [1]. A resin composition comprising: (A) 20 to 88 mass% of a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound; (B) 4 to 32 mass% of a polyester elastomer; (C) 4 to 48 mass% of a crystalline polyester (excluding those corresponding to the component (B) polyester elastomer); and (D) 4 to 42 mass% of an ethylene-unsaturated carboxylic acid copolymer, wherein the sum of the blend amounts of the component (A), the component (B), the component (C), and the component (D) is 100 mass%. [2]. The resin composition according to item [1], wherein the component (A) hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound comprises a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound, the hydrogenated block copolymer having a structural unit derived from β-farnesene. [3]. The resin composition according to item [1], wherein the component (B) polyester-based elastomer includes (B1) polybutylene terephthalate-based elastomer. [4]. The resin composition according to item [1], wherein the melting point of the component (C) crystalline polyester is 90 to 160°C. [5]. The resin composition according to item [1], further comprising 5 to 100 parts by mass of a non-aromatic rubber softener (E), where the sum of the amounts of the components (A), (B), (C), and (D) is 100 parts by mass. [6]. An article comprising the resin composition according to any one of items [1] to [6]. [Effects of the Invention]

[0007] The resin composition of the present invention exhibits excellent thermal adhesion and melt adhesion to resins having polar groups, such as ABS resin and PC resin, and exhibits sufficient tensile strain at break. Preferred resin compositions of the present invention also exhibit excellent flexibility. Therefore, the resin composition of the present invention can be suitably used as a material to be bonded to or laminated on the surface of structural members made of resins having polar groups, such as ABS resin and PC resin. Articles in which the resin composition of the present invention is bonded to or laminated on the surface of a structural member can be suitably used as parts for automobiles, buildings, furniture, home appliances, and the like. DETAILED DESCRIPTION OF THE INVENTION

[0008] In this specification, the term "resin" is used to include a resin mixture containing two or more resins, and a resin composition containing components other than resin.

[0009] In this specification, the term "film" is used interchangeably or interchangeably with "sheet." In this specification, the terms "film" and "sheet" are used to refer to materials that can be industrially wound into rolls. The term "plate" is used to refer to materials that cannot be industrially wound into rolls. In addition, in this specification, laminating one layer and another layer in order includes both directly laminating the layers and laminating the layers with one or more additional layers, such as an anchor coat, interposed between them.

[0010] In this specification, the term "more than or equal to" in relation to a numerical range means a certain number or more than a certain number. For example, 20% or more means 20% or more than 20%. The term "less than or equal to" in relation to a numerical range means a certain number or less than a certain number. For example, 20% or less means 20% or less than 20%. Furthermore, the symbol "to" in relation to a numerical range means a certain number, more than a certain number and less than another certain number, or another certain number. Here, another certain number is a number greater than the certain number. For example, 10 to 90% means 10%, more than 10% and less than 90%, or 90%. Furthermore, the upper and lower limits of a numerical range can be arbitrarily combined, and embodiments incorporating such combinations can be interpreted. For example, from a statement regarding the numerical range of a certain characteristic such as "usually 10% or more, preferably 20% or more. On the other hand, it is usually 40% or less, preferably 30% or less," or "usually 10 to 40%, preferably 20 to 30%," it can be read that the numerical range of the certain characteristic is 10 to 40%, 20 to 30%, 10 to 30%, or 20 to 40% in one embodiment.

[0011] Other than in the examples, or where otherwise specified, all numerical values ​​used in the specification and claims should be understood to be modified by the term "about." Without attempting to limit the application of the doctrine of equivalents to the claims, each numerical value should be construed in light of the number of significant digits and by applying ordinary rounding techniques.

[0012] In this specification, terms specifying shapes or geometric conditions, such as parallel, orthogonal, and perpendicular, are intended to include not only the strict meanings but also substantially the same states.

[0013] In this specification, when it is explained that "comprises a certain substance," it is to be understood that, in one embodiment, it contains a certain substance, consists of a certain substance, or consists only of a certain substance. For example, from the explanation that "composition A comprises substances a1 and a2," it is to be understood that, in one embodiment, composition A comprises substances a1 and a2, composition A consists of substances a1 and a2, or composition A consists only of substances a1 and a2.

[0014] 1.Resin composition: The resin composition of the present invention comprises (A) a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound, (B) a polyester elastomer, (C) a crystalline polyester, and (D) an ethylene-unsaturated carboxylic acid copolymer. In one embodiment, the resin composition of the present invention may further comprise (E) a non-aromatic rubber softener. Each component will be described below.

[0015] (A) Hydrogenated block copolymer of aromatic vinyl compound and conjugated diene compound: The resin composition of the present invention contains the component (A), a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound. The component (A), a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound, functions to improve flexibility, tensile properties, moldability, and thermal adhesion and melt adhesion to polyolefins such as polypropylene. Furthermore, in embodiments in which the component (E), a non-aromatic rubber softener, is used, the component (A), a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound, functions to suppress bleed-out of the component (E).

[0016] The hydrogenated block copolymer of component (A) an aromatic vinyl compound and a conjugated diene compound is a substance obtained by adding hydrogen to a block polymer containing one or more aromatic vinyl compound polymer segments (a1) and one or more conjugated diene compound polymer segments (a2), thereby converting some or all of the carbon-carbon double bonds in the block polymer into carbon-carbon single bonds. Examples of the hydrogenated block copolymer of component (A) an aromatic vinyl compound and a conjugated diene compound include those having segment structures such as (a1)-(a2), (a1)-(a2)-(a1), (a2)-(a1)-(a2), (a1)-(a2)-(a1)-(a2), and (a1)-(a2)-(a1)-(a2)-(a1).

[0017] The aromatic vinyl compound is a polymerizable monomer having a polymerizable carbon-carbon double bond and an aromatic ring. Examples of the aromatic vinyl compound include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N,N-diethyl-p-aminoethylstyrene, vinyltoluene, and p-tert-butylstyrene. The aromatic vinyl compound may preferably contain styrene. One or more of these compounds may be used as the aromatic vinyl compound.

[0018] The conjugated diene compound is a polymerizable monomer having a structure in which two carbon-carbon double bonds are bonded by one carbon-carbon single bond. Examples of the conjugated diene compound include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, 7-methyl-3-methyleneocta-1,6-diene (β-myrcene), 3,7,11-trimethyl-1,3,6,10-dodecatetraene (α-farnesene), 7,11-dimethyl-3-methylene-1,6,10-dodecatriene (β-farnesene), and chloroprene (2-chloro-1,3-butadiene). The conjugated diene compound may preferably contain one or more selected from the group consisting of 1,3-butadiene, isoprene, β-myrcene, α-farnesene, and β-farnesene, and one or more of these can be used as the conjugated diene compound.

[0019] The (a1) aromatic vinyl compound polymer segment is a polymer segment mainly containing structural units derived from the aromatic vinyl compound. Here, "mainly containing" means that the content of structural units derived from the aromatic vinyl compound is 60 to 100% by mass. From the viewpoint of heat resistance, the content of structural units derived from the aromatic vinyl compound may be preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, still more preferably 95% by mass or more, and most preferably 99 to 100% by mass.

