DE102019119630A1 - Thermoplastic elastomer composition, stopper and container - Google Patents

Abstract

[Problem to be Solved] To provide a thermoplastic elastomer composition having an excellent resealability and a low odor, thereby causing extractables to be reduced. [Solving agent] Thermoplastic elastomer composition comprising 100 parts by mass of a hydrogenated block copolymer (a), 10 to 50 parts by mass of a polypropylene-based one Resin (b), 75 to 200 parts by mass of a non-aromatic plasticizer (d), and 1 to 150 parts by mass of an inorganic filler (e), wherein the hydrogenated block copolymer (a) comprises at least one polymer block A1 consisting mainly of a monomer unit of a vinyl aromatic hydrocarbon compound, and comprising at least one polymer block B1 consisting mainly of a monomer unit of a conjugated diene compound and obtained by hydrogenation thereof hydrogenated block copolymer (a-1), the weight average molecular weight of the hydrogenated block copolymer s (a-1) is 100,000 to 550,000, the content of all monomer units of the vinyl aromatic hydrocarbon compound of the hydrogenated block copolymer (a-1) exceeding 20% by mass and being 50% by mass or less, wherein the inorganic filler (e) is a surface-treated silica ,

Description

[Technical field]

The present invention relates to a thermoplastic elastomer composition, a stopper and a container.

[State of the art]

With regard to medical containers such as infusion bags, a content liquid can remain in the medical container even after use. There is a risk of the contents liquid leaking or splashing when an injection needle is removed from a stopper attached to the medical container in a state in which the contents liquid remains. Therefore, in the stoppers used for medical containers, resealability, i.e. H. an efficiency that the needle hole is closed again after the needle is removed from the stopper and leakage of the content liquid is prevented, that is, a liquid tightness is required.

From the viewpoint of reclosability and liquid tightness, a rubber material such as isoprene rubber, butadiene rubber, butyl rubber and a mixture thereof are conventionally used as the material of stoppers for medical containers.

However, when using the rubber material, it is necessary to go through a step in which at least one additive such as fillers, plasticizers, and vulcanizing agents is added and kneaded to the rubber component to obtain a rubber mixture, and a vulcanization step in which the kneaded rubber mixture is used for a mold the plug is fed, heated and pressed to produce the rubber material. The manufacturing steps of the rubber material are complicated and require a large manufacturing facility, so that there are problems such as high manufacturing costs.

The plugs for medical containers using the rubber material also have a problem that deterioration due to the oxidation of the double bond in the rubber component occurs during the storage period of the medical container, and the deteriorated rubber component is separated into a liquid medicine.

With regard to the injection needle, from the point of view of manageability and safety, the metal needles, which are conventionally widely used, are increasingly being replaced by plastic needles.

These plastic needles have a low stiffness compared to metal needles, so that the needle diameter must be increased in order to obtain sufficient stiffness. However, there is a problem that when the needle diameter is increased, resistance to piercing the needle through the plug of the medical container, i.e. H. a needlestick resistance becomes large.

To solve this problem, various stoppers using a thermoplastic elastomer as stoppers for medical containers have been proposed in recent years.

For example, JP Patent Laid-Open No. 2012-25944 A discloses a medical rubber stopper obtained by molding a resin composition containing a hydrogenated block copolymer, a plasticizer for a hydrocarbon-based rubber and a polyolefin-based resin.

JP Patent Laid-Open No. 2012-57162 A further discloses a medical plug obtained by molding a medical resin composition consisting of a hydrogenated block copolymer, a hydrogenated petroleum resin, a polyphenylene ether resin, a peroxide-decomposable olefin resin and a non-aromatic rubber plasticizer.

SUMMARY OF THE INVENTION

OBJECT OF THE INVENTION TO BE SOLVED

However, for the medical rubber stopper disclosed in JP Patent Laid-Open No. 2012-25944 A, a tightly sealed PET bottle was used, and a condition of a small one Amount of liquid, a sealability test was carried out, and the sealability was not confirmed in the case of using a bag-shaped container. There is also a problem that for the resealability, in the case where an air hole is opened in the container using the stopper under an atmospheric pressure condition and in a state where the amount of liquid is large, the stopper is long Time has been pierced with the needle, only an inadequate property has been obtained.

Also, the medical plug disclosed in JP Patent Laid-Open No. 2012-57162 A also assumes that the state in which the plug is pierced with the needle is short in time, and in the case where it is stinging for a long time Condition of the needle was kept and after the needle was removed from the stopper, sufficient resealability was not obtained. Furthermore, there is the problem that, due to the use of polyphenylene ether resin, an odor of the rubber mixture is strong and extractables also increase.

As described above, in the medical container stopper using the conventionally proposed thermoplastic elastomer, sufficient resealability has not yet been obtained, and to increase the resealability, it is necessary to increase the thickness of the stopper or the inner volume of the outer stopper part to be fitted with the stopper. to decrease in order to increase a tightening force, i.e. caulking. However, there is a problem that since the resistance to removing and piercing the needle increases in every case, the plug cannot be stung well with the injection needle, and there is a problem of inconvenience that due to the use of polyphenylene ether resin, the The smell of the rubber compound is strong and extractables also increase, etc.

The present invention therefore addresses the above-described problems in the prior art, and the present invention aims to provide a thermoplastic elastomer composition, a stopper and a container having an excellent resealability and a low odor, thereby reducing extractables.

[Means for Solving the Task]

As a result of intensive studies to solve the problems of the prior art described above, the inventors of the present invention found that a thermoplastic elastomer composition comprising a hydrogenated block copolymer having a predetermined structure, a polypropylene-based resin, a non-aromatic plasticizer and an inorganic filler is a surface-treated silica, contains it in a predetermined ratio, which can solve the above-described problems of the prior art, and comes to completion of the present invention.

That is, the present invention is as follows.

1. (1) The thermoplastic elastomer composition comprising 100 parts by mass of a hydrogenated block copolymer (a), 10 to 50 parts by mass of a polypropylene-based resin (b), 75 to 200 parts by mass of a non-aromatic plasticizer (d), and 1 to 150 parts by mass of an inorganic filler ( e), wherein the hydrogenated block copolymer (a) has at least one polymer block A1, which mainly consists of a monomer unit of a vinyl aromatic hydrocarbon compound, and at least one polymer block B1, which mainly consists of a monomer unit of a conjugated diene compound comprising a hydrogenated block copolymer (a-1) obtained by hydrogenation thereof, the weight-average molecular weight of the hydrogenated block copolymer (a-1) being 100,000 to 550,000, the content of all monomer units of the vinyl aromatic hydrocarbon compound of hydrogenated block copolymer (a-1) exceeds 20% by mass and is 50% by mass or less, and wherein the inorganic filler (e) is a surface-treated silica.
2. (2) The thermoplastic elastomer composition according to the item ( 1 ), wherein the hydrogenated block copolymer (a) is the hydrogenated block copolymer (a-1), and at least one polymer block A2, which mainly consists of a monomer unit of a vinyl aromatic hydrocarbon compound, and at least one polymer block B2, which mainly consists of a monomer unit of a conjugated diene compound comprehensive hydrogenation block copolymer (a-2) obtained by hydrogenation thereof, the weight average molecular weight of the hydrogenated block copolymer (a-2) being 120,000 to 230,000, the content of all monomer units of the vinyl aromatic hydrocarbon compound of the hydrogenated block copolymer (a-2) 7 mass% or larger and 20 mass% or smaller, and the mass ratio ((a-1) / (a-2)) between the hydrogenated block copolymer (a-1) and the hydrogenated block copolymer (a-2) 70 / Is 30 to 95/5.
3. (3) The thermoplastic elastomer composition according to the item ( 2 ), wherein in the hydrogenated block copolymer (a-2), the amount of the vinyl bond in the monomer unit of the conjugated diene compound before the hydrogenation is 63 mol% to 95 mol%.
4. (4) The thermoplastic elastomer composition according to the item ( 2 ) or ( 3 ), wherein the hydrogenated block copolymer (a-2) has at least two polymer blocks A2, which mainly consist of a monomer unit of a vinyl aromatic hydrocarbon compound, and at least two polymer blocks B2, which mainly consist of a monomer unit of a conjugated diene compound, and wherein at least one of the Polymer blocks B2 is located at the end of the hydrogenated block copolymer (a-2), the content of this polymer block B2 located at the end being 0.5 to 9% by mass in the hydrogenated block copolymer (a-2).
5. (5) The thermoplastic elastomer composition according to one of the items ( 1 ) to ( 4 ), wherein in the hydrogenated block copolymer (a-1), the amount of the vinyl bond in the monomer unit of the conjugated diene compound before the hydrogenation is 30 mol% to 60 mol%.
6. (6) The thermoplastic elastomer composition according to one of the items ( 1 ) to ( 5 ) with a Shore A hardness of 55 or less and a needlestick resistance of 4.0 kgf or less.
7. (7) The thermoplastic elastomer composition according to one of the items ( 1 ) to ( 6 ), the inorganic filler (e) being surface-treated with a silane coupling agent.
8. (8) The thermoplastic elastomer composition according to one of the points ( 1 ) to ( 7 ), wherein the odor intensity is three or less according to the six-step display of the odor intensity.
9. (9) The stopper comprising the thermoplastic elastomer composition according to one of the items ( 1 ) till 8) .
10. (10) The container with the stopper after the point ( 9 ) is provided.
11. (11) The stopper used for medical purposes, comprising the thermoplastic elastomer composition according to one of the items ( 1 ) till 8) .
12. (12) The container is used for medical purposes, which is plugged according to the item ( 11 ) is provided.

Effects of the Invention

According to the present invention, a thermoplastic elastomer composition, a stopper and a container having an excellent resealability, low odor and reduced extractables are obtained.

list of figures

• 1(A) eine schematische Draufsicht auf ein Beispiel eines Stopfens; und 1(B) eine schematische Schnittdarstellung eines Beispiels eines Stopfens; sowie
• 2(A) eine schematische Draufsicht auf ein Beispiel eines Zustands, in dem ein Stopfen an einem Werkzeug angebracht ist; und 2(B) eine schematische Schnittdarstellung eines Beispiels des Zustands, in dem ein Stopfen an einem Werkzeug angebracht ist.

It shows:

• 1 (A) a schematic plan view of an example of a plug; and 1 (B) is a schematic sectional view of an example of a plug; such as
• 2 (A) a schematic plan view of an example of a state in which a plug is attached to a tool; and 2 B) is a schematic sectional view of an example of the state in which a plug is attached to a tool.

Embodiment of the Invention

Hereinafter, a form for carrying out the present invention (hereinafter referred to as “present embodiment”) will be explained in detail.

The following present embodiment shows an example for explaining the present invention and does not limit the present invention to the following contents. The present invention can be carried out with various modifications in the essence.

[Thermoplastic elastomer composition]

• 100 Massenteile eines hydrierten Blockcopolymers (a),
• 10 bis 50 Massenteile eines Polypropylen-basierten Harzes (b),
• 75 bis 200 Massenteile eines nichtaromatischen Weichmachers (d), und
• 1 bis 150 Massenteile eines anorganischen Füllstoffs (e); und

es geht um eine thermoplastische Elastomerzusammensetzung, wobei das hydrierte Blockcopolymer (a) ein einen Polymerblock A1, der hauptsächlich aus mindestens einer Monomereinheit einer vinylaromatischen Kohlenwasserstoffverbindung besteht, und einen Polymerblock B1, der hauptsächlich aus mindestens einer Monomereinheit einer konjugierten Dienverbindung besteht, umfassendes, und durch Hydrierung davon erhaltendes hydriertes Blockcopolymer (a-1) enthält,
wobei das gewichtsgemittelte Molekulargewicht des hydrierten Blockcopolymers (a-1) 100.000 bis 550.000 beträgt,
wobei der Gehalt aller Monomereinheiten der vinylaromatischen Kohlenwasserstoffverbindung des hydrierten Blockcopolymers (a-1) 20 Masse% überschreitet und 50 Masse% oder weniger beträgt, und
wobei der anorganische Füllstoff (e) eine oberflächenbehandelte Kieselsäure ist.The thermoplastic elastomer composition according to the present embodiment comprises:

• 100 parts by mass of a hydrogenated block copolymer (a),
• 10 to 50 parts by mass of a polypropylene-based resin (b),
• 75 to 200 parts by mass of a non-aromatic plasticizer (d), and
• 1 to 150 parts by mass of an inorganic filler (e); and

it is a thermoplastic elastomer composition, wherein the hydrogenated block copolymer (a) comprises a polymer block A1 consisting mainly of at least one monomer unit of a vinyl aromatic hydrocarbon compound and a polymer block B1 consisting mainly of at least one monomer unit of a conjugated diene compound Contains hydrogenation of the resulting hydrogenated block copolymer (a-1),
wherein the weight average molecular weight of the hydrogenated block copolymer (a-1) is 100,000 to 550,000,
wherein the content of all the monomer units of the vinyl aromatic hydrocarbon compound of the hydrogenated block copolymer (a-1) exceeds 20% by mass and is 50% by mass or less, and
wherein the inorganic filler (e) is a surface treated silica.

With the structure, the thermoplastic elastomer composition according to the present embodiment has excellent reclosability and low odor, thereby reducing extractables.

Each component of the thermoplastic elastomer composition of the present embodiment is explained in detail below.

(Hydrogenated block copolymer (a))

The hydrogenated block copolymer (a) contained in the thermoplastic elastomer of the present embodiment contains a hydrogenated block copolymer (a-1) described later.

<Hydrogenated block copolymer (a-1)>

The hydrogenated block copolymer (a-1) is a hydrogenated block copolymer obtained by hydrogenating a block copolymer having at least one polymer block A1 composed mainly of a monomer unit of a vinyl aromatic hydrocarbon compound and at least one polymer block B1 composed mainly of a monomer unit of a conjugate Diene connection exists.

The polymer block A1 composed mainly of the monomer unit of the vinyl aromatic hydrocarbon compound means that the content of the monomer unit of the vinyl aromatic hydrocarbon compound in the polymer block A1 exceeds 50% by mass, the content from the viewpoint of mechanical strength and recoverability in terms of reclosability, i. H. the performance that the needle hole closes again after removal of the needle from the plug, preferably 60 mass% or more, more preferably 70 mass% or more, more preferably 80 mass% or more and even more preferably 90 mass% or more.

Also, the polymer block B1, which mainly consists of the monomer unit of the conjugated diene compound, means that the content of the monomer unit of the conjugated diene compound in the Polymer block B1 exceeds 50% by mass, and the content is preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more from the viewpoint of the reclosability.

In the present embodiment, it is assumed that the nomenclature of each monomer unit which forms the block copolymer corresponds to the nomenclature of the monomer from which this monomer unit is derived. For example, the phrase "vinyl aromatic hydrocarbon compound monomer unit" means a component unit of a polymer produced as a result of polymerizing a vinyl aromatic hydrocarbon compound as a monomer, and its structure is a molecular structure in which two carbons of a substituted ethylene group derived from the substituted vinyl group to form an educational institution.

The wording "conjugated diene compound monomer unit" also means a component unit of a polymer produced as a result of polymerizing a conjugated diene compound as a monomer, and its structure is a molecular structure in which two carbons of an olefin derived from the conjugated diene compound monomer is to form a binding site.

In the present embodiment, the monomer that can be used as the monomer unit of a vinyl aromatic hydrocarbon compound in the polymer block A1 is a compound having a vinyl group and an aromatic ring.

For example, although the monomer of a vinyl aromatic hydrocarbon compound is not limited to the following, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N -Diethyl-p-aminoethylstyrene etc. Among these, styrene, α-methylstyrene and divinylbenzene are expediently used in view of the polymerizability. As a monomer of a vinyl aromatic hydrocarbon compound, only one of them alone or two or more of them can also be used.

A monomer that can be used as a monomer unit of a conjugated diene compound in the polymer block B1 is a diolefin with a pair of conjugated double bonds (two double bonds that are conjugated).

For example, although the conjugated diene compound monomer is not limited to the following, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, etc. Among them, 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene) are useful in view of the polymerizability used. Only one of these alone or two or more of these can also be used as the monomer of the conjugated diene compound.

