JP3303467B2 - Thermoplastic elastomer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a thermoplastic elastomer composition comprising a specific hydrogenated diene copolymer, a tackifier resin and a polyolefin resin and having excellent properties such as flexibility, transparency and molded appearance. For more details, stationery products such as desk mats and cutting mats, interior and exterior materials such as instrument panel skin materials and bumper materials, civil engineering and building materials such as decorative films and civil engineering waterproofing sheets, semiconductor-related parts such as dicing films, and medical use The present invention relates to a thermoplastic elastomer composition suitable for various uses such as materials, food-related materials such as cap liners and water purifier tubes, OA equipment-related parts, AV / home electric appliance-related parts such as vacuum cleaner bumper materials, and office equipment parts.

[0002]

2. Description of the Related Art Conventionally, flexible polyvinyl chloride resins have been widely used for extruded products such as sheets, films, tubes, etc., which require flexibility and transparency. Molded articles using the composition based on soft polyvinyl chloride resin are transparent,
It is widely used for various applications because of its excellent flexibility, heat resistance, and excellent appearance and texture. However, since this soft polyvinyl chloride resin usually contains a large amount of plasticizer, migration of plasticizer, peculiar odor due to plasticizer,
There is a risk of causing other problems in use. Further, a composition based on a soft polyvinyl chloride resin has insufficient low-temperature properties, and its flexibility is significantly reduced at a temperature of 0 ° C. or lower. More recently, the emergence of alternative materials has been strongly desired from the viewpoint of generating harmful gases during incineration.

[0003] On the other hand, polyolefin resins have attracted attention as excellent materials which do not have the problems inherent in soft polyvinyl chloride. However, since it is hard and has poor transparency, it is not used as a substitute for a flexible polyvinyl chloride resin although it is partially used as a sheet or film.

[0004] In order to take advantage of the characteristics of polyolefin resins, various types of elastomers have been blended, and a material having flexibility and excellent elastomer elasticity is commercially available under the general name of thermoplastic olefin (TPO). However, TPO is a material lacking transparency, and cannot be used in a field where transparency is required.

[0005] A thermoplastic elastomer comprising a polyolefin resin and a hydrogenated styrene-butadiene block copolymer is a material having flexibility and elastomeric elasticity. However, in comparison with a soft polyvinyl chloride resin, the transparency is insufficient and the texture of the molded article is inferior, so that at present the use is limited.

[0006] Also, molded products such as sheets, films, tubes and the like are usually formed while being wound around a paper tube or the like, and later unwound to obtain a product. At the time of this unwinding, conventional molded products other than the soft polyvinyl chloride resin are made of elastomeric material, such as distortion during winding remaining in the molded product, which appears as sheet warpage or tube twisting. In spite of this, there is a problem that it is not deformed into a shape suitable for the use environment. Hereinafter, the ability to deform into a shape suitable for the use environment will be referred to as “shaping property” to distinguish it from flexibility. There has never been a material having the same formability as a soft polyvinyl chloride resin, and the emergence of an alternative material has been desired.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and has the same flexibility, transparency, molded appearance and shapeability as soft polyvinyl chloride resin. An object is to provide a novel elastomer composition.

[0008]

