JP2016150980A - Thermoplastic elastomer resin composition - Google Patents

Abstract

[PROBLEMS] To provide high gas barrier properties, compression deformation resistance, flexibility, and mechanical strength required for medical syringe gasket materials and stopper materials for medical solution storage bottles and food storage bottles. And providing a thermoplastic elastomer resin composition having good molding processability and capable of improving productivity. SOLUTION: (a) 20-80% by mass of a crosslinked elastic body having a structural unit derived from isobutylene; (b) a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound (b1); And one or more selected from the group consisting of a block copolymer (b2) of an aromatic vinyl compound and isobutylene (80 to 20% by mass), wherein the component (a) and the component (b) A thermoplastic elastomer resin composition comprising: 100 parts by mass of a resin composition that is 100% by mass; and (c) 5 to 50 parts by mass of a polyolefin-based resin. [Selection] Figure 1

Description

The present invention relates to a thermoplastic elastomer resin composition. More specifically, it has excellent gas barrier properties, flexibility, mechanical strength, and resistance to compression deformation under high-temperature environments, has good moldability, and can be suitably used as a material for medical and food equipment. The present invention relates to a thermoplastic elastomer resin composition.

Conventionally, as materials for medical and food equipment, in particular, medical syringe gasket materials and chemical solution storage bottles and food storage bottle stoppers, gas barrier properties, compression deformation resistance, heat resistance, etc. Since properties are important, natural rubber, butyl rubber, isoprene rubber, and crosslinked rubber such as styrene-butadiene rubber have been used frequently. However, the crosslinked rubber has a problem that a large-scale crosslinking process / equipment is required and a problem that the crosslinking agent is eluted. In addition, in order to apply steam sterilization, there is also a problem that the compression deformation resistance in a high temperature environment is insufficient.

For this reason, thermoplastic elastomer resins and resin compositions thereof have attracted attention as materials for medical and food equipment. As the thermoplastic elastomer resin, various thermoplastic elastomer resins such as polyolefin resin, polyurethane resin, polyester resin, polyamide resin, polystyrene resin, and polyvinyl chloride resin have been proposed. Among these, in the field of medical and food equipment, polyolefin-based thermoplastic elastomer resins are particularly attracting attention from the viewpoints of compression deformation resistance, heat resistance, and cost in a high temperature environment. However, the polyolefin-based thermoplastic elastomer resin has a problem that a plasticizer such as a rubber softener that is blended for imparting flexibility tends to bleed out.

Patent Document 1 states that “a thermoplastic elastomer (SIBS: A component in which a polymer component (S) mainly composed of styrene and a polymer component (IB) mainly composed of isobutylene are bonded in the form of S-IB-S). ), Polybutene (component B), and ultra-high molecular weight polyethylene powder (component C), and at least a thermoplastic elastomer (component A) is dynamically cross-linked, Has been proposed. However, this technique has a problem in that the appearance of the resulting product, particularly the surface smoothness, is insufficient, and liquid leakage tends to occur when applied to bottle stoppers containing syringe gaskets or chemicals as contents. Moreover, the compression deformation resistance and heat resistance in a high temperature environment are also insufficient.

Patent Document 2 proposes “a thermoplastic pharmaceutical / medical seal article formed of a rubber material made of a block copolymer of an aromatic vinyl compound and isobutylene”. This technique is excellent in that injection molding is easy and a desired molded product can be obtained, and that elution resistance is good as compared with a crosslinked rubber. However, the compression deformation resistance under high temperature environment and the compression deformation resistance at room temperature are insufficient. In addition, depending on the type of the chemical solution that is the content, there is a problem of causing a chemical reaction with the article.

In Patent Document 3, “(A) 100 parts by weight of an isobutylene polymer having an alkenyl group at the terminal is melt-kneaded with (C) a hydrosilyl group-containing compound in the presence of 10 to 100 parts by weight of a polyolefin. And a composition for cap liner comprising (D) 0.1 to 20 parts by weight of a lubricant ”. However, as a result of testing by the inventor, it has been found that this technology does not have sufficient characteristics in a high temperature environment such as compression strain resistance in a high temperature environment and sealability in a high temperature environment.

In Patent Document 4, “(a) 100 parts by mass of an isobutylene polymer having an alkenyl group at the terminal is added in the presence of (b) 5 to 100 parts by mass of polyolefin and (c) 5 to 100 parts by mass of polybutene. d) A pharmaceutical / medical rubber compound comprising a composition (component A) crosslinked by melt-kneading with a hydrosilyl group-containing compound and an ultrahigh molecular weight polyethylene powder (component B). Has been proposed. However, as a result of testing by the inventor, it has been found that this technology does not have sufficient characteristics in a high temperature environment such as compression strain resistance in a high temperature environment and sealability in a high temperature environment.