For example, although the hydrogenated block copolymer (a-1) is not limited to the following, it has a structure represented by the following general formulas (1) to (7), respectively.

$$\text{A}1-{\left(\text{B}1-\text{A}1\right)}_{\text{n}}$$

$$\text{B}1-{\left(\text{A}1-\text{B}1\right)}_{\text{n}}$$

$${\left[{\left(\text{B}1-\text{A}1\right)}_{\text{n}}\right]}_{\text{m}}-\text{Z}$$

$${\left[{\left(\text{A}1-\text{B}1\right)}_{\text{n}}\right]}_{\text{m}}-\text{Z}$$

$${\left[{\left(\text{B}1-\text{A}1\right)}_{\text{n}}-\text{B}1\right]}_{\text{m}}-\text{Z}$$

$${\left[{\left(\text{A}1-\text{B}1\right)}_{\text{n}}-\text{A}1\right]}_{\text{m}}-\text{Z}$$

Furthermore, the hydrogenated block copolymer (a-1) may also be a mixture containing various copolymers having one of the structures represented by the following general formulas (1) to (7) in any ratio. $${\left(\text{A}1-\text{B}1\right)}_{\text{n}}$$

$$\text{A}1-{\left(\text{B}1-\text{A}1\right)}_{\text{n}}$$

$$\text{B}1-{\left(\text{A}1-\text{B}1\right)}_{\text{n}}$$

$${\left[{\left(\text{B}1-\text{A}1\right)}_{\text{n}}\right]}_{\text{m}}-\text{Z}$$

$${\left[{\left(\text{A}1-\text{B}1\right)}_{\text{n}}\right]}_{\text{m}}-\text{Z}$$

$${\left[{\left(\text{B}1-\text{A}1\right)}_{\text{n}}-\text{B}1\right]}_{\text{m}}-\text{Z}$$

$${\left[{\left(\text{A}1-\text{B}1\right)}_{\text{n}}-\text{A}1\right]}_{\text{m}}-\text{Z}$$

In the above general formulas (1) to (7), A1 is a polymer block mainly composed of a monomer unit of a vinyl aromatic hydrocarbon compound, and B1 is a polymer block mainly composed of a monomer unit of a conjugated diene compound. The boundary between polymer block A1 and polymer block B1 does not necessarily have to be clearly distinguished.

Further, n is an integer of 1 or more, and preferably an integer of 1 to 5.

m is an integer of 2 or more, and an integer of preferably 2 to 11, and more preferably 2 to 8.

Z represents the residue of a coupling agent. Here, the residue of the coupling agent means the residue after connecting a coupling agent, which is used for connecting a plurality of copolymers of the monomer unit of a conjugated diene compound and the monomer unit of a vinyl aromatic hydrocarbon compound between the polymer block A1 - the polymer block A1, the Polymer block B1 - the polymer block B1 or the polymer block A1 - the polymer block B1 is used. The coupling agent is not limited to the following, but e.g. B. Dihalogen compounds and acid esters, etc., which will be described later, can be mentioned.

In the general formulas (1) to (7) above, the monomer unit of the vinylaromatic hydrocarbon compound in polymer block A1 and in polymer block B1 can be both uniformly and tapered.

Further, when the polymer block A1 and the polymer block B1 are a copolymer block of a monomer unit of a vinyl aromatic hydrocarbon compound and a monomer unit of a conjugated diene compound, the monomer unit of the vinyl aromatic hydrocarbon compound in this copolymer block may each have several evenly distributed parts and several tapered parts. Furthermore, several parts with different contents of the monomer unit of the vinyl aromatic hydrocarbon compound can coexist in the copolymer block part.

The weight average molecular weight of the hydrogenated block copolymer (a-1) is 100,000 to 550,000.

From the viewpoint of heat distortion resistance, it is preferably 120,000 or more, more preferably 140,000 or more. It is also preferably 500,000 or less, more preferably 450,000 or less, more preferably 400,000 or less, more preferably 350,000 or less and even more preferably 300,000 or less.

It is also preferably 120,000 to 350,000, and more preferably 140,000 to 300,000.

When the weight average molecular weight of the hydrogenated block copolymer (a-1) is 100,000 or more, the recoverability tends to be good in terms of the resealability of the thermoplastic elastomer composition according to the present embodiment. When the weight average molecular weight of the hydrogenated block copolymer (a-1) is 550,000 or less, good fluidity and excellent moldability are obtained in the thermoplastic elastomer composition.

The molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (a-1) is preferably 1.01 to 8.0, more preferably 1.01 to 6.0, and more preferably 1.01 to 5.0.

If the molecular weight distribution of the hydrogenated block copolymer (a-1) is in the above range, better mechanical strength tends to be obtained.

The shape of the molecular weight distribution curve of the hydrogenated block copolymer (a-1) measured by gel permeation chromatography (GPC) is not particularly limited, and can be a polymodal molecular weight distribution in which there are two or more peaks as well as a monomodal molecular weight distribution with one have a single peak.

The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn; ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) of the hydrogenated block copolymer (a-1) can be determined based on the peak molecular weight of the chromatogram obtained by gel permeation chromatography (GPC) was measured in the method described in the embodiment described later, and determined using a calibration curve (generated using the peak molecular weight of standard polystyrene) obtained from the measurement of commercially available standard polystyrene.

The weight average molecular weight of the hydrogenated block copolymer (a-1) can be controlled by adjusting the amount of the polymerization initiator and the monomer to the above numerical range.

The number average molecular weight of the block chain of the polymer block A1, which mainly consists of the monomer unit of a vinyl aromatic hydrocarbon compound, can be measured by GPC in the same manner as described above, by a method in which, using osmium tetroxide as a catalyst, the hydrogenated block copolymer (a -1) is oxidatively decomposed with t-butyl hydroperoxide (a process described in IM KOLTHOFF, et al., J. Polym. Soi. 1, 429 (1946)), polymer block component from the monomer unit of a vinylaromatic hydrocarbon compound (a polymer component consisting of the monomer unit of vinyl aromatic compounds with an average degree of polymerization of about 30 or less is excluded) is obtained.

The content of all the monomer units of the vinyl aromatic hydrocarbon compound in the hydrogenated block copolymer (a-1) exceeds 20% by mass and is 50% by mass or less.

From the viewpoint of mechanical property and reclosability, the content exceeds 20 mass% and is preferably 22 mass% or more, more preferably 24 mass% or more, more preferably 26 mass% or more and still more preferably 28 mass% or more.

Further, from the viewpoint of flexibility, the content is 50% by mass or less, preferably 47% by mass or less, more preferably 44% by mass or less, more preferably 41% by mass or less and more preferably 38% by mass or less.

Further, from the viewpoint of the balance between recoverability and flexibility, the content is more preferably 26 to 44% by mass, more preferably 26 to 41% by mass, more preferably 28 to 41% by mass and still more preferably 28 to 38% by mass.

When the content of all the monomer units of the vinyl aromatic hydrocarbon compound in the hydrogenated block copolymer (a-1) exceeds 20% by mass, the strength of the thermoplastic elastomer composition of the present embodiment tends to be increased, while when the content of all the vinyl aromatic hydrocarbon compounds is 50% by mass or less tends to increase the flexibility of the thermoplastic elastomer composition of the present embodiment.

The content of all the monomer units of the vinyl aromatic hydrocarbon compound can be controlled by adjusting the addition amount of the monomers in the polymerization step of the hydrogenated block copolymer (a-1) to the above numerical range and can be calculated by an absorption intensity of 262 nm by an ultraviolet spectrophotometer by a method which is described in the embodiment described later is measured.

The microstructure (the cis-trans ratio and the amount of vinyl bond) of the polymer block B1 in the hydrogenated block copolymer (a-1) can be arbitrarily controlled using a polar compound etc. described later.

The amount of the vinyl bond in the monomer unit of the conjugated diene compound in the hydrogenated block copolymer (a-1) before the hydrogenation is preferably 30 mol% to 60 mol%, more preferably 31 to 57 mol%, more preferably 31 to 54 mol%, still more preferably 32 to 51 mol% and more preferably 32 to 45 mol% or less.

If the amount of the vinyl bond in the monomer unit of the conjugated diene compound is 30 mol% or more before the hydrogenation, the compatibility between the hydrogenated block copolymer (a-1) and a polypropylene-based resin (b) described later tends to further increase becomes, while if the amount of the vinyl bond in the monomer unit of the conjugated diene compound before the hydrogenation is 60 mol% or less, the strength tends to be further increased.

As described above, the content of all the monomer units of the vinyl aromatic hydrocarbon compound in the hydrogenated block copolymer (a-1) in the present embodiment exceeds 20% by mass and is 50% by mass or less, and it is further preferred that the amount of the vinyl bond in the monomer unit is conjugated diene compound before hydrogenation is 30 mol% to 60 mol%.

In the present embodiment, the amount of the vinyl bond in, for example, butadiene before hydrogenation is the ratio of the total molar amount of the conjugated diene monomer unit incorporated in the 1,2 bond and the 3,4 bond to total molar amount of the conjugated diene monomer unit incorporated in a bond form of 1,2-bond, 3,4-bond and 1,4-bond.

After hydrogenation is the ratio of the total molar amount of the conjugated diene monomer unit that is in 1,2-bond without hydrogenation, 1,2-bond after hydrogenation, 3,4-bond without hydrogenation and 3,4-bond after of the hydrogenation, to the total molar amount of the monomer unit of conjugated diene which is in a bond form of 1,2-bond without hydrogenation, 1,2-bond after hydrogenation, 3,4-bond without hydrogenation, 3,4- Binding after hydrogenation, 1,4-bond without hydrogenation and 1,4-bond after hydrogenation is incorporated, as is the amount of vinyl bond of the monomer unit of conjugated diene before hydrogenation. Therefore, the amount of the vinyl bond of the conjugated diene monomer unit before hydrogenation can be measured by the block copolymer after the hydrogenation and by the nuclear magnetic resonance spectral analysis (NMR), specifically by a method described in the embodiment described later.

The degree of hydrogenation of the aliphatic double bond derived from the conjugated diene compound in the hydrogenated block copolymer (a-1) is preferably 50% or more, more preferably 60% or more and more preferably 70% or more. When the degree of hydrogenation is 50% or more, the reduction in mechanical property due to thermal deterioration (oxidation deterioration) tends to be suppressed more effectively. Further, when the degree of hydrogenation is 70% or more, better weather resistance tends to be obtained. Although the upper limit of the degree of hydrogenation is not particularly limited, it is preferably 100% or less, and more preferably 99% or less.

Further, if the thermoplastic elastomer composition of the present embodiment is partially crosslinked using an organic peroxide (g) described later, the degree of hydrogenation of the aliphatic double bond derived from the conjugated diene compound in the hydrogenated block copolymer (a-1) is preferable from the viewpoint of heat resistance 50% or more, more preferably 60% or more, and preferably 90% or less and more preferably 85% or less from the viewpoint of processability and crosslinking reactivity.

Although the degree of hydrogenation of the aromatic double bond based on the monomer unit of the vinyl aromatic hydrocarbon compound in the hydrogenated block copolymer (a-1) is not particularly limited, it is preferably 50% or less, more preferably 30% or less, and more preferably 20 from the viewpoint of strength and heat resistance % Or less.

<Hydrogenated block copolymer (a-2)>

The hydrogenated block copolymer (a) contained in the thermoplastic elastomer composition of the present embodiment may contain the hydrogenated block copolymer (a-1) and a hydrogenated block copolymer (a-2) different from the hydrogenated block copolymer (a-1).

The hydrogenated block copolymer (a-2) is a hydrogenated block copolymer obtained by hydrogenating a block copolymer that has at least one polymer block A2 composed mainly of a monomeric unit of a vinyl aromatic hydrocarbon compound and at least one polymer block B2 composed mainly of a monomeric unit of a conjugate Diene compound contains, the weight average molecular weight being 120,000 to 230,000. The content of all the monomer units of the vinyl aromatic hydrocarbon compound of the hydrogenated block copolymer (a-2) is further 7 mass% or more and 20 mass% or less.

When the thermoplastic elastomer composition of the present embodiment is used as a plug for the purpose of needle stick, the flexibility of the thermoplastic elastomer composition affects the needle stick resistance, and if the flexibility to reduce the needle stick resistance is excessively increased, there is a risk that the needle will be used during use Plug falls out and the force to hold the needle (needle retention property) tends to decrease.

Although the flexibility of the thermoplastic elastomer composition correlates with various factors, for example, the lower the amount of the vinyl aromatic hydrocarbon compound in the hydrogenated block copolymer, the lower the amount of styrene, the more the (a-2) component is, respectively the less the polypropylene-based resin (b), the inorganic filler (e) and the inorganic porous adsorbent (f) are in the thermoplastic elastomer composition, and the more the non-aromatic plasticizer (d), the higher the flexibility, i.e. the softness of the thermoplastic elastomer composition.

From the viewpoint of improving the balance between the needlestick resistance and the resealability, the hydrogenated block copolymer (a) is preferably a mixture containing the hydrogenated block copolymer (a-1) and the hydrogenated block copolymer (a-2). In this case, the mass ratio ((a-1) / (a-2)) between the hydrogenated block copolymer (a-1) and the hydrogenated block copolymer (a-2) is preferably 70/30 to 95/5. By having the mass ratio between the hydrogenated block copolymer (a-1) and the hydrogenated block copolymer (a-2) in the above range, the balance between the needlestick resistance and the resealability can be increased. From the same point of view, the above mass ratio is more preferably 75/25 to 95/5 and more preferably 80/20 to 95/5.

In the hydrogenated block copolymer (a-2), the polymer block A2, which mainly consists of the monomer unit of the vinyl aromatic hydrocarbon compound, means that the content of the monomer unit of the vinyl aromatic hydrocarbon compound in the polymer block A2 exceeds 50 mass%, preferably 60 mass% or more, more preferably 70 Mass% or more, more preferably 80 mass% or more, and more preferably 90 mass% or more.

Also in the hydrogenated block copolymer (a-2), the polymer block B2, which mainly consists of the monomer unit of the conjugated diene compound, means that the content of the monomer unit of the conjugated diene compound in the polymer block B2 exceeds 50% by mass, preferably 60% by mass or more, more preferably Is 70 mass% or more, more preferably 80 mass% or more, and more preferably 90 mass% or more.

The monomer that can be used as the monomer unit of a vinyl aromatic hydrocarbon compound in the polymer block A2 is a compound having a vinyl group and an aromatic ring. For example, although the monomer of a vinyl aromatic hydrocarbon compound is not limited to the following, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N -Diethyl-p-aminoethylstyrene etc. Among these, styrene, α-methylstyrene and divinylbenzene are expediently used in view of the polymerizability. As a monomer of a vinyl aromatic hydrocarbon compound, only one of them alone or two or more of them can also be used.

A monomer that can be used as a monomer unit of a conjugated diene compound in the polymer block B2 is a diolefin with a pair of conjugated double bonds (two double bonds that are conjugated).

For example, although the conjugated diene compound monomer is not limited to the following, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, etc. Among these are 1,3-butadiene and 2-methyl-1,3-butadiene (Isoprene) appropriately used in view of the polymerizability. Only one of these alone or two or more of these can also be used as the monomer of the conjugated diene compound.

For example, although the hydrogenated block copolymer (a-2) is not limited to the following, it has a structure represented by the following general formulas (8) to (14), respectively.

$$\text{A}2-{\left(\text{B}2-\text{A}2\right)}_{\text{n}}$$

$$\text{B}2-{\left(\text{A}2-\text{B}2\right)}_{\text{n}}$$

$${\left[{\left(\text{B}2-\text{A}2\right)}_{\text{n}}\right]}_{\text{m}}-\text{Z}$$

$${\left[{\left(\text{A}2-\text{B}2\right)}_{\text{n}}\right]}_{\text{m}}-\text{Z}$$

$${\left[{\left(\text{B}2-\text{A}2\right)}_{\text{n}}-\text{B}2\right]}_{\text{m}}-\text{Z}$$

$${\left[{\left(\text{A}2-\text{B}2\right)}_{\text{n}}-\text{A}2\right]}_{\text{m}}-\text{Z}$$

Furthermore, the hydrogenated block copolymer (a-2) may also be a mixture containing various copolymers having a structure represented by the following general formulas (8) to (14) in any ratio. $${\left(\text{A}2-\text{B}2\right)}_{\text{n}}$$

$$\text{A}2-{\left(\text{B}2-\text{A}2\right)}_{\text{n}}$$

$$\text{B}2-{\left(\text{A}2-\text{B}2\right)}_{\text{n}}$$

$${\left[{\left(\text{B}2-\text{A}2\right)}_{\text{n}}\right]}_{\text{m}}-\text{Z}$$

$${\left[{\left(\text{A}2-\text{B}2\right)}_{\text{n}}\right]}_{\text{m}}-\text{Z}$$

$${\left[{\left(\text{B}2-\text{A}2\right)}_{\text{n}}-\text{B}2\right]}_{\text{m}}-\text{Z}$$

$${\left[{\left(\text{A}2-\text{B}2\right)}_{\text{n}}-\text{A}2\right]}_{\text{m}}-\text{Z}$$

In the above general formulas (8) to (14), A2 is a polymer block mainly composed of a monomer unit of a vinyl aromatic hydrocarbon compound, and B2 is a polymer block mainly composed of a monomer unit of a conjugated diene compound. The boundary between polymer block A2 and polymer block B2 does not necessarily have to be clearly distinguished.

Further, n is an integer of 1 or more, and preferably an integer of 1 to 5.

m is an integer of 2 or more, and an integer of preferably 2 to 11, and more preferably 2 to 8.

Z represents the residue of a coupling agent. Here, the residue of the coupling agent means the residue after connecting a coupling agent, which is used for connecting a plurality of copolymers of the monomer unit of a conjugated diene compound and the monomer unit of a vinyl aromatic hydrocarbon compound between the polymer block A2 - the polymer block A2, the Polymer block B2 - the polymer block B2 or the polymer block A2 - the polymer block B2 is used. The coupling agent is not limited to the following, but e.g. B. Dihalogen compounds and acid esters, etc., which will be described later, can be mentioned.