According to the present invention, there is provided (a) at least one hydrogenated diene copolymer selected from the group consisting of (a-1), (a-2) and (a-3) below. 1 to 98% by weight of merging, (A-1); vinyl aromatic compound polymer block (A)
(A)-(B) or (A)-(B)-(A) block copolymer composed of a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene, or a vinyl aromatic compound (A) consisting of a tapered block (C) consisting of a conjugated diene and a vinyl aromatic compound gradually increasing.
(B)-(C) a block copolymer, wherein the ratio of vinyl aromatic compound / conjugated diene is 5/95 to 6 by weight.
0/40, the sum of the bond content of the vinyl aromatic compound in the component (A) and the bond content of the vinyl aromatic compound in the component (C) is 3 to 25% by weight of the total monomers, and (A) The sum of the bond contents of the vinyl aromatic compounds in the components is 3 of the total monomers.
% By weight or more, and the conjugated diene portion in the component (B) has a vinyl bond content of 1%.
A hydrogenated diene copolymer having a number average molecular weight of 50,000 to 600,000, in which a block copolymer of 5% or more is hydrogenated to saturate a double bond of a conjugated diene portion by 80% or more, B-2); a polymer block (D) mainly composed of a vinyl aromatic compound containing 90% by weight or more of a vinyl aromatic compound, a conjugated diene polymer block (E) having a vinyl bond content of 30 to 95%, and a vinyl bond Having at least one polybutadiene polymer block (F) having a content of less than 30%, a component (D) content of 10 to 65% by weight, a component (E) content of 30 to 80% by weight, and a component (F) Is hydrogenated from a block copolymer having a content of 5 to 30% by weight, and the conjugated diene moiety has 8 double bonds.
A hydrogenated diene copolymer saturated with 0% or more and having a number average molecular weight of 40,000 to 700,000; (a-3): a polybutadiene polymer block (G) and a conjugated diene homopolymer or vinyl aromatic A compound-conjugated diene copolymer block (H), wherein the component (G) has a vinyl bond content of 20% or less, and the component (H) has a vinyl bond content of 2 in the conjugated diene portion.
5 to 95%, and the block structure is represented by (G)-[(H)-(G)] n or [(G)-(H)] n (where n is an integer of 1 or more). chain or branched structure, a is more than 80 percent of the conjugated diene portion of the block copolymer is hydrogenated, the hydrogenated diene-based copolymer number average molecular weight of from 5 to 600,000, (b) rosin Resin, polyterpene resin, synthetic petroleum tree
Fat, coumarone resin, phenol resin, xylene tree
Group consisting of fats, styrene resins and isoprene resins
1 to 98% by weight of at least one kind of tackifier resin selected from (c) 1 to 98% by weight of polyolefin resin [provided that
(A) + (b) + (c) = 100% by weight].

[0009] Hereinafter will be described a thermoplastic elastomer composition of the present invention configured to requirements by. Component (A ) Component (A) is composed of at least one hydrogenated diene copolymer selected from the group consisting of (A-1), (A-2) and (A-3). The compounding amount is 1 in the total composition.
-98% by weight, preferably 5-95% by weight, more preferably 10-90% by weight. If the amount of component (a) is less than 1% by weight, the flexibility is poor, while if it exceeds 98% by weight, the heat resistance is poor. Here, the component (a) will be further described as (a-1), (a-2), and (a-3).

(A-1) Component; (A-1) Styrene, α-methylstyrene, p-vinyl aromatic compound constituting the hydrogenated diene copolymer
-Methylstyrene, t-butylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-
Examples include aminoethylstyrene and vinylpyridine, and styrene and α-methylstyrene are particularly preferred.

The conjugated diene used in the (a-1) hydrogenated diene copolymer includes 1,3-butadiene,
Isoprene, 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,
Examples thereof include 3-octadiene, 3-butyl-1,3-octadiene, and the like. In order to obtain a hydrogenated diene copolymer which can be industrially used and has excellent physical properties, 1,3-butadiene, isoprene, 1,3-pentadiene is preferred,
1,3-butadiene is particularly preferred.

The (a-1) hydrogenated diene copolymer of the present invention comprises a vinyl aromatic polymer block (A) and a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene. (A)-(B) or (A)-
(B)-(A) a block copolymer or a taper block (C) comprising a vinyl aromatic compound and a conjugated diene and gradually increasing the vinyl aromatic compound (A)-(B)-
(C) It consists of a block copolymer. First, the ratio of vinyl aromatic compound / conjugated diene is 5 / 95-60 by weight ratio.
/ 40, preferably 7/93 to 50/50 . When the content of the vinyl aromatic compound is less than 5% by weight, when the obtained hydrogenated diene-based copolymer is pelletized, blocking is easily caused and the appearance of the molded product is deteriorated. On the other hand, when the content of the vinyl aromatic compound exceeds 60% by weight, it becomes resinous, and the effect of improving impact resistance, particularly the low-temperature impact resistance, is insufficient.

The sum of the content of the vinyl aromatic compound in the vinyl aromatic compound polymer block (A) and the content of the vinyl aromatic compound in the tapered block (C) component is 3% of the total monomers. ~ 25% by weight, preferably 4
The content of the vinyl aromatic compound in the component (A) is at least 3% by weight, preferably 4 to 15% by weight, more preferably 5 to 15% by weight. When the bond content of the component (A) or the vinyl aromatic compound of the component (A) and the component (C) is less than 3% by weight, the obtained hydrogenated diene copolymer is easily blocked when pelletized. In addition, the appearance of the molded article also deteriorates. On the other hand, if it exceeds 25% by weight, it becomes resinous and has an effect of improving impact resistance.
In particular, the low-temperature impact resistance is insufficient.

