JP2836186B2 - Thermoplastic elastomer composition - Google Patents

Description

The present invention relates to a thermoplastic elastomer composition useful for interior and exterior parts of automobiles, various industrial parts, and the like, and more specifically, exhibits excellent rubber-like properties. The present invention relates to a thermoplastic elastomer composition comprising a thermoplastic elastomer and a crystalline thermoplastic polymer and having a performance comparable to a vulcanized rubber.

[Conventional technology]

Conventionally, a polymer (SEBS) obtained by hydrogenating the butadiene portion of a block copolymer composed of polystyrene and polybutadiene is known to be a thermoplastic elastomer exhibiting excellent mechanical properties. SEBS which is marketed as Clayton G series made by the company
Is a material widely used industrially.

The block polymer consisting of polystyrene and hydrogenated polybutadiene is a thermoplastic elastomer that exhibits extremely excellent elastomer elasticity at room temperature, but has a large compression set at high temperatures and the usable temperature range is currently limited. It is.

[Problems to be solved by the invention]

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the related art, and has as its object to provide a thermoplastic elastomer composition having high strength and excellent compression set despite having low hardness.

[Means for solving the problem]

The present invention relates to (A) a vinyl aromatic compound polymer block A, a block segment B comprising a polybutadiene or a vinyl aromatic compound-butadiene copolymer, wherein the 1,2-vinyl bond content of the butadiene portion is 25 to 95%. And a polybutadiene block segment C having a 1,2-vinyl bond content of 20% or less and a block copolymer having a linear or branched block structure obtained by hydrogenating at least 90% of a butadiene portion. 10 to 90 parts by weight of a hydrogenated block copolymer, (b) 90 to 10 parts by weight of a polyolefin resin [however,
(A) + (b) = 100 parts by weight], and (c) 1 to 300 parts by weight of the non-aromatic process oil based on 100 parts by weight of the total amount of the components (a) and (b) (Hereinafter referred to as "composition (I)").

Further, in the present invention, the composition (I) is reacted in the presence of a crosslinking agent for crosslinking the component (A) while imparting shear deformation, and at least 10% by weight of the component (A) is gelled. Thermoplastic elastomer composition (hereinafter referred to as “composition (I)
I) ”).

Further, the present invention relates to a composition containing (d) an olefin-based copolymer rubber in addition to the components (a) to (c) of the composition (I), wherein the components (a) to (d) The ratio is (a)
5 to 95 parts by weight of the components, the total amount of the components (b) and (d)
95 to 5 parts by weight [(a) + (b) + (d) = 100
Parts by weight], (b) / (d) = 10 to 90% by weight / 90 to 10% by weight, and the component (c) is based on 100 parts by weight of the total amount of the components (a), (b) and (d) The present invention provides a thermoplastic elastomer composition in an amount of 1 to 400 parts by weight (hereinafter, referred to as "composition (III)").

Further, in the present invention, the composition (III) is reacted while imparting shear deformation in the presence of a crosslinking agent for crosslinking the component (d), and at least 10% of the (d) olefin-based copolymer rubber component in the composition. It is intended to provide a thermoplastic elastomer composition (hereinafter, referred to as "composition (IV)") in which the weight% is gelled.

Further, the present invention provides a polymer obtained by copolymerizing or grafting the component (A) constituting the composition (I) and the component (E) comprising a carboxylic acid derivative and / or an epoxy derivative, or a polymer obtained by adding this polymer to another polymer. Wherein (G) is a polyamide-based polymer and / or a polyester-based polymer, and (G)
A composition containing a softener, comprising (a) and (e)
The proportion of the component (a) is from 5 to 95 parts by weight of the component (a);
The total amount of the components (e) and (f) is 95 to 5 parts by weight [however,
(A) + (e) + (f) = 100 parts by weight], (e) component being 0.5 to 50% by weight of the total amount of (e) and (f) components, (g)
A composition providing a thermoplastic elastomer composition (hereinafter, referred to as "composition (V)") in which the components are 0 to 400 parts by weight based on 100 parts by weight of the total of components (a), (e), and (f). It is.

The (a) block copolymer before hydrogenation of the hydrogenated block polymer used in the present invention contains at least one polymer block A, B, or C as an essential component, and is the simplest block copolymer. The copolymer has ABC, but in addition to this basic arrangement, a block copolymer in which one or more of the three types of polymer blocks are regularly or irregularly arranged one or more times. It may be a polymer.

Further, in the block copolymer before hydrogenation, the above block copolymer unit has another 1 to 3 via a coupling agent residue.
It may be one in which the molecular chain of the polymer unit is extended or branched by bonding to the polymer unit blocks. The partner polymer block to be bonded is composed of at least one polymer block of the above-mentioned A, B or C. Among them, the block copolymers composed of A, B and C form a coupling agent residue. , For example, (AB-
C) Those having a structure of nX (where n is an integer of 2 to 4) are subjected to block copolymerization, and then diethyl adipate, divinylbenzene, silicon tetrachloride, tin tetrachloride, dimethyldichloro It can be easily obtained by adding a coupling agent such as silicon, 1,2-dibromoethane or 1,4-chloromethylbenzene. However, polymer block A in one block copolymer,
If B and C are contained, 3 is contained in the other polymer block.
It is not necessary to include all of the components, for example, (ABC) X
It may have a structure like (AB).