[0020] Examples of the (a1) aromatic vinyl compound polymer segment include a homopolymer segment of the aromatic vinyl compound, a copolymer segment of the aromatic vinyl compound and the conjugated diene compound, etc. When there are two or more (a1) aromatic vinyl compound polymer segments, they may have the same structure or different structures.

[0021] The (a2) conjugated diene compound polymer segment is a polymer segment mainly containing structural units derived from the conjugated diene compound. Here, "mainly containing" means that the content of structural units derived from the conjugated diene compound is 60 to 100% by mass. From the viewpoint of flexibility, the content of structural units derived from the conjugated diene compound may be preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, still more preferably 95% by mass or more, and most preferably 99 to 100% by mass.

[0022] Examples of the (a2) conjugated diene compound polymer segment include a homopolymer segment of the conjugated diene compound, a copolymer segment of the conjugated diene compound and the aromatic vinyl compound, etc. When there are two or more (a2) conjugated diene compound polymer segments, they may have the same structure or different structures.

[0023] The hydrogenation rate of the hydrogenated product of the block copolymer of the aromatic vinyl compound and the conjugated diene compound (component (A)) (the ratio of the number of carbon-carbon single bonds resulting from hydrogenation to the number of carbon-carbon double bonds in the block copolymer of the aromatic vinyl compound and the conjugated diene compound before hydrogenation) may be, from the viewpoint of heat resistance, usually 50 mol % or more, preferably 60 mol % or more, more preferably 70 mol % or more, even more preferably 80 mol % or more, and most preferably 90 to 100 mol %.

[0024] The content of structural units derived from the aromatic vinyl compound in the hydrogenated block copolymer of component (A) an aromatic vinyl compound and a conjugated diene compound may be preferably 5 to 60 mass %, more preferably 10 to 50 mass %, and even more preferably 20 to 40 mass %, from the viewpoints of flexibility and heat resistance.

[0025] The mass average molecular weight (Mw) of the hydrogenated block copolymer of the aromatic vinyl compound and the conjugated diene compound (component (A))) in terms of polystyrene obtained from the differential molecular weight distribution curve (hereinafter sometimes abbreviated as "GPC curve") measured by gel permeation chromatography (hereinafter sometimes abbreviated as "GPC") is preferably 1.5 × 10 in terms of tensile properties. 4 More preferably, 4.5 × 10 4 More preferably, 1.5 × 10 5 On the other hand, from the viewpoint of moldability, the mass average molecular weight (Mw) is preferably 1.5 × 10 6 Less than or equal to 1.2 × 10 6 It may be the following:

[0026] The number average molecular weight (Mn) of the hydrogenated block copolymer of the component (A), an aromatic vinyl compound and a conjugated diene compound, calculated as polystyrene from the GPC curve is preferably 1.0×10 4 More preferably, 3.0 × 10 4 More preferably, 1.0 × 10 5 On the other hand, the number average molecular weight (Mn) is preferably 1.0 × 10 or more from the viewpoint of moldability. 6 Less than or equal to 8.0 × 10 5 It may be the following:

[0027] The GPC measurement of the hydrogenated product of the block copolymer of the above component (A) aromatic vinyl compound and conjugated diene compound can be carried out using a high-performance liquid chromatography system "HLC-8320 (trade name)" of Tosoh Corporation (a system including a degasser, a liquid delivery pump, an autosampler, a column oven, and a RI (differential refractive index) detector) as a system. As GPC columns, two "KF-806L (trade name)" of Shodex, one "KF-802 (trade name)", and one "KF-801 (trade name)" are used, for a total of four columns. They are connected in series in the order of KF-806L, KF-806L, KF-802, and KF-801 from the upstream side and used. Tetrahydrofuran (without stabilizer) is used as the mobile phase, and the measurement is carried out under the conditions of a column temperature of 40 °C, a flow rate of 1.0 mL / min, a sample concentration of 1 mg / mL, and a sample injection volume of 100 μL. The elution amount at each retention volume can be obtained from the detection amount of the RI detector assuming that the molecular weight dependence of the refractive index of the measurement sample is absent. The calibration curve from each retention volume to the polystyrene-equivalent molecular weight can be created using standard polystyrene. At this time, it should be noted that the standard polystyrene to be used should be appropriately selected so that the retention volume of the measurement sample is interpolated into the plot of the calibration curve. For the theory and actual measurement of GPC, reference books such as "Size Exclusion Chromatography, High-Performance Liquid Chromatography of Polymers, Author: Sadao Mori, First Edition, First Printing, December 10, 1991" by Kyoritsu Shuppan Co., Ltd., and "Synthetic Polymer Chromatography, Editors: Hajime Ohtani, Tatsuya Takasaki (the upper part of "崎" is "立"), First Edition, First Printing, July 25, 2013" by Ohmsha, Ltd. can be referred to.

[0028] Examples of component (A), hydrogenated block copolymers of aromatic vinyl compounds and conjugated diene compounds, include styrene-ethylene-butene block copolymer (SEB), styrene-ethylene-propylene block copolymer (SEP), styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butylene-styrene copolymer (partially hydrogenated styrene-butadiene-styrene copolymer: SBBS), partially hydrogenated styrene-isoprene-styrene copolymer, partially hydrogenated styrene-isoprene-butadiene-styrene copolymer, and hydrogenated styrene-β-farnesene block copolymer.

[0029] The component (A), a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound, may preferably comprise a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound having structural units derived from β-farnesene, such as the hydrogenated styrene-β-farnesene block copolymer. β-Farnesene is obtained by fermenting sugars from sugarcane, which reduces the environmental impact. Furthermore, the inclusion of structural units derived from β-farnesene can improve the balance between flexibility and thermal and melt adhesive properties with resins containing polar groups.

[0030] As the component (A), the hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound, one or a mixture of two or more of these compounds can be used.

[0031] (B) Polyester elastomer: The resin composition of the present invention contains the component (B) polyester elastomer. The component (B) polyester elastomer is a copolymer of a polycarboxylic acid and a polyhydroxy compound, and has a polyester segment and a polyester polyol segment. Here, the polyester segment is a segment that functions as a hard segment of the component (B) polyester elastomer. The polyester polyol segment is a segment that functions as a soft segment of the component (B) polyester elastomer.

[0032] The component (B) polyester elastomer is preferably a copolymer of a polycarboxylic acid and a polyhydroxy compound, and may be a copolymer having an aromatic polyester segment (b1) and an aliphatic polyester polyol segment (b2). Here, the aromatic polyester segment (b1) serves as a hard segment of the component (B) polyester elastomer. The aliphatic polyester polyol segment (b2) serves as a soft segment of the component (B) polyester elastomer.

[0033] In this specification, a crystalline polyester that is also a polyester-based elastomer is the component (B) polyester-based elastomer. In other words, anything that falls under the component (B) polyester-based elastomer is excluded from the component (C) crystalline polyester.

[0034] The polyester elastomer component (B) functions to improve heat resistance, chemical resistance, tensile properties, moldability, and thermal adhesion and melt adhesion to resins having polar groups.

[0035] The polycarboxylic acid is a compound having two or more carboxyl groups in one molecule, or an ester-forming derivative thereof. Although omitted in the following description, the following embodiment is intended to be interpreted as including an ester-forming derivative of the compound. For example, the term "terephthalic acid" can be interpreted as "terephthalic acid or an ester-forming derivative thereof."