The vinyl bond content of the conjugated diene portion in the conjugated diene polymer or the random copolymer block (B) of the vinyl aromatic compound and the conjugated diene is 15%.
Above, preferably 15 to 90%, more preferably 20%
~ 85%. If it is less than 15%, the effect of improving flexibility and transparency are poor, which is not preferable.

The block copolymer constituting the component (A-1) is prepared by adding a coupling agent to a block copolymer having an extended or branched polymer molecular chain as represented by the following general formula. It may be a copolymer.

[(A)-(B)] n-X, [(A)-(B)-(C)] n-X, or [(A)-(B)-(A)] n-X (Wherein (A), (B) and (C) are the same as above; n is 2
X represents an integer of 4 to 4 and represents a coupling agent residue. )

As the coupling agent at this time, for example, diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, Examples include 2-dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, and 1,2,4-benzene triisocyanate.

Further, in the hydrogenated diene copolymer (A-1) of the present invention, the hydrogenation rate of the double bond of the conjugated diene portion of the block (B) is at least 80%, preferably 90% or more. It is more preferably at least 95%. 8
If it is less than 0%, heat resistance, weather resistance, ozone resistance and transparency are inferior, which is not preferable.

The (a-1) hydrogenated diene copolymer of the present invention has a number average molecular weight of 50,000 to 600,000, preferably 80,000 to 500,000. If the mechanical strength and the heat resistance of the powder are reduced, on the other hand, if it exceeds 600,000, the fluidity and the workability will be reduced and the surface appearance will be lowered.

The (a-1) hydrogenated diene copolymer used in the present invention can be obtained, for example, by the method disclosed in JP-A-3-72512.

Component (a-2): The vinyl aromatic compound and the conjugated diene used in the component (a-2) are the same as those used in the component (a-1). here,
(B-2) The polymer block (D) constituting the hydrogenated diene copolymer is a polymer block of a vinyl aromatic compound or a copolymer of a vinyl aromatic compound and a conjugated diene having 90% by weight or more. 80% or more of the double bonds in the conjugated diene portion are hydrogenated polymer blocks. If the content of the vinyl aromatic compound in the polymer block (D) is less than 90% by weight, weather resistance is undesirably reduced. The content of the polymer block (D) in the block copolymer before hydrogenation was 1
It is 0 to 65% by weight, preferably 15 to 55%, and the number average molecular weight of the polymer block (D) is preferably 5,000 to 70,000. If the content of the polymer block (D) is less than 10% by weight, the improvement of heat resistance is insufficient, while if it exceeds 65% by weight, flexibility is reduced.

The content of the polymer block (E) constituting the (a-2) hydrogenated diene copolymer is 30 to 80% by weight, preferably 35 to 70% by weight, and the vinyl bond content is 30 to 80% by weight. It is a polymer block in which 95%, preferably 40 to 90%, and the number average molecular weight is 30,000 to 300,000, and 80% or more of the double bond of the conjugated diene portion is hydrogenated. The polymer block (E) is obtained by hydrogenating a double bond of a conjugated diene portion by 100%.
A polymer block in which ethylene and butene-1 are randomly copolymerized.

If the vinyl bond content of polybutadiene in the conjugated diene block before hydrogenation to be the polymer block (E) is less than 30%, a polyethylene chain is formed when hydrogenated, and the rubbery properties are lost. , While 95%
If it exceeds, the glass transition temperature increases when hydrogenated, and rubber-like properties are lost, which is not preferable. If the content of the polymer block (E) in the block copolymer before hydrogenation is less than 30% by weight, the flexibility is reduced, while if it exceeds 80% by weight, the processability is reduced.

Further, the content of the polymer block (F) constituting the hydrogenated diene copolymer of the component (a-2) is 5 to 5.
30% by weight, preferably 5 to 25% by weight, a vinyl bond content of less than 30%, preferably 3 to 20%, and a number average molecular weight of preferably 10,000 to 300,000. 80% of binding
The above is the hydrogenated polymer block.

If the vinyl bond content of the polybutadiene before hydrogenation in the polymer block (F) is 30% or more, the resinous properties are lost when hydrogenated, and the properties of the thermoplastic elastomer as a block copolymer Is lost. Also,
Polymer block (F) in block copolymer before hydrogenation
If the content is less than 5% by weight, the mechanical strength decreases, while if it exceeds 30% by weight, the flexibility is poor, which is not preferable.