The polymer block A constituting the block copolymer of the present invention comprises one or more aromatic compounds selected from aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and pt-butylstyrene. 80% or more of a copolymer of an aromatic vinyl compound or a copolymer with 1,3-butadiene having an aromatic vinyl compound content of 90% by weight or more is hydrogenated. When the content of the aromatic vinyl compound in the polymer block A is less than 90% by weight, the surface appearance of the molded article is inferior.

Further, the 1,2-vinyl bond content of the polymer block B constituting the block copolymer of the present invention is 25 to 95%, preferably 25 to 75%, more preferably 25 to 55%, and 25% to 25%.
If it is less than 95% or more than 95%, after hydrogenation, it shows a crystal structure derived from a polyethylene chain and a polybutene-1 chain, respectively, which is not preferred because the performance of the component (a) as an elastomer is inferior.

Further, the 1,2-vinyl bond content of the polymer block C constituting the block copolymer of the present invention is 20% or less, preferably 18% or less, more preferably 15% or less.
%, The melting point of the crystal of the polymer after hydrogenation drops significantly, and the mechanical properties of the component (a) are inferior.

(A) The ratio of blocks A, B, and C in the components is as follows:
Usually, block A 5-45% by weight, block B 10-90% by weight, block C 5-45% by weight, preferably block A5-40
% By weight, block B20 to 90% by weight, block C5 to 40% by weight, more preferably block A5 to 35% by weight, block
B is 30 to 90% by weight and block C is 5 to 35% by weight. When the total amount of blocks A and C exceeds 90% by weight,
If it is less than 10% by weight, the hardness of the component (a) increases,
It is not preferable because it becomes inappropriate as a thermoplastic elastomer. On the other hand, if the total amount of the blocks A and C is less than 10% by weight and the amount of the block B exceeds 90% by weight, the hard segments serving as the constraining phase are insufficient, and the mechanical properties of the component (A) are not preferable.

In the hydrogenated block copolymer of the present invention, it is important that at least 90% or more, preferably 95 to 100% of the butadiene portion is hydrogenated, and if it is less than 90%, heat resistance, weather resistance, and ozone resistance are reduced. This is inferior and is not preferred.

In addition, (a) the weight average molecular weight of each block segment constituting the hydrogenated block copolymer is usually 5,000 or more, preferably 10,000 or more, more preferably 15,000 or more, and if it is less than 5,000, (a) It is not preferable because the mechanical properties of the components are inferior. Further, the weight average molecular weight of the entire (a) hydrogenated block copolymer of the present invention is 1.5 to 350,000, preferably 30 to 300,000. If it is less than 15,000, the mechanical properties are inferior, while on the other hand, it exceeds 350,000. And the workability is remarkably reduced.

The (a) hydrogenated block copolymer of the present invention includes:
Acid-modified with α, β-unsaturated carboxylic anhydrides such as maleic anhydride, itaconic anhydride and fumaric anhydride, or having epoxy groups such as glycidyl (meth) acrylate, allyl glycidyl ether and vinyl glycidyl ether A modified hydrogenated block copolymer obtained by modification with an unsaturated compound is also included.

The (a) hydrogenated block copolymer used in the present invention can be obtained, for example, by the method disclosed in Japanese Patent Application No. 63-285774.

The composition (I) of the present invention is a composition containing (A) the hydrogenated block copolymer, (B) a polyolefin resin, and (C) a non-aromatic process oil.

Here, a particularly preferred component (A) used in the composition (I) comprises 10 to 30% by weight of the block A, 80 to 40% by weight of the block B, and 10 to 30% by weight of the block C. It is a block copolymer in which the content of 1,2-vinyl bond in block C is 15% or less and the content of 1,2-vinyl bond in block B is 25 to 55%.

The weight average molecular weight of the component (A) used in the composition (I) is preferably from 80,000 to 300,000, particularly preferably from 10 to 300,000.
250,000.

Further, the component (b) is a polymer mainly composed of at least one resinous polymer of a polyolefin resin, for example, an α-monoolefin having 2 to 8 carbon atoms. (B) Specific examples of the component include polyethylene, polypropylene, polymethylpentene, and polybutene-1.

The proportions of the components (a) and (b) in the composition (I) are as follows:
Usually, 10 to 90 parts by weight of the component (a), 90 to 10 parts by weight of the component (b), preferably 20 to 80 parts by weight of the component (a), and 80
To 20 parts by weight, more preferably 25 to 75 parts by weight of component (a), 75 to 25 parts by weight of component (b) [provided that (a) + (b)
= 100 parts by weight]. When the component (a) is used in an amount exceeding 90 parts by weight, the heat resistance of the composition is lowered, which is not preferable. On the other hand, when the amount is less than 10 parts by weight, the elastomer elasticity is not sufficiently imparted and the thermoplastic elastomer is used. Not suitable for use.