JP 2008-228915 A JP-A-5-212104 International Publication No. 2006/098142 International Publication No. 2009/013945

An object of the present invention is to provide high gas barrier properties required for medical and food equipment, particularly medical syringe gasket materials, and chemical storage bottles and stoppers for food storage bottles, and resistance to compression deformation in high temperature environments. An object of the present invention is to provide a thermoplastic elastomer resin composition that has good properties, flexibility, and mechanical strength, has good moldability, and can improve productivity.

As a result of intensive studies, the present inventor has found that the above-mentioned problems can be achieved by a specific thermoplastic elastomer resin composition.

That is, the present invention includes (a) 20-80% by mass of a crosslinked elastic body having a structural unit derived from isobutylene,
(B) Hydrogenated product of block copolymer of aromatic vinyl compound and conjugated diene compound (b1), and block copolymer of aromatic vinyl compound and isobutylene (b2)
1 to 80% by mass selected from the group consisting of:
Here, the sum total of the said component (a) and the said component (b) is 100 mass%, 100 mass parts of resin compositions; and (c) 5-50 mass parts of polyolefin resin;
Is a thermoplastic elastomer resin composition.

The second invention is the thermoplastic elastomer resin composition according to the first invention, wherein the component (a) is a crosslinked elastic body obtained by crosslinking using a hydrosilyl group-containing compound.

In the third invention, the component (b) is a styrene-ethylene-butene block copolymer (SEB), a styrene-ethylene-propylene block copolymer (SEP), or a styrene-ethylene-butene-styrene block copolymer. (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-isobutylene-styrene block copolymer (SIBS), and The thermoplastic elastomer resin composition according to the first or second invention, which is at least one selected from the group consisting of styrene-vinyl (ethylene-propylene) -styrene copolymer (V-SEPS). .

The fourth invention is the thermoplastic elastomer resin according to any one of the first to third inventions, wherein the component (c) is at least one selected from the group consisting of a polypropylene resin and a polyethylene resin. It is a composition.

5th invention contains 5-100 mass parts further with respect to 100 mass parts of said resin compositions which (d) rubber softeners further consist of said component (a) and said component (b). It is a thermoplastic elastomer resin composition given in any 1 of inventions of -4.

A sixth invention is a medical device including the thermoplastic elastomer resin composition according to any one of the first to fifth inventions.

7th invention is the apparatus for foodstuffs containing the thermoplastic elastomer resin composition of any one of 1st-5th invention.

The thermoplastic elastomer resin composition of the present invention is excellent in gas barrier properties, compression deformation resistance in a high temperature environment, flexibility, mechanical strength, and good moldability. Therefore, using the thermoplastic elastomer resin composition of the present invention as a material, medical and food equipment, in particular, medical syringe gaskets, medical solution storage bottles and food storage bottle stoppers can be obtained with high productivity.

(A) Cross-linked elastic body having a structural unit derived from isobutylene:
The component (a) comprises isobutylene (CH ₂ ═C (CH ₃ ) ₂ ), a small amount of isoprene (CH ₂ ═C (CH ₃ ) —CH═CH ₂ ), and any monomer capable of cationic polymerization with these. It is a rubber (elastic body) obtained by crosslinking a copolymer obtained by cationic polymerization at a low temperature.

The content of the structural unit derived from isobutylene as the component (a) is usually 70 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, from the viewpoints of gas barrier properties and heat resistance. On the other hand, from the viewpoint of crosslinkability, it is usually 99.5 mol% or less, preferably 99 mol% or less.

The content of the structural unit derived from isoprene as the component (a) is usually 5 mol% or less, preferably 2.5 mol% or less, from the viewpoint of heat resistance. On the other hand, from the viewpoint of crosslinkability, it is usually at least 0.5 mol%, preferably at least 1 mol%.

The arbitrary monomer that can be contained in the component (a) is not particularly limited as long as it is a monomer that can be cationically polymerized with isobutylene or isoprene. Examples of the optional monomer include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyltoluene. And aromatic vinyl compounds such as p-tert-butylstyrene; and 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, chloroprene (2 -Conjugated dienes such as -chloro-1,3-butadiene); As said arbitrary monomer, 1 or more types of these can be used. Content of the structural unit derived from the arbitrary monomer of the said component (a) is 5 mol% or less normally, Preferably it is 2.5 mol% or less.

