WO2001072876A1 - Resin pellet with excellent nontackiness and process for producing the same - Google Patents

Abstract

A process for producing resin pellets having excellent nontackiness, characterized by coating the surface of pellets of at least one resin selected from the following group of copolymers having a modulus in tension (23°C) of 1,600 MPa or lower with both at least one liquid having a specific dynamic viscosity and a specific surface tension (e.g., dimethylpolysiloxane) and a fine powder of at least one organic substance (e.g., calcium stearate) or of silica having an average particle diameter of 50 $G(m)m or smaller. Examples of the resin include interpolymers, hydrogenated aromatic vinyl/conjugated diene random copolymers, hydrogenated aromatic vinyl/conjugated diene block copolymers, and unsaturated olefin copolymers obtained by copolymerizing at least ethylene, an aromatic vinyl, and an unconjugated polyene. The resin pellets prepared by the process are superior in nontackiness to conventional pellets of an olefin copolymer rubber, etc. and are excellent in appearance and handleability.

Description

 Description: Resin pellets excellent in non-adhesiveness and method for producing the same

 The present invention relates to a resin pellet excellent in non-adhesiveness and appearance, particularly a soft resin pellet, and a method for producing the same. Background art

 Resins such as ethylene-propylene copolymer rubber, ethylene-propylene copolymer rubber, and soft resins such as olefin-based copolymer rubber such as hydrogenated styrene-butadiene copolymer rubber are usually in the form of blocks such as veil. It is supplied to the factory in the form of

 However, such block-shaped olefin copolymer rubber is complicated in taking out from a storage place, supplying to equipment used in a molding process, complicated in transporting, and furthermore, is difficult to measure. There are drawbacks such as bad.

Therefore, if the olefin copolymer rubber can be supplied to the market in the form of pellets, the above-mentioned drawbacks can be solved, and furthermore, the olefin copolymer rubber and fillers, softeners, and additives generally used with the olefin copolymer rubber can be used. When kneading with a compounding agent such as a sulfurizing agent, a pellet-like olefin copolymer is used instead of a mixer with low production efficiency, such as the Banbury mixer, which has been used in the past. By supplying the rubber and the compounding agent, it is possible to provide a great advantage such that a compounded rubber can be prepared. However, even when the above-mentioned copolymer rubber is molded into a pellet, the copolymer rubber itself has adhesiveness, so that it coagulates in a block shape during pellet storage and is formed into a pellet shape. lose.

 Hitherto, various methods have been proposed as a method for reducing the surface tackiness of such adhesive olefin copolymer rubber pellets. For example, a method of coating the surface of a rubber belt with silicone oil (JP-A-48-47934), or an inorganic powder such as talc, silica, calcium carbonate, or the like as an anti-adhesive agent, or polyethylene. A method is known in which these powders are adhered to a pellet which is easily adhered by dusting the powder.

 However, the method of coating the surface of the rubber pellet with silicone oil has a disadvantage that a sufficient effect cannot be obtained with a highly sticky pellet. In addition, in the latter method, since inorganic materials such as talc and silica are not compatible with the olefin copolymer rubber, if these powders are adhered, performance is often adversely affected in terminal applications. Further, in this method, it is necessary to mix the anti-adhesive powder with the pellet at a ratio of several percent to several tens percent in order to substantially prevent the coagulation of the pellet. There is a disadvantage that the properties of the copolymer rubber are impaired. For example, when polyethylene powder is sprinkled on pellets of an olefin copolymer rubber, there is a disadvantage that the rubbery properties of the vulcanizate of the olefin copolymer rubber decrease when the amount of the polyethylene powder attached increases. Furthermore, this method has the drawback that dusting occurs on the surface of the pellet, impairing the appearance and making it difficult to handle.

As an excellent method for preventing sticking of rubber pellets without these defects, the present applicant has proposed a method of coating rubber pellets with higher fatty acids or Z and its salts (Japanese Patent Application Laid-Open No. 56-13633647). No.). According to these methods, rubber pellets Can be prevented and the rubbery properties are not substantially impaired.

 However, according to the method described in this publication, the higher fatty acid or Z and its salt are stably added to the rubber pellet because the higher fatty acid or Z and its salt and rubber are simply mixed by the method described in this publication. It was confirmed that it could not be adhered in a sufficient amount, and as a result, after transporting and weighing the rubber pellets, blocking might still occur during storage.

 Accordingly, the applicant of the present application has conducted further intensive research and has found that, as a method for preventing the blocking of the rubber pellet during storage, an olefin-based copolymer rubber pellet and a fine powdery fine powder having 12 to 30 carbon atoms are used. A method was proposed in which a fatty acid or Z and its salt were mixed in the presence of a monohydric alcohol having 1 to 4 carbon atoms to produce a rubber stick with low tackiness (Japanese Patent Publication No. Hei 4-110). 11 No. 1). Rubber pellets coated with higher fatty acids or salts thereof obtained by this production method are packed in bags of 25 kg of these pellets after freight transportation, and the bags are stacked in 10 tiers and left for 1 month. It does not cause blocking. This method can cause difficulties in handling due to dusting of the pellet surface.

 Recently, due to the demands of users and the like, the emergence of a method of producing a resin belt that is more excellent in non-adhesiveness and appearance and is easier to handle than resin pellets such as conventional olefin copolymer rubber has been desired. .

The present invention is intended to solve the problems associated with the prior art as described above, and is more excellent in non-adhesiveness and appearance than conventional resin pellets such as an olefin copolymer rubber and is easy to handle. It is intended to provide a simple resin pellet and a method for producing the same. Disclosure of the invention

 The resin pellet excellent in non-adhesiveness according to the present invention is

Pellet surface of resin (A) having at least one kind selected from the group consisting of the following (i) to (iv) and having a tensile modulus (YM; ASTM D-658) at 1600 MPa or less at 23 ° C: At least one liquid (B) having a kinematic viscosity at 25 ° C of 0.5 to 100; 000 cSt and a surface tension at 25 ° C of 10 to 50 dyneZcm; It is characterized by being coated with at least one kind of organic fine powder having an average particle diameter of 50 jtm or less or fine powder (C) composed of silica fine powder.