The number-average molecular weight of the hydrogenated diene copolymer (a-2) of the present invention is from 40,000 to 700,000, preferably from 50,000 to 500,000. On the other hand, when it exceeds 700,000, the fluidity and processability are reduced, and the surface appearance is reduced.

The block copolymer constituting the component (a-2) is prepared by adding a coupling agent to a block copolymer represented by the following general formula, wherein the polymer molecular chain is extended or branched. It may be a copolymer.

[(D)-(E)-(F)] nX or [(D)-(E)-(F)] X [(D)-(E)] (where n, (X is the same as described above). The coupling agent used is the same as that used in the component (A-1).

The (a-2) hydrogenated diene copolymer used in the present invention can be obtained, for example, by the method disclosed in JP-A-2-133406.

Component (a-3): The vinyl aromatic compound and the conjugated diene used in the component (a-3) are the same as those used in the component (a-1). Here, the hydrogenated diene copolymer as the component (a-3) used in the present invention comprises a polybutadiene polymer block (G) having a vinyl bond content of 20% or less, a conjugated diene homopolymer or vinyl An aromatic compound-conjugated diene copolymer comprising a polymer block (H) having a vinyl bond content of 25 to 95% in a conjugated diene portion, and having a block structure of (G)-[(H)-( G)] n or [(G)-
(H)] n (where n is an integer of 1 or more), which is obtained by hydrogenating 80% or more of the double bond of the conjugated diene portion of the linear or branched block copolymer. It is something that can be done.

The block (G) in the component (a-3) becomes a crystalline block having a structure similar to ordinary low density polyethylene (LDPE) by hydrogenation. The vinyl bond content in the block (G) is 20% or less, preferably 1%.
8% or less, more preferably 15% or less. If the vinyl bond content of the block (G) exceeds 20%, the crystal melting point after hydrogenation drops significantly, and the mechanical properties of the component (a-3) are unfavorably low.

The block (H) is a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer block, and a rubbery ethylene-butene copolymer block or a vinyl aromatic compound is obtained by hydrogenation. A polymer block having a structure similar to that of the ethylene-butene copolymer is obtained.

The amount of the vinyl aromatic compound used in the block (H) is 35% by weight or less, preferably 30% by weight or less, more preferably 25% by weight, based on the monomers constituting the block (H). % Or more, and if it exceeds 35% by weight, the glass transition temperature increases, and the mechanical properties of the component (a-3) are inferior. Also, block (H)
The vinyl bond content of the butadiene moiety of 25 to 95%,
Preferably 25-75%, more preferably 25-55
%, And if less than 25% or more than 95%, after hydrogenation, they show crystal structures derived from polyethylene chains and polybutene-1 chains, respectively, and become resinous properties,
It is not preferable because the mechanical properties of the component (a-3) are inferior.

(B) Block (G) occupying component
The weight ratio of / (H) is usually 5/95 to 90/10,
Preferably it is 10 / 90-85 / 15. When the content of the block (G) is less than 5% by weight and the content of the block (H) exceeds 95% by weight, the crystalline polymer block is insufficient, and the mechanical strength of the component (A-3) is inferior. Absent. If the content of the block (G) exceeds 90% by weight and the content of the block (H) is less than 10% by weight, the hardness of the component (a-3) increases, which is not preferable.

Further, in the hydrogenated diene copolymer (a-3) of the present invention, the hydrogenation rate of the double bond in the butadiene portion of the blocks (G) and (H) is at least 80%, preferably at least 80%. It is 90% or more, more preferably 95% or more. If it is less than 80%, heat resistance, weather resistance, ozone resistance and transparency are inferior and are not preferred. The weight average molecular weight of the block (G) and the block (H),
Usually, 5,000 or more, preferably 10,000 or more,
More preferably 15,000 or more, and 5,000
If it is less than 10%, the mechanical properties of the component (A-3) are inferior, which is not preferable.

The number average molecular weight of the (a-3) hydrogenated diene copolymer of the present invention is from 50,000 to 600,000, preferably from 10 to 50,000.
If it is less than 50,000, the mechanical strength of the obtained composition,
If the heat resistance is reduced, on the other hand, if it exceeds 600,000, the fluidity and processability are reduced, and the surface appearance is reduced.

The block copolymer constituting the component (a-3) is prepared by adding a coupling agent to a block copolymer represented by the following general formula, wherein the polymer molecular chain is extended or branched. It may be a copolymer.