In the general formulas (8) to (14), the monomer unit of the vinylaromatic hydrocarbon compound in the polymer block A2 and in the polymer block B2 can be both uniformly and tapered. Further, when the polymer block A2 and the polymer block B2 are a copolymer block of a monomer unit of a vinyl aromatic hydrocarbon compound and a monomer unit of a conjugated diene compound, the monomer unit of the vinyl aromatic hydrocarbon compound in this copolymer block may each have several evenly distributed parts and / or several tapered parts. Furthermore, several parts with different contents of the monomer unit of the vinyl aromatic hydrocarbon compound can coexist in the copolymer block part.

If the hydrogenated block copolymer (a-2) has at least two of the polymer blocks A2 and at least two of the polymer blocks B2, at least one polymer block B2 is at the end of the hydrogenated block copolymer (a-2), the content of this polymer block B2 being at the end is preferably 0.5 to 9 mass% in the hydrogenated block copolymer (a-2), more preferably 1 to 7 mass%, and more preferably 3 to 7 mass%.

At least one polymer block B2 is at the end of the hydrogenated block copolymer (a-2), and the content of the polymer block B2 which is at the end is 0.5 to 9 mass% in the hydrogenated block copolymer (a-2), so that the thermoplastic elastomer the present embodiment tends to have better flexibility. The final polymer block B2 content can be calculated by excluding the mass of conjugated diene polymerized at the end from the mass of all monomers used for the polymerization reaction.

In order that at least one polymer block B2 in the hydrogenated block copolymer (a-2) is at the end and the content of this polymer block B2 at the end is brought into the numerical range above, a method for adjusting the addition time or amount of the monomer in the polymerization step of the hydrogenated one Block copolymer (a-2) effective.

The weight average molecular weight of the hydrogenated block copolymer (a-2) is 120,000 to 230,000.

When the weight average molecular weight of the hydrogenated block copolymer (a-2) is 120,000 or more, a property of a small compression set such as C-set of the thermoplastic elastomer composition of the present embodiment can be obtained. This means that recoverability is improved. When the weight average molecular weight of the hydrogenated block copolymer (a-2) is 230,000 or less, the resilience of the thermoplastic elastomer composition increases, and when a medical container is stuffed using a thermoplastic elastomer composition of the present embodiment, sufficient resealability and an improvement effect of the needle stick resistance are obtained , From the same point of view, the weight average molecular weight of the hydrogenated block copolymer (a-2) is preferably 140,000 to 220,000, more preferably 150,000 to 210,000, and more preferably 160,000 to 200,000.

The molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (a-2) is preferably 1.01 to 8.0, more preferably 1.01 to 6.0, and more preferably 1.01 to 5.0. If the molecular weight distribution is in the above range, the thermoplastic elastomer composition of the present embodiment tends to have better recoverability and mechanical strength. Mw and Mn of the hydrogenated block copolymer (a-2) can also be measured by GPC.

The shape of the molecular weight distribution curve of the hydrogenated block copolymer (a-2) is not particularly limited and can have both a polymodal molecular weight distribution with two or more peaks and a monomodal molecular weight distribution with a peak.

The content of all monomer units of the vinyl aromatic hydrocarbon compound in the hydrogenated block copolymer (a-2) is 7 mass% to 20 mass%, preferably 9 to 18 mass% and more preferably 11 to 16 mass%. When the content of all the monomer units of the vinyl aromatic hydrocarbon compound in the hydrogenated block copolymer (a-2) is 7% by mass or more, the mechanical strength of the thermoplastic elastomer composition tends to be further increased, and when the content of all the monomer units of the vinyl aromatic hydrocarbon compound is 20% by mass. or less, the flexibility and the recoverability of the thermoplastic elastomer composition tend to be further increased and the resealability is further improved.

The amount of the vinyl bond in the monomer unit of the conjugated diene compound in the hydrogenated block copolymer (a-2) before the hydrogenation is preferably 63 mol% to 95 mol%, more preferably 65 mol% to 90 mol% and more preferably 67 mol% to 85 mol%.

If the amount of the vinyl bond in the monomer unit of the conjugated diene compound in the hydrogenated block copolymer (a-2) before the hydrogenation is 63 mol% or more, the compatibility with a polypropylene-based resin (b) described later tends to be improved, the flexibility and recoverability of the thermoplastic elastomer of the present embodiment are further increased and the resealability is further improved. When the amount of vinyl bond in the monomer unit of the conjugated diene compound before the hydrogenation is 95 mol% or less, there is further tends to further increase the mechanical strength of the thermoplastic elastomer composition of the present embodiment and further improve the coring.

From the point of view described above, the content of all the monomer units of the vinyl aromatic hydrocarbon compound in the hydrogenated block copolymer (a-2) according to the present embodiment is 7% by mass to 20% by mass, and it is more preferable that the amount of the vinyl bond in the monomer unit is before the conjugated diene compound the hydrogenation is 63 mol% to 95 mol%.

The degree of hydrogenation of the aliphatic double bond derived from the conjugated diene compound in the hydrogenated block copolymer (a-2) is preferably 80% or more, and more preferably 90% or more. If the degree of hydrogenation is 80% or more, the reduction in mechanical properties due to thermal deterioration, that is, oxidation deterioration, can be suppressed. Although there is no particular upper limit of the above degree of hydrogenation, it is preferably 100% or less, and preferably 99% or less.

The degree of hydrogenation of the aromatic double bond based on the monomer unit of the vinyl aromatic hydrocarbon compound in the hydrogenated block copolymer (a-2) is not particularly limited, being 50% or less, more preferably 30% or less, and more preferably 20% from the viewpoint of strength and heat resistance. or less.

For example, although the process for producing the hydrogenated block copolymer (a) is not limited to the following, e.g. B. Cite procedures in JP Patent Laid-Open No. S36-19286 B . JP Patent Laid-Open No. S43-17979 B . JP Patent Laid-Open No. S46-32415 B . JP Patent Laid-Open No. S49-36957 B . JP Patent Laid-Open No. S48-2423 B . JP Patent Laid-Open No. S48-4106 B . JP Patent Laid-Open No. S51-49567 B . JP Patent Laid-Open No. S59-166518 A etc. are described.

A method of obtaining a copolymer containing a monomer unit of a conjugated diene compound before hydrogenation and a monomer unit of a vinyl aromatic hydrocarbon compound of the hydrogenated block copolymer (a) is not limited to the following, but the copolymer can be, for example, by a method of performing a living one anionic polymerization can be obtained by means of a polymerization initiator such as an organic alkali metal compound, etc. in a hydrocarbon solvent.

The hydrocarbon solvent is not particularly limited, for example, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane, etc .; alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcycloheptane, etc.; as well as aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, etc.

Although the polymerization initiator is not particularly limited, an organic alkali metal compound is generally preferred, the anionic polymerization activity of which is known for the conjugated diene compound monomer and the vinyl aromatic hydrocarbon compound monomer, for example, alkali metal compound of aliphatic hydrocarbons having 1 to 20 carbon numbers , Alkali metal compound of aromatic hydrocarbons with 1 to 20 carbon numbers and organic aminoalkali metal compound with 1 to 20 carbon numbers.

Although alkali metal contained in the polymerization initiator is not limited to the following, e.g. As lithium, sodium, potassium, etc. are listed. It can contain a single alkali metal or two or more alkali metals in one molecule. Specifically, although this is not limited to the following, e.g. B. n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, reaction products from diisopropenylbenzene and sec-butyllithium, and reaction products from divinylbenzene and a low-butyllithium Amount of 1,3-butadiene, etc. are listed.

The following can also be used: in the U.S. Patent No. 5,708,092 disclosed 1- (t-butoxy) propyllithium and lithium compounds in which one or more molecules of isoprene monomer are incorporated to improve its solubility; in GB Patent No. 2,241,239 disclosed alkyllithiums containing siloxy groups such as 1- (t-butyldimethylsiloxy) hexyllithium; in U.S. Patent No. 5,527,753 disclosed alkyl groups containing amino groups, aminolithium such as diisopropylamidolithium and hexamethyldisilazide lithium.

When monomer of the conjugated diene compound and monomer of vinyl aromatic hydrocarbon compound are copolymerized using an organic alkali metal compound as a polymerization initiator, to adjust the content of vinyl bond (1,2-bond or 3,4-bond), that of copolymer-incorporated monomer of the conjugated diene compound or to adjust the random copolymerizability of the conjugated diene compound monomer and the vinyl aromatic hydrocarbon compound monomer, tertiary amine compounds, ether compounds, metal alcoholate compounds may be added as a modifier.

It is also possible to use only a single modifier alone or two or more modifiers in combination.

A compound represented by general formula R1R2R3N can be used as the tertiary amine compound of the modifier.

Here, in the above general formulas R1, R2 and R3 each show a hydrocarbon group with a carbon number of 1 to 20 or a hydrocarbon group with a tertiary amino group.

Although tertiary amine compounds are not limited to the following, e.g. For example: 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, N, N'-dioctyl-p-phenylenediamine, etc.

A linear ether compound, a cyclic ether compound, etc. can be used as the ether compound of the modifier.

Although the linear ether compounds are not limited to the following, e.g. Example: Dialkyl ether compounds of ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, etc.

Although the cyclic ether compounds are not limited to the following, e.g. For example: Tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxoranyl) propane, alkyl ether of furfuryl alcohol, etc.

Although the metal alcoholate compound of the modifier is not limited to the following, e.g. As sodium t-pentoxide, sodium t-butoxide, potassium t-pentoxide, potassium t-butoxide and so on.

The method for copolymerizing a conjugated diene compound monomer and a vinyl aromatic hydrocarbon compound monomer using an organic alkali metal compound as a polymerization initiator is not particularly limited, and both batch polymerization and continuous polymerization are possible or a combination of these is possible. From the viewpoint of adjusting the molecular weight distribution to a preferred appropriate range, the batch polymerization method is preferred.

Although the polymerization temperature is not particularly limited, it is usually 0 to 180 ° C, and preferably 30 to 150 ° C. The time required for the polymerization varies depending on the conditions, but is usually 48 hours or less, and preferably 0.1 to 10 hours.

It is further preferred to carry out polymerization in an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is carried out in a pressure range sufficient to maintain the monomers and the solvent in the liquid phase in the polymerization temperature range.

Furthermore, a coupling reaction can be carried out by adding a necessary amount of the coupling agent having two or more functional groups at the end of the polymerization. The coupling agent having two or more functional groups is not particularly limited, and known coupling agents can be used. Although the coupling agent having two functional groups is not limited to the following, e.g. Example: Dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane, and acid esters such as methylbenzoate, ethylbenzoate, phenylbenzoate, phthalic acid ester, etc.

Although the polyfunctional coupling agent having three or more functional groups is not limited to the following, e.g. For example: polyepoxy compounds such as trihydric or higher polyalcohols, epoxidized soybean oil, diglycidylbisphenol A etc., halogenated silicon compounds represented by general formula R ¹ _(4-n ) SiX _n , and halogenated tin compounds.

Here, in the general formula, R ^{1 stands} for a hydrocarbon group with 1 to 20 carbon numbers, X for a halogen and n for an integer of 3 or 4.

Although the halogenated silicon compounds are not limited to the following, e.g. For example: methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride and their bromides etc.

Although the halogenated tin compounds are not limited to the following, e.g. B. polyvalent halogen compounds such as methyltin trichloride, t-butyltin trichloride, tin tetrachloride, etc. are listed. Dimethyl carbonate, diethyl carbonate, etc. can also be used.

The hydrogenation catalyst used to prepare the hydrogenated block copolymer is not particularly limited, and for example, hydrogenation catalysts described in JP Patent Laid-Open No. S42-8704 B . JP Patent Laid-Open No. S43-6636 B . JP Patent Laid-Open No. S63-4841 B . JP Patent Laid-Open No. H1-37970 B . JP Patent Laid-Open No. H1-53851 B and JP Patent Laid-Open No. H2-9041 B etc. can be used.

Titanocene compounds and a mixture of these titanocene compounds and reducing organic metal compounds can be mentioned as preferred hydrogenation catalysts.

Although the titanocene compounds are not particularly limited, e.g. B. Connections are cited in JP Patent Laid-Open No. H8-109219 A are described. Specifically, the following can be mentioned: compounds with at least one ligand with a substituted or unsubstituted cyclopentadienyl structure, such as biscyclopentadienyltitanium dichloride and monopentamethylcyclopentadienyltitanium trichloride, etc., an indenyl structure and a fluorenyl structure.

Although the reducing organic metal compounds are not limited to the following, e.g. As organic alkali metal compounds such as organic lithium, organic magnesium compounds, organic aluminum compounds, organic boron compounds, organic zinc compounds, etc.

A known method can be used as the method of the hydrogenation reaction, the reaction temperature of the hydrogenation reaction usually being 0 to 200 ° C. and preferably 30 to 150 ° C.

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

The reaction time of the hydrogenation reaction is usually 3 minutes to 10 hours and preferably 10 minutes to 5 hours.

A batch process, a continuous process, or a combination thereof can be used for the hydrogenation reaction.

If necessary, a catalyst residue can be removed from the reaction solution after the end of the hydrogenation reaction.

For example, although the method for separating the hydrogenated block copolymer and the solvent is not limited to the following, e.g. For example, a method of adding a polar solvent such as acetone or alcohol, etc., which serves as a poor solvent for the hydrogenated block copolymer, into a solution of the hydrogenated block copolymer to precipitate and recover the hydrogenated block copolymer, or a method of adding a solution of the hydrogenated block copolymer in boiling water with stirring to remove and recover the solvent by steam stripping, a method of distilling off the solvent by directly heating a solution of the hydrogenated block copolymer, etc.

An antioxidant can also be added to the reaction solution in the preparation of the hydrogenated block copolymer (a).

Although the antioxidant is not limited to the following, e.g. As a phenol-based antioxidant, phosphorus-based antioxidant, sulfur-based antioxidant, amine-based antioxidant, etc.

Specifically, a. list: 2,6-di-t-butyl-4-methyl-phenol, n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butyl-phenyl) propionate, tetrakis [methylene -3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane], tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4,4'- Butylidene bis (3-methyl-6-t-butylphenol), 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -l, l-dimethylethyl ] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis- [3 - (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1, 3,5-triazine, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl -4-hydroxyphenyl) propionate], N, N'hexamethylenebis (3,5-di-t-butyl-4) -hydroxyhydrocinnamamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3, 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, a mixture of calcium bis (ethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate) ) and polyethylene wax (50%), octylated diphenylamine, 2,4-bis [(octylthio) methyl] -o-cresol, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, butyric acid, 3,3-bis (3-t-butyl-4-hydroxyphenyl) ethylene ester, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-tris (4-t-butyl) -3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl -phenyl acrylate and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-T-pentylphenyl acrylate.

(Polypropylene-based resin (b))

The thermoplastic elastomer composition of the present embodiment contains a polypropylene-based resin (b).

Although the polypropylene-based resin (b) is not limited to the following, e.g. For example, a propylene homopolymer, or a block copolymer or a random copolymer of propylene with an olefin other than propylene, preferably with an α-olefin having 2 to 20 carbon numbers, or mixtures thereof.

Although the α-olefin having 2 to 20 carbon numbers is not limited to the following, e.g. For example: ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene etc., it preferably being an α-olefin having 2 to 8 carbon numbers and more preferably ethylene, 1 -Butene, 1-hexene, 4-methyl-1-pentene.

For the polypropylene-based resin, only a single type can be used alone or two or more types can be used together.

In the case of the polypropylene-based resin (b), a melt flow rate (MFR), which was determined under the conditions of a temperature of 230 ° C. and a load of 2.16 kg, is preferably 0.1 to 50 g / 10 min, more preferably 0.5 to 45 g / 10 min, and more preferably 1.0 to 40 g / 10 min. If the MFR is in the above range, the formability tends to be improved.

For example, although the method for producing the polypropylene-based resin (b) is not limited to the following, e.g. B. the production process described above can be cited in which monomers are polymerized by means of a Ziegler-Natta type catalyst in which a titanium-containing solid transition metal component and an organic metal component are combined.

Although the titanium-containing solid transition metal component used for the Ziegler-Natta type catalyst is not limited to the following, e.g. For example: a solid component that contains titanium, magnesium and halogen as essential components and an electron donating compound as an optional component, or titanium trichloride. An aluminum compound can, for example, be mentioned as an organometallic component, although this is not restricted to this.

Further, although the polymerization process in the production of polypropylene-based resin (b) is not limited to the following, e.g. For example: sludge polymerization, gas phase polymerization, bulk polymerization, solution polymerization or a multi-stage polymerization process in combination of these, etc.

In these polymerization processes, only propylene is polymerized when a propylene homopolymer is obtained, and propylene and monomers other than propylene are polymerized when a copolymer is obtained.

In the thermoplastic elastomer composition of the present embodiment, the content of the polypropylene-based resin (b) is 10 to 50 parts by mass, preferably 13 to 50 parts by mass, and more preferably 15 to 45 parts by mass, based on 100 parts by mass of the hydrogenated block copolymer (a).

