Foam body, method for producing a foam body and laminate

Abstract

The present invention provides a foam body that, in the molded state, has a good appearance, exhibits good damping properties and wear resistance, and is also excellent in terms of the balance of its properties. The foam body is a foam body made of a hydrogenated block copolymer composition comprising a hydrogenated block copolymer (I), an olefin-based resin (II), a thermoplastic resin (III), and a plasticizer (IV), and includes a foam core layer and a non-foam skin layer, wherein the foam core layer has a thickness of 300 µm or more, the foaming ratio is 1.2 times or more, the content of a polymer block (a), which mainly contains a vinylaromatic monomer unit in the hydrogenated block copolymer (I), is 10 to 40 wt%, and the hydrogenated block copolymer (I) contains a hydrogenated copolymer block (b).which contains a vinylaromatic monomer unit and a conjugated diene monomer unit, wherein the content of the vinylaromatic monomer unit in the hydrogenated copolymer block (b) is 5 to 79 wt%, and the hydrogenated block copolymer composition has a 15-second hardness value, as measured by a type A durometer in accordance with JIS K6253, of 85 or more and an MFR value of 40 or more.

Description

BACKGROUND OF THE INVENTIONField of the invention

[0001] The present invention relates to a foam body, a method for producing a foam body and a laminate. Description of related technology

[0002] In recent years, a new trend in vehicles has been the focus of attention on self-driving systems and mobility services. Due to this trend, the performance requirements for vehicle components such as vehicle interior materials have changed. For example, it is predicted that vehicles will become more perceived as living spaces due to the self-driving system. Therefore, in order to create a space where passengers can feel comfortable, the quality of interior trim has been improved, and interior design has become greatly diversified. Therefore, resin compositions used as vehicle interior materials must have a molded-state appearance that can realize more elaborate designs and a foam body hardness that can achieve cushioning properties with a more comfortable feel than a conventional composition.

[0003] With the spread of car sharing, mobility services will likely require long-lasting and clean vehicles. Therefore, the frequency of cleaning vehicle components, such as interior materials, will increase, requiring resin compounds with greater wear resistance.

[0004] Due to the proliferation of self-driving systems and mobility services described above, the resin compositions must have better appearance, better foam body hardness and excellent wear resistance compared to conventional products.

[0005] As materials for vehicle components, a thermoplastic elastomer composition containing a hydrogenated product of a block copolymer consisting of a conjugated diene compound and an aromatic vinyl compound, an olefin-based resin, and a plasticizer, and a foam molded article of the thermoplastic elastomer composition have been proposed (see, for example, Japanese Patent Application Laid-Open No. 2015-98542, Japanese Patent Application Laid-Open No. 2018-24822, and International Publication No. WO2016 / 039310).

[0006] However, a conventionally proposed foam molded article of the thermoplastic elastomer composition still has a problem that there is still room for improvement from the viewpoint of the balance between the appearance in the molded state, the hardness of the foam body to be able to provide a comfortable cushioning property, and the wear resistance.

[0007] Therefore, it is an object of the present invention to provide a foam body having a foam core layer and a non-foam skin layer, which has a good molded appearance, a good cushioning property and a wear resistance and also shows an excellent balance of these properties. SUMMARY OF THE INVENTION

[0008] The inventors have conducted serious investigations to solve the problem of the above-described conventional techniques and, as a result, have found the following: In a foam body made of a hydrogenated block copolymer composition containing a hydrogenated block copolymer, an olefin-based resin, a thermoplastic resin, and a plasticizer, the foam body having a foam core layer and a non-foam skin layer adjacent thereto, if the thickness of the foam core layer contained in the foam body, the foaming ratio, the structure of the hydrogenated block copolymer, the hardness of the hydrogenated block copolymer composition, and the MFR of the hydrogenated block copolymer composition are each specified to fall within appropriate ranges, a foam body having a foam core layer and a non-foam skin layer, which has a good molded appearance,It has good damping properties and good wear resistance of the surface of the foam body, and also has an excellent balance of these properties. The present invention has thus been completed.

[0009] In particular, the present invention provides: [1] Foam body made of a hydrogenated block copolymer composition containing: a hydrogenated block copolymer (I); an olefin-based resin (II); a thermoplastic resin (III); and a plasticizer (IV), wherein the foam body contains a foam core layer and a non-foam skin layer adjacent to each other, the foam core layer has a thickness of 300 µm or more, the foam body has a foaming ratio of 1.2 times or more and the foam body meets the following conditions (1) to (5): <Bedingung (1)> the hydrogenated block copolymer (I) is a hydrogenated product of a block copolymer containing a vinyl aromatic monomer unit and a conjugated monomer unit; <Bedingung (2)> the hydrogenated block copolymer (I) contains at least one polymer block (a) mainly containing a vinyl aromatic monomer unit, and the content of the polymer block (a) mainly containing a vinyl aromatic monomer unit in the hydrogenated block copolymer (I) is 10 mass% or more and 40 mass% or less; <Bedingung (3)> the hydrogenated block copolymer (I) contains at least one hydrogenated copolymer block (b) containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, and the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 5 mass% or more and 79 mass% or less; <Bedingung (4)> the hydrogenated block copolymer composition has a 15-second hardness value, measured with a Type A durometer according to JIS K6253, of 85 or less; and <Bedingung (5)> the hydrogenated block copolymer composition has an MFR value, measured under conditions of a temperature of 230°C and a load of 2.16 kg according to JIS K7210, of 40 or more. [2] The foam body according to [1], wherein the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 15 mass% or more and 79 mass% or less. [3] The foam body according to [1] or [2], wherein the hydrogenated block copolymer (I) contains at least one polymer block (a) mainly containing a vinyl aromatic monomer unit, and the content of the polymer block (a) mainly containing a vinyl aromatic monomer unit in the hydrogenated block copolymer (I) is 15 mass% or more and 35 mass% or less. [4] The foam body according to any one of [1] to [3], wherein the hydrogenated block copolymer composition has a 15-second hardness value, measured with a Type A durometer according to JIS K6253, of 30 or more and 75 or less. [5] The foam body according to any one of [1] to [4], wherein the hydrogenated block copolymer composition has an MFR value, measured under conditions of a temperature of 230°C and a load of 2.16 kg according to JIS K7210, of 100 or more and 1000 or less. [6] Foam body according to one of the items [1] to [5], wherein the non-foam skin layer has a thickness of 10 µm to 500 µm. [7] Foam body according to one of the items [1] to [6], wherein the foam core layer has a thickness of 1000 µm to 20000 µm. [8] Foam body according to any one of items [1] to [7], wherein the olefin-based resin (II) comprises at least one polypropylene-based resin. [9] Foam body according to any one of items [1] to [8], wherein the foaming ratio is 1.5 times or more.

[10] Foam body according to one of the items [1] to [9], wherein the foam body is intended for use in a vehicle component selected from the group consisting of a side panel, a grommet or sealing ring, a gear knob, a weather strip, a window frame and a sealing material therefor, a dashboard, a grab handle, a steering wheel, a gear lever, a console, an armrest, a headrest and a door panel.

[11] A process for producing the foam body according to any one of points [1] to

[10] , comprising the steps: a step of adding a foaming agent to the hydrogenated block copolymer composition and injecting the resultant to fill a cavity formed in a mold / tool ​​of an injection molding machine and having a volume adjustable by a movable core / insert; and a step of increasing the volume of the cavity with the movable core / insert to perform foam molding or foam forming.

[12] Laminate, with: a layer containing the foam body according to one of the items [1] to

[10] ; and a layer containing a base resin.

[13] Laminate according to

[12] , wherein the layer containing the base resin and the layer containing the foam body are in direct contact with each other without an adhesive layer therebetween.

[0010] According to the present invention, a foam body having a foam core layer and a non-foam skin layer can be provided, which has a good molded appearance, a good cushioning property and a good wear resistance and also has an excellent balance of these properties. SHORT DESCRIPTION OF THE DRAWING Fig. 1 is a cross-sectional view of a laminate of Example 37. DETAILED DESCRIPTION OF THE INVENTION

[0011] An embodiment of the present invention (hereinafter referred to as "present embodiment") will be described in detail below. It should be noted that the embodiment described below is merely illustrative of the present invention and is not intended to limit the present invention, and the present invention can be modified and changed in various ways within the scope of the present invention. [Foam body]

[0012] A foam body of the present embodiment is a foam body made of a hydrogenated block copolymer composition containing: a hydrogenated block copolymer (I), an olefin-based resin (II), a thermoplastic resin (III) and a plasticizer (IV).

[0013] The foam body of the present embodiment comprises a foam core layer and a non-foam skin layer adjacent to each other, the foam core layer having a thickness of 300 μm or more, the foam body having a foaming ratio of 1.2 times or more, and satisfying the following conditions (1) to (5): <Bedingung (1)> the hydrogenated block copolymer (I) is a hydrogenated product of a block copolymer containing a vinyl aromatic monomer unit and a conjugated monomer unit; <Bedingung (2)> the hydrogenated block copolymer (I) contains at least one polymer block (a) mainly containing a vinyl aromatic monomer unit, and the content of the polymer block (a) mainly containing a vinyl aromatic monomer unit in the hydrogenated block copolymer (I) is 10 mass% or more and 40 mass% or less; <Bedingung (3)> the hydrogenated block copolymer (I) contains at least one hydrogenated copolymer block (b) containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, and the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 5 mass% or more and 79 mass% or less; <Bedingung (4)> the hydrogenated block copolymer composition has a 15-second hardness value, measured with a Type A durometer according to JIS K6253, of 85 or less; and <Bedingung (5)> the hydrogenated block copolymer composition has an MFR value, measured under conditions of a temperature of 230°C and a load of 2.16 kg according to JIS K7210, of 40 or more.

[0014] With the configuration described above, a foam body comprising a foam core layer and a non-foam skin layer can be obtained, which has a good molded appearance, a good damping property and a good wear resistance, and also has an excellent balance of these properties. (Hydrogenated block copolymer composition)

[0015] The foam body of the present embodiment is a foam body of a hydrogenated block copolymer composition, wherein the hydrogenated block copolymer composition contains a hydrogenated block copolymer (I), an olefin-based resin (II), a thermoplastic resin (III) and a plasticizer (IV). <Hydriertes Blockcopolymer (I)>

[0016] The hydrogenated block copolymer (I) used in the foam body of the present embodiment is a hydrogenated product of a block copolymer containing a vinyl aromatic monomer unit and a conjugated diene monomer unit (condition (1)). [Vinyl aromatic monomer unit]

[0017] Examples of a vinyl aromatic compound forming the vinyl aromatic monomer unit include monomer units derived from styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene.

[0018] Particularly from the viewpoint of the balance between cost and mechanical strength of a hydrogenated block copolymer composition containing the hydrogenated block copolymer (I), styrene is preferred.

[0019] One of these monomer units may be used individually, or two or more of them may be used together. [Conjugated diene monomer unit]

[0020] The conjugated diene monomer unit refers to a monomer unit derived from a diolefin having a pair of conjugated double bonds.

[0021] Examples of such a diolefin include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, and 1,3-hexadiene.

[0022] In particular, from the point of view of the balance between good processability and mechanical strength of the hydrogenated block copolymer composition, 1,3-butadiene and isoprene are preferred.

[0023] One of them can be used individually, or two or more of them can be used together.

[0024] The term “mainly containing” here, with respect to the structure of a hydrogenated block copolymer, means that the proportion in a prescribed block copolymer or a polymer block is 85 mass% or more, preferably 90 mass% or more, and more preferably 95 mass% or more.

[0025] It should be noted that the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 5 mass% or more and 79 mass% or less (condition (3)), so that the polymer block (a) and the hydrogenated copolymer block (b) can be clearly distinguished from each other. [Polymer block (a) containing mainly a vinyl aromatic monomer unit]

[0026] The hydrogenated block copolymer (I) used in the foamed body of the present embodiment contains at least one polymer block (a) mainly containing a vinyl aromatic monomer unit (condition (2)). Thus, the blocking resistance of a pellet of the hydrogenated block copolymer (I) tends to be good.

[0027] In the hydrogenated block copolymer (I), the content of the polymer block (a) is 10 mass% or more, preferably 15 mass% or more, more preferably 20 mass% or more, and further preferably 25 mass% or more.

[0028] When the content of the polymer block (a) mainly containing a vinyl aromatic monomer unit is 10 mass% or more, the blocking resistance of a pellet of the hydrogenated block copolymer (I) is good, and further, the foam body of the present embodiment has excellent wear resistance and heat resistance.

[0029] When the blocking resistance of a pellet of the hydrogenated block copolymer (I) is good, blocking tends to be difficult to occur even during transportation for a long time under higher loads and in a more severe temperature environment (such as a high external temperature area or a wide temperature range area), so it can be expected that pellets can be easily weighed and mixed during compound molding. Furthermore, since the amount of an anti-blocking agent used in the hydrogenated block copolymer (I) can be reduced, it is expected that device contamination can be avoided, environmental pollution can be reduced, and unexpected deterioration of physical properties such as transparency and mechanical strength can be suppressed.