[0036] Examples of the polycarboxylic acid include dicarboxylic acids such as aromatic dicarboxylic acids and aliphatic dicarboxylic acids.

[0037] Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid.

[0038] Examples of the aliphatic dicarboxylic acid include chain aliphatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, and eicosanedicarboxylic acid; and alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, and norbornanedicarboxylic acid.

[0039] As the polycarboxylic acid, one or more of these can be used.

[0040] The polyhydroxy compound is a compound having two or more hydroxyl groups in one molecule, or an ester-forming derivative thereof. Although omitted in the following description, the following embodiment is intended to be interpreted as including an ester-forming derivative of the compound. For example, the term "ethylene glycol" can be interpreted as "ethylene glycol or an ester-forming derivative thereof."

[0041] Examples of the polyhydric hydroxy compound include dihydric alcohols, dihydroxy compounds such as aromatic dihydroxy compounds, and saturated aliphatic polyethers.

[0042] Examples of the dihydric alcohol include chain dihydric alcohols such as ethylene glycol, diethylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,3-propanediol, and cyclic dihydric alcohols such as 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0043] Examples of the aromatic dihydroxy compound include bisphenol A (2,2-bis(4-hydroxyphenyl)propane), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane.

[0044] Examples of the saturated aliphatic polyether include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, and polymers of one or more of these.

[0045] As the polyvalent hydroxy compound, one or more of these compounds can be used.

[0046] The (b1) aromatic polyester segment is a segment of an aromatic polyester of the aromatic dicarboxylic acid and the dihydroxy compound, and serves as a hard segment of the component (B) polyester elastomer.

[0047] The aromatic dicarboxylic acid used in the (b1) aromatic polyester segment may preferably contain terephthalic acid. The dihydroxy compound used in the (b1) aromatic polyester segment may preferably contain the dihydric alcohol, more preferably a chain dihydric alcohol. The (b1) aromatic polyester segment may contain structural units derived from the aromatic dicarboxylic acid and a comonomer other than the dihydroxy compound, to the extent that they function as hard segments.

[0048] Examples of the (b1) aromatic polyester segment include a polybutylene terephthalate segment and a polyethylene terephthalate segment. The polybutylene terephthalate segment is an aromatic polyester segment of terephthalic acid and 1,4-butanediol. The polyethylene terephthalate segment is an aromatic polyester segment of terephthalic acid and ethylene glycol.

[0049] The polybutylene terephthalate segment may contain a structural unit derived from a comonomer other than terephthalic acid and 1,4-butanediol, to the extent that it functions as a hard segment. Examples of the comonomer that the polybutylene terephthalate segment may contain include the aromatic dicarboxylic acids other than terephthalic acid, such as isophthalic acid, the dicarboxylic acids, such as aliphatic dicarboxylic acids, the dihydric alcohols other than 1,4-butanediol, such as ethylene glycol, and the dihydroxy compounds, such as the aromatic dihydroxy compounds.

[0050] The polyethylene terephthalate segment may contain a structural unit derived from a comonomer other than terephthalic acid and ethylene glycol, to the extent that it functions as a hard segment. Examples of the comonomer that the polyethylene terephthalate segment may contain include the aromatic dicarboxylic acids other than terephthalic acid, such as isophthalic acid, and the dicarboxylic acids, such as the aliphatic dicarboxylic acids, as well as the dihydric alcohols other than ethylene glycol, such as 1,4-butanediol, and the dihydroxy compounds, such as the aromatic dihydroxy compounds.

[0051] When there are two or more aromatic polyester segments (b1), they may have the same structure or different structures.

[0052] The (b2) aliphatic polyester polyol segment functions as a soft segment of the component (B) polyester elastomer. Examples of the (b2) aliphatic polyester polyol segment include aliphatic polyether segments such as the saturated aliphatic polyethers and copolymers of the saturated aliphatic polyethers and the dicarboxylic acids, as well as aliphatic polyester segments such as the aliphatic polyesters of the aliphatic dicarboxylic acids and the dihydric alcohols, and ring-opening polymers of lactones such as ε-caprolactone.

[0053] The dicarboxylic acid that the aliphatic polyester polyol segment (b2) may contain may preferably be an aliphatic dicarboxylic acid such as adipic acid.

[0054] When there are two or more aliphatic polyester polyol segments (b2), they may have the same structure or different structures.

[0055] Examples of the component (B) polyester-based elastomer include (B1) polybutylene terephthalate-based elastomers such as a polyester-based elastomer having the polybutylene terephthalate segment and the aliphatic polyether segment, and a polyester-based elastomer having the polybutylene terephthalate segment and the aliphatic polyester segment.

[0056] From the viewpoint of heat resistance and chemical resistance, the above-mentioned component (B) polyester elastomer may preferably contain the above-mentioned (B1) polybutylene terephthalate elastomer.

[0057] From the viewpoints of heat resistance and chemical resistance, the component (B) polyester elastomer may preferably be crystalline. In this case, the melting point of the component (B) polyester elastomer may preferably be 130°C or higher, more preferably 140°C or higher, and even more preferably 150°C or higher. The melting enthalpy of the component (B) polyester elastomer may preferably be 5 J / g or higher, and even more preferably 10 J / g or higher. On the other hand, from the viewpoint of keeping the molding temperature low, the melting point of the component (B) polyester elastomer may preferably be 200°C or lower, more preferably 190°C or lower, and even more preferably 180°C or lower. The melting enthalpy of the component (B) polyester elastomer may preferably be 40 J / g or lower, more preferably 30 J / g or lower, and even more preferably 20 J / g or lower.

[0058] The melting point and melting enthalpy of the polyester elastomer component (B) are calculated in accordance with JIS K7121-1987 using a differential scanning calorimeter (DSC) from a second melting curve (the melting curve measured during the final heating process) measured using a temperature program in which the sample is held at 320°C for 5 minutes, cooled to -50°C at a rate of 10°C / min, held at -50°C for 5 minutes, and then heated to 320°C at a rate of 10°C / min. The melting point is the peak-top temperature of the melting peak that appears in the second melting curve. When two or more melting peaks are observed, the melting point is determined to be the peak-top temperature of the melting peak with the greatest peak top height. The melting enthalpy is the sum of the melting enthalpies calculated from the individual melting peaks. Furthermore, "having crystallinity" means that a melting peak is observed in the second melting curve.