The structural unit derived from isoprene of the copolymer or the structural unit derived from an arbitrary monomer such as a conjugated diene has a carbon-carbon double bond. The method for obtaining the component (a) by causing the double bond in the copolymer to undergo a crosslinking reaction is not particularly limited and can be carried out by a known method using any catalyst. As said catalyst, a phenol resin, a zinc oxide, a hydrosilyl group containing compound etc. can be mention | raise | lifted, for example. Among these, a hydrosilyl group-containing compound is preferable from the viewpoint of suppressing coloring and odor.

The hydrosilyl group-containing compound is not particularly limited except that it has a hydrosilyl group, and a compound having any hydrosilyl group can be used. The hydrosilyl group-containing compound is preferably a hydrosilyl group-containing polysiloxane from the viewpoint of crosslinkability. The number of hydrosilyl groups in the hydrosilyl group-containing polysiloxane is preferably 3 or more, more preferably 5 or more, from the viewpoint of crosslinkability. The number of structural units derived from siloxane is preferably 500 or less, more preferably 100 or less, from the viewpoint of miscibility with the component (a) and the like. On the other hand, from the viewpoint of crosslinkability, the number is preferably 10 or more, more preferably 20 or more.

When the copolymer is crosslinked using the hydrosilyl group-containing compound, a hydrosilylation catalyst may be used for the purpose of accelerating the reaction. Examples of the hydrosilylation catalyst include radical generators such as organic peroxides and azo compounds; and transition metal catalysts. One or more of these can be used as the hydrosilylation catalyst.

(B1) Hydrogenated block copolymer of aromatic vinyl compound and conjugated diene compound:
As the component (b), a hydrogenated product of a block copolymer of (b1) an aromatic vinyl compound and a conjugated diene compound can be used. When the component (b1) is used, particularly compression set resistance and flexibility are improved.

The aromatic vinyl compound is a polymerizable monomer having a polymerizable carbon-carbon double bond and an aromatic ring. Examples of the aromatic vinyl compound include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyltoluene. And p-tert-butylstyrene. Of these, styrene is preferred. One or more of these can be used as the aromatic vinyl compound.

The conjugated diene is a polymerizable monomer having a structure in which two carbon-carbon double bonds are connected by one carbon-carbon single bond. Examples of the conjugated diene include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and chloroprene (2-chloro-1,3-butadiene). ) Etc. Of these, 1,3-butadiene and isoprene are preferred. One or more of these can be used as the conjugated diene.

The component (b1) includes at least one polymer block A mainly composed of an aromatic vinyl compound, preferably 2 or more from the viewpoint of mechanical strength and moldability, and a heavy component mainly composed of a conjugated diene compound. It is a block copolymer composed of one or more combined blocks B. For example, a block copolymer having a structure such as A-B, A-B-A, B-A-B-A, or A-B-A-B-A can be given.

The content of the structural unit derived from the aromatic vinyl compound of the component (b1) is preferably 5 to 60% by mass, more preferably 20 to 50% by mass, from the viewpoint of heat resistance.

The polymer block A is a polymer block composed only of an aromatic vinyl compound or a copolymer block of an aromatic vinyl compound and a conjugated diene compound. When the polymer block A is a copolymer block, the content of the structural unit derived from the aromatic vinyl compound in the polymer block A is usually 50% by mass or more, preferably 70% from the viewpoint of heat resistance. % Or more, more preferably 90% by mass or more. The distribution of the structural unit derived from the conjugated diene compound in the polymer block A is not particularly limited and is arbitrary. When there are two or more polymer blocks A, these may have the same structure or different structures.

The polymer block B is a polymer block composed only of a conjugated diene compound or a copolymer block of an aromatic vinyl compound and a conjugated diene compound. When the polymer block B is a copolymer block, the content of the structural unit derived from the conjugated diene compound in the polymer block B is usually 50% by mass or more, preferably 70% by mass from the viewpoint of flexibility. As mentioned above, More preferably, it is 90 mass% or more. The distribution of the structural unit derived from the aromatic vinyl compound in the polymer block is not particularly limited and is arbitrary. The bonding mode between the conjugated diene compound and the conjugated diene compound (hereinafter sometimes abbreviated as microstructure) is not particularly limited and is arbitrary. When there are two or more polymer blocks B, these may have the same structure or different structures.

Hydrogenation rate of the component (b1) (carbon to carbon single bond by hydrogenation relative to the number of carbon to carbon double bonds in the block copolymer of the aromatic vinyl compound and conjugated diene compound before hydrogenation) The ratio of the number of bonds obtained is not particularly limited, but may be usually 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more from the viewpoint of heat resistance.