[0030] If the foam body of the present embodiment has good wear resistance, the composition can be used in a vehicle material and the like where higher wear resistance is required. For example, when it is used as a material such as a vehicle interior material and the like, a thinner molded article or more complicated / larger molded article than general molded articles, and is used for a long period of time, the appearance of the material can be expected to be maintained comparable to the general molded article described above. In addition, when the composition is used as a vehicle interior material, the appearance of the material can be expected to be maintained for a long period of time even if it is subjected to friction with a larger load or with a coarse material such asexposed to a denim fabric that is coarser than a cotton fabric made from canequim #3.

[0031] In the hydrogenated block copolymer (I), the content of the polymer block (a) is 40 mass% or less, preferably 38 mass% or less, more preferably 36 mass% or less, and further preferably 35 mass% or less.

[0032] When the content of the polymer block (a) mainly containing a vinyl aromatic monomer unit in the hydrogenated block copolymer (I) is 40 mass% or less, the foam body of the present embodiment tends to have good heat resistance, and when the content is 35 mass% or less, it tends to have better heat resistance.

[0033] The content of the polymer block (a) in the hydrogenated block copolymer (I) can be measured by a method using a nuclear magnetic resonance (NMR) apparatus, using the block copolymer before hydrogenation or the hydrogenated block copolymer as a sample (a method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY, 54, 685 (1981); hereinafter referred to as “NMR method”).

[0034] The content of the polymer block (a) in the hydrogenated block copolymer (I) can be controlled to fall within the above-described numerical range by mainly adjusting the amount of a vinyl aromatic compound added to a polymerization reactor, the reaction temperature and the reaction time. [Hydrogenated copolymer block (b)]

[0035] The hydrogenated block copolymer (I) used in the foam body of the present embodiment contains at least one hydrogenated copolymer block (b) containing a vinyl aromatic monomer unit and a conjugated diene monomer unit (condition (3)).

[0036] The content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 5 mass% or more, preferably 15 mass% or more, more preferably 30 mass% or more, and further preferably 45 mass% or more.

[0037] When the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 5 mass% or more, the foamed body of the present embodiment exhibits good wear resistance. When the content is 15 mass% or more, higher wear resistance is exhibited, and the composition can be used in a use that requires stronger wear resistance, for example, a use for forming a thinner molded article in vehicle interior materials, a use that requires maintaining the appearance for a longer period of time even when friction with a larger load occurs during travel, or with a coarse fabric such as denim, which is a fabric coarser than a cotton fabric made of canequim #3, when used as a vehicle interior material.

[0038] The content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 79 mass% or less, preferably 75 mass% or less, and more preferably 70 mass% or less.

[0039] When the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 79 mass% or less, the foamed body of the present embodiment has good heat resistance and can be used in an application requiring strong heat resistance, for example, in a use for forming a thinner molded article in vehicle interior materials or in a use requiring durability to realize the retention of touch feeling (leather texture feeling) and shape stability (resistance to heat deformation) for a long time even when used for a long time or at a higher temperature.

[0040] It should be noted that the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) can be measured with a nuclear magnetic resonance (NMR) device or the like.

[0041] The content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) can be controlled to fall within the above-described numerical range by adjusting the amounts of a vinyl aromatic compound and a conjugated diene added to a polymerization reactor, the reaction temperature, and the like. [Hydrogenated polymer block (c) containing mainly conjugated diene monomer unit]

[0042] The hydrogenated block copolymer (I) used in the foam body of the present embodiment may contain at least one hydrogenated polymer block (c) mainly containing a conjugated diene monomer unit (hereinafter sometimes referred to as hydrogenated polymer block (c)).

[0043] When the hydrogenated block copolymer (I) contains the hydrogenated polymer block (c), the foam body of the present embodiment tends to have good wear resistance, scratch resistance, and low-temperature properties. When the hydrogenated block copolymer (I) contains the hydrogenated polymer block (c), the foam body of the present embodiment tends to improve the compatibility of the hydrogenated block copolymer (I) with the polyolefin-based resin (II) or the thermoplastic resin (III) described below, improve the interfacial strength, and improve the wear resistance, scratch resistance, and low-temperature properties. [Weight average molecular weight of the hydrogenated block copolymer (I)]

[0044] The weight-average molecular weight (Mw) of the hydrogenated block copolymer (I) used in the foamed body of the present embodiment is preferably 20,000 or more, more preferably 30,000 or more, and further preferably 50,000 or more from the viewpoints of achieving extrusion moldability in producing pellets from the hydrogenated block copolymer (I) and good mechanical strength of the foamed body of the present embodiment.

[0045] The upper limit of the weight-average molecular weight (Mw) is preferably 300,000 or less, more preferably 200,000 or less, and further preferably 150,000 or less. When the weight-average molecular weight (Mw) is 300,000 or less, the hydrogenated block copolymer (I) is easily melted during the preparation (during extrusion molding) of pellets from the hydrogenated block copolymer (I), thereby stabilizing the strands and improving extrusion moldability.

[0046] The weight-average molecular weight of the hydrogenated block copolymer (I) of the present embodiment can be obtained by performing gel permeation chromatography (GPC) measurement and using a calibration curve obtained by measuring commercially available standard polystyrene (prepared using a peak molecular weight of the standard polystyrene). [Molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (I)]

[0047] The molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (I) used in the foamed body of the present embodiment is not particularly limited, and is preferably 10 or less, more preferably 3 or less, and further preferably 1.5 or less from the viewpoint of molding processability of the hydrogenated block copolymer (I). The lower limit of the Mw / Mn is preferably 1 or more, more preferably 1.005 or more, and further preferably 1.01 or more from the viewpoint of molding processability of the hydrogenated block copolymer (I).

[0048] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the hydrogenated block copolymer (I) are obtained by performing gel permeation chromatography (GPC) measurement and determining a peak molecular weight in the resulting chromatogram using a calibration curve obtained by measuring commercially available standard polystyrene (prepared using a peak molecular weight of the standard polystyrene). The molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (I) is determined from the ratio between the weight-average molecular weight (Mw) and the number-average molecular weight (Mn). [Degree of hydrogenation of the double bond of the conjugated diene monomer unit in hydrogenated block copolymer (I)]

[0049] The hydrogenation degree of double bonds of the conjugated diene monomer unit in the hydrogenated block copolymer (I) used in the foam body of the present embodiment is preferably 20% or more, more preferably 50% or more, and further preferably 92% or more from the viewpoint of achieving good weather resistance.

[0050] Since high wear resistance and weather resistance are required, especially when used as a vehicle interior material, the hydrogenation degree is preferably 92% or more.

[0051] The degree of hydrogenation of double bonds of the conjugated diene monomer unit in the hydrogenated block copolymer (I) can be controlled by adjusting the hydrogenation rate to fall within the numerical range described above. The degree of hydrogenation can be measured using a nuclear magnetic resonance (NMR) device or the like. [Structure of the hydrogenated block copolymer (I)

[0052] The hydrogenated block copolymer (I) used in the foam body of the present embodiment is not particularly limited, and examples are structures represented by the following general formulas. aba, (ab) n ac,c-(abc)nac,a-(cb)nca,c-(ac)nbcac,[(abc)n]mX,[a-(bc)n]mX,[(ab)nc]mX,[(aba)nc]mX,[(bab)nc]mX,[(cba)n]mX,[c-(ba)n]mX,[c-(aba)n]mX and[c-(bab)n]mX.

[0053] In these general formulas, a represents the polymer block (a) mainly containing a vinyl aromatic monomer unit, b represents the hydrogenated copolymer block (b) containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, and c represents the hydrogenated polymer block (c) mainly containing a conjugated diene monomer unit.

[0054] Furthermore, in these general formulas, n represents an integer of 1 or more, and is preferably an integer of 1 to 5; m represents an integer of 2 or more, and is preferably an integer of 2 to 11; and X represents a residue of a coupling agent or a residue of a multifunctional initiator.

[0055] The hydrogenated block copolymer (I) used in the foamed body of the present embodiment may be a modified block copolymer in which atomic groups each having a prescribed functional group are bonded to each other. Since the influence of the presence of a functional group on the hardness and / or MFR of the hydrogenated block copolymer (I) is small, whether or not the hydrogenated block copolymer (I) is modified, what type of functional group is used, and the like can be appropriately determined according to the structures and the like of resins to be kneaded with the hydrogenated block copolymer (I).

[0056] When the hydrogenated block copolymer (I) is a modified block copolymer, it may be a secondarily modified block copolymer. "Secondary modification" is a term characterized by a production process, where a first process of bonding a functional group to a block copolymer is referred to as primary modification, and a process of reacting the functional group with another compound is referred to as secondary modification. For example, in a typical production process of a secondarily modified block copolymer, a secondarily modified product is produced by reacting a primary modified product obtained by reacting a denaturant (such as an amine) with a polymerization terminal after polymerization in a solution with another compound (such as maleic acid) in an extruder. <Herstellungsverfahren für hydriertes Blockcopolymer (I)>

[0057] A block copolymer corresponding to a state obtained before hydrogenation of the hydrogenated block copolymer (I) used in the foam body of the present embodiment is obtained, for example, by living anionic polymerization of a vinyl aromatic compound and a conjugated diene compound in a hydrocarbon solvent using a polymerization initiator such as an organic alkali metal compound. [hydrocarbon solvent]

[0058] Examples of hydrocarbon solvents include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane and n-octane, alicyclic hydrocarbons such as cyclohexane, cycloheptane and methylcycloheptane, and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene. [Polymerization initiator]

[0059] The polymerization initiator is not particularly limited, and examples are organic alkali metal compounds such as an aliphatic hydrocarbon alkali metal compound, an aromatic hydrocarbon alkali metal compound, and an organic amino alkali metal compound, which are known to have anionic polymerization activity for an aromatic vinyl compound and a conjugated diene.

[0060] Preferred examples of organic alkali metal compounds include, but are not limited to, aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms and a compound containing one lithium in one molecule, as well as a dilithium compound, a trilithium compound and a tetralithium compound each containing a plurality of lithium in one molecule can be used.

[0061] Specific examples are n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexylithium, benzyllithium, phenyllithium, trityllithium, a reaction product of diisopropylbenzene and sec-butyllithium, and a reaction product of divinylbenzene, sec-butyllithium, and a small amount of 1,3-butadiene.

[0062] Furthermore, organic alkali metal compounds disclosed, for example, in U.S. Patent No. 5,708,092, British Patent No. 2,241,239 and U.S. Patent No. 5,527,753 can be used. [modifier]

[0063] When a vinyl aromatic compound and a conjugated diene are copolymerized using an organic alkali metal compound as a polymerization initiator, the content of vinyl bonds (e.g., 1,2-bond or 3,4-bond) derived from the conjugated diene incorporated in the polymer and the random / statistical copolymerizability between the vinyl aromatic compound and the conjugated diene can be adjusted by using a prescribed modifier.

[0064] Examples of the modifier include, but are not limited to, a tertiary amine compound, an ether compound, and a metal alcoholate compound.

[0065] One of these modifiers may be used individually, or two or more of them may be used in combination.

[0066] An example of a tertiary amine compound is a compound of the general formula R1R2R3N (wherein R1, R2 and R3 represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a tertiary amino group), but is not limited to this.

[0067] Specific examples are trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N,N,N',N'',N''-pentamethylethylenetriamine and N,N'-dioctyl-p-phenylenediamine.

[0068] Examples of ether compounds include, but are not limited to, linear ether compounds and cyclic ether compounds.

[0069] Examples of linear ether compounds include, but are not limited to, dialkyl ether compounds of ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether, and dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.

[0070] Examples of cyclic ether compounds include, but are not limited to, alkyl ethers such as tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis(2-oxolanyl)propane, and furfuryl alcohol.

[0071] Examples of metal alkoxide compounds include, but are not limited to, sodium t-pentoxide, sodium t-butoxide, potassium t-pentoxide, and potassium t-butoxide. [Polymerization process]

[0072] As a method for polymerizing a vinyl aromatic compound and a conjugated diene using an organic alkali metal compound as a polymerization initiator, a conventionally known method can be employed.

[0073] The polymerization process can be, for example, batch polymerization, continuous polymerization, or a combination of these processes, but is not limited to these. Batch polymerization is particularly suitable for obtaining a block copolymer with excellent heat resistance.

[0074] The polymerization temperature is preferably 0°C to 180°C, and more preferably 30°C to 150°C. The polymerization time depends on the conditions and is usually 48 hours or less, preferably 0.1 to 10 hours.

[0075] An inert gas atmosphere such as nitrogen gas is preferred as the atmosphere of a polymerization system.

[0076] The polymerization pressure is not particularly limited as long as it is set within a pressure range at which monomers and a solvent can be kept in a liquid phase in the temperature range described above.

[0077] It is preferable to ensure that impurities that inactivate a catalyst and a living polymer, such as water, oxygen and carbon dioxide, cannot enter the polymerization system.

[0078] At the end of the polymerization process, a coupling reaction can be carried out by adding a required amount of a bi- or higher-functional coupling agent.

[0079] Any known agent can be used as the bifunctional coupling agent, and examples thereof include, but are not limited to, alkoxysilane compounds such as trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane; dihalogen compounds such as dichloroethane, dibromoethane, dimethyldichlorosilane, and dimethyldibromosilane; and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalic acid esters.