 (i) (1) (a) at least one aromatic vinyl or vinylidene monomer

 One or

 (b) at least one binder aliphatic or cycloaliphatic vinyl or vinylidene monomer; or

 (c) from 1 to 99 mol% of polymer units derived from a combination of at least one aromatic vinyl or vinylidene monomer and at least one binder aliphatic or cycloaliphatic vinyl or vinylidene monomer; and 2) 99-1 mol% of polymer units derived from ethylene, or at least one C3-C20 olefin or a combination thereof.

A substantially random interpolymer consisting of

(ii) A hydrogenated product of a copolymer obtained by random copolymerization of an aromatic vinyl compound and a conjugated gen, wherein the structural unit derived from the conjugated gen and Z or A hydrogenated random copolymer in which a structural unit derived from an aromatic vinyl compound has a hydrogenation ratio of 90% or more.

 (iii) A hydrogenated product of a copolymer obtained by block copolymerization of an aromatic vinyl compound and a conjugated gen, and is a structural unit derived from a conjugated gen and derived from Z or an aromatic vinyl compound. A hydrogenated block copolymer whose constituent units have a hydrogenation ratio of 90% or more.

 (iv) obtained by copolymerizing ethylene (a), an aromatic vinyl compound (b), a non-conjugated polyene (c), and optionally a olefin having 3 to 20 carbon atoms (d); The molar ratio between the content of the structural unit derived from a) and the content of the structural unit derived from polyolefin having 3 to 20 carbon atoms (d) [(a) Z

(3)] An unsaturated unsaturated olefin copolymer having an iodine value in the range of 100-60 _/ 40 and an iodine value of 0.5-50.

 The method for producing a resin pellet excellent in non-adhesiveness according to the present invention,

 At least one resin selected from the group consisting of the above) to (iv) having a tensile modulus at 23 ° C (YM; ASTM D-658) of 160 OMPa or less;

At least one liquid with a kinematic viscosity at 25 ° C of 0.5 to 100,000 cSt and a surface tension at 25 ° C of 10 to 50 dyn eZcm on the pellet surface of (A). (B) and at least one organic fine powder having an average particle size of 50 m or less or a fine powder (C) comprising silica fine powder.

As the interpolymer (i), 1 to 99 mol% of polymer units derived from at least one kind of aromatic vinyl or vinylidene monomer, and at least one type of olefin having 3 to 20 carbon atoms. A substantially random polymer consisting of 99-1 mol% of the polymer unit is preferred. It is used well. Among them, 1 to 99 mol% of one unit of a polymer derived from styrene, and 99 to 95% of a polymer unit derived from ethylene or a combination of ethylene and at least one type of cycloolefin having 3 to 10 carbon atoms. A substantially random interpolymer of 1 mol% is more preferred.

 Further, as the interpolymer (i),

 A pseudo-random interpolymer consisting of 1 to 65 mol% of a polymer unit derived from styrene and 99 to 35 mol% of a polymer unit derived from ethylene, or

 It consists of 1 to 65 mol% of polymer units derived from styrene and 99 to 35 mol% of units derived from ethylene and at least one type of cycloolefin having 3 to 20 carbon atoms. Pseudo-random polymers are also preferably used.

 Here, “pseudo” of a pseudo-random interpolymer refers to a homopolymer segment composed of a vinylidene monomer in an interpolymer molecular structure, as disclosed in Japanese Patent Application Laid-Open No. 7-0723. Means no. That is, in the pseudo-random interpolymer, the insertion of the vinylidene monomer from head to head and from head to tail does not occur.

 The resin (A) may contain 0.01 to 30% by weight of unsaturated carboxylic acid or a derivative thereof based on 100% by weight of the resin (A).

 As the liquid (B), an organosilicon compound is desirable, and dimethylpolysiloxane is particularly desirable.

As the fine powder (C), an organic fine powder composed of a higher fatty acid or a higher fatty acid derivative is preferable, and among these, stearic acid, erlic acid, oleic acid, sulfonic acid, montanic acid, and metal salts thereof, Amides and esters are preferred. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, a resin pellet having excellent non-adhesiveness and a method for producing the same according to the present invention will be specifically described.

 The resin pellets having excellent non-adhesiveness according to the present invention include a pellet surface of the specific resin (A) having a viscosity at 25 ° C and a surface tension at 25 ° C within a specific range. Liquid (B) and a fine powder (C) comprising at least one organic fine powder or silica fine powder having a specific average particle size. Therefore, the specific resin (A) comprises, on the pellet surface, the specific at least one liquid (B) and at least one organic fine powder or silica fine powder having the specific average particle diameter. By coating with the fine powder (C), the resin pellet according to the present invention can be manufactured.

 First, the resin (A), the liquid (B), and the fine powder (C) used for the resin pellet having excellent non-adhesiveness according to the present invention will be described.

 Resin (A)

 The resin (A) used in the present invention has a tensile modulus at 23 ° C. (YM; ASTM D-658) of not more than 160 MPa, usually 1 to: L600 MPa, preferably 1 11200 MPa. Specific examples of such a resin (A) include an in-polymer (i), a hydrogenated random copolymer (ii), a hydrogenated block copolymer (iii), and an unsaturated olefin copolymer. Coalescence (iv). These resins (A) can be used alone or in combination of two or more. As a combination of two or more such, for example,

 (1) a combination of an interpolymer (i) and a hydrogenated random copolymer (ii),

(2) Combination of interpolymer (i) and hydrogenated block copolymer (iii) Let

 (3) Combination of interpolymer (i) and unsaturated olefin copolymer (iv),

 (4) a combination of a hydrogenated random copolymer (ii) and a hydrogenated block copolymer (iii),

 (5) a combination of a hydrogenated random copolymer (ii) and an unsaturated olefin copolymer (iv),

 (6) a combination of a hydrogenated block copolymer (iii) and an unsaturated olefin copolymer (iv),

 (7) Combination of In-Yuichi polymer (i), hydrogenated random copolymer (ii) and hydrogenated block copolymer (iii),

 (8) Combination of In-Yuichi polymer (i), hydrogenated random copolymer (ii) and unsaturated olefin copolymer (iv),

 (9) Combination of interpolymer (i), hydrogenated block copolymer (iii) and unsaturated olefin copolymer (iv)

And the like.