When the conjugated diene polymer block of the component (b) is a butadiene polymer block, the microstructure is preferably 20-50 mol%, more preferably 1,2-bonds from the viewpoint of flexibility. It may be 25 to 45 mol%. From the viewpoint of heat resistance, the 1,2-bond may be selectively hydrogenated.

When the conjugated diene polymer block of the component (b1) is a copolymer block of isoprene and butadiene, the microstructure is such that the 1,2-bond is preferably less than 50 mol% from the viewpoint of heat resistance, More preferably, it may be less than 25 mol%, and more preferably less than 15 mol%.

When the conjugated diene polymer block of the component (b1) is an isoprene polymer block, from the viewpoint of flexibility, the microstructure may be 1,4-bond, preferably 70 to 100 mol%. The hydrogenation rate is preferably 90 mol% or more from the viewpoint of heat resistance.

When the conjugated diene polymer block of the component (b1) is an isoprene polymer block, from the viewpoint of gas barrier properties, the microstructure is such that the sum of 1,2-bonds and 3,4-bonds is 80 mol%. Above, preferably 90 mol% or more, more preferably 95 mol% or more. The hydrogenation rate is preferably 90 mol% or more from the viewpoint of heat resistance. Such copolymers are often referred to as styrene-vinyl (ethylene-propylene) -styrene copolymers (V-SEPS). The glass transition temperature of the styrene-vinyl (ethylene-propylene) -styrene copolymer (V-SEPS) is preferably -40 to 20 ° C.

In this specification, according to JIS K7121-1987, the glass transition temperature is maintained at 150 ° C. for 5 minutes using a Diamond DSC differential scanning calorimeter manufactured by PerkinElmer Japan Co., Ltd., up to −100 ° C. at 10 ° C./min. It is the midpoint glass transition temperature calculated from the curve of the last temperature rising process measured by the program which cools, hold | maintains for 3 minutes at -50 degreeC, and heats up to 150 degreeC at 10 degreeC / min.

The number average molecular weight of the component (b1) is preferably 80,000 to 1,500,000, more preferably 100,000 to 550,000, more preferably from the viewpoint of molding processability and compression set resistance. Preferably it is 100,000-400,000. The molecular weight distribution (mass average molecular weight / number average molecular weight) is preferably 10 or less from the viewpoint of mechanical properties.

Examples of the component (b1) include styrene-ethylene-butene block copolymer (SEB), styrene-ethylene-propylene block copolymer (SEP), and styrene-ethylene-butene-styrene block copolymer (SEBS). , Styrene-ethylene-propylene-styrene copolymer block (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), and styrene-vinyl (ethylene-propylene) -styrene copolymer (V- SEPS). Among these, from the viewpoints of flexibility and compression strain resistance under a high temperature environment, styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), And styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS) is preferable.

(B2) Block copolymer of aromatic vinyl compound and isobutylene:
As the component (b), a block copolymer of (b2) an aromatic vinyl compound and isobutylene can be used. When the component (b2) is used, the gas barrier property is particularly good.

The component (b2) is one or more polymer blocks C mainly composed of an aromatic vinyl compound, preferably 2 or more from the viewpoint of mechanical strength, and one polymer block D mainly composed of isobutylene. A block copolymer comprising the above. For example, the block copolymer which has structures, such as CD, CDC, CDCC, and CDCC-C, can be mention | raise | lifted.

The polymer block C is a polymer block composed only of an aromatic vinyl compound or a copolymer block of an aromatic vinyl compound and another monomer. When the polymer block C is a copolymer block, the content of structural units derived from the aromatic vinyl compound in the polymer block C is usually 50% by mass or more, preferably 70% by mass from the viewpoint of heat resistance. % Or more, more preferably 90% by mass or more. The other optional monomer is any monomer copolymerizable with an aromatic vinyl compound. Examples of the other optional monomers include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and chloroprene (2-chloro-1,3). Conjugated dienes such as butadiene) and isobutylene. As said other arbitrary monomer, 1 or more types of these can be used. The distribution of the structural units derived from the other monomers in the polymer block C is not particularly limited and is arbitrary. When there are two or more polymer blocks C, these may have the same structure or different structures.

The polymer block D is a polymer block composed only of isobutylene or a copolymer block of isobutylene and other optional monomers. When the polymer block D is a copolymer block, the content of structural units derived from isobutylene in the polymer block D is preferably 50% by mass or more, preferably from the viewpoint of compression set resistance and gas barrier properties. Is 70% by mass or more, more preferably 90% by mass or more. The other optional monomers are optional monomers copolymerizable with isobutylene. Examples of the other optional monomers include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, and vinyl. Toluene and aromatic vinyl compounds such as p-tert-butylstyrene; and 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, chloroprene ( Conjugated dienes such as 2-chloro-1,3-butadiene) and the like. As said other arbitrary monomer, 1 or more types of these can be used. The distribution of structural units derived from the other monomers in the polymer block D is not particularly limited and is arbitrary. When there are two or more polymer blocks D, these may have the same structure or different structures.