[0059] The mass average molecular weight (Mw) of the component (B) polyester elastomer, calculated in terms of polystyrene, determined from the GPC curve is preferably 1.0×10 4 More preferably, 3.0 × 10 4 More preferably, 7.0 × 10 4 On the other hand, from the viewpoint of moldability, the mass average molecular weight (Mw) is preferably 1.0 × 10 6 Less than 6.0 × 10, more preferably 5 It may be the following:

[0060] The number average molecular weight (Mn) of the component (B) polyester elastomer calculated in terms of polystyrene from the GPC curve is preferably 4.0×10 3 More preferably, 1.2 × 10 4 More preferably, 2.8 × 10 4 On the other hand, the number average molecular weight (Mn) is preferably 4.0 × 10 or more from the viewpoint of moldability. 5 Less than or equal to 2.4 × 10 5 It may be the following:

[0061] The GPC measurement of the above component (B) polyester-based elastomer and the above component (C) crystalline polyester is carried out using a high-performance liquid chromatography system (a system including a degasser, a liquid delivery pump, a column oven, and a RI (differential refractive index) detector) of JASCO Corporation as a system. As GPC columns, two GPC columns "PLgel 5μm MIXED-D (trade name)" of Agilent Technologies, Inc. are connected in series and used. 10 mg of the resin is dissolved in 1 mL of 1,1,1,3,3,3-hexafluoro-2-propanol, 9 mL of chloroform (containing 50 ppm of BHT (dibutylhydroxytoluene) as an antioxidant) is added, and the filtered solution through a polytetrafluoroethylene membrane filter is used as a measurement sample. Using chloroform as a mobile phase, it can be carried out under the conditions of a column temperature of 40 °C, a flow rate of 1 mL / min, and a sample injection volume of 100 μL. The elution amount at each retention volume can be determined from the detection amount of the RI detector assuming that there is no molecular weight dependence of the refractive index of the measurement sample. The calibration curve from each retention volume to the polystyrene-equivalent molecular weight can be created using standard polystyrene. At this time, it should be noted that the standard polystyrene to be used should be appropriately selected so that the retention volume of the measurement sample is interpolated into the plot of the calibration curve. For the theory of GPC and the actual measurement, reference books such as "Size Exclusion Chromatography High-Performance Liquid Chromatography of Polymers, Author: Sadao Mori, First Edition, First Printing, December 10, 1991" by Kyoritsu Shuppan Co., Ltd. and "Synthetic Polymer Chromatography, Editors: Hajime Ohtani, Tatsuya Takasaki (the upper part of '崎' is '立'), First Edition, First Printing, July 25, 2013" by Ohmsha, Ltd. can be referred to.

[0062] As the above component (B) polyester-based elastomer, one or a mixture of two or more of these can be used.

[0063] (C) Crystalline polyester: The resin composition of the present invention contains the above-mentioned component (C) crystalline polyester. The above-mentioned component (C) crystalline polyester is a copolymer of a polycarboxylic acid and a polyhydroxy compound, and is a crystalline polymer. Here, "crystalline" means that a melting peak is observed in the second melting curve described below.

[0064] In this specification, a crystalline polyester that is also a polyester-based elastomer is the component (B) polyester-based elastomer. In other words, anything that falls under the component (B) polyester-based elastomer is excluded from the component (C) crystalline polyester.

[0065] The crystalline polyester component (C) functions to improve the thermal adhesion and melt adhesion to the resin having a polar group, in other words, it functions as a hot melt adhesive.

[0066] Specific examples of the polycarboxylic acid as a constituent monomer of the crystalline polyester (C) include those mentioned above in the description of the polyester elastomer (B). The polycarboxylic acid as a constituent monomer of the crystalline polyester (C) may preferably contain terephthalic acid in order to impart crystallinity. In this case, the content of constituent units derived from terephthalic acid in the crystalline polyester (C) may be preferably 60 mol % or more, more preferably 70 mol % or more, and even more preferably 80 to 100 mol %, based on 100 mol % of the total content of constituent units derived from the polycarboxylic acid. One or more of these polycarboxylic acids may be used as the polycarboxylic acid as a constituent monomer of the crystalline polyester (C).

[0067] Specific examples of the polyhydric hydroxy compound as a constituent monomer of the component (C) crystalline polyester include those mentioned above in the description of the component (B) polyester-based elastomer. From the viewpoint of imparting crystallinity, the polyhydric hydroxy compound as a constituent monomer of the component (C) crystalline polyester may preferably contain the chain dihydric alcohol, more preferably one or more selected from the group consisting of ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, and even more preferably 1,4-butanediol. In this case, the content of the chain dihydric alcohol-derived constituent units in the component (C) crystalline polyester may be preferably 60 mol % or more, more preferably 70 mol % or more, and even more preferably 80 to 100 mol %, based on 100 mol % of the total content of the polyhydric hydroxy compound-derived constituent units. One or more of these polyhydric hydroxy compounds may be used as the constituent monomer of the component (C) crystalline polyester.

[0068] From the viewpoint of imparting crystallinity, the crystalline polyester component (C) may preferably contain structural units derived from terephthalic acid and structural units derived from one or more selected from the group consisting of ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, more preferably structural units derived from terephthalic acid and structural units derived from 1,4-butanediol. In this case, the content of structural units derived from terephthalic acid in the crystalline polyester component (C) may be preferably 60 mol % or more, more preferably 70 mol % or more, and even more preferably 80 to 100 mol %, based on 100 mol % of the total content of structural units derived from the polycarboxylic acids. The content of structural units derived from one or more selected from the group consisting of ethylene glycol, 1,4-butanediol, and 1,6-hexanediol in the crystalline polyester of component (C) may be preferably 60 mol % or more, more preferably 70 mol % or more, and even more preferably 80 to 100 mol %, with the total content of structural units derived from the polyhydroxy compounds being 100 mol %.

[0069] The fusion enthalpy of the crystalline polyester (C) may be preferably 40 J / g or less, more preferably 30 J / g or less, and even more preferably 20 J / g or less, from the viewpoint of improving the thermal adhesion and melt adhesion with a resin having a polar group, in other words, functioning as a hot-melt adhesive. On the other hand, the fusion enthalpy of the crystalline polyester (C) may be preferably 5 J / g or more, more preferably 10 J / g or more, from the viewpoint of heat resistance and chemical resistance.

[0070] The melting point of the crystalline polyester component (C) may be preferably 160° C. or lower, more preferably 150° C. or lower, even more preferably 140° C. or lower, and even more preferably 130° C. or lower, from the viewpoint of exhibiting thermal adhesiveness and melt adhesiveness with a resin having a polar group at a lower temperature. On the other hand, the melting point of the crystalline polyester component (C) may be preferably 90° C. or higher, more preferably 100° C. or higher, and even more preferably 110° C. or higher, from the viewpoint of heat resistance and chemical resistance.

[0071] The melting point and melting enthalpy of the crystalline polyester component (C) are calculated from a second melting curve (the melting curve measured during the final heating process) measured using a differential scanning calorimeter (DSC) in accordance with JIS K7121-1987, using a temperature program consisting of holding at 230°C for 5 minutes, cooling to -50°C at a rate of 10°C / min, holding at -50°C for 5 minutes, and then heating to 230°C at a rate of 10°C / min. The melting point is the peak-top temperature of the melting peak that appears in the second melting curve. When two or more melting peaks are observed, the melting point is the peak-top temperature of the melting peak with the greatest peak-top height. The melting enthalpy is the sum of the melting enthalpies calculated from each melting peak.

[0072] The mass average molecular weight (Mw) of the crystalline polyester (C) component, calculated as polystyrene, determined from the GPC curve is preferably 3.0×10 in view of its function of improving the thermal adhesion and melt adhesion with a resin having a polar group, in other words, its function as a hot melt adhesive. 5 or less, more preferably 1.0 × 10 5 or less, more preferably 7.0 × 10 4 On the other hand, the mass average molecular weight (Mw) is preferably 5.0 × 10 or less from the viewpoint of heat resistance and chemical resistance. 3 More preferably, 1.0 × 10 4 More preferably, 3.0 × 10 4 It may be more than that.