The component (c) used in the composition (I) is a non-aromatic process oil, and specific examples thereof include a paraffin-based process oil and a naphthene-based process oil.
The amount of the component (c) is usually 1 to 300 parts by weight, preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight, based on 100 parts by weight of the total of the components (a) and (b). Parts, the softening effect cannot be expected with less than 1 part by weight, while 300 parts by weight
Exceeding the weight part is not preferred because oil bleeding and strength reduction become remarkable.

For the production of the composition (I), a usual kneading apparatus can be used. However, when productivity is taken into consideration, a twin screw extruder with L / D = 25 or more is used, and the mixture is extruded from the middle of the extruder ( C) It is most preferable that the components are continuously produced by a method of injecting the components.

Next, the composition (II) has the same composition as the composition (I), but is reacted while imparting shear deformation in the presence of a cross-linking agent for cross-linking the component (A). 10% by weight is a gelled thermoplastic elastomer composition, which is characterized by having particularly excellent compression set as compared with the composition (I).

The components and the appropriate amount of the composition (II) are the same as those described in the description of the composition (I).

The crosslinking agent for crosslinking the component (a) used in the composition (II) is preferably a system comprising an organic peroxide and a crosslinking aid. Particularly preferred organic peroxides are those having a one-minute half-life temperature of 170 ° C. or higher and 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,
And 1,3-di (t-butylperoxyisopropyl) benzene.

Particularly preferred crosslinking aids include divinylbenzene, bismaleimide, trimethylolpropane triacrylate, pentaerythritol triacrylate,
Triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl chlorendade and the like can be mentioned, and these are used alone or as a mixture.

In addition, a radical scavenging compound can be used in combination with the crosslinking aid, whereby a composition having better performance can be obtained. Preferred radical scavenging compounds are those which are rich in reactivity with free radicals and which themselves become radical sources or generate free radicals upon decomposition by scavenging free radicals, such as sulfur, sulfur compounds, p- Quinone derivatives, p-quinone dioxime derivatives, compounds containing a thiol group, and the like can be preferably used. Specific examples of the radical scavenging compound include sulfur, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, hexafluoroisopropylidenebisphenol, dihydroxybenzophenone, hydroquinone, tetrachloro-p-benzoquinone, benzoquinone, 2 Preferred are 4,4,6-trimercapto-S-triazine, dibenzothiazyldisulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide and the like, which are used alone or in combination.

The amounts of the organic peroxide and the crosslinking aid are determined according to the composition (I
It is preferable to add and calculate the amount of active oxygen in the organic peroxide to be 0.001 to 0.1 mol with respect to 100 parts by weight of the component (A) in I). It is not preferable because it does not occur.On the other hand, even if it is used in excess of 0.1 mol, further crosslinking cannot be expected, it is not economical, and it is not preferable because other undesirable side reactions such as decomposition of the polymer are likely to occur. .

The amount of the crosslinking aid used is such that the amount of unsaturated double bonds in the crosslinking aid is 1/4 of the amount of active oxygen in the added organic peroxide.
It is desirable to select and use it so as to have an equivalent of ~ 40 times. If it is less than 1/4 equivalent, improvement in crosslinking efficiency due to the addition of a crosslinking aid cannot be expected so much, and it is not preferable because sufficient crosslinking does not occur. The above crosslinking cannot be expected and is not economical.

Further, the amount (mol) of the radical scavenging compound used when the radical scavenging compound is used together with the organic peroxide and the crosslinking assistant is usually 1/20 of the active oxygen amount in the organic peroxide used. ~ 2 equivalents. At less than 1/20 equivalent,
If the addition effect cannot be expected, and if it exceeds 2 equivalents, the crosslinking efficiency is remarkably reduced or undesired phenomena such as local gelation occur, and no further effect can be expected. Not economic.

The component (a) in the composition (II) is at least 10% by weight.
Must be gelled, preferably from 15 to
It is desirable that 95% by weight, more preferably 20 to 90% by weight, particularly preferably 25 to 85% by weight is gelled.

If the gel amount is less than 10% by weight, the improvement in rubber-like elasticity due to crosslinking becomes poor, which is not preferable.

Here, the amount of gel in the composition (II) is determined by extracting the composition (II) at 170 ° C. for 90 minutes using decalin as a solvent, and measuring the gel amount. Extraction is 2
It is desirable to change the decalin up to three times. Hereinafter, the amount of gel by this method is abbreviated as the amount of decalin gel.

For the production of the composition (II), a usual kneading apparatus can be used, but in view of productivity, it is most preferable to continuously produce the composition using a twin-screw extruder. In this case, the oil is injected and the cross-linking agent is added in the middle of the extruder.

Therefore, as the extruder, a long axis type with L / D = 30 or more is desirable. The order of oil injection and addition of the cross-linking agent is not particularly limited, but it is preferable to add the cross-linking agent after oil injection to reduce the increase in load due to cross-linking.