When the content of the polypropylene-based resin (b) is 10 parts by mass or more, good fluidity and excellent moldability and pitting properties are obtained in the thermoplastic elastomer composition of the present embodiment. When the content of the polypropylene-based resin (b) is 50 parts by mass or less, good impact resilience and flexibility, as well as excellent needlestick resistance, are obtained in the thermoplastic elastomer composition of the present embodiment.

(Polyphenylene ether resin (c))

The thermoplastic elastomer of the present embodiment may contain a polyphenylene ether resin (c).

The polyphenylene ether resin (c) is preferably a homopolymer and / or a copolymer having a repeating structural unit represented by the following general formula (I).

In the general formula (I), O represents oxygen atom.

R ² to R ⁵ each independently represent hydrogen, a halogen, a primary or secondary C1 to C7 alkyl group, a phenyl group, a C1 to C7 haloalkyl group, a C1 to C7 aminoalkyl group, a C1 to C7 hydrocarbyloxy group or halohydrocarbyloxy group (where at least two carbon atoms separate a halogen atom from an oxygen atom).

The manufacturing method of the polyphenylene ether resin (c) is not particularly limited, and known methods can be used. For example, manufacturing processes can be cited that are described in U.S. Patent No. 3306874 . U.S. Patent No. 3306875 . U.S. Patent No. 3,257,357 . U.S. Patent No. 3,257,358 . JP Patent Laid-Open No. S50-51197 A . JP Patent Laid-Open No. S52-17880 B and JP Patent Laid-Open No. S63-152628 B etc. are described.

For example, although the polyphenylene ether resin (c) is not limited to the following, homopolymers such as poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4- phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether) and poly (2,6-dichloro-1,4-phenylene ether) and copolymers with 2,6-dimethylphenol and other phenols (for example copolymers with 2,3,6-trimethylphenol and copolymers with 2-methyl-6-butylphenol, which in JP Patent Laid-Open No. S52-17880 B are described).

Among them, poly (2,6-dimethyl-1,4-phenylene ether) and copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or mixtures thereof, are preferred in view of industrial productivity and heat resistance.

Furthermore, the polyphenylene ether resin (c) can be a modified polyphenylene ether resin which is wholly or partly modified.

Here, the modified polyphenylene ether resin is a polyphenylene ether resin which is modified with at least one modifying compound whose molecular structure contains at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl group.

Although the modifying compounds having at least one carbon-carbon double bond and a carboxylic acid group or an acid anhydride group in the molecular structure are not limited to the following, e.g. B. maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and their acid anhydrides.

Among them, fumaric acid, maleic acid and maleic anhydride are preferred in view of compatibility between the hydrogenated block copolymer (a) and the polyphenylene ether resin (c), and fumaric acid and maleic anhydride are more preferable.

Compounds in which one or two of the two carboxyl groups of these unsaturated dicarboxylic acids are esterified can also be used.

Although the modified compounds having at least one carbon-carbon double bond and one glycidyl group in the molecular structure are not limited to the following, e.g. As allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, epoxidized natural fats and oils, etc. can be listed. Among them, glycidyl acrylate and glycidyl methacrylate are preferred.

Although the modified compounds having at least one carbon-carbon double bond and one hydroxyl group in the molecular structure are not limited to the following, e.g. For example, unsaturated alcohols such as allyl alcohol, 4-penten-1-ol and 1,4-pentadien-3-ol etc., represented by the general formula C _n H _2n-3 OH (n is a positive integer) are unsaturated alcohols represented by general formulas C _n H _2n-5 OH, C _n H _2n-7 OH (n is a positive integer).

For the above various modified compounds, only a single type can be used alone or two or more types can be used in combination.

The addition rate of the modified compound of the modified polyphenylene ether resin (c) is preferably 0.01 to 5% by mass, and more preferably 0.1 to 3% by mass. If the amount of the polymer of the unreacted modified compound and / or modified compound in the modified polyphenylene ether resin (c) is less than 1% by mass, it may remain.

The reduced viscosity ηsp / C (0.5 g / dl, chloroform solution, measured at 30 ° C.) of the polyphenylene ether resin (c) is preferably in the range from 0.15 to 0.70 dl / g, more preferably in the range from 0.20 to 0.60 dl / g and more preferably in the range of 0.25 to 0.50 dl / g.

When the reduced viscosity of the polyphenylene ether resin (c) is 0.15 dl / g or more, good recoverability tends to be obtained in the thermoplastic elastomer composition of the present embodiment and when it is 0.70 dl / g or less , excellent workability tends to be obtained.

The reduced viscosity of the polyphenylene ether resin (c) can be controlled to the above numerical range by adjusting the kind of the catalyst, the polymerization time and the polymerization temperature in the manufacturing process of the polyphenylene ether resin (c).

In the present embodiment, two or more polyphenylene ether resins having different reduced viscosities can be mixed, and the whole can be used as the polyphenylene ether resin (c). In this case, the reduced viscosity of the mixture after mixing several polyphenylene ether resins is preferably in the range from 0.15 to 0.70 dl / g, the reduced viscosity of individual polyphenylene ether resins not in the range from 0.15 to 0.70 dl / g got to.

The reduced viscosity of the polyphenylene ether resin (c) can be measured by the method described in the exemplary embodiments described later.

The number average molecular weight Mn of the polyphenylene ether resin (c) is further preferably 1,000 to 50,000, more preferably 1,500 to 50,000, and more preferably 1,500 to 30,000. If the number average Molecular weight of the polyphenylene ether resin (c) is in the above range, there is a tendency that a thermoplastic elastomer composition with an even better recoverability is obtained.

The number average molecular weight of polyphenylene ether resin (c), like the above hydrogenated block copolymer (a), can be based on the molecular weight of the peak of the chromatogram measured by GPC, and using the calibration curve obtained from the measurement of commercially available standard polystyrene (generated under Using the peak molecular weight of standard polystyrene).

Only a single type can be used for the polyphenylene ether resin (c) or the polyphenylene ether resin (c) modified to improve processability by mixing with resins such as polystyrene-based resins or polypropylene-based resins.

Although the polystyrene-based resins are not limited to the following, e.g. Example: Universal polystyrene (GPPS), impact-resistant polystyrene (HIPS) reinforced with a rubber component, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer other than hydrogenated block copolymer (a) used in this embodiment, styrene- Maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-methyl methacrylate copolymer. These copolymers can be both random copolymers and block copolymers.

For example, although the polypropylene-based resin is not limited to the following, e.g. For example, block copolymers or statistical copolymers of propylene with olefins other than propylene, preferably with α-olefin having 2 to 20 carbon numbers, or a mixture of these.

In the thermoplastic elastomer composition of the present embodiment, the content of the polyphenylene ether resin (c) based on the hydrogenated block copolymer (a) is 100 parts by mass, preferably 5 to 100 parts by mass. It is more preferably 10 to 90 parts by mass, more preferably 20 to 85 parts by mass and more preferably 30 to 85 parts by mass.

If the content of the polyphenylene ether resin (c) is 5 parts by mass or more, sufficient recoverability and impact resilience are obtained. When the content of the polyphenylene ether resin (c) is 100 parts by mass or less, good moldability of the thermoplastic elastomer composition tends to be obtained.

From the viewpoint of odor reduction, it is preferable that no polyphenylene ether resin (c) is contained or the content is low, the content being preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and more preferably 1 part by mass or less, and it more preferably, it is not included.

Even if the polyphenylene ether resin (c) is contained, the odor can be reduced by using an inorganic porous adsorbent (f) described later, so that in this case a thermoplastic elastomer composition having a low odor can be obtained even if the content is 10 Parts by mass exceeds. However, the filler that is not surface-treated may have poor compatibility with the resin, and containing the inorganic porous adsorbent (f) that is not surface-treated may deteriorate the liquid tightness. Therefore, in order to obtain a thermoplastic elastomer composition for a medical plug with a low odor and also a low liquid leakage, it is preferable that the content of the polyphenylene ether resin (c) and also the addition amount of the inorganic porous absorbent (f) which is not surface-treated are lower ,

(Non-aromatic plasticizer (d))

The thermoplastic elastomer composition of the present embodiment contains a non-aromatic plasticizer (d).

Because the plasticizer is non-aromatic, a thermoplastic elastomer composition which has a good color tone and is suitable for hygiene and safety as well as for food and medical applications tends to be easily obtained.

In addition, the use of the non-aromatic plasticizer is also useful from the viewpoint of heat resistance, although aromatic plasticizers tend to enter the aromatic vinyl block and deteriorate the heat resistance of the thermoplastic elastomer composition.

The non-aromatic plasticizer (d) is not particularly limited as long as it shows no aromaticity and can soften the hydrogenated block copolymer. In the "softening" of the hydrogenated block copolymer, it can be assumed that the plasticizer does not destroy the aromatic vinyl block of the hydrogenated block copolymer and is in the state of being incorporated and compatible in the conjugated diene block. Although the plasticizer is not limited to the following, e.g. As paraffinic oils, naphthenic oils, paraffin wax, liquid paraffin, white mineral oil, plant-based plasticizers, etc. are listed. Among them, paraffin oil, liquid paraffin, and white mineral oil are preferred in view of the low temperature properties and the extraction resistance of a stopper for a medical container containing the thermoplastic elastomer composition of the present embodiment.

The kinematic viscosity of the non-aromatic plasticizer (d) at 40 ° C is preferably 500 mm ² / s or less. Although the lower limit of the kinematic viscosity of the non-aromatic plasticizer (d) is not particularly limited at 40 ° C, it is preferably 10 mm ² / s or more.

When the kinematic viscosity of the non-aromatic plasticizer (d) at 40 ° C is 500 mm ² / s or less, the fluidity of the thermoplastic elastomer composition of the present embodiment is improved so that the moldability tends to be improved.

The kinematic viscosity of the non-aromatic plasticizer (d) can be measured with a glass capillary viscometer.

Suitable non-aromatic plasticizers (d) are those which contain a non-aromatic plasticizer (d-1) with a kinematic viscosity at 40 ° C. in the range from 300 to 400 mm ² / s.

When the non-aromatic plasticizer (d) contains a non-aromatic plasticizer (d-1) having a kinematic viscosity at 40 ° C in the above range, the thermoplastic elastomer composition of this embodiment has a good retention property of the non-aromatic plasticizer, that is, the oil retention property, and also the balance between recoverability and impact resilience tends to be improved.

As a non-aromatic plasticizer (d), it is furthermore expedient to use a plasticizer which contains a non-aromatic plasticizer (d-2) with a kinematic viscosity at 40 ° C. of 100 mm ² / s or less.

When the non-aromatic plasticizer (d) contains a non-aromatic plasticizer (d-2) having a kinematic viscosity at 40 ° C of 100 mm ² / s or less, a thermoplastic elastomer composition with better flexibility and moldability tends to be obtained while maintaining good oil retention property ,

Furthermore, two or more non-aromatic plasticizers with different kinematic viscosities at 40 ° C. can be combined as non-aromatic plasticizers (d).

For example, the non-aromatic plasticizer (d-1) and the non-aromatic plasticizer (d-2) can be used in combination.

By combining the non-aromatic plasticizer (d-1) and the non-aromatic plasticizer (d-2), the retention property of the non-aromatic plasticizer can be improved, while also tending to further improve the balance between flexibility, recoverability, shock resilience, and moldability.

When the non-aromatic plasticizer (d-1) and the non-aromatic plasticizer (d-2) are used in combination, the mass ratio of ((d-1) / (d-2)) between the non-aromatic plasticizer (d-1) and the non-aromatic plasticizer (d-2) preferably 30/70 to 60/40, more preferably 35/75 to 60/40 and more preferably 40/60 to 60/40.

When the mass ratio (d-1) / (d-2) is in the range of 30/70 to 60/40, it is preferred because the balance between flexibility, recoverability, shock resilience and moldability tends to be further improved.

In the thermoplastic elastomer composition of the present embodiment, the content of the non-aromatic plasticizer (d) based on 100 parts by mass of the hydrogenated block copolymer (a) is 75 to 200 parts by mass, preferably 95 to 190 parts by mass, and more preferably 115 to 180 parts by mass.

If the content of the non-aromatic plasticizer (d) is in the above range, the retention property of the non-aromatic plasticizer (d) can be improved still further, and an elastomer composition with better moldability and recoverability tends to be obtained.

In the case of a combination of two or more non-aromatic plasticizers with different kinematic viscosity at 40 ° C, the total content of the total non-aromatic plasticizer (d), e.g. B. the total content of the non-aromatic plasticizer (d-1) and the non-aromatic plasticizer (d-2) based on 100 parts by mass of the hydrogenated block copolymer (a) 75 to 200 parts by mass, preferably 95 to 190 parts by mass and more preferably 115 to 180 parts by mass.

If the total content of the entire non-aromatic plasticizer (d) is in the above range, the properties of both or more non-aromatic plasticizers that are combined tend to develop well.

In the present embodiment, it is more preferable that the non-aromatic plasticizer (d) is a mixture of the non-aromatic plasticizer (d-1) with a kinematic viscosity at 40 ° C of 300 to 400 mm ² / s and the non-aromatic plasticizer (d- 2) with a kinematic viscosity at 40 ° C of 100 mm ² / s or less, the weight ratio ((d-1) / (d-2)) of the non-aromatic plasticizer (d-1) and the non-aromatic plasticizer (i.e. -2) 30 / 70-60 / 40 and the total content of the non-aromatic plasticizer (d-1) and the non-aromatic plasticizer (d-2) based on 100 parts by mass of the hydrogenated block copolymer (a) is 100 to 200 parts by mass.

(Surface treated inorganic filler (s))

The thermoplastic elastomer composition of the present embodiment contains surface-treated silica as an inorganic filler (s) in view of the needle retention property.

In the thermoplastic elastomer composition of the present embodiment, surface-treated silica is used as the inorganic filler (s), but the thermoplastic elastomer composition may additionally contain other inorganic fillers.

Other inorganic fillers can e.g. B. both non-surface-treated silicic acid, and also non-surface-treated or surface-treated talc, calcium carbonate, calcium oxide, zinc carbonate, wollastonite, zeolite, wollastonite, aluminum oxide, clay, titanium oxide, magnesium hydroxide, magnesium oxide, sodium silicate, calcium silicate, magnesium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, Zinc oxide, potassium titanate, hydrotalcite, sulfuric acid barium, titanium black etc. or carbon black such as furnace black, thermal black, acetylene black etc.

There is a tendency that when surface-treated inorganic fillers are added other than inorganic fillers, the interfacial adhesion between the hydrogenated block copolymer and the polypropylene-based resin is good, so that the interfaces rarely peel off with little energy loss, so that good resealability is obtained. On the other hand, if the non-surface-treated filler is added, the interfacial adhesion is poor, whereby the composition can easily tear, so that the needlestick resistance tends to be reduced.

In view of the reclosability, etc., of a plug for a medical container containing the thermoplastic elastomer composition of the present embodiment, among them, surface-treated talc, calcium carbonate and clay are preferred, and talc and calcium carbonate are more preferred.

When the thermoplastic elastomer composition of the present embodiment is used as a material of a rubber stopper of a medical container, it is believed that steam sterilization treatment is carried out at about 110 ° C to 121 ° C in a state in which this rubber stopper is installed in a cap or holder becomes. If the dimensions of the rubber stopper change due to heating, there is a risk that a sufficient caulking effect cannot be obtained.

The present inventors have found that a surface-treated silica is used as the inorganic filler (s), which, when this thermoplastic elastomer composition is used as a rubber stopper of a medical container, can prevent deterioration in the resealability after the steam sterilization treatment.

By observing the surface condition before and after the surface treatment using microscopic IR, it can be determined whether the silica has been “surface treated”. In the non-surface-treated state, the surface of the silica is covered with a hydrophilic group and the compatibility with the hydrocarbon resin and / or the hydrogenated block copolymer is not high. On the other hand, when the silica is surface-treated with a fatty acid, etc., the surface is modified with a hydrocarbon, so that the compatibility with the hydrocarbon resin and / or the hydrogenated block copolymer is improved. This improves the dispersion of the silica in the hydrocarbon resin and / or the hydrogenated block copolymer and also improves the adhesion of the interface.

Inorganic fillers other than silica can also be observed in terms of surface condition by the same method as described above.

As a method for obtaining an inorganic filler (e), there can be mentioned a method of bringing the surface treatment agent and / or the solution thereof into contact with the surface of silica.

If the surface treatment agent e.g. B. is a fatty acid, a resin acid, a fat or oil, or a surfactant, a powdery surface treatment agent is mixed with silica as a dry treatment and using a pulverizing mill such as a heated ball mill or roller mill, or using a mixer such as a belt mixer or a Henschel mixer, etc. crushed, melted and chemically reacted to carry out the surface treatment.

If a non-water-soluble surface treatment agent having a high melting point is used, it is brought into an emulsion state or injected as a solution dissolved in alcohol into the pulverizer or the mixer and stirred / mixed with the silica and then dried to carry out the surface treatment.