 [In Yuichi Polymer (i)]

 The interpolymer (i) used in the present invention includes:

 (1) (a) at least one aromatic vinyl or vinylidene monomer, or

(b) at least one selected from a hindered aliphatic vinyl monomer, a hindered cycloaliphatic vinyl monomer, a hindered aliphatic vinylidene monomer and a hindered cycloaliphatic vinylidene monomer, or (c) at least one aromatic vinyl or vinylidene monomer, and at least one selected from a hindered aliphatic vinyl monomer, a hindered cycloaliphatic vinyl monomer, a hindered aliphatic vinylidene monomer and a hindered cycloaliphatic vinylidene monomer Combination of

 From 1 to 99 mol% of polymer units derived from

 (2) A substantially random interpolymer comprising 99 to 1 mol% of polymer units derived from ethylene or at least one type of olefin having 3 to 20 carbon atoms or a combination thereof.

 As used herein, the term “interpolymer” refers to a copolymer of at least two monomers polymerized into an interpolymer.

 As used herein, “copolymer” means a polymer obtained by polymerizing at least two types of monomers into a copolymer.

 As used herein, the olefin comprises an aromatic vinyl monomer, an aromatic vinylidene monomer, a hindered aliphatic pinyl monomer, a hindered cycloaliphatic vinyl monomer, a hindered aliphatic vinylidene monomer or a hindered cycloaliphatic vinylidene monomer. The term “substantially random” in a substantially random interpolymer refers to “POL YMER SEQUENCE DEDERM IATI〇N, Carbour—13 NMR, published in Academia Press, New York, 1977. As described in J. C. R anda 11 on pages 71-78 of “Me th od”, the monomer distribution of the polymer was determined by “Bernuri's statistical model” or “No. Or a second-order Marcobian statistical model ”.

Preferably, a substantially random copolymer consisting of ethylene or a olefin having 3 to 20 carbon atoms and an aromatic vinyl or vinylidene monomer is used. One polymer is a block of more than 3 units of aromatic vinyl or vinylidene monomer (for example, a styrene monomer having at least 4 units of repeating units derived from styrene) in a block of one unit of the total amount of aromatic vinyl or vinylidene monomer. Does not contain more than 5%. More preferably, the interpolymer is not characterized by a high degree of isotacticity or syndiotacticity. The peak region corresponding to the main chain methylene and methine carbon, which indicates either the mesodiad sequence or the racemic diad sequence in the spectrum, should not exceed 75% of the total peak region of the main chain methylene and methine carbon Means that. Inorganic polymers suitable for preparing the resin pellets of the present invention include one or more α-olefins, one or more aromatic vinyl or vinylidene monomers and or one or more binder aliphatic or cycloaliphatic aliphatic. Includes, but is not limited to, interpolymers obtained by polymerizing with vinyl or vinylidene monomers.

 Examples of preferred freeolefins include those having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and more preferably 3 to 8 carbon atoms. Among them, propylene, tributene, 4-methyltripentene, trihexene, and trioctene are particularly preferred. These -olefins do not contain aromatic groups. Also, ethylene is particularly preferably used.

Examples of the aromatic vinyl or vinylidene monomer suitable for producing the interpolymer (i) used in the present invention include a monomer represented by the following formula. R ¹

In this formula, R ¹ is an atom or group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group.

Each R ² is independently an atom or group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group.

 Ar is a phenyl group or a phenyl group substituted with 1 to 5 substituents selected from the group consisting of a halogen atom, an alkyl group having 1 to 4 carbon atoms and a haloalkyl group having 1 to 4 carbon atoms. .

n is an integer of 0 to 4, preferably 0 to 2, and most preferably 0. Specific examples of the aromatic monovinyl or monovinylidene monomer include styrene, vinyltoluene, α-methylstyrene, t-butylstyrene, chlorostyrene and the like, and all isomers thereof are also included. Particularly preferred aromatic monovinyl or monovinylidene monomers include styrene and its lower alkyl- or halogen-substituted derivatives. Preferred monomers include styrene, -methylstyrene, lower alkyl (alkyl having 1 to 4 carbon atoms) mono- or phenyl ring-substituted derivatives of styrene, for example, ortho-, meta-, para-methylstyrene, ring-substituted There are styrene, para-vinyl toluene or a mixture thereof. A more preferred aromatic monovinyl monomer is styrene. The term "hindered aliphatic or cycloaliphatic vinyl or vinylidene compound" means an addition polymerizable vinyl or vinylidene monomer corresponding to the compound represented by the following formula.

A ¹

R ¹ one C - In C ²⁾ 2 This equation, A ¹ is a sterically bulky aliphatic 2 0 or less carbon atoms or a cyclic aliphatic substituents.

R ¹ is an atom or group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group.

 Each is independently an atom or group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group.

R ¹ and A ¹ may be taken together to form a ring system.

 The term "sterically bulky" means that the monomer having this aliphatic or cycloaliphatic substituent cannot normally be addition polymerized with a standard Ziegler-Natta catalyst at a rate comparable to ethylene polymerization.

Preferred hindered aliphatic or cycloaliphatic vinyl or vinylidene compounds are monomers in which one of the carbon atoms having an ethylenically unsaturated bond is tertiary or quaternary substituted. Examples of these substituents include cycloaliphatic groups such as cyclohexyl, cyclohexenyl and cyclooctenyl, or cyclic alkyl or aryl substituted derivatives thereof. The most preferred hindered aliphatic or cycloaliphatic vinyl or vinylidene compounds are cyclohexane and various isomeric vinyl-ring-substituted derivatives of substituted cyclohexanes, and 5-ethylidene- 2- Norbornene. Particularly preferred are 1-, 3- and 4-vinylcyclohexene.

 An copolymer obtained by polymerizing ethylene and / or one or more olefins used in the present invention with one or more aromatic vinyl or vinylidene monomers and Z or one or more binder aliphatic or cycloaliphatic vinyl or vinylidene monomers. One polymer is a substantially random polymer. These polymers typically comprise from 1 to 99 mol%, preferably from 1 to 65 mol%, of at least one aromatic pinyl or vinylidene monomer and Z or a hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer. And more preferably 5 to 50 mol%, and 99 to 1 mol%, preferably 35 to 99 mol% of ethylene, or at least one C3 to C20 phosphorefin or a combination thereof. , More preferably 50 to 95 mol%.

 The number average molecular weight (Mn) of the interpolymer is usually at least 100,000, preferably at least 20,000 to 1,000, more preferably at least 50,000. 5500, 0000.