[(G)-(H)] n-X or [(G)-(H)-(G)] n-X (wherein n and X are as defined above) As the coupling agent, those similar to the compound used in the component (a-1) can be used.

The (a-2) hydrogenated diene copolymer used in the present invention can be obtained, for example, by the method disclosed in Japanese Patent Application Laid-Open No. 2-110467.

The hydrogenated diene copolymer which is the component (a) of the present invention is obtained by modifying the above components (a-1), (a-2) and (a-3) with a functional group. Are preferably used. The components (a-1) to (a-3) are at least one kind selected from the group consisting of an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group, an isocyanate group and an epoxy group. Using an unsaturated compound having a functional group, modified with various extruders such as a single-screw extruder and a twin-screw extruder, various kneading devices such as a Banbury mixer, a kneader, and a continuous kneader, and a device using any combination thereof. can do.

Component (b) The tackifying resin used in the component (b) of the present invention includes rosin-based resins, polyterpene-based resins, synthetic petroleum resins, coumarone-based resins, phenol-based resins, xylene-based resins, styrene-based resins, and isoprene-based resins. Resin ((b) with adhesive
Resin) . Hereinafter, specific examples of these tackifying resins will be described.

The rosin resin used in the present invention includes natural rosin, polymerized rosin, partially and completely hydrogenated rosin, glycerin ester, pentaerythritol ester, ethylene glycol ester of these various rosins.
Esterified products such as methyl esters, and further, rosin derivatives obtained by disproportionation, fumaration, lime formation, or a combination thereof as appropriate.

Examples of polyterpene resins include homopolymers or copolymers of cyclic terpenes such as α-pinene, β-pinene and dipentene, and copolymers of the above various terpenes with phenol compounds such as phenol and bisphenol. Terpene-phenolic resins such as α-pinene-phenol resin, dipentene-phenol resin, and terpene-bisphenol resin which are coalesced, and further, aromatic modified terpene resins which are copolymers of the above various terpenes and aromatic monomers. Can be

As the synthetic petroleum resin, naphtha cracked oil C
Homopolymers or copolymers of ₅ fractions, C ₆ -C ₁₁ fractions, and other olefinic fractions, and hydrogenated aliphatic petroleum resins, aromatic petroleum resins, and alicycles of these polymers Aliphatic petroleum resins, aliphatic-alicyclic copolymer resins, and the like. Further, copolymers of the above-mentioned various naphtha-decomposed oils with the above-mentioned various terpenes and copolymerized petroleum resins which are hydrogenated products thereof are also included. Examples of the C ₅ fraction of naphtha cracked oil, isoprene, cyclopentadiene, 1,3
Methylbutenes such as pentadiene, 2-methyl-1-butene and 2-methyl-2-butene, 1-pentene, 2
- pentenes such as pentene, preferably dicyclopentadiene, indene as C ₆ -C ₁₁ fraction, styrene, o-, m-, p-vinyltoluene, alpha-, methylstyrene such as β- methylstyrene , Methyl indene, ethyl indene, vinyl xylene, propenyl benzene, and the like, and other olefinic fractions such as butene, hexene, heptene, octene, butadiene,
Octadiene is preferred.

Examples of the phenolic resin include an alkylphenol resin, an alkylphenol-acetylene resin obtained by condensation of an alkylphenol and acetylene, and modified products thereof. Here, these phenolic resins may be any of a novolak resin obtained by converting phenol to methylol with an acid catalyst, and a resol type resin obtained by converting phenol to methylol with an alkali catalyst.

Examples of the xylene-based resin include a xylene-formaldehyde resin composed of m-xylene and formaldehyde, and a modified resin obtained by adding and reacting the third component to the xylene-formaldehyde resin.

Examples of the styrene resin include a low molecular weight product of styrene, a copolymer resin of α-methylstyrene and vinyl toluene, and a copolymer resin of styrene, acrylonitrile and indene.

[0048] As the isoprene-based resin include a resin obtained by copolymerization of C ₁₀ alicyclic compound is a dimer product of isoprene and C ₁₀ chain compound.

Among the above various tackifying resins, rosin-based resins, polyterpene-based resins, synthetic petroleum resins and the like are preferable, and among these, those having an aliphatic and / or alicyclic structure ((b ′) Resin) is more preferable from the viewpoint of the transparency of the composition. Here, as a particularly preferable tackifying resin having an aliphatic and / or alicyclic structure, a rosin resin is partially or completely hydrogenated rosin and a derivative thereof, and a polyterpene resin is a homopolymer or copolymer of cyclic terpene. For coalescing and synthetic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, aliphatic-alicyclic copolymer resins, and hydrogenated ((b)) adhesives of copolymers of naphtha-decomposed oil and various terpenes tackifying resin) and the like. these tackifying resins may be used singly or in combination of two or more.