Next, the composition (III) is the same as the composition (I) (a) to (a).
The composition contains an olefin copolymer rubber as the component (d) in addition to the component (c).

As the components (A) to (C) in the composition (III), those described in the description of the composition (I) are preferably used.
The composition (III) is obtained by adding (d) an olefin copolymer rubber to the composition of the composition (I), and is particularly a low-hardness elastomer composition.

Here, as the olefin-based copolymer rubber of the component (d), a rubber-like polymer mainly composed of an α-monoolefin having 2 to 8 carbon atoms or a polymer mainly composed of a conjugated diene is hydrogen. A rubber-like polymer obtained by addition, specifically ethylene-propylene rubber,
Preferred examples include ethylene-propylene-diene rubber, ethylene-butene rubber, ethylene-butene-diene rubber, ethylene-acrylate rubber, chlorinated polyethylene, chlorosulfonated polyethylene, hydrogenated styrene-butadiene rubber, and hydrogenated nitrile rubber. It is listed as. These (iv) olefin copolymer rubbers can be used alone or as a mixture.

The amount of each component used in the composition (III) is 5 to 95 parts by weight, preferably 15 to 85 parts by weight, and more preferably 20 to 80 parts by weight of the component (A).

If the component (a) is less than 5 parts by weight, the mechanical properties are poor,
It is not preferable because the composition becomes insufficient in strength.

On the other hand, when the component (A) is used in an amount exceeding 95 parts by weight, the heat resistance of the composition may be reduced, which is not preferable.

The total amount of the component (b) and the component (d) is usually 95
To 5 parts by weight, preferably 85 to 15 parts by weight, more preferably 80 to 20 parts by weight [however, (a) + (b) + (d) = 10
0 parts by weight].

If the total amount of the components (b) and (d) exceeds 95 parts by weight, the mechanical properties tend to be poor, so that it is not preferable. Is not preferred because the heat resistance is lowered.

Here, the usage ratio of the component (b) to the component (d) is usually (b) polyolefin resin / (d) olefin copolymer rubber = 10 to 90% by weight / 90 to 10% by weight, preferably 1 to 90% by weight.
It is 5 to 85% by weight / 85 to 15% by weight, more preferably 20 to 80% by weight / 80 to 20% by weight. (B) less than 10% by weight of polyolefin resin, and (iv) 90% of olefin copolymer rubber
If the amount is more than 90% by weight, it is not preferable because the mechanical properties are inferior. On the other hand, if the amount of the polyolefin resin exceeds 90% by weight and the amount of the olefin copolymer rubber is less than 10% by weight, It is not preferable because the reduction in hardness, which is the purpose of compounding the polymer rubber, is insufficient.

Furthermore, (c) the amount of non-aromatic process oil used is
Total amount of component (a), component (b) and component (d) 100
The amount is 1 to 400 parts by weight, preferably 5 to 300 parts by weight, more preferably 10 to 250 parts by weight with respect to parts by weight. (C)
If the amount of the component is less than 1 part by weight, the softening effect cannot be expected.
If used in excess of 0 parts by weight, bleeding of the oil and reduction in strength become remarkable, which is not preferable.

For the production of the composition (III), a usual kneading apparatus can be used, but in consideration of productivity, it is most preferable to continuously produce the composition using a twin-screw extruder. In this case, the component (a), the component (b) and the component (d) may be mixed and melted, and the component (c) may be pressed in from the middle, or only the components (b) and (d) May be melt-mixed, and the components (a) and (c) may be added in the middle.

Next, the composition (IV) has the same composition as the composition (III), but reacts while giving shear deformation in the presence of a crosslinking agent for crosslinking the olefin-based copolymer rubber as the component (d). An elastomer composition in which at least 10% by weight of the olefin copolymer rubber component in the composition is gelled, and has particularly excellent mechanical strength and compression set as compared with the composition (III). It is characterized by the following.

The components and the appropriate amount of the composition (IV) are the same as those described in the description of the composition (III),
As the olefin copolymer rubber (d), ethylene-propylene-diene rubber, ethylene-butene-diene rubber and various partially hydrogenated rubbers having an appropriate amount of unsaturated bond in the molecule are particularly preferred examples. .

Examples of the crosslinking agent for crosslinking the olefin copolymer rubber of the component (d) include those commonly used for crosslinking rubber. That is, as the crosslinking agent for the composition (IV), a sulfur vulcanization system, a resin crosslinking agent such as an alkyl-phenol-formaldehyde resin, or a combination of the organic peroxide described in the composition (II) and a crosslinking assistant is used. And the like are preferably used. The amount of these crosslinking agents used is
It can be appropriately determined according to the performance required for the intended final composition. However, in the case of a sulfur vulcanization system or a resin cross-linking agent, the main component is usually (d) 100 parts by weight of the olefin copolymer rubber. Crosslinking agent 0.1 to 8 parts by weight, vulcanization accelerator 0.1
~ 10 parts by weight, vulcanization accelerator 0.5 ~ 10 parts by weight, activator 0.5 ~
It is in the range of 10 parts by weight and 0.1 to 10 parts by weight of the crosslinking aid, but may be determined appropriately according to the desired composition.