As a wet treatment, a surface treatment agent is added to the sludge in the silica synthesis and stirred with heating by means of a mixer, etc., in order to carry out the surface treatment of the silica. When a surface treatment agent having a high melting point is used, the surface treatment is carried out by using it in the emulsion state and also adding and stirring it in the synthesis of silica.

When a water-soluble coupling agent is used as the surface treatment agent, a liquid mixture of water and ethanol is usually subjected to pH control, then the coupling agent is added to this solution, and this is sprayed into a heated quick-stirring mixer containing silica, such as a Henschel mixer, thereby a chemical reaction with the surface of the silica and the surface treatment takes place. When a water-insoluble coupling agent is used as the surface treatment agent, the coupling agent is dissolved in acetone, alcohol, etc., and sprayed as described above into a heated, high-speed mixer containing silica, such as a Henschel mixer, to carry out the surface treatment of silica.

The surface treatment can be carried out using the same method with materials other than silica.

As the surface treatment agent, fatty acids, resin acids, oils and fats, surfactants, silicone oils, coupling agents (silanes, titanium, phosphoric acids, carboxylic acids, etc.) are representative, but it is not these are restricted as long as it can act on the surface of silica and as required by other inorganic fillers.

Although fatty acid is not limited to the following, e.g. For example, saturated fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and their metal salts, and modified products thereof; as well as unsaturated fatty acids such as oleic acid, linoleic acid, erucic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, eicosatetraenoic acid, tetracosapentaenoic acid and docosahexaenoic acid and their metal salts, and modified products thereof.

Although the resin acid is not limited to the following, e.g. As rosin, which consists mainly of abietic acid, neoabietic acid, parastric acid, pimaric acid, isopimaric acid, dehydroabietic acid, etc., and derivatives of these are listed.

Although the fats and oils are not limited to the following, e.g. B. soybean oil, linseed oil, coconut oil, safflower oil, etc. are listed.

Although surfactant is not limited to the following, e.g. For example: fatty acid type anionic surfactant such as sodium stearate, potassium stearate; Polyoxyethylene alkyl ether sulfate esters, long chain alcohol sulfuric acid esters, etc. and their sodium salts, sulfate ester type anionic surfactant such as potassium salts; Alkyl benzene sulfonate, alkyl naphthalene sulfonate, paraffin sulfonate, α-olefin sulfonate, alkyl sulfosuccinate, etc. and their sodium salts, sulfonic acid type anionic surfactants such as potassium salts, etc .; and nonionic surfactants such as polyethylene glycol, polyvinyl alcohol and their derivatives, etc.

Although silicone oil is not limited to the following, e.g. For example: dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxy-modified silicone oil, carbinol-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, etc.

Although silane coupling agent is not limited to the following, e.g. B. Listed: alkyl group-containing silane coupling agents such as dimethyldichlorosilane, trimethylchlorosilane, dimethyldimethoxysilane, trimethylmethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysiloxysilane, hexyltrilysilane, hexyltrilysilane, Phenyl group-containing silane coupling agents such as phenyltrichlorosilane, phenyltrimethoxysilane and phenyltriethoxysilane; Silane coupling agents containing vinyl groups such as vinyltrimethoxysilane and vinyltriethoxysilane; Silane coupling agents containing styryl groups such as p-styryltrimethoxysilane; Silane coupling agents containing epoxy groups such as 3-glycidoxypropylmethyldimethoxysilane; Silane coupling agents containing methacrylic groups such as 3-methacryloxypropylmethyldimethoxysilane, silane coupling agents containing acrylic groups such as 3-acryloxypropylmethyldimethoxysilane; and silane coupling agents containing amino groups such as hexamethyldisilazane and N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, etc.

Although the titanium-based coupling agent is not limited to the following, e.g. B. be cited: Titanisostearat, tetrastearyl titanate, tetraisopropyl titanate, isopropyltriisostearoyl titanate, Titanoctylenglykolatverbindung, Titandiethanolaminat, Titanaminoethylaminoethanolat, bis (dioctylpyrophosphate) oxyacetate titanate, tris (dioctyl pyrophosphate) ethylene, Isopropyldioctylpyrophosphat titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyl tris (dodecylbenzenesulfonyl) titanate, tetra -n-butyltitanate, tetra-2-ethylhexyltitanate, tetraoctylbis (ditridecylphosphite) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, etc.

Although the phosphoric acid-based coupling agent is not limited to the following, e.g. B. be cited: phosphate triesters such as tributyl phosphate, Tripentylphosphat, trihexylphosphate, Triheptylphosphat, trioctyl phosphate, Torinonylphosphat, tridecyl, Triundecylphosphat, tridodecylphosphate, Tritridecylphosphat, Tritetradecylphosphat, Tripentadecylphosphat, Trihexadecylphosphat, Triheptadecylphosphat, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, xylenyldiphenyl ; acid Phosphatester such as mono butyric acid phosphate, Monopentylsäurephosphat, Monohexylsäurephosphat, Monoheptylsäurephosphat, Monooctylsäurephosphat, Monononylsäurephosphat, Monodecylsäurephosphat, Monoundecylsäurephosphat, Monododecylsäurephosphat, Monotoridecylsäurephosphat, Monotetradecylsäurephosphat, Monopentadecylsäurephosphat, Monohexadecylsäurephosphat, Monoheptadecylsäurephosphat, Monooctadecylsäurephosphat, monooleyl, Dibutylsäurephosphat, Dipentylsäurephosphat, Dihexylsäurephosphat, Diheptyl Acid Phosphate, Dioctyl Acid Phosphate, Dinonyl Acid Phosphate, Didecyl Acid Phosphate, Diundecyl Acid Phosphate, Didodecyl Acid Phosphate, Ditridecyl Acid Phosphate, Ditetradecyl Acid Phosphate, Dipentadecyl Acid Phosphate, Dihexadecyl Acid Phosphate, Diheecadyl Acid Phosphate Thiophosphoric esters such as Tributylphosphorothionat, Tripentylphosphorothionat, Trihexylphosphorothionat, Triheptylphosphorothionat, Trioctylphosphorothionat, Torinonylphosphorothionat, Tridecylphosphorothionat, Triundecylphosphorothionat, Tridodecylphosphorothionat, Tritridecylphosphorothionat, Tritetradecylphosphorothionat, Tripentadecylphosphorothionat, Trihexadecylphosphorothionat, Triheptadecylphosphorothionat, Trioctadecylphosphorothionat, Trioleylphosphorothionat, triphenylphosphorothionate, Tricresylphosphorothionat, Trixylenylphosphorothionat, Kresyldiphenylphosphorothionat, Xylenyldiphenylphosphorothionat; chlorinated phosphate esters such as tris-dichloropropyl phosphate, trischloroethyl phosphate, tris-chlorophenyl phosphate, polyoxyalkylene bis [di (chloroalkyl)] phosphate; Phosphite esters such as dibutyl, Dipentylphosphit, dihexyl, diheptyl, dioctylphosphite, Dinonylphosphit, didecyl, Diundecylphosphit, Didodecylphosphit, dioleyl phosphite, diphenyl phosphite, dicresyl, tributyl, tripentylphosphite, trihexyl, Triheptylphosphit, trioctyl, Turinonylphosphit, tridecyl, Triundecylphosphit, tridodecyl, trioleyl, triphenylphosphite, Tricresylphosphite etc ,

Although the carboxylic acid coupling agent is not limited to the following, e.g. For example, carboxylated polybutadiene and its hydrogenated product, carboxylated polyisoprene and its hydrogenated product, carboxylated polyolefin, carboxylated polystyrene, carboxylated styrene-butadiene copolymer and hydrogenated product thereof, and carboxylated nitrile rubber.

When the thermoplastic elastomer composition of the present embodiment is used as a stopper, particularly as a material of a stopper of a medical container, a silane coupling agent is preferable as a surface treatment agent from among the resealability after the steam sterilization treatment, with a trimethylsilylsilane coupling agent and a dimethylsilylsilane coupling agent being further preferred.

As described above, the surface treatment tends to improve the interfacial adhesion between the silica and the hydrogenated block copolymer (a) or the polypropylene-based resin (b), particularly by using the trimethylsilylsilane coupling agent and the dimethylsilylsilane coupling agent as a surface treatment agent for silica Peeling at the interface can be further prevented. It can be assumed that this is due to chemical bonding of the trimethylsilylsilane coupling agent and the dimethylsilylsilane coupling agent with the silica.

As other inorganic fillers which are combined with the surface-treated silica in the thermoplastic elastomer of the present embodiment, from the viewpoint of the resealability after the steam sterilization treatment, there is a calcium carbonate treated with a fatty acid or a modified product thereof.

In the thermoplastic elastomer composition of the present embodiment, the content of the surface-treated silica which is the inorganic filler (e) based on 100 parts by mass of the hydrogenated block copolymer (a) is 1 to 150 parts by mass, preferably 3 to 130 parts by mass, more preferably 5 to 110 parts by mass , more preferably 10 to 100 parts by mass, and more preferably 15 to 90 parts by mass.

When the content of the surface-treated silica which is the inorganic filler (e) is in the above range, a plug, particularly a plug used for a medical container, which comprises the thermoplastic elastomer composition of the present embodiment tends to be excellent Needle retention property is obtained.

The average primary particle size of the silica as an inorganic filler (e) is preferably 0.001 μm to 2 μm.

A more preferred upper limit of the average primary particle size is 1 µm and more preferably 0.05 µm. A more preferred lower limit of the average primary particle size is 0.01 µm. and more preferably 0.015 µm.

The fact that the average primary particle size of the silica as an inorganic filler (s) is 0.001 μm or more, has the effect of increasing the flexibility of the thermoplastic Obtaining the elastomer composition, and by being 2 µm or less, the effect of increasing the uniform dispersibility in the thermoplastic elastomer composition is obtained.

In the thermoplastic elastomer composition of the present embodiment, as described above, in addition to the surface-treated silica, an inorganic filler that is not subjected to the surface treatment can be used in combination as another inorganic filler.

By adding the non-surface-treated inorganic filler to reduce the adhesion of the interface, the effect of reducing the needlestick resistance can be expected. With regard to the amount of the non-surface-treated inorganic filler added, the upper limit in terms of maintaining good resealability is preferably about half of the total inorganic filler added.

(Inorganic porous absorbent (f))

The thermoplastic elastomer composition of the present embodiment may also contain an inorganic porous adsorbent (f) in view of improving the smell.

As the inorganic porous adsorbent (f) is preferably a powdery porous inorganic compound having a specific surface area of 50 m ² / g or more according to the BET method, although, although not limited to the following, it is e.g. For example: not only zeolite, ie the component that mainly consists of SiO ₂ and Al ₂ O ₃ and simply consists of the mixture of these, but the component that has a three-dimensional crystal structure as a single compound, specifically with aluminosilicates a composite structure represented by the following Formula II; Composites of SiO ₂ and Al ₂ O ₃ with other metal oxides or metal salts (not a simple mixture, but with a three-dimensional crystal structure as a single compound); a porous silica, such as silica gel or mesoporous silica; Activated carbon, porous ceramics such as γ-aluminum oxide or θ-aluminum oxide and titanium oxide in nano size.

For these inorganic compounds, only a single type or two or more types can be used in combination.

Among them, in the case of use for a stopper of a medical container with a view to improving odor, zeolite; a composite of SiO ₂ , Al ₂ O ₃ and other metal oxides or metal salts is preferred. (M ^I , M ^II _1/2 ) _m (Al _m Si _n O _{2 (m + n)} ) xH ₂ O (II) (where M ^{I is} a monovalent metal cation such as Li ⁺ , Na ⁺ , K ⁺ etc., M ^{II is} a divalent metal cation such as Ca ²⁺ , Mg ²⁺ , Ba ²⁺ etc., and these are identical or different from one another in the multiplicity n and m are each an integer of 2 or more, where n ≥ m.)

The specific surface area of the inorganic porous adsorbent (f) according to the BET method is preferably 50 m ² / g or more, more preferably 100 m ² / g or more and more preferably 200 m ² / g or more.

The thermoplastic elastomer composition of the present embodiment uses surface-treated silica as the inorganic filler (e), and this silica has a specific surface area which is approximately equal to the above numerical value, so that the silica which is the inorganic filler (e) can function as an adsorbent , even if the inorganic porous adsorbent (f) is not added separately.

If a higher adsorption performance is required, it is preferred to continue to add an adsorbent with a higher specific surface area such as porous silica as the inorganic porous adsorbent (f). The specific surface area of the porous silica as this inorganic porous adsorbent (f) is preferably 400 m ² / g or more, more preferably 600 m ² / g or more, and more preferably 800 m ² / g or more.

In the thermoplastic elastomer composition of the present embodiment, the content of the inorganic porous adsorbent (f) is 100 parts by mass of the hydrogenated one Block copolymer (a) preferably 1 to 30 parts by mass, more preferably 3 to 30 parts by mass, more preferably 4 to 25 parts by mass and still more preferably 5 to 20 parts by mass.

When the mixing amount of the inorganic porous adsorbent (f) is in the above range, there is a tendency to obtain a thermoplastic elastomer composition which further improves the smell of the plug of the present embodiment.

(Organic peroxide (g))

The thermoplastic elastomer composition of the present embodiment may be partially crosslinked for recoverability in the presence of the organic peroxide (g).

Although the organic peroxide (g) is not limited to the following, e.g. For example: 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumylperoxide-2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, t-butylcumylperoxide, diisopropylbenzene hydroxyperoxide, 1,3-bis (t-butylperoxyisopropyl) benzene, benzoyl peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, di -t-butyl peroxide, 1,1-di-t-butylperoxy-cyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexy-3, n-butyl-4,4-bis (t-butylperoxy ) valerate, t-butyl peroxy isobutyrate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy isopropyl carbonate, etc.

Of these, only a single type can be used alone, or two or more organic peroxides can be used in combination.

The amount of the organic peroxide (g) used is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 4 parts by mass and more preferably 0.3 to 3 parts by mass based on 100 parts by mass of the hydrogenated block copolymer (a).

When the amount of the organic peroxide (g) used is in the above range, a thermoplastic elastomer composition excellent in recoverability tends to be obtained without reducing the processability.

(Crosslinking aid (h))

Further, when the thermoplastic elastomer composition of the present embodiment is partially crosslinked, a crosslinking aid may have been used, if necessary, to adjust the degree of crosslinking.

Although the crosslinking aid (h) is not limited to the following, e.g. For example: Trimethylolpropane triacrylate, triallyl isocyanurate, triallyl cyanurate, triallyl formal, triallyl trimellitate, N, N'-m-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate, triallyl phosphate, divyl benzyl methacrylate, ethylenedimethyl methacrylate, polyethylenedimethacrylate, divinyl benzyl methacrylate acrylates, unsaturated silane compounds (e.g. vinyl trimethoxysilane, vinyl triethoxysilane, etc.) etc.

Of these, only a single type can be used alone, or, if necessary, two or more types can be used together.

The amount of the crosslinking aid (h) used is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, more preferably 0.5 to 7 parts by mass, based on 100 parts by mass of the hydrogenated block copolymer (a).

(Other components)

In addition to the above-mentioned components (a) to (h), the thermoplastic elastomer composition of the present embodiment may also contain further additives to an extent that the purpose of the present embodiment is not neglected.

Other additives that can be mentioned are: heat stabilizers, antioxidants, UV absorbers, anti-aging agents, plasticizers, light stabilizers, nucleating agents, impact modifiers, pigments, Lubricants, antistatic agents, flame retardants, flame retardants, protective agents, the phase volume agents, and tackifiers, etc.

In particular, the addition of silicone oil as a lubricant improves the lubricity and is effective in reducing the needlestick resistance and improving the coring.

As the type of silicone oil, general dimethylpolysiloxane, phenylmethylpolysiloxane, etc. can be mentioned, with dimethylpolysiloxane being particularly preferred.

The amount of silicone oil added is preferably 0.5 to 10 parts by mass, more preferably 0.7 to 7 parts by mass, and more preferably 1.0 to 5 parts by mass based on 100 parts by mass of the hydrogenated block copolymer (a). There is no particular limitation on the kinematic viscosity of the silicone oil, but it is preferably 10 to 10000 mm ² / sec, more preferably 50 to 7000 mm ² / sec, and more preferably 100 to 5000 mm ² / sec.

Of these additives, only a single type can be used alone, or two or more can be used in combination.

(Properties of the thermoplastic

Elastomer composition)

The thermoplastic elastomer composition of the present embodiment preferably has a Shore A hardness of 55 or less and a pin puncture resistance of 4.0 kgf or less in terms of flexibility, elongation recovery, needle penetration, and liquid tightness, and it is more preferable that the Shore A hardness 55 or less, the tear strength measured according to JIS K6252 is 45 N or less, and the needle stick resistance is 4.0 kgf or less.

For the needlestick resistance, a stopper made of the thermoplastic elastomer of the present embodiment is attached upward to a PET bottle by means of a tensile tester TG-5kN (manufactured by Minebea Co., Ltd.), and a resin needle (plastic bottle needle) with a diameter (a maximum Root diameter) of 5 mm at a speed of 200 mm / min through the center of the stopper 1 from above, the value with the measured maximum load at this time being taken as the needlestick resistance.