The amount of the component (b) in the thermoplastic elastomer composition of the present invention is 1 to 98% by weight, preferably 1 to 85% by weight, and more preferably 1 to 70% by weight. If it is less than 1% by weight, the shaping properties are poor, and if it exceeds 98% by weight, the molded appearance and surface properties are unfavorably poor.

(C) Component The (C) polyolefin resin used in the present invention comprises:
A resin obtained from polymerization of one or more monoolefins by either a high-pressure method or a low-pressure method. Here, the monoolefin includes ethylene, propylene,
-Butene, 2-methyl-1-butene, 2-butene, 1-
Pentene, 1-hexene, 4-methyl-1-pentene,
2-methyl-1-propene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 5-methyl-1-hexene, and mixtures thereof. And preferably ethylene, propylene, 4-methyl-1-pentene, and more preferably propylene.

Preferred (c) polyolefin resins are
Polyethylene, polypropylene, poly 4-methyl-1-
Pentene, and the copolymer type (c) component includes ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 2-methyl-1-propene, and 3-methyl Examples thereof include polypropylene in which at least one monoolefin selected from the group consisting of -1-pentene and 5-methyl-1-hexene is copolymerized. (C) Polyolefin resins are more preferably polypropylene and the above-mentioned copolymer type polypropylene, and particularly preferably a copolymer type polypropylene.

As the component (c), a copolymer resin of the above-mentioned olefin and acrylic acid or acrylic acid ester is also preferably used. Here, as the acrylic acid and acrylic acid ester copolymerized with the olefin, any compound having an acrylic skeleton is used. Among these compounds, acrylic acid includes acrylic acid and methacrylic acid. Further, the ester group of the acrylate ester includes a methyl group, an ethyl group, a propyl group, n
-Butyl group, t-butyl group, n-amyl group, t-amyl group, n-hexyl group, 2-ethylhexyl group, octadecyl group, o-toluyl group, benzyl group, cyclohexyl group, 2-chloroethyl group, vinyl group , Allyl group, isobutenyl group and the like. Copolymers of these acrylic acids and acrylic esters with olefins include ethylene-acrylic acid, ethylene-methyl acrylate, ethylene-ethyl acrylate, ethylene-n-butyl acrylate, ethylene-methacrylic acid, ethylene-methacrylic acid. Acid methyl and the like.

The amount of the polyolefin resin (c) in the composition of the present invention is from 1 to 98% by weight, preferably from 5 to 95% by weight. When 1% by weight or more is used, heat resistance and mechanical strength are excellent. Although it has an effect, if it exceeds 98% by weight, the flexibility is undesirably reduced.

The thermoplastic elastomer composition of the present invention comprises:
If necessary, crosslinking such as sulfur crosslinking, peroxide crosslinking, metal ion crosslinking, and silane crosslinking can be performed by a conventionally known method.

The thermoplastic elastomer composition of the present invention may further comprise, in addition to the above components (A) to (C),
Flexibility, transparency, antioxidant, antistatic agent, weathering agent, ultraviolet absorber, slip agent, antiblocking agent, sealability improver, crystal nucleating agent, in an amount not to impair the molded appearance
Flame retardants, vulcanizing agents, vulcanizing aids, antibacterial and antifungal agents, dispersants, tackifiers, viscosity modifiers, coloring inhibitors, foaming agents, coloring agents such as titanium oxide, carbon black, and phyllite. Metal powders, glass fibers, inorganic fibers such as metal fibers, organic fibers such as carbon fibers, aramid fibers, glass beads, glass balloons, glass flakes, asbestos, mica,
Inorganic whiskers such as calcium carbonate and potassium titanate whiskers, talc, silica, calcium silicate, kaolin, diatomaceous earth, graphite, pumice, evo powder, cotton floc, cork powder, filler such as barium sulfate, fluororesin, or Other rubbery polymers, thermoplastic resins and the like can be appropriately compounded.