As said component (b2), a styrene-isobutylene-styrene block copolymer (SIBS) can be mention | raise | lifted, for example.

As said component (b), these 1 type, or 2 or more types of mixtures can be used.

The compounding ratio of the component (a) and the component (b) is 20% by mass or more of the component (a) (80% by mass or less of the component (b) from the viewpoint of mechanical strength and compression set resistance. ), Preferably 25% by mass or more of the component (a) (75% by mass or less of the component (b)). On the other hand, from the viewpoint of flexibility, mechanical strength, and compression set resistance, the component (a) is 80% by mass or less (the component (b) is 20% by mass or more), preferably the component (a) is 70% by mass. It is below (the above component (b) 30% by mass or more). Here, the sum of the component (a) and the component (b) is 100% by mass.

(C) Polyolefin resin:
The component (c) is a polyolefin resin and functions to stabilize molding processability. Examples of polyolefin resins include polyethylene resins such as high density polyethylene, linear low density polyethylene, low density polyethylene, and ethylene / α-olefin copolymer (ethylene plastomer); propylene homopolymer, propylene Copolymers (block copolymers and random copolymers) with other small amounts of α-olefins (for example, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc.) And the like.) Polybutene-1; and poly-4-methylpentene-1 and the like. Among these, polypropylene resins are preferable from the viewpoints of heat resistance and moldability.

When the component (c) is a polypropylene resin, the melting enthalpy is preferably 60 J / g or less, more preferably 40 J / g or less, from the viewpoint of flexibility. From the viewpoint of mechanical strength, it is preferably 60 J / g or more, more preferably 80 J / g or more. From the viewpoint of heat resistance, it is preferably 100 J / g or more, more preferably 110 J / g or more. The melting point is preferably 130 ° C. or higher, more preferably 135 ° C. or higher, from the viewpoints of heat resistance and mechanical strength. Although there is no upper limit of the melting point, it is usually about 167 ° C. because it is a crystalline propylene polymer.

In this specification, the melting enthalpy of the polypropylene resin is a Diamond DSC type differential scanning calorimeter manufactured by PerkinElmer Japan Co., Ltd., held at 230 ° C. for 5 minutes, cooled to −10 ° C. at 10 ° C./minute, The temperature was calculated from a second melting curve (melting curve measured in the last heating process) measured by a program in which the temperature was maintained at −10 ° C. for 5 minutes and the temperature was raised to 230 ° C. at 10 ° C./min. The melting point was calculated from the peak top appearing on the highest temperature side in the second melting curve. A calculation example is shown in FIG.

The melt mass flow rate measured under the conditions of 230 ° C. and 21.18 N in accordance with JIS K 7210: 1999 of the above polypropylene resin is the thermoplastic elastomer of the present invention from the viewpoint of the balance between molding processability and mechanical strength. When applying a resin composition to injection molding, Preferably it is 0.1-100 g / 10min, More preferably, it is 0.3-30 g / 10min. When the thermoplastic elastomer resin composition of the present invention is applied to extrusion molding, it is preferably 0.1 to 7 g / 10 minutes, more preferably 0.3 to 5 g / 10 minutes.

From the viewpoint of improving gas barrier properties and mechanical strength, a polyethylene-based resin having a density of preferably 930 Kg / m ³ or more, more preferably 950 to 965 Kg / m ³ may be used as the component (c). In the present specification, the density of the polyethylene-based resin is a value measured by an underwater substitution method in accordance with JIS K 7112: 1999.

The melt mass flow rate measured under the conditions of 190 ° C. and 21.18 N in accordance with JIS K 7210: 1999 of the polyethylene resin is preferably 5 to 50 g / 10 min from the viewpoint of moldability, particularly injection moldability. More preferably, it is 10-40 g / 10min.

The blending amount of the component (c) is preferably 5 parts by mass or more, from the viewpoint of molding processability, heat resistance, and flexibility, with respect to 100 parts by mass in total of the component (a) and the component (b). Is 10 parts by mass or more. On the other hand, from the viewpoint of flexibility, it is 50 parts by mass or less, preferably 30 parts by mass or less.

(D) Rubber softener:
The above-mentioned component (d) can be used in the thermoplastic elastomer resin composition of the present invention as desired. Flexibility can be increased. Examples of the component (d) include non-aromatic rubber softeners, aromatic rubber softeners, and ester plasticizers. Among these, non-aromatic rubber softeners are preferable from the viewpoint of compatibility.