When the Shore A hardness is 55 or less, the tensile strength is 45 N or less, and the pin puncture resistance is 4.0 kgf or less, sufficient flexibility and pin puncture penetration tend to be obtained more reliably and excellent liquid tightness is also obtained ,

From the same point of view, more preferably, the Shore A hardness is 53 or less, the tear strength is 42 N or less, and the pinprick resistance is 3.7 kgf or less, and more preferably, the Shore A hardness is 50 or less, the tear strength is 38 N or less, and the needle stick resistance is 3.5 kg or less.

Although there is no lower limit, the Shore A hardness is preferably 20 or more, the tensile strength 20 N or more, and the needlestick resistance is 1.0 kgf or more.

The Shore A hardness, tear strength and needlestick resistance can be measured using the methods described in the exemplary embodiments below.

In the thermoplastic elastomer of the present embodiment, the content of the hydrogenated block copolymer (a), the polypropylene-based resin (b), and the non-aromatic plasticizer (d), the structure such as content or molecular weight of the monomer unit of the vinyl aromatic hydrocarbon compound in the hydrogenated block copolymer (a ), or the molecular weight, the MFR, the viscosity, etc. of the components (b) to (c), whereby the Shore A hardness, the tear strength and the needle stick resistance can be controlled to the above numerical range.

Furthermore, the thermoplastic elastomer composition of the present embodiment has an odor intensity of preferably 3 or less in view of low-odor and low extractability and more preferably 2.5 or less according to a "six-step odor intensity display method" (an administrative manual for prevention of bad odor published in April 2002 by the Ministry of the Environment, Office for Environmental Management, Room for Atmosphere, Life, Environment).

The odor intensity can be measured by the method described in the exemplary embodiments described later.

(Process for producing a thermoplastic elastomer composition)

There is no particular limitation on methods of manufacturing the thermoplastic elastomer composition of the present embodiment, and a conventionally known method is applicable.

For example, a method of melting and kneading using a general mixing machine such as pressure kneader, Banbury mixer, internal mixer, laboplast mill, mixing laboratory, single screw extruder, twin screw extruder, Conida, multi-screw extruder, etc., and a method of heating and removing a solvent after dissolving or dispersing and Mixing each component, etc.

When the thermoplastic elastomer composition of the present embodiment is partially crosslinked with the above-mentioned organic peroxide (g), the composition of components (a) to (f) and the partially crosslinked with the organic peroxide (g) (and a crosslinking aid added if necessary (h)) are carried out simultaneously or, depending on the composition of components (a) to (f), the organic peroxide (g) and, if necessary, a crosslinking aid (h) are added in order to partially crosslink.

Furthermore, after mixing and crosslinking a part of component (a) to component (f), the organic peroxide (g) and, if necessary, the crosslinking aid (h), the remaining components can be mixed.

Partial crosslinking can be carried out at a temperature at which decomposition of the organic peroxide (g) used occurs, and generally at a temperature condition of 150 to 250 ° C.

When the composition of a part or the whole of the components (a) to (f) and the crosslinking with the organic peroxide (g) (and a crosslinking aid (h) added if necessary) are carried out simultaneously, the composition can u. a. were carried out by means of the melt kneader at a temperature at which decomposition of the organic peroxide (g) used occurred.

[Stopper and container]

The plug of the present embodiment contains the thermoplastic elastomer composition of the present embodiment, and the container of the present embodiment includes the plug of the present embodiment.

(Usage)

The plug of the present embodiment is preferably used for a medical airtight container or a sealed container, and in the case of the use of piercing an injection needle in a representative embodiment, a cylindrical plug is inserted into a substantially cylindrical lid or a predetermined tool and integrally with the lid or the tool is used.

Although the tool is not limited to the following, e.g. For example, cite: a predetermined frame, a cap, a case, a sealing material, etc. Specifically, a shape is cited in which it is used as a cap of an infusion bag.

In contrast, the cylindrical stopper can be used alone, where it is inserted into the opening of a glass bottle and acts as a stopper.

In the case where an injection needle is not pierced, a disc-shaped plug is inserted into the inner surface of the lid of the container, which can be sealed by a screw or the like, thereby contributing to improving the sealing property.

The container of the present embodiment includes the stopper of the present embodiment.

An airtight container or a sealed container is preferable as a container for medical use, although, although not limited to the following, for example, an infusion bag, peritoneal dialysis bag, infusion bottle, soft infusion bottle, glass vial, plastic vial, etc.

The shape of the plug of the present embodiment is not particularly limited, but e.g. B. a truncated cone, a column and a disc, the diameter of which is usually about 5 to 25 mm. The thickness of the plug of the present embodiment, i.e. H. the thickness in the direction of piercing the hypodermic needle is also not particularly limited in the purpose of piercing the hypodermic needle, and is usually about 2 to 10 mm.

(Process for producing the stopper)

The above stopper is not particularly limited, but can be manufactured, for example, by injection molding, compression molding, stamping by extrusion, or the like.

From the standpoint of dimensional accuracy and reproducibility of the surface roughness, it is preferable to manufacture by injection molding.

[Embodiments]

The present embodiment is explained in detail below using specific exemplary embodiments and comparative examples, but the present embodiment is not restricted to the following exemplary embodiments.

First, evaluation methods and measurement methods for physical properties applied to the embodiments and comparative examples are shown below.

(Evaluation method for hydrogenated block copolymer (a))

(Weight average molecular weight, number average molecular weight, molecular weight distribution)

The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (a) were determined using a calibration curve obtained from a measurement of a commercially available standard polystyrene (generated under Using the peak molecular weight of a standard polystyrene), and determined on the basis of the molecular weight of the peak of the chromatogram.

The HLC-8320 ECOSEC collection was used as measurement software and the HLC-8320 ECOSEC analysis as analysis software.

(Measurement Conditions)

• GPC; HLC-8320GPC (manufactured by Tosoh Corporation) detector; RI
• Detection sensitivity; 3 MV / min
• Sensing; 600 MSEC
• Pillar; 4 TSK GEL SUPER HZ M-N (6 MMI.D × 15 CM)
• (manufactured by Tosoh Corporation)
• Solvent; THF
• Flow rate; 0.6 ml / min
• Concentration; 0.5 mg / ml
• Column temperature; 40 ° C
• Injection volume; 20 ml

(Number average molecular weight of polymer block A1 in hydrogenated block copolymer (a-1), and polymer block A2 in hydrogenated block copolymer (a-2))

Regarding the polymer block A1 in the hydrogenated block copolymer (a-1), and the polymer block A2 in the hydrogenated block copolymer (a-2), ie the number average molecular weight Mn of the polystyrene block, according to the method described in IM KOLTHOFF, et al., J. Polym. Soi. 1,429 (1946) described the later described <hydrogenated block copolymers ( 1 ) to (8) and (12)> as well as the <hydrogenated block copolymers ( 9 ) to (11) and (13)> oxidatively decomposed with t-butyl hydroperoxide using osmium tetraoxide as a catalyst and, likewise as in the previous section (( 1 ) weight-average molecular weight, number-average molecular weight, molecular weight distribution) described methods, measured by GPC to determine the number-average molecular weight, converted into polystyrene.

(Polystyrene block content in hydrogenated block copolymers (a-1) and (a-2))

The content of the polystyrene block was determined by using the <hydrogenated block copolymers ( 1 ) to (8) and (12)> and the <hydrogenated block copolymers (9) to (11) and (13)> were oxidatively decomposed with t-butyl hydroperoxide using osmium tetraoxide as catalyst and then precipitated with methanol, solid liquid was separated off wherein the precipitate was measured by an ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation) and the content of a polystyrene block was calculated from a peak intensity of an absorption wavelength (262 nm) derived from a vinyl aromatic compound component (styrene) by a calibration curve is.

(Content of all monomer units of the vinyl aromatic hydrocarbon compound (total styrene content))

A certain amount of the hydrogenated block copolymer was dissolved in chloroform and measured with the ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation), from the peak intensity of an absorption wavelength (262 nm) derived from a vinyl aromatic hydrocarbon compound component by means of a calibration curve the content of the monomer unit of the vinyl aromatic hydrocarbon compound was determined.

(Amount of vinyl bond)

The amount of vinyl binding of the conjugated diene monomer unit in the block copolymer was measured by a nuclear magnetic resonance (NMR) machine under the following conditions.

The block copolymer was precipitated by adding a large amount of methanol to the reaction solution after completion of all reactions (for the hydrogenated block copolymer, after completion of the hydrogenation reaction). Next, the block copolymer was extracted with acetone and the extract was dried in vacuo and used as a sample for the ¹ H-NMR measurement.

The conditions for the ¹ H-NMR measurement are described below.

(Measurement Conditions)

• Measurement equipment: JNM-LA400 (manufactured by JEOL)
• Solvent: deuterated chloroform
• Sample concentration: 50 mg / ml
• Observation frequency: 400 MHz
• Chemical displacement standard: TMS (tetramethylsilane)
• Pulse delay: 2.904 seconds
• Number of scans: 64 times
• Pulse width: 45 °
• Measuring temperature: 26 ° C

The amount of vinyl binding was determined by the ratio of the total peak area of the 1,2-bond and 3,4-bond to the total area of all peaks (1,2-bond, 3,4-bond, 1,4-bond) related to the conjugated diene monomer units in the peak obtained.

(Hydrogenation ratio)

The degree of hydrogenation of the double bond of the conjugated diene monomer unit in the block copolymer was measured by a nuclear magnetic resonance apparatus (NMR) under the same conditions as in the above ((5) vinyl bond amount).

The degree of hydrogenation was calculated by taking the ratio of the total peak area of the hydrogenated 1,2-bond, 3,4-bond and 1,4-bond to the total area of all peaks (1,2-bond, 3,4-bond, 1,4 -Binding), which relate to the double bond in the conjugated diene monomer unit in the peak obtained.

(Evaluation method for polyphenylene ether resin (c))

(Reduced viscosity of polyphenylene ether resin (c))

A 0.5 g / dl chloroform solution of polyphenylene ether resin (c) was prepared and the reduced viscosity (ηsp / c) [dl / g] at 30 ° C. was determined using an Ubbelohde viscosity tube.

(Number average molecular weight of polyphenylene ether resin (c))

The measurement was carried out using GPC, HLC-8320GPC (manufactured by Tosoh Corporation) under the same conditions as in the previous section ( 1 ) carried out.

(Average particle diameter of the polyphenylene ether resin (c))

The average particle diameter of the polyphenylene ether resin (c) was measured three or more times by means of a laser diffraction particle size distribution analyzer (manufactured by Coulter, product name LS-230) by dispersing in a 1-butanol solvent, with the arithmetic mean of the average diameter of each volume being the average Particle diameter was taken.

[Production of a thermoplastic

Elastomer composition]

(Embodiments 1 to 59 , Comparative examples 1 to 23 )

On the basis of the mixture proportions (mass parts) given in Tables 3 to 11 below, pellets of a thermoplastic elastomer composition were obtained by using a twin-screw extruder (“TEX-30αII” manufactured by Japan Steel Works, cylinder diameter 30 mm) at a set temperature of 230 ° C. Melting and kneading take place.

Evaluation Method of Thermoplastic Elastomer Composition

(Melt Flow Rate (MFR))

The melt flow rate (MFR) of the pellets of the thermoplastic elastomer composition obtained as described above was measured according to ASTM D1238 under the conditions of a temperature of 230 ° C and a load of 2.16 kg.

[Production of the press sheet]

By means of the pellets of the thermoplastic elastomer composition obtained as described above using a mold (size: 110 mm × 220 mm × 2 mm thickness) in a 50 ton electric heat press manufactured by Toho Press Co. under a pressure condition of 200 ° C., 0.5 kgf / cm ² preheated for five minutes and pressed under a pressure condition of 200 ° C, 100 kgf / cm ² for two minutes to produce a 2 mm thick press sheet.

The physical properties were measured using the obtained press sheet according to the following measurement method.

[Evaluation Procedure of the Press Journal]

(Hardness)

It was measured according to JIS K6253 using a type A durometer.

The Shore A hardness of 55 or less was judged to be sufficiently flexible.

(Tear strength)

The tear strength was measured according to JIS K6252 using a test piece in the form of an angle without a cut at a test speed of 200 mm / min.

[Production of the plug]

By means of the pellets of the thermoplastic elastomer composition obtained in the above section [Production of a thermoplastic elastomer composition], a cylindrical plug was formed 1 molded with a FE120S18A injection molding machine (manufactured by Nissei Resin Co., Ltd.) into a diameter of 20 mm × a thickness of 4 mm.

1 (A) shows a schematic plan view of the plug 1 and 1 (B) shows a schematic cross-sectional view of the plug 1 ,

The injection molding conditions were as follows: resin temperature: 240 ° C, injection speed: 45 cm ³ / s, injection time: 10 seconds, mold temperature: 40 ° C, cooling time: 40 seconds.

[Evaluation method of stuffing]

(Pinhole resistance)

The in 1 shown plugs 1 was introduced into a predetermined tool, as in 2 shown.

2 (A) shows a schematic plan view of the tool 2 and 2 B) shows a schematic cross-sectional view of the tool 2 ,

The tool 2 has a tubular holder at the opening of a predetermined container 22 on that via a thread pitch 21 can be attached to an object.

The stopper 1 was in the open end of this tool 2 introduced and through the retaining ring 23 fixed.

Next, the tool was placed on the closure section of the PET bottle filled with 500 ml of water 2 attached and fastened in a state in which the plug 1 was introduced.

On a tensile tester TG-5kN (manufactured by Minebea Co., Ltd.), the above-mentioned PET bottle with the stopper was attached 1 attached upwards and the resin needle (plastic bottle needle) with a diameter (a maximum root diameter) of 5 mm through the center of the stopper 1 passed at a speed of 200 mm / min from above. The maximum load at that time was measured.

The needle used was Terumo Infusion Set (TK-U200L) from Terumo Corporation.

It was judged that the smaller the maximum load, the lower and the better the needlestick resistance.

The number of measurements was four and a value obtained by simple average was taken as the measurement value.

The evaluation of the evaluation was as follows: o: 4 kgf or less, ×: more than 4 kgf, where o is practically good.

(Resealable after steam sterilization treatment)

First, the in 1 shown plugs 1 into a predetermined tool 2 introduced as in 2 shown.

Next was the retaining ring 23 attached with another tool so he can use the holder 22 into which the stopper 1 is fully contacted, and the steam sterilization process was carried out with an SN500 autoclave manufactured by Yamato Scientific Co., Ltd at 121 ° C for 20 minutes and a steam pressure of 0.104 MPa.

Then, after cooling, it was taken out for two hours in the device and after further cooling at room temperature of 23 ° C for two hours, also as in the section described above (( 13 ) Needlestick resistance), in the state in which the plug 1 of 1 in the tool 2 of 2 is inserted and attached to the closure section of a PET bottle filled with 500 ml of water.

The bottle was turned over and the stopper part was placed on the lower side. Here, the height from the surface of the inside of the stopper to the liquid surface was 18.5 cm.

A hole with a diameter of 3 mm was opened in the bottom (top) of the bottle and a resin needle (plastic bottle needle) with a diameter (maximum root diameter) of 5 mm was in the center of the stopper 1 pierced to the section of the maximum diameter of the needle.

After standing for 4 hours, the needle was removed and the mass of water emerging from the needle track was measured.

It was judged that the smaller the leak, the better the reclosability.

The number of measurements was eight and a value obtained by simple average was taken as the measurement value.

The evaluation of the evaluation was as follows: ⊙: the leak is 0.5 g or less, o: the leak is more than 0.5 g and 1.0 g or less, ×: the leak is more than 1.0 g , where ⊙ is extremely excellent, and o is practically good.

(Odor sensory test)

100 g of the pellets of the thermoplastic elastomer composition were placed in a pressure-proof 500 ml glass bottle and sealed, and, after heating for 1 hour at 70 ° C., were left at room temperature for 48 hours.

Afterwards 10 test persons confirmed the smell from the opening of the glass bottle and evaluated it based on the following <smell intensity>.

The evaluation was carried out with the following reference standard by determining the following average value of the odor intensity.

The evaluation: o: odor intensity of less than 3, ×: odor intensity of 3 or more, where o is practically good.

<Odor intensity>

0; odorless, 1; barely perceptible smell, 2; faint smell to know what smell is, 2.5; medium between 2 and 3; 3; easily noticeable smell, 3.5; medium between 3 and 4; 4; strong smell, 5 intense smell

(Coring property)

Also like in the section ((13) needlestick resistance) described above, the stopper became 1 of 1 into the tool 2 from 2 introduced and attached and attached to the closure portion of a PET bottle filled with 500 ml of water.

After stinging and pulling the center of the stopper five times 1 from the bottle through a resin needle (plastic bottle needle) with a diameter (a maximum root diameter) of 5 mm, the presence of chips of the stopper was visually observed in the content water or on the needle surface.

Those without chips were judged to be gutting.

The number of measurements was five and the evaluation of the evaluation was as follows: o: no chips at all, ×: at least one chip, where o is practically good.