[0080] A trifunctional or higher coupling agent is not particularly limited, and any of the conventionally known agents can be used, and examples are trifunctional or higher polyhydric alcohols, polyhydric epoxy compounds such as epoxidized soybean oil, diglycidylbisphenol A, and 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane; a silicon halide compound represented by the general formula R4-n Six n (wherein R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4), such as methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride, and a bromide of any of these; and a tin halide compound represented by the general formula R 4-n SnX n (wherein R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4), such as methyltin trichloride, t-butyltin trichloride, and tin tetrachloride. Alternatively, dimethyl carbonate, diethyl carbonate, or the like can also be used. [Modification procedure]

[0081] The hydrogenated block copolymer (I) used in the foam body of the present embodiment may be a modified block copolymer in which atomic groups each having a functional group are bonded to each other. The atomic groups having a functional group are preferably bonded in a process preceding the hydrogenation process, which will be described later.

[0082] An example of an “atomic group having a functional group” is, without limitation, an atomic group having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group, a thioaldehyde group, a carboxylic acid ester group, an amide group, a sulfonic acid group, a sulfonic acid ester group, a phosphoric acid group, a phosphoric acid ester group, an amino group, an imino group, a nitrile group, a pyridyl group, a quinoline group, an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxysilicone group, a tin halide group, a boronic acid group, a boron-containing group,a boronate group, an alkoxytin group, and a phenyltin group. Particularly preferred is an atomic group having at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group.

[0083] The “atom group having a functional group” may be bonded to a denaturant.

[0084] Examples of denaturants include, but are not limited to, tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidine, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, and N-methylpyrrolidone.

[0085] Although there is no particular limitation thereto, the modified block copolymer can be obtained, for example, by anionic living polymerization for carrying out polymerization using a polymerization initiator having a functional group or an unsaturated monomer having a functional group to form a functional group at a living end, or for carrying out an addition reaction with a denaturant having a functional group.

[0086] As another method for obtaining the modified block copolymer, a method can be used in which a block copolymer is reacted with an organic alkali metal compound such as an organic lithium compound (metallization reaction), and the thus-obtained block polymer to which the organic alkali metal has been added is subjected to an addition reaction with a denaturing agent having a functional group to obtain the modified block copolymer.

[0087] However, in the latter method, the metallization reaction can be carried out after obtaining the hydrogenated block copolymer, and then the resulting product can be reacted with a denaturant to produce a modified hydrogenated block copolymer.

[0088] The temperature for conducting the modification reaction is preferably 0°C to 150°C, and more preferably 20°C to 120°C. The time required for the modification reaction varies depending on the other conditions and is preferably 24 hours or less, and more preferably 0.1 to 10 hours.

[0089] Depending on the type of denaturant used, an amino group or the like is sometimes converted into an organic metal salt when the denaturant is reacted. In such a case, the organic metal salt can be converted into an amino group or the like by treatment with water or a compound containing active hydrogen, such as an alcohol. Note that such a modified block copolymer may partially contain an unmodified block copolymer.

[0090] The modified block copolymer may be a secondarily modified block copolymer. A secondarily modified block copolymer may be obtained by reacting a modified block copolymer with a secondary denaturant that reacts with a functional group of the modified block copolymer.

[0091] The secondary denaturant is not particularly limited, and an example is a denaturant having a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group, and the secondary denaturant has at least two functional groups selected from these functional groups. However, if the functional group is an acid anhydride group, the secondary denaturant may also have only one acid anhydride group.

[0092] When the modified block copolymer is reacted with the secondary denaturant as described above, the amount of the secondary denaturant used per equivalent of a functional group bonded to the modified block copolymer is preferably 0.3 mol to 10 mol, more preferably 0.4 mol to 5 mol, and further preferably 0.5 mol to 4 mol.

[0093] The method of reacting the modified block copolymer with the secondary denaturant is not particularly limited, and known methods can be used. Examples of the method include the melt-kneading method described later and a method in which the respective components are dissolved or dispersed in a solvent or the like to mix them for the reaction. This secondary modification is preferably carried out after the hydrogenation process of the block copolymer.

[0094] Preferred examples of secondary denaturants include, but are not limited to, maleic anhydride, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, tolylene diisocyanate, tetraglycidyl-1,3-bisaminomethylcyclohexane, and bis-(3-triethoxysilylpropyl)-tetrasulfane.

[0095] The hydrogenated block copolymer (I) used in the foam body of the present embodiment may be a modified block copolymer graft-modified with α,β-unsaturated carboxylic acid or a derivative thereof such as an anhydride, an esterified product, an amidated product, or an imidated product thereof.

[0096] Examples of the α,β-unsaturated carboxylic acid or a derivative thereof include, but are not limited to, maleic anhydride, maleic anhydride imide, acrylic acid or an ester thereof, methacrylic acid or an ester thereof, and endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid or an anhydride thereof.

[0097] The amount of the α,β-unsaturated carboxylic acid or a derivative thereof to be added is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the hydrogenated block copolymer before modification.

[0098] The reaction temperature during the graft modification is preferably 100°C to 300°C and more preferably 120°C to 280°C.

[0099] The method for graft modification is not particularly limited, and, for example, a method described in Japanese Patent Application Laid-Open No. 62-79211 can be used. [Hydrogenation reaction process]

[0100] The hydrogenated block copolymer (I) used in the foam body of the present embodiment can be obtained by subjecting the above-described unhydrogenated, unmodified or modified block copolymer to a hydrogenation reaction using a prescribed hydrogenation catalyst.

[0101] Examples of the hydrogenation catalyst include, but are not limited to, known catalysts such as (1) a heterogeneous hydrogenation catalyst on a support in which a metal such as Ni, Pt, Pd or Ru is supported on carbon, silica, alumina, diatomaceous earth or the like, (2) a so-called Ziegler hydrogenation catalyst in which an organic acid salt of Ni, Co, Fe, Cr or the like or a transition metal salt such as an acetylacetone salt and a reducing agent such as organic aluminum are used, and (3) a homogeneous hydrogenation catalyst referred to as an organic metal complex of an organic metal compound or the like of Ti, Ru, Rh, Zr or the like.

[0102] Alternatively, as the hydrogenation catalyst, there may be used, without limitation, hydrogenation catalysts described in Japanese Patent Publication Nos. 42-8704, 43-6636, 63-4841, 1-37970, 1-53851 and 2-9041.

[0103] Suitable examples of the hydrogenation catalyst are a titanocene compound, a reducing organometallic compound or a mixture of these compounds.

[0104] The titanocene compound is not particularly limited, and, for example, a compound described in Japanese Patent Application Laid-Open No. 8-109219 can be used. A specific example is a compound having at least one ligand with a (substituted) cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton, such as bis-cyclopentadienyltitanium dichloride or mono-pentamethylcyclopentadienyltitanium trichloride.

[0105] Examples of reducing organometallic compounds include, but are not limited to, an organic alkali metal compound such as organolithium, an organic magnesium compound, an organic aluminum compound, an organic boron compound, and an organic zinc compound.

[0106] The hydrogenation reaction is now described.

[0107] The reaction temperature is generally preferably in a temperature range of 0°C to 200°C and more preferably in a temperature range of 30°C to 150°C.

[0108] The hydrogen pressure used in the hydrogenation reaction is preferably 0.1 MPa to 15 MPa, more preferably 0.2 MPa to 10 MPa and further preferably 0.3 MPa to 5 MPa.

[0109] The duration of the hydrogenation reaction is usually preferably 3 minutes to 10 hours, and more preferably 10 minutes to 5 hours.

[0110] The hydrogenation reaction can be carried out by a batch process, a continuous process or a combination of these processes.

[0111] It is preferable to remove a catalyst residue, if necessary, from a solution of a hydrogenated block copolymer resulting from the hydrogenation reaction and to separate the hydrogenated block copolymer from the solution.

[0112] Examples of a separation method include, but are not limited to, a method in which a polar solvent that acts as a poor solvent for a hydrogenated modified copolymer, such as acetone or alcohol, is added to the reaction solution after hydrogenation to precipitate and recover the polymer; a method in which the reaction solution is added to hot water with stirring and the solvent is removed by steam stripping to recover the polymer; and a method in which the polymer solution is directly heated to remove the solvent.

[0113] A stabilizer such as various phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers may be added to the hydrogenated block copolymer (I) used in the foam body of the present embodiment. <Harz auf Olefinbasis (II)>

[0114] The hydrogenated block copolymer composition contained in the foam body of the present embodiment contains the olefin-based resin (II).

[0115] Examples of olefin-based resins (II) used in the foam body of the present embodiment include, but are not limited to, homopolymers of α-olefins such as polyethylene (PE), polypropylene (PP), 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, and 1-octene. Other examples include random copolymers or block copolymers containing a combination of olefins selected from the group consisting of ethylene, propylene, butene, pentene, hexene, and octene.

[0116] Specific examples are ethylene and / or propylene-α-olefin copolymers such as an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-3-methyl-1-butene copolymer, an ethylene-4-methyl-1-pentene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, an ethylene-1-decene copolymer, a propylene-1-butene copolymer, a propylene-1-hexene copolymer, a propylene-1-octene copolymer, a propylene-4-methyl-1-pentene copolymer, an ethylene-propylene-1-butene copolymer, a propylene-1-hexene-ethylene copolymer, and a propylene-1-octene-ethylene copolymer.

[0117] An ethylene and / or propylene copolymer includes a copolymer with another unsaturated monomer except the α-olefin.

[0118] Examples of copolymers with other unsaturated monomers include, without limitation, copolymers of ethylene and / or propylene with unsaturated organic acids or derivatives thereof, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, methyl methacrylate, maleic anhydride, arylmaleimide, and alkylmaleimide; copolymers of ethylene and / or propylene with vinyl esters such as vinyl acetate; and copolymers of ethylene and / or propylene with non-conjugated dienes such as dicyclopentadiene, 4-ethylidene-2-norbornene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene.

[0119] The olefin-based resin (II) preferably contains at least one polypropylene-based resin from the viewpoint of economy and good compatibility with another component contained in the hydrogenated block copolymer composition contained in the foam body of the present embodiment in order to achieve high transparency.

[0120] The olefin-based resin (II) may be modified with a prescribed functional group.

[0121] The functional group is not particularly limited and includes, for example, an epoxy group, a carboxy group, an acid anhydride group and a hydroxyl group.

[0122] A functional group-containing compound or denaturant for use in modifying the olefin-based resin (II) is not particularly limited and includes the following compounds: unsaturated epoxides such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, and allyl glycidyl ether; and unsaturated organic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, maleic anhydride, fumaric anhydride, and itaconic anhydride. Other non-limiting examples include an ionomer and chlorinated polyolefins.

[0123] From the viewpoint of achieving economic efficiency and good compatibility in the hydrogenated block copolymer composition contained in the foam body of the present embodiment, in order to achieve high transparency, the olefin-based resin (II) is preferably a polypropylene-based resin such as a polypropylene homopolymer or an ethylene-propylene random copolymer or block copolymer.

[0124] Particularly from the viewpoint of transparency and flexibility, the olefin-based resin (II) is preferably a random ethylene-propylene copolymer.

[0125] The olefin-based resin (II) may contain a single material or may contain two or more materials. <Thermoplastisches Harz (III)>

[0126] The hydrogenated block copolymer composition contained in the foam body of the present embodiment contains the thermoplastic resin (III).

[0127] Examples of the thermoplastic resin (III) include, but are not limited to, a block copolymer of a conjugated diene compound and a vinyl aromatic compound or a hydrogenated product thereof (which, however, is different from the hydrogenated block copolymer (I) of the present embodiment), polymers of the vinyl aromatic compound, copolymer resins of the vinyl aromatic compound and another vinyl monomer such as ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid and acrylic esters such as methyl acrylate, methacrylic acid and methacrylic esters such as methyl methacrylate, acrylonitrile or methacrylonitrile, a rubber-modified styrene-based resin (HIPS), an acrylonitrile-butadiene-styrene copolymer resin (ABS), and a methacrylic ester-butadiene-styrene copolymer resin (MBS).

[0128] Other examples of the thermoplastic resin (III) are a polymer of acrylic acid and an ester or amide thereof, a polyacrylate-based resin, a polymer of acrylonitrile and / or methacrylonitrile, a nitrile resin which is a copolymer of another copolymerizable monomer containing 50 mass% or more of such an acrylonitrile-based monomer, a polyamide-based resin such as nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12 or nylon-6-nylon-12 copolymer, a polyester-based resin, a thermoplastic polyurethane-based resin, a polycarbonate-based polymer such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate, thermoplastic polysulfone such as polyethersulfone or polyallylsulfone, a polyoxymethylene-based resin, a polyphenylene ether-based resin such as poly(2,6-dimethyl-1,4-phenylene) ether, a resin based Polyphenylene sulfide-based resin such as polyphenylene sulfide, or poly-4,4'-diphenylene sulfide, a polyarylate-based resin,a polyetherketone polymer or copolymer, a polyketone-based resin, a fluorine-based resin, a polyoxybenzoyl-based polymer, a polyimide-based resin, and a polybutadiene-based resin such as 1,2-polybutadiene and trans-polybutadiene.