The composition of the present invention is melt-kneaded by a conventionally known kneader such as a roll, a Brabender mixer, various extruders, a kneader, a Banbury mixer, a continuous kneader, and dried by an injection molding machine. It can be obtained by blending. In order to produce the composition of the present invention, the respective components may be mixed at once, or after pre-mixing arbitrary components in advance, the remaining components may be added and mixed. The most preferable mixing apparatus is a single-screw or twin-screw extruder, which can continuously knead efficiently and pelletize. The composition of the present invention is a conventionally known method, for example, extrusion molding, injection molding, hollow molding, compression molding, calender molding, etc.
It can be processed into practically useful molded products. If necessary, processing such as foaming, powdering, stretching, bonding, printing, painting, plating and the like can be performed.

The thermoplastic elastomer composition of the present invention comprises:
Excellent transparency, flexibility, shapeability, heat resistance, impact resistance, processability, low temperature properties, temperature dependence, compatibility, paintability, printability, hot stamping properties, deep drawability, hot water resistance, rubber Utilizing elasticity, rubber touch, flexibility, slip resistance, stress crack resistance, etc., it can be used for various applications. Further, as molded articles obtained by using the composition of the present invention, sheets, films, tubes, deformed articles, nets,
Stationery products such as desk mats and cutting mats, automotive interior and exterior materials such as instrument panel skin materials and bumper materials, civil engineering and building materials such as decorative films and civil engineering waterproof sheets, semiconductor-related parts such as dicing films, and medical equipment It can be used in various applications such as materials for food, food-related materials such as cap liners and water purifier tubes, OA equipment-related parts, AV / home electric appliance-related parts such as vacuum cleaner bumper materials, and office equipment parts.

[0059]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. The evaluation of various physical properties in the examples was performed by the following methods. Tensile properties : Measured according to JIS K6301. Transparency : The transparency of a sheet having a thickness of about 2 mm was visually evaluated according to the following criteria. ：: Completely transparent ○: Almost transparent ×: Completely opaque Flexibility : JIS-A hardness was measured according to JIS K6301. Surface properties : White turbidity and stickiness of the sheet were visually observed, and good was evaluated as good and bad was evaluated as bad. Formability : A sheet having a length of about 140 mm and a thickness of about 2 mm is wound around a paper tube having a diameter of about 90 mm and kept at 40 ° C. for 24 hours. Then remove the sheet from the paper tube,
After standing at 23 ° C. for 24 hours on a horizontal surface, the degree of warpage of the sheet was evaluated. The evaluation results were expressed according to the following criteria. ◎: Completely horizontal, no warpage at all ○: Almost horizontal, Δ: Back to some level, but considerably warped X: Not at all horizontal, warped

Examples 1 to 8 and Comparative Examples 1 to 5 Hydrogenated copolymers Q-1 to Q-7 having the microstructure, number average molecular weight and degree of hydrogenation shown in Table 1, a tackifying resin and a polyolefin resin Was melt-kneaded in a plastmill at 150 to 250 ° C. using the formulation shown in Table 2 to obtain a blend. Using the obtained blend, a sheet having a thickness of 2 mm was formed by pressure forming, and Examples 1 to 8 and Comparative Examples 1 to 5 were obtained. In the hydrogenated diene copolymer shown in Table 1, Q1 to Q6 are copolymers having a structure within the range of the component (A) of the present invention, and Q7 is the copolymer of the component (A). (A) The content of the vinyl aromatic compound in the portion is outside the scope of the present invention.

As is clear from the results shown in Table 2, it is understood that the composition of the present invention is an elastomer having excellent transparency and flexibility and having good shapeability.

On the other hand, Comparative Example 1 is an example in which the component (A) is not used, but is extremely inferior in all of transparency, flexibility and shapeability as compared with the composition of the present invention. I understand. Comparative Example 2 is an example in which the component (ii) is not used. Transparency and flexibility are good, but shapeability and surface properties are insufficient. Comparative Example 3 is an example in which the component (c) was not used, but it can be seen that the surface properties were extremely poor. Comparative Example 4 is an example in which the structure of the hydrogenated diene copolymer is out of the range of the present invention. It turns out that transparency and flexibility are inferior compared with the composition of this invention. Comparative Example 5 is an example in which a softener was used instead of the component (b) of the present invention. Although the flexibility and transparency are almost the same as those of the composition of the present invention, it can be seen that the shapeability is insufficient and the surface properties are extremely poor.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