The non-aromatic rubber softener is a non-aromatic mineral oil (hydrocarbon compound derived from petroleum or the like) or a synthetic oil (synthetic hydrocarbon compound). Is. Here, the non-aromatic system means that the mineral oil is not classified into the aromatic system in the following classification (the aromatic carbon number is less than 30%). For synthetic oils, it means that no aromatic monomer is used.

Mineral oil used as a rubber softener is a mixture of any one or more of paraffin chains, naphthene rings, and aromatic rings, and those having a naphthenic ring carbon number of 30 to 45% are naphthenic, Those having an aromatic carbon number of 30% or more are referred to as aromatic, and those that do not belong to naphthenic or aromatic systems and whose paraffin chain carbon number occupies 50% or more of the total carbon number are paraffinic. It is called and distinguished.

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

The dynamic viscosity at 37.8 ° C. of the non-aromatic rubber softener is preferably 20 to 50,000 cSt, more preferably 20 to 1,000 cSt from the viewpoint of moldability. The dynamic viscosity at 100 ° C. is preferably 5 to 1,500 cSt, more preferably 5 to 100 cSt from the viewpoints of bleed-out resistance and heat resistance. The pour point is preferably −10 to −25 ° C. from the viewpoint of handleability during production of the composition. The flash point (COC) is preferably 170 to 350 ° C. from the viewpoint of safety. The mass average molecular weight is preferably 100 to 2,000 from the viewpoint of bleed-out resistance.

Commercial examples of the above non-aromatic rubber softener include isoparaffinic hydrocarbon oil “NA Solvent (trade name)” from Nippon Oil & Fats Co., Ltd., n-paraffinic process oil “Diana Process Oil PW” from Idemitsu Kosan Co., Ltd. -90 (trade name) ”and“ Diana Process Oil PW-380 (trade name) ”, synthetic isoparaffinic hydrocarbon“ IP-solvent 2835 (trade name) ”from Idemitsu Petrochemical Co., Ltd., and Sanko Chemical Co., Ltd. n -Paraffinic process oil "Neothiozole (trade name)" can be listed. Among these, paraffinic mineral oil is preferable from the viewpoint of compatibility, and paraffinic mineral oil having a small number of aromatic carbon atoms is more preferable. One or more of these can be used as the component (d).

The blending amount of the component (d) is preferably 100 parts by mass or less, more preferably 60 parts by mass, from the viewpoint of bleed resistance with respect to a total of 100 parts by mass of the component (a) and the component (b). It is as follows. On the other hand, the lower limit of the amount of component (d) is not particularly limited because it is an optional component, but it is preferably 5 parts by mass or more, more preferably 20 parts by mass or more, from the viewpoint of obtaining a flexibility improving effect. .

The thermoplastic aelastomer resin composition of the present invention can further contain an inorganic filler as long as it does not contradict the purpose of the present invention. It has an effect of improving tensile strength and an economic advantage by increasing the amount. Examples of the inorganic filler include calcium carbonate, talc, magnesium hydroxide, mica, clay, barium sulfate, natural silicic acid, synthetic silicic acid (white carbon), titanium oxide, and carbon black. One or more of these can be used as the inorganic filler. The compounding quantity of an inorganic filler is 50 mass parts or less normally by making the total amount of the said component (a)-(d) into 100 mass parts.

The thermoplastic elastomer resin composition of the present invention includes phenol-based, phosphorus-based, and sulfur-based antioxidants; anti-aging agents, light stabilizers, ultraviolet absorbers, etc., as long as the object of the present invention is not adversely affected. Weathering agents for acids; Lubricants such as acid amides, fatty acids, fatty acid metal salts, waxes, silicone oils and modified silicone oils; Nucleating agents such as aromatic phosphate metal salts and gelols; Charges such as glycerin fatty acid esters Various additives such as an inhibitor; various organic and inorganic flame retardants; and a copper damage inhibitor can be further included. These additives are compatible with the above components (a) to (c), which are essential components of the thermoplastic elastomer composition of the present invention, in order to prevent troubles such as bleeding out on the surface of the molded product. Higher ones are preferred.