(Test procedure for extractable substances)

The properties, pH, zinc, potassium permanganate reducing substance, evaporation residue, and the like were determined according to the extractable substance test method of the infusion rubber stopper test method of the 17th revision of the Japanese Pharmacopoeia and by means of the press sheet obtained in the above [Production of the press sheet] measured the UV absorption spectrum.

The evaluation was made according to the extractable substance test method of infusion rubber stopper test method of the 17th revision of the Japanese Pharmacopoeia as follows.

<Properties>

When, according to the test method for extractables of infusion rubber stopper test method of the 17th revision of the Japanese Pharmacopoeia, the test solution prepared was colorless and transparent, and the transmittances measured at wavelengths of 430 nm and 650 nm compared to a blind test solution were 99.9% or more, respectively was rated as consistent.

<PH>

When the pH values of the prepared test solution and a blank test solution were measured and the difference was 1.0 or less according to the extractable substance test method of infusion rubber stopper test method of the 17th revision of the Japanese Pharmacopoeia, it was judged to be the same.

<Zinc>

When the test was performed by atomic absorption photometry and according to the extractable substance test method of infusion rubber stopper test method of the 17th revision of the Japanese Pharmacopoeia, the absorption of the prepared sample solution was lower than the absorption of the standard solution, it was judged to be the same.

Table 10 and Table 11 show the matching case with "○" and the non-matching case with "×".

<Potassium permanganate reducing substance>

When the test solution and a blind test solution were titrated with a 0.001 mol / L sodium thiosulfate solution, and the difference in consumption of the 0.002 mol / L potassium permanganate solution was 2.0 ml or less, according to the extractable substance test method of the infusion rubber stopper test method of the 17th revision of the Japanese Pharmacopoeia this was rated as consistent.

<Evaporation residue>

When the test solution prepared was evaporated to dry according to the extractable substance test method of infusion rubber stopper test method of the 17th revision of the Japanese Pharmacopoeia, and a residue after drying was 2.0 mg or less, it was judged to be the same.

<UV absorption spectrum>

When, according to the test method for extractables of infusion rubber stopper test method of the 17th revision of the Japanese Pharmacopoeia, the test solution prepared was subjected to the ultraviolet spectrophotometric test compared to a blind test solution and the difference in absorption at a wavelength of 220 to 350 nm 0, Was 20 or less, this was judged to be the same.

Each component used will be explained next.

<Production of a hydrogenated catalyst>

The hydrogenation catalyst used in the production of a hydrogenated block copolymer in the later-mentioned embodiments and comparative examples was produced by the following method.

The reaction vessel equipped with a stirrer was purged with nitrogen and then charged with 1L of dried and cleaned cyclohexane.

Next, 100 mmol of bis (η5-cycloPentadienyl) titanium dichloride was added.

While stirring sufficiently, an n-hexane solution containing 200 mmol of trimethyl aluminum was added and the mixture was allowed to react at room temperature for about three days to obtain a hydrogenation catalyst.

<Hydrogenated block copolymer (1)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution containing 5 parts by mass of 1,3-butadiene monomer based on 100 parts by mass of the total monomer, 0.080 part by mass of n-butyllithium and 0.38 mol of tetramethylethylenediamine (hereinafter TMEDA) based on 1 mol of butyllithium were added, and this was done Polymerized at 70 ° C for 15 minutes.

Then, a cyclohexane solution containing 18 parts by mass of styrene monomer was added to polymerize it at 70 ° C for 25 minutes, and further a cyclohexane solution containing 60 parts by mass of 1,3-butadiene monomer was added to do so at 70 ° C for 40 minutes to polymerize.

Finally, a cyclohexane solution containing 17 parts by mass of styrene monomer was added and this was polymerized at 70 ° C for 25 minutes.

After the completion of the polymerization reaction, 0.95 mol of methanol was added based on 1 mol of n-butyllithium to deactivate the reaction catalyst and to obtain a polymer.

Next, from the above hydrogenation catalyst, 100 ppm as titanium per 100 parts by mass of the polymer was added to the obtained polymer, whereby a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C.

After the hydrogenation reaction had ended, 0.3 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer, based on 100 parts by weight of the polymer, to give a hydrogenated block copolymer ( 1 ) to obtain.

The hydrogenated block copolymer obtained ( 1 ) had a total styrene content of 34.3 mass%, a polystyrene block content of 33.8 mass%, a vinyl bond amount of 37.5 mol% before hydrogenation in the polybutadiene block, the weight average molecular weight of the entire polymer: 204,000, the number average molecular weight of the polystyrene block: 34,000 and the molecular weight distribution of the hydrogenated block copolymer: 1.35. The degree of hydrogenation of the aliphatic double bonds derived from 1,3-butadiene was also 99.8%.

<Hydrogenated block copolymer (2)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution containing 16 parts by mass of styrene monomer, based on 100 parts by mass of all monomers, 0.067 parts by mass of n-butyllithium and based on 1 mol of n-butyllithium, 0.48 mol of TMEDA were added, and this was polymerized at 70 ° C. for 25 minutes.

Then a cyclohexane solution containing 69 parts by mass of 1,3-butadiene monomer was added to polymerize it at 70 ° C for 40 minutes, and finally a cyclohexane solution containing 15 parts by mass of styrene monomer was added to do so at 70 ° C for 25 minutes to polymerize.

After the completion of the polymerization reaction, 0.95 mol of methanol was added based on 1 mol of n-butyllithium to deactivate the reaction catalyst and to obtain a polymer.

Next, from the above hydrogenation catalyst, 100 ppm as titanium per 100 parts by mass of the polymer was added to the obtained polymer, whereby a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C. After the hydrogenation reaction was completed, 0.3 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate based on 100 parts by mass of the polymer was added as a stabilizer to obtain a hydrogenated block copolymer (2).

The obtained hydrogenated block copolymer (2) had a total styrene content of 30.7% by mass, a polystyrene block content of 30.1% by mass, a vinyl bond amount of 39.4 mol% before hydrogenation in the polybutadiene block, the weight average molecular weight of the entire polymer: 264,000 number average molecular weight of the polystyrene block: 39,000 and the molecular weight distribution of the hydrogenated block copolymer: 1.31. The degree of hydrogenation of the aliphatic double bond, which is derived from 1,3-butadiene, was also 99.4%.

<Hydrogenated block copolymer (3)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution with 16 parts by mass of styrene monomer based on 100 parts by mass of all monomers, 0.067 parts by mass of n-butyllithium and based on 1 mol of n-butyllithium 0.45 mol of TMEDA were added and this was polymerized at 70 ° C. for 25 minutes.

Then a cyclohexane solution containing 69 parts by mass of 1,3-butadiene monomer was added to polymerize it at 70 ° C for 40 minutes, and finally a cyclohexane solution containing 15 parts by mass of styrene monomer was added to do so at 70 ° C for 25 minutes to polymerize.

After the completion of the polymerization reaction, 0.95 mol of methanol was added based on 1 mol of n-butyllithium to deactivate the reaction catalyst and to obtain a polymer.

Next, from the above hydrogenation catalyst, 70 ppm as titanium per 100 parts by mass of the polymer was added to the obtained polymer, whereby a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C. After the hydrogenation reaction was completed, 0.3 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate based on 100 parts by mass of the polymer was added as a stabilizer to obtain a hydrogenated block copolymer (3).

The hydrogenated block copolymer (3) obtained had a total styrene content of 31.3% by mass, a polystyrene block content of 31% by mass, a vinyl bond amount of 35.6 mol% before hydrogenation in the polybutadiene block, the weight average molecular weight of the entire polymer: 267,000, the number average molecular weight of the polystyrene block: 40,000 and the molecular weight distribution of the hydrogenated block copolymer: 1.28. The degree of hydrogenation of the aliphatic double bonds derived from 1,3-butadiene was also 76.3%.

<Hydrogenated block copolymer (4)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution containing 16 parts by mass of styrene monomer, based on 100 parts by mass of all monomers 0.044 parts by mass of n-butyllithium and based on 1 mol of n-butyllithium 0.50 mol of TMEDA were added and this was polymerized at 70 ° C. for 25 minutes.

Then a cyclohexane solution containing 70 parts by mass of 1,3-butadiene monomer was added to polymerize it at 70 ° C for 40 minutes, and finally a cyclohexane solution containing 14 parts by mass of styrene monomer was added to do so at 70 ° C for 25 minutes to polymerize.

After the completion of the polymerization reaction, 0.95 mol of methanol was added based on 1 mol of n-butyllithium to deactivate the reaction catalyst and to obtain a polymer.

Next, from the above hydrogenation catalyst, 100 ppm as titanium per 100 parts by mass of the polymer was added to the obtained polymer, whereby a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C. After the hydrogenation reaction was completed, 0.3 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate based on 100 parts by mass of the polymer was added as a stabilizer to obtain a hydrogenated block copolymer (4)

The hydrogenated block copolymer (4) obtained had a total styrene content of 29.8% by mass, a polystyrene block content of 29.4% by mass, a vinyl bond amount of 34.7 mol% before hydrogenation in the polybutadiene block, the weight average molecular weight of the entire polymer: 423,000 number average molecular weight of the polystyrene block: 61,000 and the molecular weight distribution of the hydrogenated block copolymer: 1.34. The degree of hydrogenation of the aliphatic double bonds, derived from 1,3-butadiene, was also 99.1%.

<Hydrogenated block copolymer (5)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution containing 17 parts by mass of styrene monomer based on 100 parts by mass of all monomers, 0.115 parts by mass of n-butyllithium and based on 1 mol of n-butyllithium was added 0.35 mol of TMEDA and this was polymerized at 70 ° C. for 25 minutes.

Then a cyclohexane solution containing 67 parts by mass of 1,3-butadiene monomer was added to polymerize it at 70 ° C for 40 minutes, and finally a cyclohexane solution containing 16 parts by mass of styrene monomer was added to do so at 70 ° C for 25 minutes to polymerize.

Next, 0.2 mol of silicon tetrachloride was added based on 1 mol of n-butyllithium, and the coupling reaction was carried out for 20 minutes. After the reaction was completed, 0.15 mol of methanol based on 1 mol of n-butyllithium was added to deactivate the reaction catalyst and obtain a polymer.

Next, from the above-mentioned hydrogenation catalyst, 100 ppm as titanium per 100 parts by mass of the polymer was added to the obtained polymer, whereby a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C. After the hydrogenation reaction was completed, 0.3 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate based on 100 parts by mass of the polymer was added as a stabilizer to obtain a hydrogenated block copolymer (5).

The hydrogenated block copolymer (5) obtained had a total styrene content of 33.1% by mass, a polystyrene block content of 32.9% by mass, a vinyl bond amount of 37.3 mol% before hydrogenation in the polybutadiene block, the weight average molecular weight of the entire polymer: 413,000 number average molecular weight of the polystyrene block: 34,000 and the molecular weight distribution of the hydrogenated block copolymer: 1.35. The degree of hydrogenation of the aliphatic double bonds derived from 1,3-butadiene was also 99.5%.

<Hydrogenated block copolymer (6)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution containing 16 parts by mass of styrene monomer, based on 100 parts by mass of all monomers, 0.142 parts by mass of n-butyllithium and based on 1 mol of n-butyllithium was added 0.24 mol of TMEDA and this was polymerized at 70 ° C. for 25 minutes.

Then a cyclohexane solution containing 70 parts by mass of 1,3-butadiene monomer was added to polymerize it at 70 ° C for 40 minutes, and finally a cyclohexane solution containing 14 parts by mass of styrene monomer was added to do so at 70 ° C for 25 minutes to polymerize.

After the completion of the polymerization reaction, 0.95 mol of methanol was added based on 1 mol of n-butyllithium to deactivate the reaction catalyst and to obtain a polymer.

Next, from the above-mentioned hydrogenation catalyst, 100 ppm as titanium per 100 parts by mass of the polymer was added to the obtained polymer, whereby a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C. After the hydrogenation reaction was completed, 0.3 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate based on 100 parts by mass of the polymer was added as a stabilizer to obtain a hydrogenated block copolymer (6).

The hydrogenated block copolymer (6) obtained had a total styrene content of 30.2% by mass, a polystyrene block content of 29.7% by mass, a vinyl bond amount of 33.3 mol% before hydrogenation in the polybutadiene block, the weight average molecular weight of the entire polymer: 88,000 number average molecular weight of the polystyrene block: 22,000 and the molecular weight distribution of the hydrogenated block copolymer: 1.27. The degree of hydrogenation of the aliphatic double bonds derived from 1,3-butadiene was also 99.7%.

<Hydrogenated block copolymer (7)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution containing 28 parts by mass of styrene monomer, based on 100 parts by mass of all monomers, 0.078 parts by mass of n-butyllithium and based on 1 mol of n-butyllithium, 0.8 mol of TMEDA were added, and this was polymerized at 70 ° C. for 30 minutes.

Then a cyclohexane solution containing 45 parts by mass of 1,3-butadiene monomer was added to polymerize it at 60 ° C for 60 minutes, and finally a cyclohexane solution containing 27 parts by mass of styrene monomer was added to do so at 70 ° C for 30 minutes to polymerize.

After the completion of the polymerization reaction, 0.95 mol of methanol was added based on 1 mol of n-butyllithium to deactivate the reaction catalyst and to obtain a polymer.

Next, from the above-mentioned hydrogenation catalyst, 100 ppm as titanium was added per 100 parts by mass of the polymer to the obtained polymer, with a hydrogenation reaction at one Hydrogen pressure of 0.8 MPa and a temperature of 85 ° C was carried out. After the hydrogenation reaction was completed, 0.3 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate based on 100 parts by mass of the polymer was added as a stabilizer to obtain a hydrogenated block copolymer (7).

The hydrogenated block copolymer (7) obtained had a total styrene content of 55.3% by mass, a polystyrene block content of 55.1% by mass, a vinyl bond amount of 66.8 mol% before hydrogenation in the polybutadiene block, the weight average molecular weight of the entire polymer: 208,000 number average molecular weight of the polystyrene block 56,000 and the molecular weight distribution of the hydrogenated block copolymer: 1.33. The degree of hydrogenation of the aliphatic double bonds derived from 1,3-butadiene was also 99.5%.

<Hydrogenated block copolymer (8)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution containing 16 parts by mass of styrene monomer, based on 100 parts by mass of all monomers 0.066 parts by mass of n-butyllithium and based on 1 mol of n-butyllithium 0.45 mol of TMEDA were added and this was polymerized at 70 ° C. for 25 minutes.

Then a cyclohexane solution containing 69 parts by mass of 1,3-butadiene monomer was added to polymerize this at 70 ° C for 40 minutes, and finally a cyclohexane solution containing 15 parts by mass of styrene monomer was added to do so for 25 minutes at 70 ° C to polymerize for 25 minutes.

After the completion of the polymerization reaction, 0.95 mol of methanol was added based on 1 mol of n-butyllithium to deactivate the reaction catalyst and to obtain a polymer.

Next, from the above hydrogenation catalyst, 50 ppm as titanium per 100 parts by mass of the polymer was added to the obtained polymer, whereby a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C. After the hydrogenation reaction was completed, 0.3 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate based on 100 parts by mass of the polymer was added as a stabilizer to obtain a hydrogenated block copolymer (8).

The obtained hydrogenated block copolymer (8) had a total styrene content of 30.8% by mass, a polystyrene block content of 30.1% by mass, a vinyl bond amount of 36.4 mol% before hydrogenation in the polybutadiene block, the weight average molecular weight of the entire polymer: 283,000 number average molecular weight of the polystyrene block: 42,000 and the molecular weight distribution of the hydrogenated block copolymer: 1.26. The degree of hydrogenation of the aliphatic double bonds derived from 1,3-butadiene was also 56.1%.

<Hydrogenated block copolymer (9)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution containing 5 parts by mass of 1,3-butadiene monomer, based on 100 parts by mass of all monomers 0.085 parts by mass of n-butyllithium and based on 1 mol of n-butyllithium 1.5 mol of TMEDA and also based on 1 mol of n-butyllithium 0.04 mol of sodium t-pentoxide was added and this was polymerized at 60 ° C for 20 minutes.

Then, a cyclohexane solution containing 7 parts by mass of styrene monomer was added to polymerize it at 70 ° C for 20 minutes, and further a cyclohexane solution containing 82 parts by mass of 1,3-butadiene monomer was added to do this at 60 ° C for 1, To polymerize 5 hours.

Finally, a cyclohexane solution containing 6 parts by mass of styrene monomer was added and this was polymerized at 70 ° C for 20 minutes. After the completion of the polymerization reaction, 0.95 mol of methanol was added based on 1 mol of n-butyllithium to deactivate the reaction catalyst and to obtain a polymer.

Next, from the above-mentioned hydrogenation catalyst, 100 ppm as titanium per 100 parts by mass of the polymer was added to the obtained polymer, whereby a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C. After the hydrogenation reaction was completed, 0.3 part by mass of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate per 100 parts by mass of the polymer was added as a stabilizer to obtain a hydrogenated block copolymer (9).