According to the present invention, there is provided a composition comprising a specific hydrogenated diene-based copolymer, a tackifier resin and a polyolefin-based resin. It is possible to provide an excellent material having both properties and shapeability. The composition of the present invention can meet a wide variety of demands from the industry due to the above excellent properties. Stationery products such as desk mats and cutting mats, automotive interior and exterior materials such as instrument panel skin materials and bumper materials, civil engineering and construction materials such as decorative films and civil engineering waterproofing sheets, semiconductor-related parts such as dicing films, medical materials, and caps Various applications such as food-related materials such as liners and water purifier tubes, OA equipment-related parts, AV / home appliances-related parts such as vacuum cleaner bumper materials, office equipment parts, etc., and the composition of the present invention is suitable for these uses. Can be used for

Continuation of the front page (72) Inventor Junji Shinji 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-5-98086 (JP, A) JP-A-5 -43770 (JP, A) JP-A-4-139253 (JP, A) JP-A-7-53844 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 53/02 C08L 23/02 C08L 91/00 C08L 93/00

Claims (3)

(57) [Claims] (1) 1 to 98% by weight of at least one hydrogenated diene copolymer selected from the group consisting of the following (A-1), (A-2) and (A-3): B-1); vinyl aromatic compound polymer block (A)
(A)-(B) or (A)-(B)-(A) block copolymer composed of a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene, or a vinyl aromatic compound (A) consisting of a tapered block (C) consisting of a conjugated diene and a vinyl aromatic compound gradually increasing.
(B)-(C) a block copolymer, wherein the ratio of vinyl aromatic compound / conjugated diene is 5 by weight.
/ 95-60 / 40, wherein the sum of the content of the vinyl aromatic compound in the component (A) and the content of the vinyl aromatic compound in the component (C) is 3 to 25% by weight of all the monomers, and (A) The sum of the bond contents of the vinyl aromatic compound in the component is 3% of the total monomers.
% By weight or more, and the conjugated diene portion in the component (B) has a vinyl bond content of 1%.
5% or more of the block copolymer is hydrogenated, and the double bond of the conjugated diene portion is saturated by 80% or more, and the number average molecular weight is 5% or more.
A hydrogenated diene copolymer having a molecular weight of 10,000 to 600,000, (a-2); a polymer block (D) containing a vinyl aromatic compound containing 90% by weight or more of a vinyl aromatic compound and a vinyl bond content of 30 (D) having at least one conjugated diene polymer block (E) of at least 95% and at least one polybutadiene polymer block (F) having a vinyl bond content of less than 30%; ) The content of the component is 30 to 80% by weight, the content of the component (F) is 5 to 30% by weight, and a block copolymer having a linear or branched block structure is hydrogenated to obtain a conjugated diene. The double bond of the moiety is saturated by 80% or more, and the number average molecular weight is 4
(B) a polybutadiene polymer block (G) and a conjugated diene homopolymer or a vinyl aromatic compound-conjugated diene copolymer block (H). The vinyl bond content in the component (G) is 20% or less, and the vinyl bond content in the conjugated diene portion in the component (H) is 2% or less.
5 to 95%, and the block structure is represented by (G)-[(H)-(G)] n or [(G)-(H)] n (where n is an integer of 1 or more). chain or branched structure, a is more than 80 percent of the conjugated diene portion of the block copolymer is hydrogenated, the hydrogenated diene-based copolymer number average molecular weight of from 5 to 600,000, (b) rosin Resin, polyterpene resin, synthetic petroleum tree
Fat, coumarone resin, phenol resin, xylene tree
Group consisting of fats, styrene resins and isoprene resins
1 to 98% by weight of at least one kind of tackifier resin selected from (c) 1 to 98% by weight of polyolefin resin [provided that
(A) + (b) + (c) = 100% by weight]. 2. The method according to claim 1, wherein the tackifying resin is aliphatic or
Rosin-based resin and / or polytel having an alicyclic structure
Selected from the group consisting of pen-based resins and synthetic petroleum resins
2. A resin according to claim 1, which is at least one kind of (b ') tackifying resin.
5. The thermoplastic elastomer composition according to item 1. 3. The method according to claim 1, wherein the tackifying resin is partially or
Rosin based on fully hydrogenated rosin or their derivatives
Resin or cyclic terpene homopolymer or copolymer
Polyterpene resin, aliphatic petroleum resin, alicyclic
Aliphatic petroleum resin, aliphatic-alicyclic copolymer resin or naphtha
Synthesis of hydrogenated copolymer of cracked oil and various terpenes
At least one selected from the group consisting of synthetic petroleum resins
(B) The thermoplastic resin according to claim 1, which is a tackifier resin.
Elastomer composition.