[0073] The number average molecular weight (Mn) of the crystalline polyester (C) as calculated in terms of polystyrene, determined from the GPC curve, is preferably 1.5×10 in view of its function of improving the thermal adhesion and melt adhesion with a resin having a polar group, in other words, its function as a hot melt adhesive. 5 or less, preferably 5.0 × 10 4 or less, more preferably 3.5 × 10 4 On the other hand, the number average molecular weight (Mn) is preferably 2.5 × 10 or less from the viewpoint of heat resistance and chemical resistance. 3More preferably, 5.0 × 10 3 More preferably, 1.5 × 10 4 The method for measuring the GPC curve has been described above in the description of the polyester elastomer as component (B).

[0074] As the component (C) crystalline polyester, one of these may be used alone or in combination with two or more thereof.

[0075] (D) Ethylene-unsaturated carboxylic acid copolymer: The resin composition of the present invention contains the above-mentioned component (D), an ethylene-unsaturated carboxylic acid copolymer, which is one or more selected from the group consisting of an ethylene-unsaturated carboxylic acid ester copolymer, an ethylene-unsaturated carboxylic acid copolymer, an ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid ester copolymer, an ionomer of an ethylene-unsaturated carboxylic acid copolymer, and an ionomer of an ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid ester copolymer.

[0076] The component (D) ethylene-unsaturated carboxylic acid copolymer contains structural units derived from ethylene, which allows it to be well miscible or compatible with the component (A) hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound. Furthermore, the component (D) ethylene-unsaturated carboxylic acid copolymer contains structural units derived from an unsaturated carboxylic acid or an unsaturated carboxylic acid ester, which allows it to be well miscible or compatible with the component (B) polyester elastomer and the component (C) crystalline polyester. Therefore, the component (D) ethylene-unsaturated carboxylic acid copolymer functions as a miscible or compatibilizer for the component (A) hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound, the component (B) polyester elastomer, and the component (C) crystalline polyester.

[0077] Furthermore, the ethylene-unsaturated carboxylic acid copolymer (D) mentioned above functions to improve tensile properties, moldability, and heat adhesion and melt adhesion to polyolefins such as polyethylene.

[0078] The unsaturated carboxylic acid is a compound having one or more carbon-carbon double bonds and one or more carboxyl groups (including acid anhydrides) in one molecule. Examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, and ethacrylic acid; unsaturated dicarboxylic acids such as itaconic acid, fumaric acid, and maleic acid; unsaturated dicarboxylic acid monoesters such as maleic acid monoester, fumaric acid monoester, and itaconic acid monoester; and unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. The unsaturated carboxylic acid may preferably contain an unsaturated monocarboxylic acid, and more preferably contain one or more selected from the group consisting of acrylic acid and methacrylic acid. One or more of these may be used as the unsaturated carboxylic acid.

[0079] The unsaturated carboxylic acid ester is a compound in which all carboxyl groups (including acid anhydrides) of the unsaturated carboxylic acid are esterified. Examples of the unsaturated carboxylic acid ester include alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; unsaturated monocarboxylic acid monoalkyl esters such as alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; and unsaturated dicarboxylic acid dialkyl esters such as dialkyl maleates such as dimethyl maleate and diethyl maleate. The unsaturated carboxylic acid ester may preferably include one or more selected from the group consisting of alkyl acrylates and alkyl methacrylates. One or more of these can be used as the unsaturated carboxylic acid ester.

[0080] Examples of the ethylene-unsaturated carboxylic acid ester copolymer include ethylene-acrylic acid alkyl ester copolymers such as ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer; and ethylene-methacrylic acid alkyl ester copolymers such as ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, and ethylene-butyl methacrylate copolymer.

[0081] Examples of the ethylene-unsaturated carboxylic acid copolymer include an ethylene-acrylic acid copolymer and an ethylene-methacrylic acid copolymer.

[0082] Examples of the ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid ester copolymer include ethylene-methacrylic acid-methacrylic acid alkyl ester copolymers such as ethylene-methacrylic acid-ethyl methacrylate copolymer, ethylene-methacrylic acid-acrylic acid alkyl ester copolymers such as ethylene-methacrylic acid-butyl acrylate copolymer, ethylene-acrylic acid-methacrylic acid alkyl ester copolymers such as ethylene-acrylic acid-ethyl methacrylate copolymer, and ethylene-acrylic acid-acrylic acid alkyl ester copolymers such as ethylene-acrylic acid-butyl acrylate copolymer.

[0083] The ionomer of the ethylene-unsaturated carboxylic acid copolymer is a substance in which some or all of the carboxyl groups of the ethylene-unsaturated carboxylic acid copolymer are neutralized with metal ions. The ionomer of the ethylene-unsaturated carboxylic acid-unsaturated carboxylic ester copolymer is a substance in which some or all of the carboxyl groups of the ethylene-unsaturated carboxylic acid-unsaturated carboxylic ester copolymer are neutralized with metal ions.

[0084] Examples of the metal ions that can be used in the ionomer of the ethylene-unsaturated carboxylic acid copolymer and the ionomer of the ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid ester copolymer include lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, zinc ions, magnesium ions, and manganese ions. Among these, the metal ions may preferably include one or more selected from the group consisting of magnesium ions, sodium ions, and zinc ions, and more preferably include one or more selected from the group consisting of sodium ions and zinc ions.

[0085] The content of ethylene-derived structural units in the component (D) ethylene-unsaturated carboxylic acid copolymer can be appropriately selected from the viewpoints of functioning as a compatibilizer or compatibilizer, tensile properties, moldability, and thermal adhesion and melt adhesion with polyolefins such as polyethylene. From the viewpoint of functioning as a compatibilizer or compatibilizer, the content of ethylene-derived structural units in the component (D) ethylene-unsaturated carboxylic acid copolymer may be preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. On the other hand, from the viewpoints of tensile properties, moldability, and thermal adhesion and melt adhesion with polyolefins such as polyethylene, the content may be preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more.

[0086] The melt mass flow rate of the component (D) ethylene-unsaturated carboxylic acid copolymer, measured in accordance with JIS K7210-1:2014 at a temperature of 190°C and a load of 21.18 N, may be preferably 1 g / 10 min or more, more preferably 10 g / 10 min or more, and even more preferably 15 g / 10 min or more, from the viewpoints of thermal adhesion and melt adhesion to polyolefins such as polyethylene. On the other hand, from the viewpoints of tensile properties and moldability, it may be preferably 150 g / 10 min or less, more preferably 80 g / 10 min or less, even more preferably 50 g / 10 min or less, and even more preferably 40 g / 10 min or less.

[0087] As the component (D), ethylene-unsaturated carboxylic acid copolymer, one of these or a mixture of two or more thereof can be used.

[0088] Amount of ingredients (A) to (D): The amount of component (A) hydrogenated block copolymer of aromatic vinyl compound and conjugated diene compound, the amount of component (B) polyester elastomer, the amount of component (C) crystalline polyester, and the amount of component (D) ethylene-unsaturated carboxylic acid copolymer are explained below. Here, the sum of the amounts of components (A), (B), (C), and (D) is 100% by mass.