Preferred examples of the organic peroxide and the crosslinking aid are the same as those described in the composition (II).
Further, also in the composition (IV), it is preferable to use a radical-scavenging compound in combination similarly to the composition (II), and preferable examples are the same as those described in the composition (II).

Here, the amounts of the organic peroxide, the crosslinking assistant, and the radical scavenging compound used are the same as in the case of the composition (II), except that the amounts used are based on (d) the olefin-based copolymer rubber.

Component (II) in composition (IV) is at least 10% by weight
Is required to be gelled, preferably at least 20% by weight, more preferably at least 50% by weight, particularly preferably at least 80% by weight.

If the gel amount is less than 10% by weight, the improvement in rubber-like elasticity due to crosslinking becomes poor, which is not preferable.

Here, the gel amount in the composition (II) is a decalin gel amount.

The production of the composition (IV) is carried out by using a conventional extruder, for example, a twin-screw extruder, for example, by preliminarily mixing all the polymer components (a), (b) and (d),
(C) Oil injection and addition of a cross-linking agent may be performed in the middle of the extruder, or (b) and (d) components are kneaded, and after crosslinking, component (a) and (c) oil are injected. May be
After kneading the components (b) and (d), (c) a part of the oil is press-fitted, a crosslinking agent is added, and then the component (a) is added.
(C) The method of producing the oil again in the order of press-in is most preferable.

Next, the composition (V) is a polymer obtained by copolymerizing or grafting the component (i) used in the composition (I) and a component (e) comprising a carboxylic acid derivative and / or an epoxy derivative, or the polymer And (f) a polyamide-based polymer and / or a polyester-based polymer, and (g) a thermoplastic elastomer composition containing a softening agent.

The component (e) in the composition (V) comprises the component (f) and the component (a)
It is added for the purpose of improving the miscibility with the component.For example, a component having a functional group such as a carboxylic acid derivative or an epoxy derivative is copolymerized or grafted with an aromatic vinyl polymer or an olefin polymer. Or a polymer in which another polymer of this polymer is bonded in a graft or block form. (E) Specific examples of the carboxylic acid derivative in the component include acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride,
And itaconic anhydride.

In addition, specific examples of the epoxy derivative in the component (e) include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether.

Preferred examples of the polymer to which these carboxylic acid derivatives and epoxy derivatives are copolymerized or grafted are a polymer having α-monoolefin having 2 to 8 carbon atoms as a main component or a polymer having conjugated diene as a main component. It is a polymer obtained by hydrogenating the coalesced polymer, or a polymer containing an aromatic vinyl compound as a main component, specifically, polyethylene, polypropylene, propylene-ethylene copolymer, propylene-butene copolymer, hydrogen Polybutadiene, hydrogenated butadiene-styrene copolymer, polystyrene, styrene-α-methylstyrene copolymer, and the like.

In addition, other polymers that are grafted or block bonded to a polymer obtained by copolymerization or grafting of a carboxylic acid derivative or an epoxy derivative are added to control the reactivity or miscibility of the functional group component. The type is not particularly limited, and an acrylic polymer, a styrene polymer, or the like is appropriately used.

Specific examples of the component (e) include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, styrene-maleic anhydride copolymer, ethylene-glycidyl methacrylate copolymer, Allyl glycidyl ether-modified polyethylene, acrylic glycidyl ether-modified polypropylene, acrylic glycidyl ether-modified ethylene
Propylene copolymer, styrene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer grafted with polymethyl methacrylate, ethylene-glycidyl methacrylate copolymer grafted with polystyrene, ethylene-glycidyl methacrylate copolymer Preferred examples include a graft polymer obtained by grafting a styrene-acrylonitrile copolymer onto a polymer.

The component (f) is a polyamide-based polymer and / or a polyester-based polymer, specifically, nylon 6, nylon 6,6, nylon 4,6, nylon 11, nylon
Polyamides such as 12; thermoplastic polyamide elastomers; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polybutylene terephthalate-poly (tetramethylene oxide) glycol; polybutylene terephthalate-polybutylene isophthalate-poly (tetramethylene oxide) glycol; Thermoplastic polyester elastomers such as butylene terephthalate-polybutylene phthalate-poly (tetramethylene oxide) glycol, polybutylene terephthalate-polyhexane methylene terephthalate-polyethylene glycol, polyhexamethylene terephthalate-poly (tetramethylene oxide) glycol, and the like.

The ratio of the component (a) to the components (e) to (f) is such that the component (a) is 10 to 90 parts by weight, and the total amount of the components (e) and (f) is
90 to 10 parts by weight, preferably (A) component is 15 to 85 parts by weight,
The total amount of the components (e) and (f) is 85 to 15 parts by weight (provided that (a) + (e) + (f) = 100 parts by weight).
If the amount of the component (a) is less than 5 parts by weight and the total amount of the components (e) and (f) exceeds 95 parts by weight, the composition becomes hard and inferior in flexibility. If the amount exceeds 5 parts by weight and the total amount of the components (e) and (f) is less than 5 parts by weight, the heat resistance of the composition is insufficient, which is not preferable.