[0129] As the thermoplastic resins (III), polystyrene, a styrene-based resin such as a rubber-modified styrene-based resin, a polyamide-based resin, a polyester-based resin, and a polycarbonate-based resin are particularly preferred. The number-average molecular weights of the thermoplastic resins (III) are generally 1,000 or more, preferably 5,000 to 5,000,000, and more preferably 10,000 to 1,000,000. <Weichmacher (IV)>

[0130] The hydrogenated block copolymer composition contained in the foam body of the present embodiment contains the plasticizer (IV).

[0131] The plasticizer (IV) is preferably a rubber plasticizer that softens the hydrogenated block copolymer composition and imparts flowability and processability to it.

[0132] The plasticizer may, for example, be, without limitation, a mineral oil or a liquid or low molecular weight synthetic plasticizer, with particular preference being given to naphthene-based and / or paraffin-based process oils or plasticizer oils.

[0133] A mineral oil-based rubber plasticizer is a mixture of an aromatic ring, a naphthene ring, and a paraffin chain. A plasticizer containing a paraffin chain with a carbon number equal to 50% or more of all carbons is called a paraffin-based plasticizer. A plasticizer containing a naphthene ring with a carbon number of 30 to 45% is called a naphthene-based plasticizer. A plasticizer with a number of aromatic carbons exceeding 30% is called an aromatic plasticizer.

[0134] In the hydrogenated block copolymer composition of the present embodiment, a synthetic plasticizer can be used. Examples of the synthetic plasticizer include, but are not limited to, polybutene, low-molecular-weight polybutadiene, and liquid paraffin. As the plasticizer (IV), a mineral oil-based rubber plasticizer is more preferable.

[0135] When the hydrogenated block copolymer composition contained in the foam body of the present embodiment is required to have high heat resistance and mechanical properties, a mineral oil-based rubber softener to be used therein has a kinematic viscosity at 40°C of preferably 60 cst or more, and more preferably 120 cst or more.

[0136] One of the plasticizers (IV) can be used individually, or two or more of them can be used together. <Gehalt der Komponenten (I) bis (IV) in der hydrierten Blockcopolymerzusammensetzung>

[0137] The contents of components (I) to (IV) in the hydrogenated block copolymer composition contained in the foam body of the present embodiment will now be described.

[0138] The content of the hydrogenated block copolymer (I) is preferably 3 mass% or more and 95 mass% or less, more preferably 5 mass% or more and 70 mass% or less, further preferably 7 mass% or more and 60 mass% or less, and still more preferably 9 mass% or more and 50 mass% or less.

[0139] When the content of the hydrogenated block copolymer (I) in the hydrogenated block copolymer composition falls within the above-described range, the foams tend to be fine and highly independent, exhibiting high foaming properties during molding. Therefore, thermal insulation is improved, and thus excellent foam stability, moldability, and wear resistance tend to be achieved for a long period of time.

[0140] The content of the olefin-based resin (II) is preferably 1 mass% or more and 42 mass% or less, more preferably 3 mass% or more and 38 mass% or less, further preferably 6 mass% or more and 34 mass% or less, and still more preferably 10 mass% or more and 30 mass% or less.

[0141] When the content of the olefin-based resin (II) falls within the range described above, the balance between the foaming property, flexibility and heat resistance tends to be good.

[0142] The content of the thermoplastic resin (III) is preferably 1 mass% or more and 60 mass% or less, more preferably 3 mass% or more and 50 mass% or less, further preferably 6 mass% or more and 40 mass% or less, and still further preferably 10 mass% or more and 30 mass% or less.

[0143] When the content of the thermoplastic resin (III) falls within the range described above, the balance among the foaming property, flexibility, molding processability and toughness tends to be good.

[0144] The content of the plasticizer (IV) is preferably 1 mass% or more and 65 mass% or less, more preferably 5 mass% or more and 60 mass% or less, further preferably 10 mass% or more and 55 mass% or less, and even more preferably 20 mass% or more and 50 mass% or less.

[0145] When the content of the plasticizer (IV) falls within the range described above, the balance between the foaming property, flexibility and molding processability tends to be good. <additive>

[0146] In the hydrogenated block copolymer composition contained in the foam body of the present embodiment, in addition to the components (I), (II), (III) and (IV), any additive may be blended as needed.

[0147] The type of additive is not particularly limited as long as it is one that is generally used for blending into a thermoplastic resin or a rubber-like polymer.

[0148] The additive is not particularly limited and may be a filler, a lubricant, a release agent, a plasticizer, an antioxidant, a heat stabilizer, a light stabilizer, a UV absorber, a flame retardant, an antistatic agent, a reinforcing agent, a colorant, and the like generally used in a thermoplastic resin and a rubbery polymer.

[0149] Examples of the filler include, but are not limited to, inorganic fillers such as silicon dioxide, talc, mica, calcium silicate, hydrotalcite, kaolin, diatomite, graphite, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate and barium sulfate, and organic fillers such as carbon black or carbon black.

[0150] Examples of the lubricant include, but are not limited to, stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene bis-stearamide.

[0151] Examples of plasticizers include, but are not limited to, organic polysiloxane and mineral oil.

[0152] An example of an antioxidant includes, but is not limited to, a hindered phenol-based antioxidant.

[0153] Examples of heat stabilizers include, but are not limited to, phosphorus-, sulfur-, and amine-based heat stabilizers.

[0154] An example of the light stabilizer is, but is not limited to, a hindered amine light stabilizer.

[0155] An example of the UV absorber is, but is not limited to, a benzotriazole-based UV absorber.

[0156] Examples of the reinforcing agent include, but are not limited to, organic fibers, glass fibers, carbon fibers, and metal whiskers.

[0157] Examples of the colorant include, but are not limited to, titanium oxide, iron oxide, and carbon black.

[0158] Other examples include those described in, for example, "Gomu / Plastic Haigo Yakuhin (Rubber / Plastic Compounding Chemicals)" (published by Rubber Digest Co., Ltd.). (Process for producing a hydrogenated block copolymer composition)

[0159] The hydrogenated block copolymer composition contained in the foam body of the present embodiment can be produced by a conventionally known method.

[0160] Examples of a production method of the hydrogenated block copolymer composition of the present embodiment include, but are not limited to, a method in which the respective components (the hydrogenated block copolymer (I), the polyolefin-based resin (II), the thermoplastic resin (III), the plasticizer (IV), and, if necessary, another additive) are melt-kneaded using a mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, or a multi-screw extruder, and a method in which the respective components are dissolved or dispersed in a solvent to be mixed, followed by removal of the solvent by heating.

[0161] In particular, from the perspective of productivity and good kneadability, a melt kneading process with an extruder is suitably used.

[0162] The hydrogenated block copolymer composition can be in any shape, including, but not limited to, pellets, films, strands, or chips. After melt-kneading, a molded article can be directly produced. (Hardness of the hydrogenated block copolymer composition)

[0163] The hydrogenated block copolymer composition contained in the foam body of the present embodiment has a 15-second hardness value, measured with a Type A durometer according to JIS K6253, of 85 or less, preferably 80 or less, more preferably 75 or less, and further preferably 70 or less.

[0164] When the value of 15-second hardness, measured with a type A durometer according to JIS K6253, of the hydrogenated block copolymer composition contained in the foam body of the present embodiment is 85 or less, the foam body of the present embodiment can obtain a very good cushioning feeling and soft touch feeling.

[0165] The hydrogenated block copolymer composition contained in the foam body of the present embodiment has a 15-second hardness value, measured with a Type A durometer according to JIS K6253, of preferably 30 or more, more preferably 35 or more, and further preferably 40 or more. Thus, a pellet of the hydrogenated block copolymer composition tends to have good blocking resistance.

[0166] When the blocking resistance of the pellets of the hydrogenated block copolymer composition is high, blocking tends to be difficult to occur even under conditions of long-term transportation, greater stress, and more severe temperature environments, such as in a high-temperature region or a wide-temperature-range region. It can be expected that the pellets can be easily weighed, mixed, or the like during compound molding. Furthermore, since the amount of anti-blocking agent to be added can be reduced, device contamination can be avoided, environmental pollution can be reduced, and unexpected deterioration in physical properties, such as deterioration in transparency, mechanical strength, or the like, can be suppressed.

[0167] The hardness of the hydrogenated block copolymer composition can be controlled to fall within the above-described numerical range by adjusting the hardness of the hydrogenated block copolymer (I) contained in the hydrogenated block copolymer composition, the hardness of component (III) in the hydrogenated block copolymer composition, the flexural strength of component (II), the viscosity of component (IV), and the composition ratio of components (I) to (IV).

[0168] The hardness of the hydrogenated block copolymer (I) can be controlled by appropriately adjusting the weight-average molecular weight of the hydrogenated block copolymer (I), the content of the polymer block (a) in the hydrogenated block copolymer composition, the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b), the content of the hydrogenated polymer block (c), the vinyl bond content in the conjugated diene monomer unit of the hydrogenated block copolymer (I), the hydrogenation degree of double bonds of the conjugated diene monomer unit of the hydrogenated block copolymer (I), and the like.

[0169] Alternatively, the hardness of the hydrogenated block copolymer (I) can be controlled by adjusting the tanδ peak temperature (loss tangent) at -25°C to 60°C in a viscoelasticity measurement chart of the hydrogenated block copolymer (I), namely, by adjusting a glass transition temperature derived from the hydrogenated copolymer block (b), by conducting a polymerization reaction using a prescribed modifier to adjust the vinyl bond content of the hydrogenated copolymer block (b), adjusting the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b), and adjusting the copolymerizability between the vinyl aromatic compound and the conjugated diene. (MFR of the hydrogenated block copolymer composition)

[0170] The hydrogenated block copolymer composition contained in the foam body of the present embodiment has an MFR (melt flow rate) measured under the conditions of a temperature of 230°C and a load of 2.16 kg according to JIS K7210 of 40 or more, preferably 60 or more, and more preferably 100 or more.

[0171] When the MFR of the hydrogenated block copolymer composition contained in the foam body of the present embodiment is 40 or more, good processability can be expected.

[0172] When the processability of the hydrogenated block copolymer composition contained in the foamed body of the present embodiment is good, the foamed body can be formed as a very thin layer, and in particular, a foamed body having a thin non-foam skin layer can be obtained. Furthermore, when molding a foamed body, a striped pattern such as a flow mark, a pockmark, and a swirl mark is difficult to form, so a foamed body with a good surface appearance can be obtained. Furthermore, molding can be performed in a more complicated shape or in a thin shape, so the weight of the resulting article can be reduced due to the reduction in thickness.Furthermore, better processability tends to be beneficial for improving surface appearance, forming with a complex shape, and reducing thickness.

[0173] Furthermore, since the processability is better, the amount of a processing aid such as the plasticizer (IV) used in the hydrogenated block copolymer composition can be reduced, so that there is a tendency that the freedom of compounding is improved, the mechanical strength and touch feeling of the hydrogenated block copolymer composition are improved, and a reduction in environmental pollution can be achieved.

[0174] The upper limit of the MFR of the hydrogenated block copolymer composition contained in the foam body of the present embodiment is preferably 2000 or less, more preferably 1000 or less, and further preferably 500 or less from the viewpoint of heat resistance.

[0175] The MFR of the hydrogenated block copolymer composition can be controlled to fall within the numerical range described above by adjusting the MFR of components (I), (II) and (III) in the hydrogenated block copolymer composition, the viscosity of component (IV) and the composition ratio of components (I) to (IV).

[0176] The MFR of the hydrogenated block copolymer (I) is controlled by adjusting the weight-average molecular weight, the content of the polymer block (a), the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b), the content of the hydrogenated polymer block (c), the vinyl bond content in the conjugated diene monomer unit before hydrogenation of the hydrogenated block copolymer (I), and the hydrogenation degree of double bonds of the conjugated diene monomer unit of the hydrogenated block copolymer (I).

[0177] For example, the MFR of the hydrogenated block copolymer (I) tends to be increased when the weight-average molecular weight of the hydrogenated block copolymer (I) is decreased, the content of the polymer block (a) is decreased, the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is increased, the content of the hydrogenated polymer block (c) in an end block is increased, the content of the hydrogenated polymer block (c) in an inner block is decreased, the vinyl bond content in the conjugated diene monomer unit is increased, or the hydrogenation degree of double bonds of the conjugated diene monomer unit is decreased.

[0178] In particular, the weight-average molecular weight of the hydrogenated block copolymer (I) has a linear relationship with the logarithm of the MFR. Therefore, after adjusting the content of the polymer block (a) in the hydrogenated block copolymer (I) and the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) to exhibit the blocking resistance of a pellet of the hydrogenated block copolymer composition and the heat resistance and wear resistance of the hydrogenated block copolymer composition, a weight-average molecular weight for achieving a desired MFR can be determined based on the linear relationship between the weight-average molecular weight of the hydrogenated block copolymer (I) and the logarithm of the MFR. [Process for producing the foam body]

[0179] A method for producing a foamed body of the present embodiment includes a step of adding a foaming agent (V) to the hydrogenated block copolymer composition and injecting the resultant to fill a cavity formed in a mold of an injection molding machine and having a space volume adjustable with a movable core, and a step of enlarging the space volume of the cavity with the movable core to perform foam molding.

[0180] Specifically, the hydrogenated block copolymer composition is injected into a cavity formed in a mold, and immediately thereafter or after a prescribed period of time, a movable mold or a movable core / insert provided in the movable mold is returned to a prescribed position at a prescribed speed. Thus, the hydrogenated block copolymer composition expands within the cavity, thereby performing foam molding.