[0089] The blending amount of the hydrogenated block copolymer of aromatic vinyl compound and conjugated diene compound (Component (A)) can be appropriately selected from the viewpoints of flexibility, tensile properties, moldability, thermal adhesion and melt adhesion to polyolefins such as polypropylene, and thermal adhesion and melt adhesion to resins having polar groups, and, in embodiments using the non-aromatic rubber softener (Component (E)), from the viewpoint of suppressing bleed-out of the non-aromatic rubber softener (Component (E)). The blending amount of the hydrogenated block copolymer of aromatic vinyl compound and conjugated diene compound (Component (A)) can be preferably 20% by mass or more, more preferably 24% by mass or more, even more preferably 28% by mass or more, even more preferably 32% by mass or more, and most preferably 36% by mass or more, from the viewpoints of flexibility, tensile properties, moldability, thermal adhesion and melt adhesion to polyolefins, and suppressing bleed-out of the non-aromatic rubber softener (Component (E)). On the other hand, the blending amount of the hydrogenated block copolymer of the above-mentioned component (A), an aromatic vinyl compound and a conjugated diene compound, may be preferably 88% by mass or less, more preferably 76% by mass or less, even more preferably 64% by mass or less, still more preferably 56% by mass or less, and most preferably 52% by mass or less, from the viewpoint of thermal adhesion and melt adhesion to resins having polar groups.

[0090] The blend amount of the polyester elastomer (B) can be appropriately selected from the viewpoints of heat resistance, chemical resistance, tensile properties, moldability, thermal adhesion and melt adhesion to polyolefins such as polypropylene, and thermal adhesion and melt adhesion to resins having polar groups. From the viewpoints of heat resistance, chemical resistance, tensile properties, moldability, and thermal adhesion and melt adhesion to resins having polar groups, the blend amount of the polyester elastomer (B) may be preferably 4% by mass or more, more preferably 8% by mass or more, and even more preferably 12% by mass or more. On the other hand, from the viewpoint of thermal adhesion and melt adhesion to polyolefins such as polypropylene, the blend amount of the polyester elastomer (B) may be preferably 32% by mass or less, more preferably 26% by mass or less, and even more preferably 20% by mass or less.

[0091] The amount of the crystalline polyester (C) can be appropriately selected from the viewpoints of thermal adhesion, melt adhesion, flexibility, tensile properties, moldability, and thermal adhesion and melt adhesion with resins having polar groups, as well as with polyolefins such as polypropylene. From the viewpoints of thermal adhesion and melt adhesion with resins having polar groups, the amount of the crystalline polyester (C) may be preferably 4% by mass or more, more preferably 8% by mass or more, even more preferably 12% by mass or more, and even more preferably 16% by mass or more. On the other hand, from the viewpoints of flexibility, tensile properties, moldability, and thermal adhesion and melt adhesion with polyolefins such as polypropylene, the amount of the crystalline polyester (C) may be preferably 48% by mass or less, more preferably 44% by mass or less, even more preferably 40% by mass or less, and even more preferably 36% by mass or less.

[0092] The amount of the ethylene-unsaturated carboxylic acid copolymer (D) can be appropriately selected from the viewpoints of tensile properties, moldability, thermal adhesion and melt adhesion with polyolefins such as polypropylene, and thermal adhesion and melt adhesion with resins having polar groups, as well as its function as an admixture or compatibilizer. From the viewpoints of tensile properties, moldability, thermal adhesion and melt adhesion with polyolefins such as polypropylene, and its function as an admixture or compatibilizer, the amount of the ethylene-unsaturated carboxylic acid copolymer (D) may be preferably 4% by mass or more, more preferably 8% by mass or more, and even more preferably 12% by mass or more. On the other hand, from the viewpoints of thermal adhesion and melt adhesion with resins having polar groups, the amount of the ethylene-unsaturated carboxylic acid copolymer (D) may be preferably 42% by mass or less, more preferably 36% by mass or less, even more preferably 30% by mass or less, and even more preferably 24% by mass or less.

[0093] (E) Non-aromatic rubber softeners: In one embodiment, the resin composition of the present invention may further contain (E) a non-aromatic rubber softener. By including the component (E) non-aromatic rubber softener, flexibility can be improved.

[0094] The non-aromatic rubber softener (component (E)) is a non-aromatic mineral oil (a hydrocarbon compound derived from petroleum, etc.) or synthetic oil (synthetic hydrocarbon compound). Here, "non-aromatic" means that, for mineral oils, they are not classified as aromatic (the number of aromatic carbon atoms is less than 30%). For synthetic oils, this means that they do not contain aromatic monomers.

[0095] Mineral oils used as rubber softeners are mixtures of one or more of paraffin chains, naphthenic rings, and aromatic rings. They are classified as follows: those with 30 to 45% naphthenic ring carbon atoms are called naphthenic; those with 30% or more aromatic carbon atoms are called aromatic; and those that are neither naphthenic nor aromatic and have 50% or more paraffin chain carbon atoms are called paraffinic.

[0096] Examples of the non-aromatic rubber softener include paraffinic mineral oils such as linear saturated hydrocarbons, branched saturated hydrocarbons, and derivatives thereof; naphthenic mineral oils; and synthetic oils such as hydrogenated polyisobutylene, polyisobutylene, and polybutene.

[0097] Among these, the non-aromatic rubber softener may preferably contain a paraffinic mineral oil from the viewpoint of suppressing bleed-out. The paraffinic mineral oil may have an aromatic carbon number of preferably 20% or less, more preferably 10% or less, and even more preferably 0 to 5%.

[0098] The amount of the non-aromatic rubber softener (Component (E)) is an optional component and is not particularly limited as long as it does not detract from the objectives of the present invention. From the viewpoint of obtaining a desired level of flexibility, the amount of the non-aromatic rubber softener (Component (E)) may be 0 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, or 30 parts by mass or more, where the sum of the amounts of Components (A), (B), (C), and (D) is taken as 100 parts by mass. On the other hand, from the viewpoint of thermal adhesion and melt adhesion to resins having polar groups and of suppressing bleed-out, the amount of the non-aromatic rubber softener (Component (E)) may be preferably 100 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and most preferably 50 parts by mass or less.

[0099] The resin composition of the present invention may further contain optional components other than the above components (A) to (E), as desired, to the extent that the object of the present invention is not adversely affected.

[0100] Examples of the optional components include component (A) a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, component (B) a polyester elastomer, component (C) a crystalline polyester, and component (D) a thermoplastic resin other than an ethylene-unsaturated carboxylic acid copolymer, component (E) a softener or plasticizer other than a non-aromatic rubber softener, as well as additives, colorants, fillers, and flame retardants.

[0101] Examples of the other thermoplastic resins include thermoplastic polyurethane, thermoplastic polyamide, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, acrylic thermoplastic resins such as polymethyl methacrylate, and polyvinyl chloride resins such as vinyl chloride homopolymer.

[0102] Examples of the other softeners or plasticizers include esters of polycarboxylic acids such as di(2-ethylhexyl) phthalate with saturated aliphatic alcohols, plasticizers for polyvinyl chloride such as polyester-based plasticizers, and softeners for aromatic rubbers.