In addition, the ratio of the component (e) is as follows:
It is 0.5 to 50% by weight, preferably 0.5 to 40% by weight, more preferably 0.5 to 30% by weight. If the component (e) is less than 0.5% by weight, the effect of improving the miscibility is poor. On the other hand, if it is used in excess of 50% by weight, no further mixing effect can be expected, and it is not economical.

The composition (V) may contain another component, for example, a rubber-like component such as an olefin copolymer rubber used in the composition (III).

Since the addition of the rubber component is effective in lowering the hardness of the composition, it is a preferable method when a hard composition is required. When a rubber component is added as another component, the property of the rubber component to be added is not particularly limited, but the component (f) is at least 10% by weight, preferably 15% by weight in the total composition, more preferably, It is preferable that the content is 20% by weight or more. In this case, the component (f) is 10% by weight.
If the amount is less than the above, the addition of the rubber component is not preferred because the heat resistance of the resulting composition may be reduced.

Further, the rubbery component to be compounded can be crosslinked as required. An appropriate crosslinking method may be such that a crosslinking agent is added during kneading after compounding to dynamically crosslink, or a rubber component which has been appropriately crosslinked in advance may be compounded. By crosslinking the rubbery component, the compression set of the composition tends to be improved, which is preferable.

Examples of the cross-linking agent include organic peroxides alone or peroxide cross-linking such as bismaleimide-based, dimethacryl-based, diallyl-based, trimethacryl-based, and oxime compound-based cross-linking agents, sulfur alone, tetramethyl Sulfur-containing organic compounds such as thiuram disulfide may be used alone or in combination with a vulcanization accelerator.

The vulcanization accelerator is one or more selected from thiazoles, sulfenamides, thiurams, dithioates, guanidines, aldehyde ammonias, and xanthates.

Further, vulcanization accelerators and activators used in combination with the vulcanization accelerator include zinc white, magnesium oxide, stearic acid, oleic acid, lauric acid, zinc stearate, and organic amines such as triethanolamine. Are used alone or in combination of two or more.

Further, an organic peroxide can be used in combination as a vulcanization accelerator.

In addition to the organic peroxide-based crosslinking agent and the sulfur-based crosslinking agent, a phenolic resin-based resin crosslinking agent can also be used. Further, known scorch agents and anti-aging agents are also used.

The (g) softening agent to be blended in the composition (V) is a plasticizer for a polyamide polymer or a polyester polymer, or a non-aromatic process oil. Of these, phthalic esters, trimellitic esters, phosphoric esters, and the like can be preferably used as the plasticizer. The non-aromatic process oil is the same as that blended in the composition (I). These (g) softeners,
It is appropriately used when it is necessary to further reduce the hardness of the composition (V).
The amount is from 0 to 400 parts by weight, preferably from 0 to 300 parts by weight, more preferably from 10 to 250 parts by weight, based on 100 parts by weight of the total amount of the components and the components (e) to (f). (G) If the softening agent is used in an amount exceeding 400 parts, the bleeding of the softening agent and the decrease in the strength of the composition become remarkable, which is not preferable.

For the production of the composition (V), a usual kneading apparatus can be used, but in view of productivity, it is desirable to use a twin-screw extruder. In this case, the method of kneading is not particularly limited, but (g) the softener is preferably added in the middle of the extruder after the polymer component in the composition is melted.

The thermoplastic elastomer compositions (I) to (V) of the present invention
When using glass fiber, carbon fiber, metal fiber,
Fillers such as glass beads, glass flakes, wastolite, calcium carbonate, talc, barium sulfate, mica, potassium titanate, aramid fibers, molybdenum disulfide, and fluororesins can be added alone or in combination.

Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more.

These fillers are used in an amount of 5 to 150 parts by weight based on 100 parts by weight of the composition of the present invention.

Further, other various compounding agents can be added to the composition of the present invention.

These compounding agents include, for example, 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,2-methylene-
Bis- (4-ethyl-6-t-butylphenol), 4,
Antioxidants such as 4'-thiobis- (6-t-butyl-3-methylphenol), dilaurylthiodipropionate, tris (di-nonylphenyl) phosphite, wax; pt-butylphenyl salicylate; 2,2'-
Dihydroxy-4-methoxybenzophenone, 2-
(2'-hydroxy-4'-n-octoxyphenyl)
UV absorbers such as benzotriazole; lubricants such as paraffin wax, stearic acid, hardened oil, stearamide, methylenebisstearamide, n-butylstearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride; antimony oxide , Ammonium hydroxide, zinc borate, tricresyl phosphate, tris (dichloropropyl) phosphate, chlorinated paraffin, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A and other flame retardants; stearoamidopropyldimethyl-β- Antistatic agents such as hydroxyethylammonium nitrate; coloring agents such as titanium oxide and carbon black; and pigments.