By the way, during the production of a substantially random vinyl polymer, some amount of a vinyl aromatic vinyl or vinylidene homopolymer may be formed by homopolymerization of an aromatic vinyl or vinylidene monomer under heating. The presence of an aromatic vinyl or vinylidene homopolymer is generally not preferred for the purposes of the present invention and cannot be ignored. Separation of the aromatic vinyl or vinylidene homopolymer from the interpolymer, if desired, by extraction techniques such as selective precipitation from solution using a non-solvent for either the vinyl polymer or the aromatic vinyl or vinylidene homopolymer. Can be. For the purposes of the present invention, the abundance of aromatic vinyl or vinylidene homopolymer is It is desirable that the content be 20% by weight or less, preferably 15% by weight or less of the total amount of the polymer.

 Substantially random in-set polymers are disclosed in U.S. application Ser. No. 07 545,403, filed Jul. 3, 1990, by James C. Stevens, et al. (EP-A—0, 416, 815) And US Patent Application No. 087469,828, filed and granted on June 6, 1995 (US Patent No. 5,703,187). All of these disclosures in these U.S. applications are incorporated herein by reference. Preferred operating conditions for these polymerization reactions are a pressure of atmospheric pressure to 3,000 atm and a temperature of -30 to 200 ° C. If polymerization and unreacted monomer removal are performed at temperatures higher than the autopolymerization temperature of the respective monomers, free radical polymerization may produce some amount of homopolymerized polymerization products.

 An example of a preferred catalyst and method for preparing the substantially random interpolymer used in the present invention is described in US application 07Z545, filed July 3, 1990, corresponding to EP-A-416,815. , 403; U.S. application filed May 20, 1999 corresponding to EPA-514, 828 07 / 702,475; U.S. application filed May 1, 992 corresponding to EPA-520,732 Application No. 0 / 876,268; U.S. application filed May 12, 1994, 08 241 523 (U.S. Pat. No. 5,470,993); U.S. Pat. No. 5,055,438; 5,057,475; 5, 096, 867; 5, 064, 802; 5, 1 32, 380; 5,

1 89, 1 92; 5, 32 1, 106; 5, 347, 024; 5, 350, 7

23; 5, 374, 696; 5, 399, 635 and 5, 556, 928. All of these disclosures are cited herein.

The substantially random olefin Z aromatic vinyl or vinylidene interpolymer used in the present invention is also described in WO 95/32095 John. The method described by Bradfute et al. (WR G race & Co) in C., the method described by RB Panel 11 (Exxon Chemica 1 Patents, Inc.) in WO 94/00500, and " P1 astics Technology, page 25 (September 992), and the disclosures of all of which are incorporated herein. Also, at least one free fin disclosed in U.S. Application 08Z708,809 (U.S. Patent 5,879,149) filed on September 4, 1996 by Francis J. Timmers, et al. Preference is also given to a substantially random interpolymer of aromatic vinyl / aromatic vinyl phosphoolefin tetrad. These interpolymers have additional signals with intensities more than three times peak-to-peak noise. These signals appear in the chemical shift range of 43.75-44.25 ppm and 38.0-38.5 ppm. In particular, peaks are observed at 44.1, 43.9 and 38.2 ppm. Proton test NMR experiments show that the signal in the chemical shift region at 43.75-44.25 ppm is methine carbon and the signal in the 38.0-38.5 ppm region is methylene carbon.

 The pseudorandom-in-one polymer comprising an aliphatic olefin and an aromatic monovinyl or monovinylidene compound used in the present invention is disclosed in US Patent Application No. 545403 filed on July 3, 1990 (European Patent (Corresponding to Publication No. 0416815).

These in-situ polymers (i) can be prepared by performing the polymerization at a temperature of from 30 to 250 ° C. in the presence of a catalyst of the following formula and, if desired, preferably a cocatalyst.

Wherein each C p is independently in each case a substituted cyclopentagenyl group 7Γ-bonded to M, E is a carbon or silicon atom, and M is an element of group IV of the periodic table A metal, preferably Zr or Hf, most preferably Zr, wherein each R is independently in each occurrence a hydrogen atom or hydrocarbyl, silahydrocarbyl or hydrocarbylsilyl, preferably 30 or less, preferably Or a group having 1 to 20 carbon atoms or more preferably 1 to 10 carbon atoms, and each R ′ is independently a hydrogen atom, a halogen atom, or a carboxy or hydrocarbyl A hydroxy or silahydrocarbyl or hydrocarbylsilyl group having 30 or less, preferably 1 to 20 and more preferably 1 to 10 carbon or gayon atoms, or 2 The connexion C such R 'groups together, _ ₁₀ hydrocarbyl substituted 1, 3 - butadiene forms a, m is Ru 1 or 2 der. A particularly preferred substituted cyclopentenyl group includes a group represented by the following formula.

Wherein each R is independently in each case a hydrogen atom, or hydrocarbyl, silahydrocarbyl or hydrocarbylsilyl, preferably 30 or less, preferably Or a group having 1-20, more preferably 1-10 carbon or silicon atoms, or two R groups taken together to form a divalent derivative of these groups I have. Preferably, R is independently at each occurrence (including all isomers, if any), hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl, or When possible, two of these R groups combine to form a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, or oxyhydrofluorenyl. ing.

 Specific examples of particularly preferred catalysts include:

 Racemic (dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl) zirconium dichloride,

 Racemic (dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl) zirconium 1,4-diphenyl-1,3-butadiene,

Rasemi (dimethylsilane Jiiru) - bis - (2-methyl-4-Fueniruindeni Le) zirconium di - C _1-4 alkyl,

Racemic (dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl) zirconium di-C _M alkyl,

 Racemic (dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl) zirconium di-CH alkoxide,

Or a combination thereof.

 In addition, the following titanium-based constrained geometry catalyst

geomet ry catalysts) [N- (1,1-dimethylethyl) -1,1-dimethyl-1-[(1,2,3,4,5-7?) 1-1,5,6,7-tetrahydro-s-indaccent Yl] silane aminato (2-) -N] titanium dimethyl:

 (Triindenyl) (t-butylamido) dimethyl-silane titanium dimethyl; ((3-1-butyl) (1,2,3,4,5-77) -triindenyl) (tributylamido) dimethylsilane titanium dimethyl; and

 (3-Iso-propyl) (1,2,3,4,5-7?)-Triindenyl) (t-butylamide) dimethylsilane Titanium dimethyl, or a combination thereof.