[0181] A foaming process may be a chemical process or a physical process, and in both processes, after adding a chemical foaming agent such as an inorganic foaming agent or an organic foaming agent, or a physical foaming agent, the foaming agent is volatilized and / or decomposed by heating or the like so that foam is dispersed in the hydrogenated block copolymer composition.

[0182] The foam body of the present embodiment can be manufactured, for example, by core-back injection molding, and is characterized in that the non-foam skin layer and the foam core layer are integrally molded, and the foam core layer and the non-foam skin layer are adjacent to each other. When core-back injection molding is adopted, a foam core layer with a cushioning property and a non-foam skin layer having a design and being harder than the foam core layer can be molded in a single process, so this method can effectively reduce molding processes. Furthermore, a back pressure device can be used to eliminate a swirl mark formed on the surface of the foam body. (Foaming agent (V))

[0183] As foaming agent (V) an inorganic foaming agent, an organic foaming agent or a physical foaming agent can be used.

[0184] Examples of inorganic foaming agents include, but are not limited to, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, an azide compound, sodium borohydride, aluminum acetate, and a metal powder.

[0185] Examples of organic foaming agents include, but are not limited to, azodicarbonamide, azobisformamide, azobisisobutyronitrile, barium azodicarboxylate, N,N'-dinitrosopentamethylenetetramine, N,N'-dinitroso-N,N'-dimethylterephthalamide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, p,p'-oxybenzenesulfonyl hydrazide, and p-toluenesulfonyl semicarbazide.

[0186] Examples of physical foaming agents include, but are not limited to, hydrocarbons such as pentane, butane and hexane, halogenated hydrocarbons such as methyl chloride and methylene chloride, gases such as nitrogen, carbon dioxide and air, and fluorinated hydrocarbons such as trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, chlorodifluoroethane and hydrofluorocarbon.

[0187] These foaming agents (V) can also be used in combination.

[0188] The amount of the foaming agent (V) to be added is preferably 0.1 to 30 parts by mass, more preferably 2 to 25 parts by mass, and further preferably 3 to 20 parts by mass, based on 100 parts by mass of the hydrogenated block copolymer composition. (foaming agent)

[0189] In the production of the foam body, a foaming aid can also be used together with the foaming agent (V) described above.

[0190] The foaming aid is not particularly limited, and those commonly used as foaming aids can be used.

[0191] Examples include a urea compound, a zinc compound such as zinc oxide, zinc stearate, zinc benzenesulfinate, zinc toluenesulfonate, zinc trifluoromethanesulfonate and zinc carbonate, and a lead compound such as lead dioxide and tribasic lead.

[0192] When the foaming agent (V) and the foaming aid are used together, the amount of the foaming aid to be added, based on 100 parts by mass of the foaming agent, is preferably 0.1 to 1000 parts by mass, more preferably 0.5 to 500 parts by mass, and further preferably 1 to 200 parts by mass. (Nucleating foaming agent)

[0193] A nucleating foaming agent can be used in the production of the foam body.

[0194] The nucleating foaming agent is not particularly limited, and those commonly used as nucleating foaming agents can be used.

[0195] Examples include titanium oxide, talc, kaolin, clay, calcium silicate, silicon dioxide, sodium citrate, calcium carbonate, diatomite, calcined perlite, zeolite, bentonite, glass, limestone, calcium sulfate, aluminum oxide, titanium oxide, magnesium carbonate, sodium carbonate, iron carbonate and a polytetrafluoroethylene powder.

[0196] The amount of the nucleating foaming agent to be added is preferably 0.01 to 100 parts by mass, more preferably 0.05 to 50 parts by mass, and further preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the hydrogenated block copolymer composition. [Structure of the foam body]

[0197] The foam body of the present embodiment can be manufactured by core-back injection molding as described above. The foam body of the present embodiment has a structure in which the non-foam skin layer and the foam core layer are integrally molded, with the foam core layer, which has a cushioning property, and the non-foam skin layer, which is harder than the foam core layer, adjacent to each other. (Foaming ratio)

[0198] The foaming ratio of the foam body of the present embodiment is 1.2 times or more, preferably 1.5 times or more, more preferably 1.7 times or more, further preferably 1.9 times or more, and even more preferably 2 times or more.

[0199] When the foaming ratio is 1.2 times or more, excellent damping properties and excellent appearance can be obtained.

[0200] The foaming ratio of the foam body can be calculated as a value obtained by dividing the thickness (mm) of the foam core layer of the foam body after core-back injection molding by the thickness (mm) of an empty portion of a cavity in a mold of an injection molding machine when filling the cavity with the hydrogenated block copolymer composition.

[0201] The foaming ratio of the foamed body can be controlled to fall within the above-described numerical range by adjusting, in the manufacturing process of the foamed body, the types and compositions of the components (I) to (IV) in the hydrogenated block copolymer composition, the type and amount of the foaming agent (V) to be added, the amount of the hydrogenated block copolymer composition to be filled, and the molding temperature and pressure used in the molding process.

[0202] Particularly in the case of core-back injection molding, the foaming ratio can be controlled to fall within the above-described range of numbers by appropriately adjusting, in the manufacturing process of the foamed body, the types and compositions of components (I) to (IV) in the hydrogenated block copolymer composition, the type of foaming agent (V), the amount of the hydrogenated block copolymer composition to be filled, the core-back opening, the amount of foaming agent to be added, the temperature of the hydrogenated block copolymer composition to be injected, the temperature of the mold (fixed section / movable section), the injection speed, the injection pressure, the delay time after filling until the start of core retraction, the number of core retraction stages, the opening and core retraction speed in each stage, the cooling time, and the shape of the mold. (Non-foam skin layer)

[0203] The foam body of the present embodiment has a structure in which the foam core layer and the non-foam skin layer are adjacent to each other.

[0204] The thickness of the non-foam skin layer is preferably 10 µm to 1000 µm, more preferably 10 µm to 700 µm, and further preferably 10 µm to 500 µm from the viewpoint of achieving good cushioning property and molded appearance.

[0205] When the foamed body of the present embodiment is produced by core-back injection molding, the thickness of the non-foam skin layer can be controlled to fall within the above-described numerical range by adjusting, in the foamed body manufacturing process, the types and compositions of components (I) to (IV) in the hydrogenated block copolymer composition, the type of the foaming agent (V), the amount of the hydrogenated block copolymer composition to be filled, the core-back opening, the amount of the foaming agent to be added, the temperature of the resin to be injected, the temperature of the mold (fixed section / movable section), the injection speed, the injection pressure, the delay time after filling until the start of core retraction, the number of core retraction stages, the opening and core retraction speed in each stage, the cooling time, and the mold shape. (foam core layer)

[0206] The foam body of the present embodiment has a structure in which the foam core layer and the non-foam skin layer are adjacent to each other.

[0207] From the viewpoint of achieving good damping properties, the thickness of the foam core layer is 300 µm or more, preferably 700 µm or more, and more preferably 1000 µm or more. The upper limit of the thickness of the foam core layer is not particularly limited and is preferably 20,000 µm or less.

[0208] When core-back injection molding is used, in order to perform molding to obtain a good as-molded appearance (free from flow marks, swirl marks, pockmarks, and depressions), the thickness of the foam core layer can be controlled to fall within the above numerical range by selecting, in the manufacturing process of the foam body, the kinds and compositions of the components (I) to (IV) in the hydrogenated block copolymer composition, the kind of the foaming agent (V), the amount of the hydrogenated block copolymer composition to be filled, the core-back opening, and the like.Core back opening, the amount of foaming agent to be added, the temperature of the resin to be injected, the temperature of the mold (fixed section / movable section), the injection speed, the injection pressure, the delay time after filling until the start of core retraction, the number of core retraction stages, the opening and core retraction speed in each stage, the cooling time and the shape of the mold can be adjusted. [Use of the foam body]

[0209] The foam body of the present embodiment can be used in, for example, a vehicle component, a food packaging material, a medical device, a household appliance element, an electronic appliance element, a building material, an industrial component, a household article, a toy material, a shoe material, a fiber material, and the like.

[0210] Examples of a vehicle component include, but are not limited to, a side panel, a grommet or ring, a shift knob, a weatherstrip / seal, a window frame and sealing material therefor, an instrument panel, a grab handle, a steering wheel, a shift lever, a console, an armrest, a headrest, and a door panel.

[0211] Examples of the medical device / instrument include, but are not limited to, a medical probe, a medical tube, a catheter, a blood bag, an IV bag, a platelet storage bag, and a dialysis bag.

[0212] Examples of building materials include, but are not limited to, wall materials and floor materials.

[0213] Other examples include, but are not limited to, an industrial hose, a food hose, a vacuum cleaner hose, an electrically cooling gasket, various coating materials for electrical wires and the like, a coating material for a handle, and a soft doll.

[0214] The foam body of the present embodiment can be processed in a suitable manner, e.g., by foaming, crushing, stretching, bonding, printing, coating, or plating. [Laminate]

[0215] A laminate of the present embodiment comprises a layer containing the foam body of the present embodiment and a layer containing a base resin.

[0216] Examples of the base resin include, but are not limited to, polypropylene, polyethylene, methyl polymethacrylate, polyacrylonitrile, polymethacrylonitrile, a rubber-modified styrene-based resin (HIPS), an acrylonitrile-butadiene-styrene copolymer resin (ABS), and a methacrylic acid ester-butadiene-styrene copolymer resin (MBS).

[0217] The base resin is particularly preferably polypropylene or an ABS resin in order that the laminate of the present embodiment has good rigidity.

[0218] The layer containing the foam body may consist only of the foam body of the present embodiment or may be a laminate with another material layer.

[0219] The layer containing the base resin may consist of the base resin only, or may be a laminate of the base resin and another resin, or may contain a mixed resin of the base resin and another resin.

[0220] An example of a method for laminating the foam body-containing layer and the base resin-containing layer is a method in which the base resin is injection-molded and then subjected to core-back molding with the hydrogenated block copolymer composition of the present embodiment by two-color injection molding. As a result, the base resin-containing layer and the foam body-containing layer have good adhesion, so that the laminate can be obtained without an adhesive layer. It is thus possible to reduce the molding processes of the laminate and improve recyclability.

[0221] The laminate of the present embodiment may have the above-mentioned structure in which the base resin-containing layer and the foam body-containing layer are in direct contact with each other without an adhesive layer therebetween, but may also have a structure in which these layers are laminated via a prescribed adhesive layer. Examples

[0222] The present embodiment will now be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to these examples and comparative examples.

[0223] The measurement and evaluation methods of physical properties used in the examples and comparative examples are as follows.

[0224] The structural specification and measurement of physical properties of the hydrogenated block copolymers used in the foam bodies of Examples and Comparative Examples were carried out as follows. [Method for determining the structure of a hydrogenated block copolymer]((1) Content of all vinyl aromatic monomer units (styrene) in hydrogenated block copolymer (I))

[0225] A hydrogenated block copolymer was used to measure the content of all vinyl aromatic monomer units (styrene) using a UV spectrophotometer (UV-2450, manufactured by Shimadzu Corporation). ((2) Degree of hydrogenation of double bond(s) of the conjugated diene monomer unit in hydrogenated block copolymer (I))

[0226] The hydrogenation degree of double bond(s) of the conjugated diene monomer unit was measured using the hydrogenated block copolymer with a nuclear magnetic resonance apparatus (ECS400, manufactured by JEOL RESONANCE Inc.). ((3) Content of polymer block (a) in hydrogenated block copolymer (I))

[0227] The content of the polymer block (a) mainly containing a vinyl aromatic monomer unit was measured using the hydrogenated block copolymer with a nuclear magnetic resonance (NMR) apparatus (according to a method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY, 54, 685 (1981); hereinafter referred to as "NMR method"). ((4) Content of hydrogenated copolymer block (b) in hydrogenated block copolymer (I))

[0228] The content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (I) was calculated according to the calculation formula 100 - (content of the hydrogenated copolymer block (a) in the hydrogenated block copolymer (I)). ((5) Vinyl bond content in hydrogenated block copolymer (I))

[0229] The vinyl bond content of the hydrogenated block copolymer was measured using a nuclear magnetic resonance (NMR) device.

[0230] The vinyl bond content in the conjugated diene monomer unit in the hydrogenated block copolymer was determined based on the ratio of the total area of ​​the 1,2-bond and 3,4-bond peaks to the total area of ​​all the peaks involved in the conjugated diene monomer unit (1,2-bond, 3,4-bond, and 1,4-bond peaks) among the peaks obtained by NMR measurement. ((6) Content of vinyl aromatic monomer units in the hydrogenated copolymer block (b) contained in the hydrogenated block copolymer (I))

[0231] Based on the difference between the content of all vinyl aromatic monomer units in the hydrogenated block copolymer (I) measured as described in (1) above and the content of the polymer block (a) mainly containing a vinyl aromatic monomer unit in the hydrogenated block copolymer (I) measured as described in (3) above, the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) in the entire polymer was calculated, and based on the ratio to the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (I) measured as described in (4) above, the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) was calculated. [Method for measuring physical properties of hydrogenated block copolymer]((1) Hardness)

[0232] 15-second hardness values ​​were measured using a Type A durometer and a Type D durometer according to JIS K6253, respectively.