[0103] Examples of the additives include weathering agents such as antioxidants, light stabilizers, and ultraviolet absorbers; antioxidants such as hindered phenol antioxidants, phosphite antioxidants, thioether antioxidants, and amine antioxidants; lubricants such as acid amides, fatty acids, fatty acid esters, fatty acid metal salts, waxes, silicone oils, and modified silicone oils; nucleating agents such as aromatic phosphate metal salts and gelols; antistatic agents such as glycerin fatty acid esters; and mold release agents, processing aids, and antifouling agents.

[0104] Examples of the colorant include inorganic colorants such as titanium dioxide (titania), red iron oxide, ultramarine (ultramarine blue), and carbon black; and organic colorants such as aniline black, quinacridone red, isoindolinone yellow, and phthalocyanine blue.

[0105] Examples of the filler include inorganic fillers such as calcium carbonate, silica (silicon dioxide), talc, mica, clay, hydrotalcite, and zeolite; and organic fillers such as crosslinked acrylic resin particles.

[0106] Examples of the flame retardant include antimony-based flame retardants, halogen-based flame retardants, metal hydroxides, zinc-based flame retardants, organic phosphate ester-based flame retardants, and nitrogen-containing compound-based flame retardants.

[0107] As the optional component, one or more of these may be used.

[0108] The amount of the optional components is not particularly limited as long as it does not contradict the object of the present invention. In one embodiment, the amount of the optional components may be about 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 1 part by mass or less, 0.5 parts by mass or less, 0 to 0.5 parts by mass, or 0.01 to 50 parts by mass, where the sum of the amounts of components (A), (B), (C), and (D) is taken as 100 parts by mass.

[0109] In one embodiment, the resin composition of the present invention may not contain any one or more of the optional components described above.

[0110] As used herein, "not containing a certain component" means that the component is not intentionally blended. In the technical field of resin compositions, when a component is intentionally blended, it is typically blended in an amount of 0.01 part by mass or more. Therefore, "not containing a certain component" can also be rephrased as meaning that the content of the component is typically less than 0.01 part by mass, preferably 0.001 part by mass or less, and more preferably 0 to 0.0001 part by mass, where the sum of the blended amounts of the above-mentioned components (A), (B), (C), and (D) is taken as 100 parts by mass.

[0111] The resin composition of the present invention can be obtained by using any melt kneader to charge the above components (A) to (D) and any optional components used as desired into the melt kneader simultaneously or in any order and melt kneading, preferably at a resin temperature of 200 to 260°C.

[0112] Examples of the melt kneader include batch kneaders such as pressure kneaders and mixers, extrusion kneaders such as single-screw extruders, co-rotating twin-screw extruders, and counter-rotating twin-screw extruders, and calendar roll kneaders. These may be used in any combination.

[0113] The resulting resin composition can be pelletized by any method and then molded into any article by any method, such as hot cutting, strand cutting, or underwater cutting.

[0114] Alternatively, the resulting resin composition may be subjected to molding as it is (without going through a pelletizing step).

[0115] 2. Goods: The article of the present invention comprises the resin composition of the present invention. In one typical embodiment, the article of the present invention has the resin composition of the present invention adhered or laminated to the surface of a structural member made of a resin having a polar group, such as an ABS resin or a PC resin.

[0116] The article of the present invention may be a part of an automobile, building, furniture, home appliance, or the like. In one typical embodiment, the article of the present invention may be a part of an automobile, building, or the like. Examples of the automobile part as the article of the present invention include a window molding, a window seal, a glass run channel, a gasket, a belt molding, a door trim, a shift knob, a parking brake, an assist grip, and a seat belt cover. Examples of the building part as the article of the present invention include a window molding, a window seal, a gasket, a window frame, a handrail, and a door knob. [Example]

[0117] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0118] Measurement method The following tests (a) to (e) were carried out after conditioning the test specimens in an environment of 23±2°C temperature and 50±10% humidity for 16 hours or more, and then under the same temperature and humidity conditions unless otherwise specified.

[0119] (a) Injection moldability: The resin composition was injection-molded into a sheet measuring 130 mm in length, 130 mm in width, and 2 mm in thickness using an injection molding machine with a clamping pressure of 120 tons under the following conditions: molding temperature 240°C, mold temperature 30°C, injection speed 55 mm / sec, injection pressure 140 MPa, dwell pressure 40 MPa, injection time 5 seconds, and cooling time 20 seconds. The obtained sheet was visually observed and evaluated according to the following criteria. ○: No flow marks or sink marks were observed. ×: At least one of flow marks and sink marks was observed.

[0120] (b) Miscibility: The sheet obtained in the above test (c) Injection moldability was visually observed and evaluated according to the following criteria. ◯: The sheet surface was smooth. ×: Powdery bumps were observed on the surface of the sheet.

[0121] (c) Durometer hardness (Type A): In accordance with JIS K6253-2012, a 6.3 mm thick press sheet made using the resin composition was used as a test piece, and the 15-second value of the durometer hardness (Type A) was measured. In the table, the durometer hardness (Type A) is referred to as "A hardness."

[0122] (d) Melt mass flow rate: The melt mass flow rate (unit: g / 10 min) of the resin composition was measured in accordance with JIS K7210-1:2014 under conditions of a temperature of 230°C and a load of 21.18 N. In the table, the melt mass flow rate is abbreviated as "MFR."

[0123] (e) Tensile properties: In accordance with JIS K6251:2017, a dumbbell-shaped No. 3 test piece was punched out from the sheet obtained in the above test (c) Injection Molding. A tensile test was performed at a test speed of 500 mm / min. From the obtained stress-strain curve, the tensile stress at break (unit: MPa), 100% strain tensile stress (unit: MPa), and tensile strain at break (unit: %) were calculated. In the table, the 100% strain tensile stress is indicated as "100% MO."

[0124] (f) Peel strength 1 (thermal adhesion to ABS resin): (F-1) Molding of resin plates: Using Denka ABS resin "Denka ABS GR-1000 (product name)" manufactured by Denka Company Limited, an injection molding machine with a clamping pressure of 120 tons was used to injection mold a resin plate measuring 150 mm in length, 25 mm in width, and 4 mm in thickness under the following conditions: molding temperature 260°C, mold temperature 60°C, injection speed 40 mm / sec, injection pressure 200 MPa, dwell pressure 50 MPa, injection time 10 seconds, and cooling time 30 seconds.

[0125] (F-2) Molding of laminate (test piece): A release paper was attached to the front edge of one short side of one surface of the resin plate obtained in (T-1) above using double-sided tape. Next, using an injection molding machine with a clamping pressure of 120 tons, the resin plate was inserted into a mold so that the surface with the release paper attached was the laminated surface with the resin composition. The resin composition was then injected under the following conditions: molding temperature 240°C, mold temperature 30°C, injection speed 55 mm / sec, injection pressure 140 MPa, dwell pressure 0 MPa, injection time 5 seconds, and cooling time 30 seconds. A laminate (test piece) having a 2 mm-thick resin composition layer on the surface of the resin plate was molded. A conceptual diagram of the cross section of the resulting laminate (test piece) is shown in Figure 1.

[0126] (F-3) Peel strength: In accordance with JIS K6854-2:1999, the peel strength (unit: N / 25 mm) was measured using the laminate (test piece) obtained in (T-2) above at a peel angle of 180° and a gripping movement speed of 50 mm / min.