Other methods for producing the interpolymers used in the present invention are described in Long ο and Gr assi. (Makromo 1. Chem., Vol. 191, 2387 — 2396 (1990)), and D 'Ann. ie 1 lo et al. (Journa 1 of Applied Polymer Science, Vol. 58, 1701-1706 (1995)), in which methylalminoxane (MAO) and cyclopentyl genenyl are described. titanium trichloride (C Τ ί C 1 ₃₎ using a system of catalysts are prepared ethylene styrene copolymer scratch. Xu and Lin (PolymerPrerints, Am. Chem. SoC., Div. Po1ym. Chem.) Vol. 35, 686, 687 (1 994)) _{is, MgC l 2 ZT i C l} / N d C 1, using / a 1 (i B u) 3 catalyst, is prepared random copolymer of styrene and propylene. Moreover, Lu and the like (J ou rnalof Ap plied Po ly me r S cience, Vo l. 53, 1453- 1460 pp (199 4)) _{is, T i C 1 4 ZNd C} 1 3 / M g C 1 2/1 It reports the copolymerization of ethylene and styrene using (E t) ₃ catalyst. Sernets and Mulhaupt (Macromol. Chem. Phys., V. 197, pp. 1071-1083, 1997) are based on Me ₂ S 1 (Me ₄ C p) (Nt-butyl ) T i C 1 ₂ Z methylaluminoxane, describes the effects of the polymerization conditions in the copolymerization of styrene and ethylene using a Ziegler-Summer evening catalyst.

 For the ethylene-styrene copolymers produced by the ridge-type meta-mouth catalysts, see Arai, Toshiaki and Suzuki (Polymer Preprints, Am. Chem. Soc., Div. Polym. Chem.) Vol. 38, p. 349, 350, 1997) and U.S. Pat. No. 5,652,315 (Mitsui Toatsu Chemical Co., Ltd.).

 For a method for producing an insoluble polymer composed of a-olefinin aromatic vinyl monomer (for example, propylene Z styrene / butene / styrene), see US Pat. No. 5,244,996 (Mitsui Petrochemical Industries, Ltd.) or US Pat. , 3 15 (Mitsui Petrochemical Industry Co., Ltd.), and in German publication DE 197 1 1 339 A1 and US Patent 5,883,213 (Electrical Chemical Industry Co., Ltd.) Are also described.

 The method of preparing the interpolymer component disclosed above is incorporated herein by reference.

 The ethylene Z styrene random copolymer disclosed by Aria, Toru et al. In Polymer Preprints Vol. 39, No. 1, March 1998 can also be used as a component of the present invention.

Examples of suitable catalysts and methods for producing the pseudorandom interpolymer suitably used in the present invention are described in U.S. Patent Application No. 5 45403 filed July 3, 1990 (European Patent Publication No. 0416815), U.S. Patent Application No. 547718 filed on July 3, 1990 (European Patent Publication No. 468651), U.S. Patent Application No. 702475 filed on May 20, 1991 (European Patent Publication No. 514 288), U.S. Patent Application No. 876 268 filed May 1, 1992 (European Patent Publication No. 5207332) ), U.S. Patent Application No. 8003 filed on Jan. 21, 1993 (U.S. Pat. No. 5,374,696), filed on Jun. 24, 1993. U.S. patent application Ser. No. 08 / 197,727 (corresponding to WO 95/05056) and U.S. patent application Ser. Nos. 5,055,54,6, 5,057,4,75,5,0 Nos. 9 686 7, 5 0 6 8 8 0 2, 5 13 8 3 8 0 8 and 5 9 9 1 9 2 are disclosed in the respective specifications, all of which are incorporated herein by reference. Quote for reference.

 The interpolymer (i) used in the present invention may be graft-modified with a radically polymerizable monomer having a reactive polar group. The graft amount of the radical polymerizable monomer in the modified interpolymer is 0.01 to 30% by weight, preferably 0.01 to 1% by weight, based on 100% by weight of the interpolymer before the graft modification. It is desirable to be in the range of 10% by weight, more preferably 0.1 to 2% by weight.

 The radically polymerizable monomer having a reactive polar group used in the present invention is a monomer containing at least one radically polymerizable double bond in a molecule, and is a hydroxyl group-containing ethylenically unsaturated compound, amino. At least one selected from a group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and its derivatives, a vinyl ester compound, a nitrile group-containing unsaturated compound, and vinyl chloride It is.

 As the hydroxyl group-containing ethylenically unsaturated compound, specifically,

Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-propyl (meth) acrylate, 3-chloro-2- Hydroxypropyl Rire (meta) acrylate, glycerin mono (meta) acrylate, penyu erythri] rumono (meta) acrylate, trimethylolpropane mono (meta) acrylate, tetramethylolethane mono (meta) acrylate, butanediol mono (meta) acrylate (Meth) acrylates such as polyethylene glycol mono (meth) acrylate,-(6-hydroxyhexanoyloxy) ethyl acrylate;

 10-Pendecentol, octen-3-ol, 2-methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol acrylamide, 2- (meth) acryloyl xychetyl acid Examples include phosphate, glycerin monoallyl ether, aryl alcohol, aryloxyethanol, 2-butene-1,4-diol, and glycerol monoalcohol.

 The amino group-containing ethylenically unsaturated compound is a compound having an ethylenic double bond and an amino group. Examples of such a compound include vinyl having at least one kind of an amino group and a substituted amino group represented by the following formula. System monomers can be mentioned.

R

 /

 ■ N

 \

In the formula, R ³ represents a hydrogen atom, a methyl group or an ethyl group, and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 or a carbon atom having 6 carbon atoms. -12, preferably 6-8 cycloalkyl groups. The above-mentioned alkyl group and cycloalkyl group may further have a substituent. Examples of such an amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, Alkyl ester derivatives of acrylic acid or methacrylic acid, such as phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate;

Vinylamine-based derivatives such as N-vinylgetylamine and N-acetylvinylamine;

 Arylamine derivatives such as arylamine, methylacrylamine, N-methylacrylamine, N, N-dimethylacrylamide and Ν, Ν-dimethylaminopropylacrylamide;

 Acrylamide derivatives such as acrylamide and Ν-methylacrylamide; aminostyrenes such as Ρ-aminostyrene;

 6-aminohexylsuccinimide, 2-aminoethylsuccinimide and the like are used.