The thermoplastic elastomer resin composition of the present invention can be obtained by melt-kneading the above-mentioned components (a) to (c) and optional components used as required using an optional melt-kneader. Any manufacturing method may be employed as long as each component of the composition is substantially uniformly dispersed, and is not limited. For example, each component of the composition is dry blended or hot blended using a Henschel mixer, ribbon blender, tumbler mixer, etc., and then a batch kneader such as a pressure kneader and a mixer; It can be obtained by using an extruder, an extrusion kneader such as a different-direction rotating twin-screw extruder; a calender roll kneader; and a kneader in which these are arbitrarily combined.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Measuring method (1) Injection moldability:
Using an injection molding machine with a clamping force of 120 tons, resin temperature 230 ° C., mold temperature 40 ° C., injection speed 55 mm / second, injection pressure 600 Kg / cm ² , holding pressure 400 Kg / cm ² , injection time 6 seconds, A sheet having a length of 13.5 cm, a width of 13.5 cm, and a thickness of 2 mm was molded under the condition of a cooling time of 15 seconds. Appearances such as delamination, surface layer peeling, sink marks, deformation, and the presence or absence of flow marks were visually observed and evaluated according to the following criteria.
A: There is no defect at all.
○: Only a few flow marks are recognized, and there are no other problems.
Δ: Flow marks and sink marks are observed.
X: Appearance is poor.

(2) Hardness:
Using the injection sheet obtained above, a 6 mm thick press sheet was prepared by hot pressing under conditions of preheating at 220 ° C. for 3 minutes, pressure at 220 ° C. for 3 minutes. Using the obtained press sheet as a sample, a durometer hardness (type A) of 15 seconds was measured according to JIS K 6253-2012.

(3) Compression set 1 (compression resistance 1 under high temperature environment):
In accordance with JIS K 6262-2003, a 6 mm thick press sheet obtained in the same manner as in the above test (2) was used as a test piece, and the measurement was performed under conditions of 25% compression deformation, temperature of 70 ° C., and 22 hours.

(4) Compression set 2 (Compression deformation resistance 2 under high temperature environment):
All measurements were performed in the same manner as in the above test (3) except that the test temperature was changed from 70 ° C to 120 ° C.

(5) Bleed-out resistance:
The injection sheet obtained above was exposed to a gear oven at 70 ° C. for 168 hours, and then the surface thereof was visually observed or touched by hand, and evaluated according to the following criteria.
○: The sheet surface does not feel sticky. △: The sheet surface feels sticky. ×: Touching the sheet surface makes it dirty.

(6) Oxygen permeability coefficient:
In accordance with the gas chromatograph method of Appendix 2 of JIS K7126-1: 2006, the oxygen permeability coefficient was measured under the conditions of a temperature of 23 ° C. and a humidity of 0%. A 1 mm-thick press sheet obtained by hot pressing under conditions of preheating at 220 ° C. for 3 minutes and pressure at 220 ° C. for 3 minutes was used as the test piece. In the results table, the unit (× 10 ⁻¹⁶ mol / m · sec · Pa) is omitted.

(7) Tensile test:
In accordance with JIS K 6251-2010, a No. 3 dumbbell punched from the 2 mm-thick injection sheet obtained above was used as a test piece, and measurement was performed under the condition of a tensile speed of 500 mm / min.

Raw materials used:
Component (a):
(A-1) An uncrosslinked isobutylene rubber was obtained according to Production Example 1 of International Publication No. 2006/098142. Subsequently, component (a) 100 was prepared according to Production Example 3 of WO 2006/098142 except that the following (c-1) was used instead of HDPE and the following (d-2) was used instead of 100R. An isobutylene-based elastic body composition containing part by mass, 11 parts by mass of component (c), and 40 parts by mass of component (d) was obtained.
(A-2) An isobutylene-based elastic body composition was obtained in the same manner as in the above (a-1) except that the following (c-4) was used as HDPE and the following (d-3) was used instead of 100R. It was.
(A-3) An isobutylene-based elastic composition was obtained in the same manner as (a-1) except that the following (c-4) was used as the HDPE.

Component (b):
(B-1) Kuraray Co., Ltd. styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS) “SEPTON 4077 (trade name)”. Content of structural unit derived from styrene 30% by mass, number average molecular weight 280000, molecular weight distribution (mass average molecular weight / number average molecular weight) 1.23.
(B-2) A styrene-isobutylene-styrene block copolymer (SIBS) “SIBSTAR103T (trade name)” of Kaneka Corporation. Content of structural unit derived from styrene 31% by mass, number average molecular weight 92000, molecular weight distribution (mass average molecular weight / number average molecular weight) 1.10, durometer hardness (type A, 15 second value) 57.
(B-3) Kuraray Co., Ltd. styrene-vinyl (ethylene-propylene) -styrene copolymer (V-SEPS) “HIBLER KL-7135 (trade name)”. Content of structural unit derived from styrene 33% by mass, durometer hardness (type A, 15 sec value) 68, glass transition temperature -15 ° C.