[0233] A hardness value was measured 15 seconds after a sample was touched by a durometer probe.

[0234] In Tables 1 to 2 below, these hardness values ​​are given as hardness (JIS-A, 15 seconds) and hardness (JIS-D, 15 seconds).

[0235] If the hardness measured with the Type D durometer was below 20, the value determined with the Type A durometer was used as the hardness value, and if the hardness measured with the Type A durometer was above 90, the value determined with the Type D durometer was used.

[0236] As a guideline, a hardness of 94, measured with a Type A durometer, corresponds to a hardness of 45, measured with a Type D durometer. ((2) Melt flow rate (MFR, unit: g / 10 min))

[0237] The MFR was measured under the conditions of a temperature of 230°C and a load of 2.16 kg according to JIS K7210. [Method for measuring physical properties of a hydrogenated block copolymer composition]

[0238] The hydrogenated block copolymer compositions used in the foam bodies of Examples and Comparative Examples were measured for their physical properties as follows. ((1) Hardness)

[0239] The 15-second hardness value was measured using a Type A durometer according to JIS K6253.

[0240] A hardness value was measured, which was obtained 15 seconds after a test sample was touched by a durometer probe.

[0241] In Tables 3 to 12 below, the hardness thus obtained is given as hardness (JIS-A, 15s). ((2) MFF)

[0242] The MFR was measured according to JIS K7210 under the conditions of a temperature of 230°C and a load of 2.16 kg. [Measurement of physical properties and evaluation of the properties of foam bodies]

[0243] The measurement of physical properties and evaluation of properties of the foam bodies of the examples and the comparative examples were carried out as follows. ((1) Foaming ratio)

[0244] The foaming ratio was calculated as a value obtained by dividing the thickness (mm) of the foam core layer of each foam body after core-back injection molding by the thickness (mm) of an empty portion of a cavity in a mold of an injection molding machine when filling the cavity with the hydrogenated block copolymer composition. ((2) Measurement of the thickness of the non-foam skin layer)

[0245] Each foam body was cut in the thickness direction perpendicular to the injection plane, and the resulting cross-section was observed with a light microscope.

[0246] The thickness of the skin layer was measured at the observed section. ((3) Measurement of the thickness of the foam core layer)

[0247] Each foam body was cut in the thickness direction perpendicular to the injection plane, and the resulting cross-section was observed with a light microscope.

[0248] The thickness of the core layer was measured at the observed section. ((4) Wear resistance of the surface of the foam body)

[0249] A colorfastness rubbing tester (AB-301, manufactured by Tester Sangyo Co., Ltd.) was used to rub a leather-textured surface of each foam body obtained by core-back injection molding with a Canequim #3 rubbing cloth under a load of 1000 g, and the wear resistance was evaluated according to a volume reduction caused by rubbing using the following criteria: <bewertungskriterien> 4: The volume decrease caused by 1000 rubbings was less than 50 mg. 3: The volume decrease caused by 1000 rubbings was 50 mg or more and less than 150 mg. 2: The volume decrease caused by 1000 times of rubbing was 150 mg or more and less than 250 mg. 1: The volume decrease caused by 1000 rubbings was 250 mg or more.

[0250] Regarding wear resistance, an acceptable score is 2 or more, and such a score was evaluated as excellent from the viewpoints of improving durability and improving freedom of mixing when a thinner / more complicated molded article is used and when the foam body is rubbed with a larger load or with a coarse cloth.

[0251] If the wear resistance is good, the composition can be used in applications such as automotive materials and the like where higher wear resistance is required. For example, when used as automotive interior materials or the like, even when molding with a thinner thickness or when molding a more complex / larger molded article, it can be expected to retain its appearance even during long-term use compared to a compact general molded article with a simple shape.

[0252] In addition, when the hydrogenated block copolymer composition is used as a vehicle interior material, the appearance of the material can be expected to be maintained for a long period of time even when the material is subjected to friction with a larger load or with a coarse fabric (such as denim, which is coarser than a cotton fabric of Canequim #3) during driving. ((5) Surface appearance of the foam body)

[0253] In the foam body obtained by injection molding of the hydrogenated block copolymer composition, it was examined whether or not there was a flow mark, a pockmark (gas release), a swirl mark, or transfer unevenness such as a leather-like surface or a mold-caused depression mark.

[0254] When evaluating the appearance, a sample that had no problem in practice was rated 3, a sample that had slight defects and might have a problem in practice was rated 2, and a sample that had obvious defects and had a practical problem was rated 1.

[0255] The acceptable score was set at 2 or more. ((6) Damping properties of the foam body)

[0256] Five people measured whether the foam body was dented when pressed with a finger or not.

[0257] A sample with high damping property was rated 3, a sample with medium damping property was rated 2 and a sample with no damping property was rated 1: <bewertungskriterien> 5: The total score was 15. 4: The total score was 12 to 14. 3: The total score was 9 to 11. 2: The total score was 6 to 8. 1: The total score was 5.

[0258] An acceptable score was set at 2 or more, and such a sample was evaluated as a damping foam body. [Foam body]

[0259] A foam body was prepared using a hydrogenated block copolymer (I), an olefin-based resin (II), a thermoplastic resin (III), and a plasticizer (IV) as described below. (Preparation of hydrogenated block copolymer (I))<Herstellung von Hydrierungskatalysator>

[0260] A hydrogenation catalyst used for the preparation of a hydrogenated block copolymer in the examples and comparative examples described below was prepared as follows.

[0261] A nitrogen-exchanged reaction vessel equipped with a stirrer was filled with 1 liter of dried and purified cyclohexane.

[0262] Subsequently, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added.

[0263] An n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring, followed by reaction at room temperature for about 3 days. Thus, a hydrogenation catalyst was obtained. < Preparation Example 1: Hydrogenated Block Copolymer (I)-1>

[0264] To carry out batch polymerization, a container reactor (with a capacity of 10 l) equipped with a stirrer and a jacket was used.

[0265] First, a cyclohexane solution (concentration of 20 mass%) containing 15 mass parts of styrene was added.

[0266] Subsequently, n-butyllithium was added in a ratio of 0.107 mass parts with respect to 100 mass parts of all monomers, N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") was added in a ratio of 0.9 mol per mol of n-butyllithium, and the resultant was polymerized at 65°C for 1 hour.

[0267] Then, a cyclohexane solution (concentration of 20 mass%) containing 29 mass parts of butadiene and 41 mass parts of styrene was added, followed by polymerization at 80°C for 2 hours. Finally, a cyclohexane solution (concentration of 20 mass%) containing 15 mass parts of styrene was added, followed by polymerization at 65°C for 1 hour. Methanol was then added to stop the polymerization reaction.

[0268] The block copolymer thus obtained had a styrene content of 71 mass%, a polystyrene block content of 30 mass%, a vinyl bond content of 22 mass%, and a weight-average molecular weight of 60,000.

[0269] To the block copolymer thus obtained, the hydrogenation catalyst prepared as described above was added in an amount of 100 ppm, expressed as Ti, per 100 parts by mass of the block copolymer, followed by a hydrogenation reaction at a hydrogen pressure of 0.7 MPa and a temperature of 65°C.

[0270] Subsequently, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate used as a stabilizer was added in an amount of 0.3 parts by mass based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (I)-1.

[0271] The hydrogenated block copolymer (I)-1 thus obtained had a hydrogenation degree of 98%. The other physical properties are given in Table 1. <Herstellungsbeispiele 2 bis 16: Hydrierte Blockcopolymere (I)-2 bis -13, (I)-A bis -C>

[0272] In the process for preparing hydrogenated block copolymer (I)-1, the polymerization method and hydrogenation conditions were adjusted to prepare hydrogenated block copolymers (I)-2 to (I)-13 and (I)-A to (I)-C. The physical properties of these polymers are shown in Tables 1 and 2 below. [Preparation of hydrogenated block copolymer compositions]

[0273] Hydrogenated block copolymer compositions were prepared using the hydrogenated block copolymers (I)-1 to (I)-13 and (I)-A to -C and the following components (II) to (IV). (Olefin-based resin (II))<Komponente (II)-1>

[0274] Olefin-based resin: Polypropylene resin, PM801A (manufactured by Sun Allomer, Ltd.) <Komponente (II)-2>

[0275] Olefin-based resin: Polypropylene resin, PMB00A (manufactured by Sun Allomer, Ltd.) <Komponente (II)-3>

[0276] Olefin-based resin: Polypropylene resin, PL500A (manufactured by Sun Allomer, Ltd.) (Thermoplastic resin (III))<Komponente (III)-1>

[0277] Thermoplastic resin: Styrene-based thermoplastic elastomer, N504 (manufactured by Japan Elastomer Co., Ltd.) <Komponente (III)-2>

[0278] Thermoplastic resin: Styrene-based thermoplastic elastomer

[0279] Content of polymer block (a): 35 mass%, content of hydrogenated copolymer block (b): 65 mass%, content of vinyl aromatic compound in hydrogenated copolymer block (b): 21 mass%, average molecular weight: 250,000, vinyl bond content: 35 mass%, degree of hydrogenation: 98 mass% (Plasticizer (IV))<Komponente (IV)>

[0280] Plasticizer: Paraffin oil, PW-90 (manufactured by Idemitsu Kosan Co., Ltd.) [Preparation of a hydrogenated block copolymer composition and a foam body] (Example 1)<Herstellung einer hydrierten Blockcopolymerzusammensetzung>

[0281] The hydrogenated block copolymer (I)-1 formed into a pellet shape, the olefin-based resin (II), the thermoplastic resin (III) and the plasticizer (IV) were mixed in the ratio (parts by mass) shown in Table 3, and the resultant was kneaded into a pellet shape by a twin-screw extruder (TEX-30), thereby obtaining a hydrogenated block copolymer composition.

[0282] The extrusion conditions were a cylinder temperature of 230°C and a screw speed of 300 rpm.

[0283] The hydrogenated block copolymer composition thus obtained was used and injection-molded at 210°C to prepare an injection-molded sheet having a thickness of 2 mm, thereby obtaining a sample for measuring physical properties.

[0284] The results of the physical property measurements are shown in Table 3. (Examples 2 to 36, and comparative examples 1 to 7)<Herstellung einer hydrierten Blockcopolymerzusammensetzung>

[0285] Hydrogenated block copolymer compositions were prepared in the same manner as in Example 1 except that the respective components were changed as shown in Tables 3 to 12, and their physical properties were measured.

[0286] The results of the physical property measurements are shown in Tables 3 to 12. (Production of foam bodies of Examples 1 to 36 and Comparative Examples 1 to 7)

[0287] To the pellets of the hydrogenated block copolymer compositions prepared based on the blending ratios (parts by mass) shown in Tables 3 to 12, a sodium bicarbonate-based foaming agent, Polythren EE-25C (manufactured by EIWA CHEMICAL IND. CO., LTD.), was added as a foaming agent (V) in an amount, expressed as an external amount, of 4 to 6 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer composition, and the resultant was dry blended.

[0288] The resulting dry blend product of the hydrogenated block copolymer composition and foaming agent pellets was molded into a 30 × 40 cm flat sheet using an injection molding machine with core back function (MD450S, manufactured by UBE MACHINERY CORPORATION, Ltd.). One surface of the flat sheet was processed into a leather-textured surface.

[0289] The resulting molded product was injection molded using a one-shot method in a mold with a thickness of 0.5 to 3.5 mm at a nozzle temperature of 220°C, a mold temperature of 40°C in a fixed section and 35°C in a movable section, and an injection speed of 100 mm / s. Then, the mold core was retracted at 480 mm / s to effect foaming at a prescribed foaming ratio. After cooling the resulting product for 20 seconds, a target foamed body was molded. The resulting foamed body had a structure comprising a non-foam skin layer, a foam core layer, and another non-foam skin layer contiguous to each other in the specified order.