 The epoxy group-containing ethylenically unsaturated compound is a monomer having at least one polymerizable unsaturated bond and at least one epoxy group in one molecule. Specific examples of such an epoxy group-containing ethylenically unsaturated compound include: In general,

 Glycidyl acrylate, dalicidyl methacrylate;

 Mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, mono and diglycidyl esters of tetrahydrofuroic acid, mono and glycidyl esters of itaconic acid Esters, mono- and diglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, end-cis-bicyclo

To [2.2.1] mono- and di-pto-5-ene-2,3-dicarboxylic acids (Nadic acid ™) Glycidyl esters, endo-cis-picilo [2.2.1] hept-5-ene-2-methyl-2,3-dicarboxylic acid (methylnadic acid ™) mono- and diglycidyl esters, and arylsuccinic acid Dicarboxylic acid mono and alkyl glycidyl esters such as mono and glycidyl esters (1 to 12 carbon atoms of the alkyl group in the case of monodaricidyl ester);

 Alkyl glycidyl ester of P-styrene carboxylic acid, aryl glycidyl ether, 2-methylaryl glycidyl ether, styrene-glycidyl ether, 3,4-epoxy-tobutene, 3,4-epoxy-3-methyl- 1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-topentene, 5,6-epoxy-1-hexene, vinylcyclohexene monooxide, etc. Examples can be given.

 Examples of the aromatic vinyl compound include a compound represented by the following formula.

In the above formula, R ⁵ and R ⁶ may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group and An isopropyl group can be mentioned.

R ⁷ represents a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom, and specifically includes a methyl group, an ethyl group, a propyl group and an isopropyl group, and a chlorine atom, a bromine atom and an iodine atom. be able to.

N represents an integer of usually 0 to 5, preferably 1 to 5. Specific examples of such aromatic vinyl compounds include styrene, permethylstyrene, 0-methylstyrene, p-methylstyrene, m-methylstyrene, P-chlorostyrene, m-chlorostyrene, and P-chlorostyrene. Methylstyrene, 4-vinylpyridin, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridin, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline, N-vinyl Carbazole, N-vinylpyrrolidone and the like can be mentioned.

 Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrofluoric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and Nadic. Acid ™ (endcis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid Acids and the like.

 Examples of the derivative of the unsaturated carboxylic acid include, for example, an acid halide compound, an amide compound, an imide compound, an acid anhydride, and an ester compound of the above-described unsaturated sulfonic acid. In particular,

 Malenyl chloride, malenilimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrofluoric anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride Dimethyl maleate, monomethyl maleate, dimethyl maleate, getyl maleate, getyl fumarate, dimethyl itaconate, getyl citraconic acid, dimethyl tetrahydrofluorate, bicyclo

[2,2,1] hept-2-ene-5,6-dicarboxylate, glycidyl maleate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, Examples thereof include aminoethyl methacrylate and aminopropyl methacrylate. Of these, (meth) acrylic acid, maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate, and aminopropyl methacrylate are preferred.

 Specific examples of the above vinyl ester compounds include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl propylate, vinyl versatate, vinyl laurate, and vinyl stearate. And vinyl benzoate, p-t-butyl vinyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate and the like.

 Specific examples of the nitrile group-containing unsaturated compound include acrylonitrile, methacrylonitrile, fumaronitrile, arylicyanide, and cyanoethyl acrylate.

 Among these radically polymerizable monomers, maleic anhydride, (meth) acrylic acid, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (methyl) acrylate, aminoethyl (meth) acrylate, ) Pyraminoethyl acrylate, glycidyl (meth) acrylate, styrene, methyl (meth) acrylate, methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile Preferably.

 The graft modification of the above-mentioned polymer with a radical polymerizable monomer can be carried out by using a conventionally known graft polymerization method.

For example, there are a method in which the above-mentioned interpolymer is melted and an unsaturated carboxylic acid is added to carry out graft polymerization, and a method in which the above-mentioned interpolymer is dissolved in a solvent and a radical polymerizable monomer is added to carry out graft polymerization. In these methods, when the graft polymerization is carried out in the presence of a radical initiator, the radical polymerizable monomer can be efficiently graft-polymerized. In this case, the radical initiator is usually used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the interpolymer.

 Organic radicals, azo compounds and the like are used as such radical initiators. As such a radical initiator, specifically,

 Benzoylperoxide, Dichlorobenzoylperoxide, Dicumylperoxide, Di-1-butylperoxide, 2,5-Dimethyl-2,5-di (peroxide benzoate) Hexin-3, 1 , 4-bis (t-butylperoxyisopropyl) benzene, lauroylbeloxide, t-butylperacetate, 2,5-dimethyl-2,5-di- (t-butylperoxide) hexine- 3,2,5-dimethyl-2,5-di (t-butylperoxide) hexane, t-butylperbenzoate, t-butylperphenylacetate, t-butylperisobutyrate, t-butylper-sec-octe Tert-butyl perpivalate, cumyl pervivalate, t-butyl perjethyl acetate; azobisisobutyronitrile, dimethylazoisobutyrate, and the like.

 Of these, dicumylperoxide, di-1-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5 -Dialkylperoxides such as di (t-butylperoxy) hexane and 1,4-bis (t-butylperoxysopropyl) benzene are preferably used. The reaction temperature of the graft polymerization reaction using a radical initiator as described above or the graft polymerization reaction performed without using a radical initiator is usually 60 to 300 ° C., preferably 80 to 200 ° C. Set within the range of 30 ° C.

[Hydrogenated random copolymer (ii)] The hydrogenated random copolymer (ii) used in the present invention is a hydrogenated product of a copolymer obtained by random copolymerization of an aromatic vinyl compound and a conjugated gen, and is a component derived from the conjugated gen. And / or an unsaturated carboxylic acid or its copolymer is added to the hydrogenated random copolymer (Π-a) or the copolymer (ii-a) having a hydrogenation ratio of the component derived from the aromatic vinyl compound of 90% or more. A modified hydrogenated random copolymer (ii-b) obtained by grafting a derivative, which has a tensile modulus at 23 ° C (YM; ASTM D-658) of 1600 MPa or less, usually 1 to 1600 MPa, Preferably:! ~ 1 200MPa.