[0127] (G) Peel strength 2 (thermal adhesion with PC resin): The peel strength (unit: N / 25 mm) was measured in the same manner as in (F) Peel strength 1 above, except that in molding the resin plate (F-1) above, a PC resin "Iupilon S-3000R (product name)" manufactured by Mitsubishi Engineering Plastics Corporation was used.

[0128] Raw materials used (A) Hydrogenated block copolymer of aromatic vinyl compound and conjugated diene compound: (A-1) Kuraray Co., Ltd.'s hydrogenated styrene-β-farnesene block copolymer "Septon BIO SF903 (trade name)," with a styrene-derived structural unit content of 30% by mass. (A-2) Kuraray Co., Ltd. hydrogenated block copolymer of styrene and isoprene (styrene-ethylene-ethylene-propylene-styrene copolymer) "Septon 4055 (trade name)", with a styrene-derived structural unit content of 30% by mass. (A-3) Kuraray Co., Ltd. hydrogenated block copolymer of styrene and isoprene (styrene-ethylene-ethylene-propylene-styrene copolymer) "Septon 4033 (trade name)", with a styrene-derived structural unit content of 30% by mass. (A-4) Kuraray Co., Ltd. hydrogenated block copolymer of styrene and isoprene (styrene-ethylene-propylene-styrene copolymer) "Septon 2002 (trade name)", with a styrene-derived structural unit content of 30% by mass.

[0129] (B) Polyester elastomer: (B-1) "Hytrel 2401 (trade name)," a polyester-based elastomer having a polybutylene terephthalate hard segment and an aliphatic polyether soft segment, manufactured by Toray Celanese Co., Ltd., with a melting point of 162°C, a melting enthalpy of 14 J / g, and a mass-average molecular weight (Mw) of 1.0 x 10 5 , number average molecular weight (Mn) 4.1×10 4 . (B-2) SK Chemicals' polyester elastomer "SKYPEL G130D (trade name)", which is a block copolymer polyester of polybutylene terephthalate and poly(tetramethylene oxide) glycol according to JP-A-2000-080222.

[0130] (C) Crystalline polyester: (C-1) Toyobo Co., Ltd. crystalline polyester "Vylon GA-3410 (trade name)", melting point 122°C, fusion enthalpy 15 J / g, mass average molecular weight (Mw) 5.7 × 10 4 , number average molecular weight (Mn) 2.9×10 4 . (C-2) Toyobo Co., Ltd. crystalline polyester "Vylon GA-3200 (trade name)", melting point 123°C, fusion enthalpy 19 J / g, mass average molecular weight (Mw) 2.8 × 10 4 , number average molecular weight (Mn) 1.4×10 4 .

[0131] (D) Ethylene-unsaturated carboxylic acid copolymer: (D-1) ENEOS NUC Corporation's ethylene-ethyl acrylate copolymer "NUC-6570 (product name)" Content of structural units derived from ethyl acrylate: 25% by mass (content of structural units derived from ethylene: 75% by mass), melt mass flow rate (190°C, 21.18N): 20g / 10min, (D-2) ENEOS NUC Corporation's ethylene-ethyl acrylate copolymer "NUC-6940 (trade name)" Content of structural units derived from ethyl acrylate: 35% by mass (content of structural units derived from ethylene: 65% by mass), melt mass flow rate (190°C, 21.18N): 20g / 10min, (D-3) Ethylene-methacrylic acid copolymer "Nucrel N1525 (trade name)" from Mitsui Dow Polychemicals Co., Ltd., content of structural units derived from methacrylic acid: 15% by mass (content of structural units derived from ethylene: 85% by mass), melt mass flow rate (190°C, 21.18N): 25g / 10min,

[0132] (E) Non-aromatic rubber softeners: (E-1) Paraffin oil "Diana Process Oil PW-90 (product name)" from Idemitsu Kosan Co., Ltd.

[0133] (F) Other ingredients: (F-1) Calcium stearate. (F-2) ADEKA Corporation's benzophenone-based ultraviolet absorber (2-hydroxy-4-n-octyloxybenzophenone) "ADEKA STAB 1413 (trade name)", CAS number 1843-05-6.

[0134] Example 1 A blend consisting of 22 parts by mass of component (A-1), 26 parts by mass of component (A-2), 17 parts by mass of component (B-1), 14 parts by mass of component (C-1), 21 parts by mass of component (D-1), 42 parts by mass of component (E-1), 0.15 parts by mass of component (F-1), and 0.05 parts by mass of component (F-2) was melt-kneaded using a co-rotating twin-screw extruder at a die outlet resin temperature of 220°C to obtain a resin composition. Tests (a) to (h) were performed. The results are shown in Table 1.

[0135] Examples 2 to 21 Resin compositions were obtained in the same manner as in Example 1, except that the formulation was changed as shown in Table 1 or 2. The above tests (A) to (G) were carried out. The results are shown in Table 1 or 2. Note that, since Examples 19 and 21 had poor injection moldability and miscibility (evaluated as ×), the above tests (C) to (G) were omitted.

[0136] [Table 1]

[0137] [Table 2]

[0138] It has been found that the resin composition of the present invention has good injection moldability and miscibility, excellent thermal adhesion and melt adhesion with resins having polar groups, such as ABS resin and PC resin, and exhibits sufficient tensile break strain. It has also been found that a preferred resin composition of the present invention has excellent flexibility. Therefore, it is believed that the resin composition of the present invention can be suitably used as a material to be bonded to or laminated on the surface of structural members made of resins having polar groups, such as ABS resin and PC resin. It is also believed that articles in which the resin composition of the present invention is bonded to or laminated on the surface of structural members can be suitably used as parts for automobiles, buildings, furniture, home appliances, and the like. [Brief explanation of the drawings]

[0139] [Figure 1] FIG. 1 is a conceptual diagram of a cross section of a laminate (test piece) prepared for a peel strength test. [Explanation of symbols]

[0140] 1: Resin plate 2: Resin composition layer 3: Release paper

Claims

1. (A) 20 to 88% by mass of a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound, (B) polyester elastomer 4 to 32% by mass, (C) 4 to 48 mass% of a crystalline polyester (excluding those corresponding to the above-mentioned component (B) polyester-based elastomer), and (D) 4 to 42 mass% of an ethylene-unsaturated carboxylic acid copolymer, wherein the sum of the blending amount of the component (A), the blending amount of the component (B), the blending amount of the component (C), and the blending amount of the component (D) is 100 mass%.

2. 2. The resin composition according to claim 1, wherein the component (A), a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, comprises a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, the hydrogenated product having a structural unit derived from β-farnesene.

3. The resin composition according to claim 1, wherein the component (B) polyester-based elastomer comprises (B1) a polybutylene terephthalate-based elastomer.

4. 2. The resin composition according to claim 1, wherein the melting point of the component (C) crystalline polyester is 90 to 160°C.

5. The resin composition according to claim 1, further comprising 5 to 100 parts by mass of a non-aromatic rubber softener (E), where the sum of the amounts of the components (A), (B), (C), and (D) is 100 parts by mass.

6. An article comprising the resin composition according to any one of claims 1 to 6.

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