The thermoplastic elastomer composition of the present invention is injection-molded,
It can be formed into various molded products by sheet molding, vacuum molding, heterogeneous molding, foam molding, blow molding, stampable molding and the like.

The obtained molded article can be used for exterior and interior parts of automobiles, various electric / electronic parts, housings and the like by utilizing its excellent properties.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, parts and% are by weight unless otherwise specified.

In the examples, various measurements were made by using a test piece cut out from a sheet formed from the obtained composition into a sheet shape with a dumbbell cutter, and the physical properties were evaluated according to JIS K6301.

Examples 1 to 4 and Comparative Examples 1 to 3 [Experimental Examples for Composition (I)] A twin-screw extruder (L / D = 32.5, PCM, manufactured by Ikegai Seisakusho Co., Ltd.) using the formulation shown in Table 1. -45), and a molded product having a side of 10 cm was injection-molded using the obtained pellets. Test pieces for measurement were cut out with a dumbbell cutter. Manufacturing with twin screw extruder
First, after mixing the components (a) and (b) (dry blending), the mixture was passed through an extruder, and the component (c) was pressed halfway while the mixture was uniformly melted.

As is clear from Table 1, it can be seen that the composition (I) is a low-curing elastomer having excellent rubber-like elasticity and mechanical properties.

On the other hand, Comparative Example 1 was an example in which a process oil exceeding a specified amount was used, and bleeding of the oil was severe and molding was impossible. Comparative Examples 2 and 3 are examples in which Clayton G1650 manufactured by Shell Co. was used instead of the component (A) of the present invention. Although the hardness and mechanical properties are almost the same as those of the elastomer composition of the present invention, they are inadequate in compression set and therefore are unsuitable for use as an elastomer.

Examples 5 to 8 and Comparative Examples 4 to 6 [Experimental examples relating to composition (II)] Using a compounding recipe shown in Table 2, using a twin screw extruder (manufactured by Nippon Steel Corporation, TEX-44). The composition was manufactured, and a molded product having a side length of 10 cm was injection-molded using the obtained pellets.The test specimen for measurement was prepared by cutting out with a dumbbell cutter. ) ~
After mixing the component (b) and the crosslinking assistant (dry blending), the mixture is passed through an extruder, and while the mixture is homogeneously melted, the component (c) is injected halfway and a crosslinking agent (organic peroxide) is added. Was done. The order of the component (c) and the addition of the crosslinking agent is not particularly limited.

As is evident from Table 2, the composition (II) has particularly improved compression set and improved performance as an elastomer.

On the other hand, in Comparative Example 4, since the amount of the crosslinking agent was too large, the gelation of the component (A) was severe and injection molding was not possible. Comparative Examples 5 to 6 are examples in which Clayton G1650 manufactured by Shell Co., Ltd. was used instead of the component (A) of the present invention. The hardness and mechanical properties were almost the same as those of the elastomer composition of the present invention, but the compression set was insufficiently improved.

Examples 9 to 12 and Comparative Examples 7 to 9 [Experimental Examples Related to Composition (III)] Test pieces for measurement were obtained in the same manner as in Example 1 using the compounding recipe shown in Table 3. In the case of manufacturing with a twin-screw extruder, (a), (b), and (d) are first mixed (dry blending), then passed through an extruder, and the mixture is mixed and melted. Was used.

As is evident from Table 3, the composition (III) was an extremely low-hardness composition, had a sufficient compression set, and was suitable for use as an elastomer. On the other hand, Comparative Example 7 was an example in which a process oil exceeding a specified amount was used, and the bleeding of the oil was so severe that molding was impossible. Comparative Examples 8 and 9 are examples in which Clayton G1650 manufactured by Shell Co. was used instead of the component (A) of the present invention.

Although the hardness and mechanical properties are almost the same as those of the elastomer composition of the present invention, they are inadequate in compression set and therefore are unsuitable for use as an elastomer.

Examples 13 to 16 and Comparative Examples 10 to 12 [Experimental Examples Related to Composition (IV)] Test pieces for measurement were obtained in the same manner as in Example 2 using the compounding recipe shown in Table 4. In the production using a twin-screw extruder, first, (a), (b), (d) components and a crosslinking aid are mixed (dry blending) and then passed through an extruder, and the mixture is uniformly melted. The component (c) was press-fitted and a cross-linking agent was added halfway. The order of the component (c) and the addition of the crosslinking agent is not particularly limited.

As is evident from Table 4, the composition (IV) provides an ultra-low hardness elastomer composition not found in the conventional elastomer composition, and particularly has excellent physical properties and compression set. Met.

On the other hand, in Comparative Example 10, the process oil was used in excess of the specified amount, and bleeding of the oil from the composition was so severe that molding was impossible.

Further, Comparative Example 11 is an example in which the component (A) was not used, and it can be seen that the mechanical properties are insufficient and are not suitable for practical use. Comparative Example 12 is an example in which Clayton G1650 manufactured by Shell Co. was used instead of the component (A) of the present invention.
The hardness and mechanical properties were almost the same as those of the elastomer composition of the present invention, but the compression set was insufficiently improved.