 Specific examples of the aromatic vinyl compound include styrene, permethylstyrene, 3-methylstyrene, P-methylstyrene, 4-propylstyrene, 4-dodecylstyrene, 4-cyclohexylstyrene, and 2-ethyl. -4-benzyl styrene, 4- (phenylbutyl) styrene, vinyl naphthylene, 2-vinyl naphthalene, and the like. Of these, styrene is preferred.

 Specific examples of the conjugated diene include butadiene, isoprene, toluene diene, 2,3-dimethylbutadiene, and combinations thereof. Of these, butadiene, isoprene, and a combination of butadiene and isoprene are preferred.

 The aromatic vinyl compound as described above ♦ The conjugated gen random copolymer contains 5 to 50% by weight, preferably 5 to 35% by weight, of a structural unit derived from the aromatic vinyl compound. It is desirable that the derived structural unit is contained in a proportion of 50 to 95% by weight, preferably 65 to 95% by weight.

The content of the structural unit derived from the aromatic vinyl compound can be measured by a conventional method such as infrared spectroscopy and NMR spectroscopy. The melt flow rate (MFR; ASTM D 1238, 200 ° C, load: 2.16 kg) of the aromatic vinyl compound / conjugated gen-random copolymer is usually 0.001 to 2 OO g / 10 minutes, preferably 0. . 01 ~ :! OO gZl O content, more preferably 0.01 to 50 10 minutes.

 The aromatic vinyl compound / conjugated gen random copolymer as described above can be prepared by a conventionally known method.

 The hydrogenated random copolymer (ii) used in the present invention is a product obtained by hydrogenating the above aromatic vinyl compound / conjugated genomic random copolymer by a known method, and is derived from conjugated gen. The hydrogenation ratio of the structural unit derived from Z or the aromatic vinyl compound is 90% or more.

 The hydrogenation rate is defined as 100% when the total amount of carbon-carbon double bonds in the structural units derived from the conjugated gen and / or the structural units derived from the aromatic vinyl compound is hydrogenated. It is the value when doing.

 Specific examples of such a hydrogenated random copolymer (ii) include a hydrogenated product of a styrene / isoprene random copolymer, a hydrogenated product of a styrene / butadiene random copolymer, and the like.

 The modified hydrogenated random copolymer (共 -b) used as the hydrogenated random copolymer (ii) in the present invention is obtained by adding unsaturated carboxylic acid or unsaturated carboxylic acid to the hydrogenated random copolymer (Π-a). It is a soft resin grafted with its derivative (hereinafter referred to as unsaturated carboxylic acid, etc.).

The unsaturated carboxylic acid and the like used in the production of the modified random copolymer (ii-b) are the same as those used in the production of the modified ethylene-hydroxyolefin-aromatic vinyl compound copolymer (i-111b). It is the same compound as the unsaturated carboxylic acid or the like used at the time. The amount of grafting of unsaturated carboxylic acid and the like in the modified random copolymer (ii-b) is 0.01 to 30% by weight based on 100% by weight of the hydrogenated random copolymer (Πa) before the graft modification. , Preferably 0.01 to 10% by weight, and more preferably 0.1 to 2% by weight.

 The graft modification of the hydrogenated random copolymer (ii-a) with an unsaturated carboxylic acid or the like can be performed using a conventionally known graft polymerization method.

 For example, a method of melting a hydrogenated random copolymer (ii-a) and adding an unsaturated carboxylic acid or the like to perform graft polymerization, dissolving the hydrogenated random copolymer (ii-a) in a solvent, There is a method of performing graft polymerization by adding an unsaturated carboxylic acid or the like.

 In these methods, when the graft polymerization is performed in the presence of a radical initiator, the graft monomer such as the unsaturated carboxylic acid can be efficiently graft-polymerized. In this case, the radical initiator is usually used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the hydrogenated random copolymer (ii-a). Organic radicals, azo compounds and the like are used as such radical initiators. As a specific example of such a radical initiator, a specific example of the radical initiator used in the production of the above-mentioned modified ethylene / hydroxyolefin / aromatic vinyl compound copolymer (i1-1b) is given. The compounds listed may be mentioned. The reaction temperature of the graft polymerization reaction using a radical initiator or the graft polymerization reaction performed without using a radical initiator is usually in the range of 60 to 300 ° C, preferably 80 to 230 ° C. Is set.

 [Hydrogenated block copolymer (iii)]

The hydrogenated block copolymer (iii) used in the present invention is a hydrogenated product of a copolymer obtained by block copolymerizing an aromatic vinyl compound and a conjugated gen. A hydrogenated block copolymer (iii-a) wherein the hydrogenation ratio of the structural unit derived from the role-gen and the structural unit derived from the Z aromatic vinyl compound is 90% or more, or a copolymer thereof ( iii-a) A modified hydrogenated block copolymer (iii-b) obtained by grafting an unsaturated carboxylic acid or a derivative thereof to a) and having a tensile modulus at 23 ° C (YM; AST D-658) of 160 OMP. a, usually 1 to 1600 MPa, preferably 1 to: 120 OMPa.

 The hydrogenated block copolymer (iii) used in the present invention is an aromatic vinyl compound comprising a block polymerization unit (X) derived from an aromatic pinyl compound and a block polymerization unit (Y) derived from a conjugated gen. It is a hydrogenated product of a conjugated diene block copolymer.

The form of the aromatic vinyl compound / conjugated gen block copolymer having such a structure is represented by, for example, X (YX) „or (XY) _n (n is an integer of 1 or more). _{n In} particular, the form of X—Y—X is preferable, and specifically, a polystyrene-polybutadiene (or polyisoprene or polyisoprene-butadiene) -polystyrene block copolymer is preferable.

In such a styrenic block copolymer, a physical crosslink (domain) is formed as a bridge point between the aromatic vinyl compound block polymer unit (X) and the conjugated gen rubber block polymer unit (Y), which are the hard segments. are doing. The conjugated gen rubber block polymerized unit (Y) existing between the aromatic vinyl compound block polymerized unit (X) is a soft segment and has rubber elasticity. Specific examples of the aromatic vinyl compound forming the block polymerized unit (X) include styrene, methyl styrene, 3-methyl styrene, P-methyl styrene, 4-propyl styrene, and 4-dodecyl. Styrene, 4-cyclohexylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, tributyl Vinyl naphthylene, 2-vinyl naphthalene and the like. Of these, styrene is preferred.