Component (c):
(C-1) Prime Polymer Co., Ltd. polypropylene-based resin “Prime Polypro J106MG (trade name)”. Melting enthalpy 100 J / g, melting point 160 ° C., melt mass flow rate (230 ° C., 21.18 N) 15 g / 10 min.
(C-2) Polypropylene resin “PB270A (trade name)” of Sun Allomer Co., Ltd. Melting enthalpy 98 J / g, melting point 161 ° C., melt mass flow rate (230 ° C., 21.18 N) 0.7 g / 10 min.
(C-3) Polypropylene resin “Adflex Q-100F (trade name)” of Sun Allomer Co., Ltd. Melting enthalpy 36 J / g, melting point 142 ° C., melt mass flow rate (230 ° C., 21.18 N) 0.6 g / 10 min.
(C-4) High density polyethylene “Novatech HJ490 (trade name)” manufactured by Nippon Polyethylene Corporation. Density 960 kg / m ³ , melt mass flow rate (190 ° C., 21.18 N) 20 g / 10 min.

Component (d):
(D-1) Idemitsu Kosan Co., Ltd. n-paraffinic process oil “Diana Process Oil PW-380 (trade name)”. Mw750, Mn652, Mw / Mn 1.15.
(D-2) A polybutene synthetic oil “Nisseki Polybutene HV-300 (trade name)” manufactured by JX Nippon Oil & Energy Corporation. Mn 1400.
(D-3) Idemitsu Kosan Co., Ltd. n-paraffinic process oil “Diana Process Oil PW-100 (trade name)”. Mw 720, Mn 540, Mw / Mn 1.33.

Examples 1-15, Comparative Examples 1-9
A compound having a compounding ratio (parts by mass) shown in any one of Tables 1 to 4 is a 28 mm diameter, L / D = 42 twin screw extruder manufactured by Nippon Steel Co., Ltd., screw rotation speed 200 rpm, die outlet The mixture was melt-kneaded under a resin temperature of 220 ° C., and pellets of a thermoplastic elastomer resin composition were obtained by a strand cut method. The following tests (1) to (7) were performed. The results are shown in any one of Tables 1 to 4.

The thermoplastic elastomer resin composition of the present invention is excellent in gas barrier properties, compression deformation resistance in a high temperature environment, flexibility, mechanical strength, and good moldability. It also has excellent bleed-out resistance.
On the other hand, in the comparative example, at least one of gas barrier properties, compression deformation resistance under high temperature environment, flexibility, mechanical strength, molding processability, and bleed-out resistance is insufficient.

It is a conceptual diagram of the second melting curve measured with the differential scanning calorimeter.

1: Melting point curve 2: Baseline 3: Area representing melting enthalpy 4: Melting point 5: Integration start point of melting enthalpy calculation 6: Integration end point of melting enthalpy calculation

Claims (7)

(A) 20-80% by mass of a crosslinked elastic body having a structural unit derived from isobutylene;
(B) Hydrogenated product of block copolymer of aromatic vinyl compound and conjugated diene compound (b1), and block copolymer of aromatic vinyl compound and isobutylene (b2)
1 to 80% by mass selected from the group consisting of:
Here, the sum total of the said component (a) and the said component (b) is 100 mass%, 100 mass parts of resin compositions; and (c) 5-50 mass parts of polyolefin resin;
A thermoplastic elastomer resin composition comprising:
The thermoplastic elastomer resin composition according to claim 1, wherein the component (a) is a crosslinked elastic body obtained by crosslinking using a hydrosilyl group-containing compound.
The component (b) is a styrene-ethylene-butene block copolymer (SEB),
Styrene-ethylene-propylene block copolymer (SEP),
Styrene-ethylene-butene-styrene block copolymer (SEBS),
Styrene-ethylene-propylene-styrene block copolymer (SEPS),
Styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS),
Styrene-isobutylene-styrene block copolymer (SIBS) and styrene-vinyl (ethylene-propylene) -styrene copolymer (V-SEPS)
The thermoplastic elastomer resin composition according to claim 1, wherein the thermoplastic elastomer resin composition is at least one selected from the group consisting of:
The thermoplastic elastomer resin composition according to any one of claims 1 to 3, wherein the component (c) is at least one selected from the group consisting of a polypropylene resin and a polyethylene resin.
Furthermore, (d) 5-100 mass parts of softening agents for rubber | gum are included in 5-100 mass parts with respect to 100 mass parts of said resin compositions which consist of said component (a) and said component (b). 2. The thermoplastic elastomer resin composition according to item 1.
A medical device comprising the thermoplastic elastomer resin composition according to any one of claims 1 to 5.
A food device comprising the thermoplastic elastomer resin composition according to any one of claims 1 to 5.