[0290] The physical properties of the hydrogenated block copolymers (I) are shown in Tables 1 and 2, and the physical properties of the hydrogenated block copolymer compositions, the physical properties of the foam bodies, and the property evaluation results are shown in Tables 3 to 12 below. [Table 1] Manufacturer Example 1 Manufacturer Example 2 Manufacturer Example 3 Manufacturer Example 4 Manufacturer Example 5 Manufacturer Example 6 Manufacturer Example 7 Manufacturer Example 8 Manufacturer Example 9 Hydrogenated block copolymer (I)-1 (I)-2 (I)-3 (I)-4 (I)-5 (I)-6 (I)-7 (I)-8 (I)-9 Content of all vinyl aromatic monomer units (mass%) 71 82 58 45 41 34 40 66 65 Content of polymer block (a) (mass%) 30 30 30 30 30 30 30 16 14 Content of hydrogenated copolymer block (b) (mass%) 70 70 70 70 70 70 70 84 86 Content of vinyl aromatic monomer unit in the hydrogenated copolymer block (b) (mass%) 59 74 40 21 16 5 14 59 59 Content of vinyl aromatic monomer unit in the hydrogenated copolymer block (b) in the total polymer (mass%) 41 52 28 15 11 4 10 50 51 Content of conjugated diene in the hydrogenated copolymer block (b) in the total polymer (mass%) 29 18 42 55 59 67 60 34 35 Vinyl bond content in hydrogenated block copolymer (I) (mass%) 46 15 48 60 70 75 70 46 46 Degree of hydrogenation of the double bond in the conjugated diene monomer unit (%) 98 99 98 97 98 98 99 98 96 MFR (230° C, 2.16 kg) 101 100 102 103 101 101 101 103 100 Hardness (JIS-A,15s) 84 - 80 73 69 66 69 56 53 Hardness (JIS-D,15s) - 49 - - - - - - - [Table 2] Manufacturer Example 10 Herst-Example 11 Herst-Example 12 Herst-Example 13 Herst-Example 14 Manufacturing Example 15 Herst-Example 16 Hydrogenated block copolymer (I)-10 (I)-11 (I)-12 (I)-13 (I)-A (I)-B (I)-C Content of all vinyl aromatic monomer units (mass%) 64 15 71 71 32 63 33 Content of polymer block (a) (mass%) 11 11 30 30 30 9 15 Content of hydrogenated copolymer block (b) (mass%) 89 89 70 70 70 91 85 Content of vinyl aromatic monomer unit in the hydrogenated copolymer block (b) (mass%) 59 5 59 59 3 59 21 Content of vinyl aromatic monomer unit in the hydrogenated copolymer block (b) in the total polymer (mass%) 53 4 41 41 2 54 18 Content of conjugated diene in the hydrogenated copolymer block (b) in the total polymer (mass%) 36 85 29 29 68 37 67 Vinyl bond content in hydrogenated block copolymer (I) (mass%) 46 75 46 46 76 46 77 Degree of hydrogenation of the double bond in the conjugated diene monomer unit (%) 98 98 99 98 99 98 98 MFR (230° C, 2.16 kg) 102 102 25 15 100 101 50 Hardness (JIS-A,15s) 49 40 84 84 65 47 45 Hardness (JIS-D,15s) - - - - - - - [Table 3] Mass-produced parts Example 1 Example 2 Example 3 Example 4 Example 5 Hydrogenated block copolymer composition (parts by mass) Hydrogenated block copolymer (I)-1 40 Hydrogenated block copolymer (I)-2 40 Hydrogenated block copolymer (I)-3 40 Hydrogenated block copolymer (I)-4 40 Hydrogenated block copolymer (I)-5 40 Hydrogenated block copolymer (I)-6 Hydrogenated block copolymer (I)-7 Hydrogenated block copolymer (I)-8 Hydrogenated block copolymer (I)-9 Hydrogenated block copolymer (I)-10 Hydrogenated block copolymer (I)-11 Hydrogenated block copolymer (I)-12 Hydrogenated block copolymer (I)-13 Hydrogenated block copolymer (I)-A Hydrogenated block copolymer (I)-B Hydrogenated block copolymer (I)-C Olefin-based resin (II)-1 18 18 18 18 18 Olefin-based resin (II)-2 Olefin-based resin (II)-3 Thermoplastic resin (III)-1 14 14 14 14 14 Thermoplastic resin (III)-2 Plasticizers (IV) 28 28 28 28 28 Physical properties of the hydrogenated block copolymer composition MFR (230°C, 2.16kg) 150 150 140 140 130 Hardness (JIS-A,15s) 68 72 67 67 66 Foaming agent (V) Polythrene EE25-C (phr VS hydrogenated block copolymer composition) 6 6 6 6 6 Physical properties of foam bodies, properties Foaming ratio 1,75 1,75 1,75 1,75 1,75 Total thickness of the foam body (µm) 4000 4000 4000 4000 4000 Thickness of the non-foam skin layer (µm) 300 300 300 300 300 Thickness of the foam core layer (µm) 3400 3400 3400 3400 3400 Evaluation of wear resistance on the surface of the foam body 4 4 4 4 4 Evaluation of the surface appearance of the foam body 3 3 3 3 3 Evaluation of the damping properties of the foam body 5 5 5 5 5 [Table 4] Mass-produced parts Example 6 Example 7 Example 8 Example 9 Example 10 hydrogenated block copolymer composition (parts by mass) Hydrogenated block copolymer (I)-1 Hydrogenated block copolymer (I)-2 Hydrogenated block copolymer (I)-3 Hydrogenated block copolymer (I)-4 Hydrogenated block copolymer (I)-5 Hydrogenated block copolymer (I)-6 40 Hydrogenated block copolymer (I)-7 40 Hydrogenated block copolymer (I)-8 40 Hydrogenated block copolymer (I)-9 40 Hydrogenated block copolymer (I)-10 40 Hydrogenated block copolymer (I)-11 Hydrogenated block copolymer (I)-12 Hydrogenated block copolymer (I)-13 Hydrogenated block copolymer (I)-A Hydrogenated block copolymer (I)-B Hydrogenated block copolymer (I)-C Olefin-based resin (II)-1 18 18 18 18 18 Olefin-based resin (II)-2 Olefin-based resin (II)-3 Thermoplastic resin (III)-1 14 14 14 14 14 Thermoplastic resin (III)-2 Plasticizers (IV) 28 28 28 28 28 Physical properties of the hydrogenated block copolymer composition MFR (230°C, 2.16kg) 130 130 130 130 130 Hardness (JIS-A,15s) 66 66 63 63 61 Foaming agent (V) Polythrene EE25-C (phr VS hydrogenated block copolymer composition) 6 6 6 6 6 Physical properties of foam bodies, properties Foaming ratio 1,75 1,75 1,75 1,75 1,75 Total thickness of the foam body (µm) 4000 4000 4000 4000 4000 Thickness of the non-foam skin layer (µm) 300 300 300 300 300 Thickness of the foam core layer (µm) 3400 3400 3400 3400 3400 Evaluation of the wear resistance of the surface of the foam body 3 3 4 3 3 Evaluation of the surface appearance of the foam body 3 3 3 3 3 Evaluation of the damping properties of the foam body 5 5 5 5 5 [Table 5] Mass-produced parts Example 11 Example 12 Example 13 Example 14 Example 15 hydrogenated block copolymer composition (parts by mass) Hydrogenated block copolymer (I)-1 40 40 Hydrogenated block copolymer (I)-2 Hydrogenated block copolymer (I)-3 Hydrogenated block copolymer (I)-4 Hydrogenated block copolymer (I)-5 Hydrogenated block copolymer (I)-6 Hydrogenated block copolymer (I)-7 Hydrogenated block copolymer (I)-8 Hydrogenated block copolymer (I)-9 Hydrogenated block copolymer (I)-10 Hydrogenated block copolymer (I)-11 40 Hydrogenated block copolymer (I)-12 40 Hydrogenated block copolymer (I)-13 40 Hydrogenated block copolymer (I)-A Hydrogenated block copolymer (I)-B Hydrogenated block copolymer (I)-C Olefin-based resin (II)-1 18 18 18 12 Olefin-based resin (II)-2 18 Olefin-based resin (II)-3 Thermoplastic resin (III)-1 14 14 14 14 16 Thermoplastic resin (III)-2 Plasticizers (IV) 28 28 28 28 32 Physical properties of the hydrogenated block copolymer composition MFR (230°C, 2.16kg) 130 95 80 65 190 Hardness (JIS-A,15s) 59 69 68 68 56 Foaming agent (V) Polythrene EE25-C (phr VS hydrogenated block copolymer composition) 6 6 6 6 6 Physical properties of foam bodies, properties Foaming ratio 1,75 1,75 1,75 1,75 1,75 Total thickness of the foam body (µm) 4000 4000 4000 4000 4000 Thickness of the non-foam skin layer (µm) 300 300 300 300 300 Thickness of the foam core layer (µm) 3400 3400 3400 3400 3400 Evaluation of the wear resistance of the surface of the foam body 2 4 4 4 4 Evaluation of the surface appearance of the foam body 3 2 2 2 3 Evaluation of the damping properties of the foam body 5 5 5 5 5 [Table 6] Mass-produced parts Example 16 Example 17 Example 18 Example 19 hydrogenated block copolymer composition (parts by mass) Hydrogenated block copolymer (I)-1 40 40 40 40 Hydrogenated block copolymer (I)-2 Hydrogenated block copolymer (I)-3 Hydrogenated block copolymer (I)-4 Hydrogenated block copolymer (I)-5 Hydrogenated block copolymer (I)-6 Hydrogenated block copolymer (I)-7 Hydrogenated block copolymer (I)-8 Hydrogenated block copolymer (I)-9 Hydrogenated block copolymer (I)-10 Hydrogenated block copolymer (I)-11 Hydrogenated block copolymer (I)-12 Hydrogenated block copolymer (I)-13 Hydrogenated block copolymer (I)-A Hydrogenated block copolymer (I)-B Hydrogenated block copolymer (I)-C Olefin-based resin (II)-1 15 21 24 26 Olefin-based resin (II)-2 Olefin-based resin (II)-3 Thermoplastic resin (III)-1 15 13 12 11 Thermoplastic resin (III)-2 Plasticizers (IV) 30 26 24 23 Physical properties of the hydrogenated block copolymer composition MFR (230°C, 2.16kg) 180 140 120 110 Hardness (JIS-A,15s) 61 74 79 84 Foaming agent (V) Polythrene EE25-C (phr VS hydrogenated block copolymer composition) 6 6 6 6 Physical properties of foam bodies, properties Foaming ratio 1,75 1,75 1,75 1,75 Total thickness of the foam body (µm) 4000 4000 4000 4000 Thickness of the non-foam skin layer (µm) 300 300 300 300 Thickness of the foam core layer (µm) 3400 3400 3400 3400 Evaluation of the wear resistance of the surface of the foam body 4 4 4 4 Evaluation of the surface appearance of the foam body 3 3 3 3 Evaluation of the damping properties of the foam body 5 5 4 4 [Table 7] Mass-produced parts Example 20 Example 21 Example 22 Example 23 Example 24 hydrogenated block copolymer composition (parts by mass) Hydrogenated block copolymer (I)-1 50 30 20 10 40 Hydrogenated block copolymer (I)-2 Hydrogenated block copolymer (I)-3 Hydrogenated block copolymer (I)-4 Hydrogenated block copolymer (I)-5 Hydrogenated block copolymer (I)-6 Hydrogenated block copolymer (I)-7 Hydrogenated block copolymer (I)-8 Hydrogenated block copolymer (I)-9 Hydrogenated block copolymer (I)-10 Hydrogenated block copolymer (I)-11 Hydrogenated block copolymer (I)-12 Hydrogenated block copolymer (I)-13 Hydrogenated block copolymer (I)-A Hydrogenated block copolymer (I)-B Hydrogenated block copolymer (I)-C Olefin-based resin (II)-1 16 20 23 26 Olefin-based resin (II)-2 Olefin-based resin (II)-3 18 Thermoplastic resin (III)-1 14 17 19 22 21 Thermoplastic resin (III)-2 Plasticizers (IV) 28 33 38 42 21 Physical properties of the hydrogenated block copolymer composition MFR (230°C, 2.16kg) 150 140 130 120 120 Hardness (JIS-A,15s) 68 69 72 74 74 Foaming agent (V) Polythrene EE25-C (phr VS hydrogenated block copolymer composition) 6 6 6 6 6 Physical properties of foam bodies, properties Foaming ratio 1,75 1,75 1,75 1,75 1,75 Total thickness of the foam body (µm) 4000 4000 4000 4000 4000 Thickness of the non-foam skin layer (µm) 300 300 300 300 300 Thickness of the foam core layer (µm) 3400 3400 3400 3400 3400 Evaluation of the wear resistance of the surface of the foam body 4 4 4 4 4 Evaluation of the surface appearance of the foam body 3 3 3 3 3 Evaluation of the damping properties of the foam body 5 5 5 5 5 [Table 8] Mass-produced parts Example 25 Example 26 Example 27 Example 28 Example 29 hydrogenated block copolymer composition (parts by mass) Hydrogenated block copolymer (I)-1 40 40 40 40 40 Hydrogenated block copolymer (I)-2 Hydrogenated block copolymer (I)-3 Hydrogenated block copolymer (I)-4 Hydrogenated block copolymer (I)-5 Hydrogenated block copolymer (I)-6 Hydrogenated block copolymer (I)-7 Hydrogenated block copolymer (I)-8 Hydrogenated block copolymer (I)-9 Hydrogenated block copolymer (I)-10 Hydrogenated block copolymer (I)-11 Hydrogenated block copolymer (I)-12 Hydrogenated block copolymer (I)-13 Hydrogenated block copolymer (I)-A Hydrogenated block copolymer (I)-B Hydrogenated block copolymer (I)-C Olefin-based resin (II)-1 18 18 18 18 18 Olefin-based resin (II)-2 Olefin-based resin (II)-3 Thermoplastic resin (III)-1 11 14 14 14 14 Thermoplastic resin (III)-2 Plasticizers (IV) 31 28 28 28 28 Physical properties of the hydrogenated block copolymer composition MFR (230°C, 2.16kg) 200 150 150 150 150 Hardness (JIS-A,15s) 67 68 68 68 68 Foaming agent (V) Polythrene EE25-C (phr VS hydrogenated block copolymer composition) 6 6 6 6 4 Physical properties of foam bodies, properties Foaming ratio 1,75 1.3 1,5 2 1,75 Total thickness of the foam body (µm) 4000 4000 4000 4000 4000 Thickness of the non-foam skin layer (µm) 300 300 300 300 300 Thickness of the foam core layer (µm) 3400 3400 3400 3400 3400 Evaluation of the wear resistance of the surface of the foam body 4 4 4 4 4 Evaluation of the surface appearance of the foam body 3 3 3 3 3 Evaluation of the damping properties of the foam body 5 4 5 5 5 [Table 9] Mass-produced parts Example 30 Example 31 Example 32 Example 33 hydrogenated block copolymer composition (parts by mass) Hydrogenated block copolymer (I)-1 40 40 40 40 Hydrogenated block copolymer (I)-2 Hydrogenated block copolymer (I)-3 Hydrogenated block copolymer (I)-4 Hydrogenated block copolymer (I)-5 Hydrogenated block copolymer (I)-6 Hydrogenated block copolymer (I)-7 Hydrogenated block copolymer (I)-8 Hydrogenated block copolymer (I)-9 Hydrogenated block copolymer (I)-10 Hydrogenated block copolymer (I)-11 Hydrogenated block copolymer (I)-12 Hydrogenated block copolymer (I)-13 Hydrogenated block copolymer (I)-A Hydrogenated block copolymer (I)-B Hydrogenated block copolymer (I)-C Olefin-based resin (II)-1 12 18 18 18 Olefin-based resin (II)-2 Olefin-based resin (II)-3 Thermoplastic resin (III)-1 16 14 14 14 Thermoplastic resin (III)-2 Plasticizers (IV) 32 28 28 28 Physical properties of the hydrogenated block copolymer composition MFR (230°C, 2.16kg) 190 150 150 150 Hardness (JIS-A,15s) 55 68 68 68 Foaming agent (V) Polythrene EE25-C (phr VS hydrogenated block copolymer composition) 6 6 6 6 Physical properties of foam bodies, properties Foaming ratio 1,3 1,75 1,75 1,75 Total thickness of the foam body (µm) 4000 4000 4000 1700 Thickness of the non-foam skin layer (µm) 300 400 600 300 Thickness of the foam core layer (µm) 3400 3200 2800 1100 Evaluation of the wear resistance of the surface of the foam body 4 4 4 4 Evaluation of the surface appearance of the foam body 3 3 3 3 Evaluation of the damping properties of the foam body 4 5 4 5 [Table 10] Mass-produced parts Example 34 Example 35 Example 36 hydrogenated block copolymer composition (parts by mass) Hydrogenated block copolymer (I)-1 40 40 40 Hydrogenated block copolymer (I)-2 Hydrogenated block copolymer (I)-3 Hydrogenated block copolymer (I)-4 Hydrogenated block copolymer (I)-5 Hydrogenated block copolymer (I)-6 Hydrogenated block copolymer (I)-7 Hydrogenated block copolymer (I)-8 Hydrogenated block copolymer (I)-9 Hydrogenated block copolymer (I)-10 Hydrogenated block copolymer (I)-11 Hydrogenated block copolymer (I)-12 Hydrogenated block copolymer (I)-13 Hydrogenated block copolymer (I)-A Hydrogenated block copolymer (I)-B Hydrogenated block copolymer (I)-C Olefin-based resin (II)-1 18 18 24 Olefin-based resin (II)-2 Olefin-based resin (II)-3 Thermoplastic resin (III)-1 14 14 12 Thermoplastic resin (III)-2 Plasticizers (IV) 28 28 24 Physical properties of the hydrogenated block copolymer composition MFR (230°C, 2.16kg) 150 150 120 Hardness (JIS-A,15s) 68 68 79 Foaming agent (V) Polythrene EE25-C (phr VS hydrogenated block copolymer composition) 6 6 6 Physical properties of foam bodies, properties Foaming ratio 1,75 1,75 1,3 Total thickness of the foam body (µm) 1500 1000 2100 Thickness of the non-foam skin layer (µm) 300 300 600 Thickness of the foam core layer (µm) 900 400 900 Evaluation of the wear resistance of the surface of the foam body 4 4 4 Evaluation of the surface appearance of the foam body 3 3 3 Evaluation of the damping properties of the foam body 4 4 2 [Table 11] Mass-produced parts Comparison Example 1 Comparison Example 2 Compare Example 3 hydrogenated block copolymer composition (parts by mass) Hydrogenated block copolymer (I)-1 40 Hydrogenated block copolymer (I)-2 Hydrogenated block copolymer (I)-3 Hydrogenated block copolymer (I)-4 Hydrogenated block copolymer (I)-5 Hydrogenated block copolymer (I)-6 Hydrogenated block copolymer (I)-7 Hydrogenated block copolymer (I)-8 Hydrogenated block copolymer (I)-9 Hydrogenated block copolymer (I)-10 Hydrogenated block copolymer (I)-11 Hydrogenated block copolymer (I)-12 Hydrogenated block copolymer (I)-13 Hydrogenated block copolymer (I)-A 40 Hydrogenated block copolymer (I)-B 40 Hydrogenated block copolymer (I)-C Olefin-based resin (II)-1 18 18 28 Olefin-based resin (II)-2 Olefin-based resin (II)-3 Thermoplastic resin (III)-1 14 14 11 Thermoplastic resin (III)-2 Plasticizers (IV) 28 28 21 Physical properties of the hydrogenated block copolymer composition MFR (230°C, 2.16kg) 150 130 110 Hardness (JIS-A,15s) 65 61 87 Foaming agent (V) Polythrene EE25-C (phr VS hydrogenated block copolymer composition) 6 6 6 Physical properties of foam bodies, properties Foaming ratio 1,75 1,75 1,75 Total thickness of the foam body (µm) 4000 4000 4000 Thickness of the non-foam skin layer (µm) 300 300 300 Thickness of the foam core layer (µm) 3400 3400 3400 Evaluation of the wear resistance of the surface of the foam body 1 1 4 Evaluation of the surface appearance of the foam body 3 3 3 Evaluation of the damping properties of the foam body 5 5 1 [Table 12] Mass-produced parts Compare Example 4 Compare Example 5 Compare Example 6 Compare Example 7 hydrogenated block copolymer composition (parts by mass) Hydrogenated block copolymer (I)-1 0 40 40 Hydrogenated block copolymer (I)-2 Hydrogenated block copolymer (I)-3 Hydrogenated block copolymer (I)-4 Hydrogenated block copolymer (I)-5 Hydrogenated block copolymer (I)-6 Hydrogenated block copolymer (I)-7 Hydrogenated block copolymer (I)-8 Hydrogenated block copolymer (I)-9 Hydrogenated block copolymer (I)-10 Hydrogenated block copolymer (I)-11 Hydrogenated block copolymer (I)-12 Hydrogenated block copolymer (I)-13 Hydrogenated block copolymer (I)-A Hydrogenated block copolymer (I)-B Hydrogenated block copolymer (I)-C 39 Olefin-based resin (II)-1 27 12 18 Olefin-based resin (II)-2 22 Olefin-based resin (II)-3 Thermoplastic resin (III)-1 24 16 14 Thermoplastic resin (III)-2 26 Plasticizers (IV) 49 32 13 28 Physical properties of the hydrogenated block copolymer composition MFR (230°C, 2.16kg) 110 190 20 150 Hardness (JIS-A,15s) 75 56 74 68 Foaming agent (V) Polythrene EE25-C (phr VS hydrogenated block copolymer composition) 6 6 6 6 Physical properties of foam bodies, properties Foaming ratio 1,75 1,15 1,75 1,75 Total thickness of the foam body (µm) 4000 4000 4000 850 Thickness of the non-foam skin layer (µm) 300 300 300 300 Thickness of the foam core layer (µm) 3400 3400 3400 250 Evaluation of the wear resistance of the surface of the foam body 1 4 4 4 Evaluation of the surface appearance of the foam body 3 3 1 3 Evaluation of the damping properties of the foam body 5 1 5 1