The hydrogenated block copolymer (9) obtained had a total styrene content of 13.4% by mass, a vinyl bond amount of 76.4 mol% before hydrogenation in the polybutadiene block, the weight average molecular weight of the entire polymer: 183,000 and the molecular weight distribution: 1.35. The degree of hydrogenation of the aliphatic double bonds derived from 1,3-butadiene was also 99.6%.

<Hydrogenated block copolymer (10)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution containing 10 parts by mass of styrene monomer, based on 100 parts by mass of all monomers, 0.140 parts by mass of n-butyllithium and based on 1 mol of n-butyllithium, 0.50 mol of TMEDA were added, and this was polymerized at 70 ° C. for 25 minutes.

Then a cyclohexane solution containing 81 parts by mass of 1,3-butadiene monomer was added to polymerize it at 70 ° C for 50 minutes, and finally a cyclohexane solution containing 9 parts by mass of styrene monomer was added to do so at 70 ° C for 25 minutes to polymerize.

After the completion of the polymerization reaction, 0.95 mol of methanol was added based on 1 mol of n-butyllithium to deactivate the reaction catalyst and to obtain a polymer.

Next, from the above-mentioned hydrogenation catalyst, 100 ppm as titanium per 100 parts by mass of the polymer was added to the obtained polymer, whereby a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C. After the hydrogenation reaction was completed, 0.3 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate based on 100 parts by mass of the polymer was added as a stabilizer to obtain a hydrogenated block copolymer (10).

The obtained hydrogenated block copolymer (10) had a total styrene content of 18.6% by mass, a vinyl bond amount of 52.1 mol% before hydrogenation in the polybutadiene block, the weight average molecular weight of the entire polymer: 93,000 and the molecular weight distribution: 1.24. The degree of hydrogenation of the aliphatic double bonds derived from 1,3-butadiene was also 99.8%.

<Hydrogenated block copolymer (11)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution containing 13 parts by mass of styrene monomer, based on 100 parts by mass of all monomers 0.066 parts by mass of n-butyllithium and based on 1 mol of n-butyllithium 1.5 mols of TMEDA and additionally based on 1 mol of n-butyllithium were 0.04 mols Sodium t-pentoxide was added and this was polymerized at 70 ° C for 25 minutes.

Next, a cyclohexane solution containing 75 parts by mass of 1,3-butadiene monomer was added, and this was polymerized at 60 ° C for 1.5 hours. Finally, a cyclohexane solution containing 12 parts by mass of styrene monomer was added and this was polymerized at 70 ° C for 25 minutes.

After the completion of the polymerization reaction, 0.95 mol of methanol was added based on 1 mol of n-butyllithium to deactivate the reaction catalyst and to obtain a polymer.

Next, from the above-mentioned hydrogenation catalyst, 100 ppm as titanium per 100 parts by mass of the polymer was added to the obtained polymer, whereby a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C. After the hydrogenation reaction was completed, 0.3 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate based on 100 parts by mass of the polymer was added as a stabilizer to obtain a hydrogenated block copolymer (11).

The hydrogenated block copolymer (11) obtained had a total styrene content of 25.4% by mass, a vinyl bond amount of 76.2 mol% before hydrogenation in the polybutadiene block, the weight-average molecular weight of the entire polymer: 263,000 and the molecular weight distribution: 1.38. The degree of hydrogenation of the aliphatic double bond derived from 1,3-butadiene was also 99.4%.

<Hydrogenated block copolymer (12)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution containing 22 parts by mass of styrene monomer based on 100 parts by mass of all monomers, 0.115 parts by mass of n-butyllithium and based on 1 mol of n-butyllithium were added 0.55 mol of TMEDA and this was polymerized at 70 ° C. for 30 minutes.

Then a cyclohexane solution containing 58 parts by mass of 1,3-butadiene monomer was added to polymerize it at 65 ° C for 60 minutes, and finally a cyclohexane solution containing 20 parts by mass of styrene monomer was added to do so at 70 ° C for 30 minutes to polymerize.

After the completion of the polymerization reaction, 0.95 mol of methanol was added based on 1 mol of n-butyllithium to deactivate the reaction catalyst and to obtain a polymer.

Next, from the above hydrogenation catalyst, 100 ppm as titanium per 100 parts by mass of the polymer was added to the obtained polymer, whereby a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C. After the hydrogenation reaction was completed, 0.3 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate based on 100 parts by mass of the polymer was added as a stabilizer to obtain the hydrogenated block copolymer (12).

The hydrogenated block copolymer (12) obtained had a total styrene content of 42.3% by mass, a polystyrene block content of 42.1% by mass, a vinyl bond amount of 58.6 mol% before hydrogenation in the polybutadiene block, the weight average molecular weight of the entire polymer: 122,000 number average molecular weight of the polystyrene block: 26,000 and the molecular weight distribution of the hydrogenated block copolymer: 1.26. The degree of hydrogenation of the aliphatic double bonds derived from 1,3-butadiene was also 99.3%.

<Hydrogenated block copolymer (13)>

The stirrer with an inner volume of 10 L and the jacketed tank reactor were washed, dried and purged with nitrogen to carry out batch polymerization.

First, after adding a cyclohexane solution containing 5 parts by mass of styrene monomer, based on 100 parts by mass of all monomers, 0.078 parts by mass of n-butyllithium and based on 1 mol of n-butyllithium, 0.8 mol of TMEDA were added, and this was polymerized at 70 ° C. for 20 minutes.

Then a cyclohexane solution containing 81 parts by mass of 1,3-butadiene monomer was added to polymerize this at 60 ° C for 1.5 hours, and finally a cyclohexane solution containing 4 parts by mass of styrene monomer was added to do so at 70 ° C for To polymerize for 20 minutes.

After the completion of the polymerization reaction, 0.95 mol of methanol was added based on 1 mol of n-butyllithium to deactivate the reaction catalyst and to obtain a polymer.

Next, from the above-mentioned hydrogenation catalyst, 100 ppm as titanium per 100 parts by mass of the polymer was added to the obtained polymer, whereby a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C. After the hydrogenation reaction was completed, 0.3 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate based on 100 parts by mass of the polymer was added as a stabilizer to obtain a hydrogenated block copolymer (13).

The hydrogenated block copolymer (13) obtained had a total styrene content of 8.8% by mass, a vinyl bond amount of 65.1 mol% before hydrogenation in the polybutadiene block, the weight average molecular weight of the entire polymer: 203,000 and the molecular weight distribution: 1.28. The degree of hydrogenation of the aliphatic double bonds derived from 1,3-butadiene was also 99.8%.

<Polypropylene-based resin (b)>

The following commercial product was used as the polypropylene-based resin (b).

Polypropylene-based resin (b): Sun Aroma Co., Ltd., PM801A, propylene homopolymer 9-polymer, MFR (230 ° C, 2.16 kg) 13 g / 10 min

<Polyphenylene ether resin (c)>

The polyphenylene ether resin (c) was produced according to the following procedure.

Based on a known method, polyphenylene ether was polymerized and purified by oxidative coupling polymerization of 2,6-dimethylphenol to obtain a polyphenylene ether resin (c).

The reduced viscosity (ηsp / c) (0.5 g / dl chloroform solution measured at 30 ° C), the number average molecular weight and the average particle size of the obtained polyphenylene ether resin (c) are shown below.

(C-1): Reduced viscosity = 0.45 dl / g, number average molecular weight = 17,400, average particle diameter = 290 µm

<Non-aromatic plasticizer (d)>

The following commercial products were used as the non-aromatic plasticizer (d).

Non-aromatic plasticizer (d-1): manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil PW380, paraffin oil, weight average molecular weight 750, kinematic viscosity (40 ° C) = 380 mm ² / s

Non-aromatic plasticizer (d-2): manufactured by Idemitsu Kosan Co., Ltd., Diana process oil PW90, paraffin oil, weight average molecular weight 530, dynamic viscosity (40 ° C) = 90.5 mm ² / s

<Inorganic filler (s)>

The following commercial products were used for the inorganic filler (e).

Inorganic filler (e-1): Whiton SB-Red, manufactured by Shiraishi Calcium Kaisha, Ltd., with an average particle diameter of 1.8 µm, BET method, specific surface area 1.2 m ² / g, calcium carbonate

Inorganic filler (e-2): Lighton A, manufactured by Shiraishi Calcium Kaisha, Ltd., average primary particle diameter 1.8 µm, BET process, specific surface area 3 m ² / g, calcium carbonate surface-treated with modified fatty acid

Inorganic filler (e-3): Aerosil OX 50, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 40 nm, BET method, specific surface 50 m ² / g, silica

Inorganic filler (e-4): Aerosil R 972 V, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 16 nm, BET process, specific surface area 110 m ² / g, silica treated with dimethylsilyl

Inorganic filler (e-5): Aerosil R976S manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 7 nm, BET method, specific surface area 240 m ² / g, silica treated with dimethylsilyl

Inorganic filler (e-6): Aerosil RX50, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 40 nm, BET process, specific surface 35 m ² / g, silica treated with trimethylsilyl

Inorganic filler (e-7): Aerosil RY50, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 40 nm, BET method, specific surface 30 m ² / g, silica surface-treated with dimethyl silicone oil

Inorganic filler (e-8): Aerosil R104, manufactured by Nippon Aerosil Co. Ltd., average primary particle diameter 12 nm, BET method specific surface area of 150 m ² / g, silica treated with octamethylcyclotetrasiloxane

Inorganic filler (e-9): Aerosil RA 200 HS, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 12 nm, BET process, specific surface 140 m ² / g, silica treated with hexamethyldisilazane and aminosilane

Inorganic filler (e-10): Aerosil R 805, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 12 nm, BET method, specific surface area 150 m ² / g, silica treated with octylsilane

Inorganic filler (e-11): Aerosil R711, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 12 nm, BET method, specific surface area 150 m ² / g, silica surface-treated with methacryloxysilane

Inorganic filler (e-12): Kisuma 5B, manufactured by Kyowa Chemical Industry Co., Ltd., average primary particle diameter 0.92 µm, BET process, specific surface area 4.3 m ² / g, magnesium hydroxide surface-treated with higher fatty acid

Inorganic filler (e-13): Pyroquisma 5301 K, manufactured by Kyowa Chemical Industry Co., Ltd., average primary particle diameter 2 µm, BET method, specific surface area 1.4 m ² / g, magnesium oxide surface-treated with silane coupling agent

<Inorganic porous absorbent (f)>

The following commercial products were used for the inorganic porous absorbent (f).

Inorganic porous adsorbent (f-1): molecular sieve USYZ 2000, manufactured by Union Showa Co., Ltd., average particle diameter 3 to 5 µm, BET process, specific surface area 500 m ² / g, synthetic zeolite (sodium aluminosilicate)

Inorganic porous adsorbent (f-2): Seven Thor OM-1, manufactured by Osaka Gas Chemical Co., Ltd., average particle diameter 2 to 2.5 µm, BET process, specific surface area ≥ 200 m ² / g, synthetic zeolite (sodium aluminosilicate)

<Silicone Oil>

The following commercial product was used for the silicone oil.

Silicone oil: SH200-100 Cs, manufactured by Toray Dow Corning Co., Ltd., dimethylpolysiloxane, kinematic viscosity 100 mm ² / s

The types and physical properties of each of the hydrogenated block copolymers (a-1) and (a-2) contained in the hydrogenated block copolymer (a) are shown in Tables 1 and 2 below.

The block copolymer type is represented by A as a styrene block and B as a butadiene block in one of the hydrogenated block copolymers (a-1) and (a-2).

The composition and properties of the thermoplastic elastomer composition are shown in Tables 3 to 11.

[Table 1] (A-1) (1) (2) (3) (4) (5) (6) (7) (8th) (12) Type BABA ABA ABA ABA (AB) 4 X ABA ABA ABA ABA Total styrene content (mass%) 34.3 30.7 31.3 29.8 33.1 30.2 55.3 30.8 42.3 Polystyrene block content (mass%) 33.8 30.1 31 29.4 32.9 29.7 55.1 30.1 42.1 Amount of vinyl bond in the polybutadiene block (mol%) 37.5 39.4 35.6 34.7 37.3 33.3 66.8 36.4 58.6 weight average molecular weight of the hydrogenated block copolymer (ten thousand) 20.4 26.4 26.7 42.3 41.3 8.8 20.8 28.3 12.2 number average molecular weight of polystyrene block A1 (ten thousand) 3.4 3.9 4 6.1 3.4 2.2 5.6 4.2 2.6 Molecular weight distribution of the hydrogenated block copolymer (Mw / Mn) 1:35 1.31 1.28 1:34 1:35 1.27 1:33 1.26 1.26 Degree of hydrogenation (mol%) 99.8 99.4 76.3 99.1 99.5 99.7 99.5 56.1 99.3

[Table 2] (A-2) (9) (10) (11) (13) Type BABA ABA ABA ABA Total styrene content (mass%) 13.4 18.6 25.4 8.8 Polystyrene block content (mass%) - - - - Amount of vinyl bond in the polybutadiene block (mol%) 76.4 52.1 76.2 65.1 weight average molecular weight of the hydrogenated block copolymer (ten thousand) 18.3 9.3 26.3 20.3 number average molecular weight of polystyrene block A2 (ten thousand) - - - - Molecular weight distribution of the hydrogenated block copolymer (Mw / Mn) 1:35 1.24 1:38 1.28 Degree of hydrogenation (mol%) 99.6 99.8 99.4 99.8

[Industrial applicability]

The thermoplastic elastomer composition of the present invention and the plug of a medical container using the same have an excellent balance between a needlestick resistance, a reclosability, and a coring property, etc. Because they are also excellent in processability, moldability and hygiene compared to vulcanized rubber they can also be used industrially as stoppers for various medical containers such as infusion bags.

[Explanation of the Reference Numbers]

1

Plug

2

Tool

21

Thread

22

holder

23

retaining ring

QUOTES INCLUDE IN THE DESCRIPTION

This list of documents listed by the applicant has been generated automatically and is only included for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

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Claims (12)

Thermoplastic elastomer composition comprising 100 parts by mass of a hydrogenated block copolymer (a), 10 to 50 parts by mass of a polypropylene-based resin (b), 75 to 200 parts by mass of a non-aromatic plasticizer (d), and 1 to 150 parts by mass of an inorganic filler (s), wherein the hydrogenated block copolymer (a) comprises a hydrogenated block copolymer (a -1) contains wherein the weight average molecular weight of the hydrogenated block copolymer (a-1) is 100,000 to 550,000, wherein the content of all the monomer units of the vinyl aromatic hydrocarbon compound of the hydrogenated block copolymer (a-1) exceeds 20% by mass and is 50% by mass or less, and wherein the inorganic filler (e) is a surface-treated silica. Thermoplastic elastomer composition after Claim 1 , wherein the hydrogenated block copolymer (a) is the hydrogenated block copolymer (a-1), and at least one polymer block A2, which mainly consists of a monomer unit of a vinyl aromatic hydrocarbon compound, and at least one polymer block B2, which mainly consists of a monomer unit of a conjugated diene compound, comprising hydrogenated block copolymer (a-2) obtained by hydrogenation thereof, the weight average molecular weight of the hydrogenated block copolymer (a-2) being 120,000 to 230,000, the content of all monomer units of the vinyl aromatic hydrocarbon compound of the hydrogenated block copolymer (a-2) 7 Mass% or larger and 20 mass% or smaller, and the mass ratio ((a-1) / (a-2)) between the hydrogenated block copolymer (a-1) and the hydrogenated block copolymer (a-2) 70/30 is up to 95/5. Thermoplastic elastomer composition after Claim 2 wherein in the hydrogenated block copolymer (a-2), the amount of the vinyl bond in the monomer unit of the conjugated diene compound before the hydrogenation is 63 mol% to 95 mol%. Thermoplastic elastomer composition after Claim 2 or 3 , wherein the hydrogenated block copolymer (a-2) has at least two polymer blocks A2 consisting mainly of a monomer unit of a vinyl aromatic hydrocarbon compound and at least two polymer blocks B2 consisting mainly of a monomer unit of a conjugated diene compound, and wherein at least one of the polymer blocks B2 is at the end of the hydrogenated block copolymer (a-2), the content of this end-located polymer block B2 being 0.5 to 9% by mass in the hydrogenated block copolymer (a-2). Thermoplastic elastomer composition according to one of the Claims 1 to 4 wherein in the hydrogenated block copolymer (a-1), the amount of the vinyl bond in the monomer unit of the conjugated diene compound is 30 mol% to 60 mol% before the hydrogenation. Thermoplastic elastomer composition according to one of the Claims 1 to 5 where the Shore A hardness is 55 or less and the needle stick resistance is 4.0 kgf or less. Thermoplastic elastomer composition according to one of the Claims 1 to 6 wherein the inorganic filler (e) is surface treated with a silane coupling agent. Thermoplastic elastomer composition according to one of the Claims 1 to 7 , wherein the odor intensity is three or less according to the method of displaying the odor intensity in six steps. Stopper comprising the thermoplastic elastomer composition according to one of the Claims 1 to 8th , Container with the stopper after Claim 9 is provided. Plugs used for medical purposes, comprising the thermoplastic elastomer composition according to one of the Claims 1 to 8th , Container used for medical purposes, the one with the stopper after Claim 11 is provided.

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