Examples 17 to 20 and Comparative Examples 13 to 15 Experimental Examples Related to [Composition (V)] Test pieces for measurement were obtained in the same manner as in Example 1 using the compounding formulations shown in Table 5.

In addition, manufacturing with a twin-screw extruder first (a)
After mixing the components (e) and (f) (dry blending), the mixture is passed through an extruder, and the mixture is uniformly melted (g)
A method was used in which components were injected halfway.

As is clear from Table 5, the composition (V) is an elastomer having excellent mechanical properties and good compression set.

On the other hand, Comparative Example 13 lacks the component (e) and is inferior in mechanical properties. In Comparative Examples 14 and 15, Clayton G1650 manufactured by Shell was used instead of the component (A) of the present invention.
This is an example using. Mechanical properties are almost the same as the elastomer composition of the present invention, but because of poor compression set,
It was unsuitable for use as an elastomer.

(Effect of the Invention) The thermoplastic elastomer composition of the present invention, by using a novel hydrogenated block copolymer, to provide an elastomer composition of particularly low hardness, high strength, good compression set, It is capable of responding to a wide variety of performance requirements from the industry.

Specific applications include automotive interior parts, interior skin materials, rack and pinion boots, bellows, vacuum connectors, tubes, side moldings, headrests, regulators, armrests, shift lever boots, weather strips, air spoilers, suspension boots, and belts. Covers, foil covers, knobs, bumpers, window frames, sight shields, bumper moldings, etc.
Industrial parts include hydraulic hoses, air tubes, rubber hoses, out covers, various gaskets, containers, O-
Rings, packing materials, keyboard materials, shoes,
Sandals and other footwear, various color tiles, flooring, furniture,
It can be used for home appliance skin materials, electric prevention materials, sporting goods, especially grip skin materials.

Furthermore, the thermoplastic elastomer composition of the present invention has excellent performance as a shape memory resin, and can be used for mechanical parts, joint materials and the like.

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 67/00 C08L 67/00 77/00 77/00 91/00 91/00 (56) References JP-A-3-292342 (JP, A JP-A-63-57662 (JP, A) JP-A-62-34951 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 53/00-53/02 C08L 23 / 00-23/36 C08L 91/00 C08L 67/00-67/08 C08L 77/00-77/12 C08J 3/24

Claims (5)

(57) [Claims] 1. A block segment comprising (a) a vinyl aromatic compound polymer block A, a polybutadiene or a vinyl aromatic compound-butadiene copolymer, wherein the 1,2-vinyl bond content of the butadiene portion is 25 to 95%. B and a polybutadiene block segment C having a 1,2-vinyl bond content of 20% or less, and a block copolymer having a linear or branched block structure is obtained by hydrogenating at least 90% of a butadiene portion. 10 to 90 parts by weight of a hydrogenated block copolymer, (b) 90 to 10 parts by weight of a polyolefin resin [provided that
(A) + (b) = 100 parts by weight], and (c) 1 to 300 parts by weight of the non-aromatic process oil based on 100 parts by weight of the total amount of the components (a) and (b) A thermoplastic elastomer composition comprising: 2. The composition according to claim 1, which is reacted while imparting shear deformation in the presence of a crosslinking agent for crosslinking the component (a), and at least 10% by weight of the component (a) is gelled. Thermoplastic elastomer composition comprising: 3. A composition comprising (d) an olefin copolymer rubber in addition to the components (a) to (c) according to claim 1, wherein the proportion of the components (a) to (d) is , (A) component 5
95 parts by weight, the total amount of components (b) and (d) is 95 to 5 parts by weight (provided that (a) + (b) + (d) = 100 parts by weight), (b) / (d) = 10 ~ 90% by weight / 90 ~ 10% by weight,
(C) Component is the total amount of (A), (B) and (D)
1 to 400 parts by weight per 100 parts by weight of the thermoplastic elastomer composition. 4. The composition according to claim 3, which is reacted while imparting shear deformation in the presence of a crosslinking agent for crosslinking the component (d), so that at least one of the (d) olefin copolymer rubber components in the composition is obtained. A thermoplastic elastomer composition in which 10% by weight is gelled. 5. A polymer obtained by copolymerizing or grafting the component (a) according to claim 1 and a component comprising (e) a carboxylic acid derivative and / or an epoxy derivative, or a polymer obtained by grafting or grafting this polymer to another polymer. A composition comprising a polymer bonded in a block shape, (f) a polyamide-based polymer and / or a polyester-based polymer, and (g) a softener, wherein (a) and (e) to (g) components Is 5 to 95 parts by weight of the component (a), and the total amount of the components (e) and (f) is 95 to 5 parts by weight [provided that (a) + (e) + (f) = 10
0 parts by weight], the component (e) is 0.5 to 50% by weight of the total amount of the components (e) and (f), and the component (g) is 100% by weight of the total amount of the components (a), (e) and (f) 0 to 400 parts by weight per part by weight of the thermoplastic elastomer composition.