[0291] It was thus found that the foam body of the present invention has a good molded appearance, a good cushioning property and a good wear resistance, and is further excellent in the balance of these properties. [Manufacture of laminate](Example 37)

[0292] A 1.8 mm thick PP (polypropylene) substrate was injection-molded at a die temperature of 220°C and a mold temperature of 40°C. Then, in the same manner as described above, the hydrogenated block copolymer composition (I)-1 was laminated thereon by core-back molding according to the two-stage method, thereby obtaining a laminate in which a foam body of the hydrogenated block copolymer composition was laminated to the PP substrate.

[0293] Fig. 1 is a cross-sectional view of the laminate.

[0294] The layer of the foam body containing the hydrogenated block copolymer composition had a thickness of 2 mm before foaming and a thickness of 3.9 mm after foaming, the non-foam skin layer not in contact with the PP substrate had a thickness of 300 µm, the non-foam skin layer in contact with the PP substrate had a thickness of 150 µm, and the foam core layer had a thickness of 3450 µm.

[0295] It was found that the laminate thus obtained had good appearance, good wear resistance and good damping properties as well as good stiffness. Industrial applicability

[0296] A foam body according to the present invention is industrially applicable in the fields of vehicle components (vehicle interior materials and vehicle exterior materials), materials for medical devices / instruments, various containers including food packaging containers, household appliances, industrial components, toys, and the like. QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] JP 2015-98542

[0005] JP 2018

[0005] JP 24822

[0005] WO 2016 / 039310

[0005] US 5,708,092

[0062] GB 2,241,239

[0062] US 5,527,753

[0062] JP 62-79211

[0099] JP 8-109219

[0104] PL 500A

[0276] Cited non-patent literature

[0000] Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY, 54, 685 (1981); hereinafter referred to as "NMR method"

[0033] Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY, 54, 685 (1981); hereinafter referred to as the "NMR method"

[0227] < / bewertungskriterien> < / bewertungskriterien> < / additive>

Claims

[1] Foam body of a hydrogenated block copolymer composition comprising: a hydrogenated block copolymer (I); an olefin-based resin (II); a thermoplastic resin (III); and a plasticizer (IV), wherein the foam body comprises a foam core layer and a non-foam skin layer adjacent to each other, the foam core layer has a thickness of 300 µm or more, the foam body has a foaming ratio of 1.2 times or more and the foam body meets the following conditions (1) to (5): <Bedingung (1)> the hydrogenated block copolymer (I) is a hydrogenated product of a block copolymer containing a vinyl aromatic monomer unit and a conjugated monomer unit; <Bedingung (2)> the hydrogenated block copolymer (I) contains at least one polymer block (a) mainly containing a vinyl aromatic monomer unit, and the content of the polymer block (a) mainly containing a vinyl aromatic monomer unit in the hydrogenated block copolymer (I) is 10 mass% or more and 40 mass% or less; <Bedingung (3)> the hydrogenated block copolymer (I) contains at least one hydrogenated copolymer block (b) containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, and the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 5 mass% or more and 79 mass% or less; <Bedingung (4)> the hydrogenated block copolymer composition has a 15-second hardness value, measured with a Type A durometer according to JIS K6253, of 85 or less; and <Bedingung (5)> the hydrogenated block copolymer composition has an MFR value, measured under conditions of a temperature of 230°C and a load of 2.16 kg according to JIS K7210, of 40 or more. [2] The foam body according to claim 1, wherein the content of the vinyl aromatic monomer unit in the hydrogenated copolymer block (b) is 15 mass% or more and 79 mass% or less. [3] Foam body according to claim 1, wherein the hydrogenated block copolymer (I) contains at least one polymer block (a) which mainly contains a vinyl aromatic monomer unit, and the content of the polymer block (a) mainly containing a vinyl aromatic monomer unit in the hydrogenated block copolymer (I) is 15 mass% or more and 35 mass% or less. [4] The foam body according to claim 1, wherein the hydrogenated block copolymer composition has a 15-second hardness value measured with a Type A durometer according to JIS K6253 of 30 or more and 75 or less. [5] The foam body according to claim 1, wherein the hydrogenated block copolymer composition has an MFR value, measured under conditions of a temperature of 230°C and a load of 2.16 kg according to JIS K7210, of 100 or more and 1000 or less. [6] The foam body according to claim 1, wherein the non-foam skin layer has a thickness of 10 µm to 500 µm. [7] Foam body according to claim 1, wherein the foam core layer has a thickness of 1000 µm to 20000 µm. [8] The foam body according to claim 1, wherein the olefin-based resin (II) comprises at least one polypropylene-based resin. [9] The foam body according to claim 1, wherein the foaming ratio is 1.5 times or more. [10] The foam body according to claim 1, wherein the foam body is adapted for use in a vehicle component selected from the group consisting of a side panel, a grommet, a shift knob, a weather strip, a window frame and a sealing material therefor, an instrument panel, a grab handle, a steering wheel, a shift lever, a console, an armrest, a headrest, and a door panel. [11] A process for producing the foam body according to any one of claims 1 to 10, comprising the steps of: a step of adding a foaming agent to the hydrogenated block copolymer composition and injecting the resulting product to fill a cavity formed in a mold of an injection molding machine and having a volume adjustable by a movable core; and a step of increasing the volume of the cavity with the movable core to perform foam molding. [12] Laminate, with: a layer containing the foam body according to any one of claims 1 to 10; and a layer containing a base resin. [13] The laminate according to claim 12, wherein the base resin-containing layer and the foam body-containing layer are in direct contact with each other without an adhesive layer therebetween.

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