 Further, specific examples of the conjugated gen forming the block polymerized unit (Y) include butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene and a combination thereof. Of these, butadiene, isoprene, and a combination of butadiene and isoprene are preferred.

 When the polymer is derived from butadiene and isoprene, the unit derived from isoprene is preferably contained in an amount of 40 mol% or more.

 Further, as described above, the conjugated genomic block polymerized unit (Y) composed of butadiene / isoprene copolymerized unit may be any of a random copolymerized unit of butadiene and isoprene, a block copolymerized unit or a tapered copolymerized unit. Good. The aromatic vinyl compound / conjugated gen block copolymer as described above has an aromatic vinyl compound block polymerized unit (X) content of 50% by weight or less, preferably 5 to 22% by weight. . The content of the aromatic vinyl compound unit can be measured by a conventional method such as infrared spectroscopy and NMR spectroscopy.

 The melt flow rate (MFR; ASTM D 1238, 200 ° C, load 2.16 kg) of the aromatic vinyl compound / conjugated gen block copolymer is usually 5 g Z 10 minutes or more, preferably 5 to 10 minutes. : 100 g Z l 0 min.

 The aromatic vinyl compound · conjugated gen block copolymer as described above can be produced by various methods. For example, as such a production method,

(1) a method of sequentially polymerizing an aromatic vinyl compound and then a conjugated diene using an alkyl lithium compound such as n-butyl lithium as an initiator, (2) a method of polymerizing an aromatic vinyl compound and then a conjugated diene, and coupling this with a coupling agent,

 (3) A method of sequentially polymerizing a conjugated gen and then an aromatic vinyl compound using a lithium compound as an initiator can be used.

 The hydrogenated block copolymer (iii) used in the present invention is a product obtained by hydrogenating the above aromatic vinyl compound / conjugated gen block copolymer by a known method, and is derived from a conjugated gen. The hydrogenation ratio of the structural unit derived from the structural unit and / or the aromatic pinyl compound is 90% or more.

 The hydrogenation rate is defined as 100% when the total amount of carbon-carbon double bonds in the conjugated gen rubber block polymerized units (Y) and / or structural units derived from an aromatic vinyl compound is hydrogenated. It is the value when doing.

Specific examples of the hydrogenated block copolymer (iii) include a hydrogenated product of styrene / isoprene block copolymer (SEP) and a hydrogenated product of styrene / isoprene / styrene block copolymer. (SEPS; polystyrene / polyethylene Z propylene / polystyrene block copolymer), hydrogenated styrene / butadiene block copolymer (SEB), hydrogenated styrene / butadiene / styrene block copolymer (SEB S Polystyrene, polyethylene butylene, polystyrene block copolymer), and more specifically, HYBR AR (manufactured by Kuraray Co., Ltd.), Kraton (trade name, manufactured by Shell Chemical Co., Ltd.), and Kyreflex. TR (manufactured by Shell Chemical Co., Ltd.), Sorprene (manufactured by Filitz Buspetro Rifam), Europrene SOLT (manufactured by Anich) ), Yufuprene (made by Asahi Kasei Corporation), Sorprene-I T (manufactured by Nippon Elastomer Co., Ltd.), JSR TR (manufactured by Nippon Synthetic Rubber Co., Ltd.) Kui Clayton G (manufactured by Shell Chemical Co., Ltd.), Yufutec (manufactured by Asahi Kasei Corporation) (all trade names), and the like.

 In the present invention, as the hydrogenated block copolymer (iii), SEBS having a polymerized unit derived from an aromatic vinyl compound of 22% by weight or less and a melt flow rate of 510 minutes or more among them is used. Alternatively, SEPS is preferably used.

 Further, the modified hydrogenated block copolymer (iii-b) used as the hydrogenated block copolymer (iii) in the present invention is characterized in that the hydrogenated block copolymer (iii-a) has an unsaturated force rubonic acid or It is a soft resin grafted with its derivative (hereinafter referred to as unsaturated carboxylic acid, etc.).

 Unsaturated carboxylic acid and the like used in the production of the modified block copolymer (iii-b) are the same as those used in the production of the modified ethylene / phosphorin / aromatic vinyl compound copolymer (i-111b). This is the same compound as the unsaturated carboxylic acid or the like used in this case.

 The amount of the unsaturated carboxylic acid and the like in the modified block copolymer (iii-b) is 0.01 to 0.1% based on 100% by weight of the hydrogenated block copolymer (iii-a) before the graft modification. 30% by weight, preferably 0.01 to 10% by weight, more preferably 0.0 :! ~ 2% by weight.

 The graft modification of the hydrogenated block copolymer (iii-a) with an unsaturated carboxylic acid or the like can be carried out using a conventionally known graft polymerization method.

For example, a method of melting a hydrogenated block copolymer (iii-a) and adding an unsaturated carboxylic acid or the like to perform graft polymerization, dissolving the hydrogenated block copolymer (iii-a) in a solvent to obtain an unsaturated polymer There is a method of performing graft polymerization by adding a carboxylic acid or the like. In these methods, when the graft polymerization is carried out in the presence of a radical initiator, the graft monomer such as the unsaturated carboxylic acid can be efficiently graft-polymerized. In this case, the radical initiator is usually used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the hydrogenated block copolymer (iii-a). Organic radicals, azo compounds and the like are used as such radical initiators. Specific examples of such a radical initiator include the specific examples of the radical initiator used in the production of the above-mentioned modified ethylene / hydroxyolefin / aromatic vinyl compound copolymer (i-111b). The compounds listed as are mentioned. The reaction temperature of the graft polymerization reaction using a radical initiator or the graft polymerization reaction carried out without using a radical initiator is usually in the range of 60 to 300 ° C, preferably 80 to 230 ° C. Is set.

 [Unsaturated oligomeric copolymer (iv)]

The unsaturated olefin copolymer (iv) used in the present invention comprises ethylene (a), an aromatic vinyl compound (b), a non-conjugated polyene (c) and, if necessary, 3 to 20 carbon atoms. Molar ratio between the content of the structural unit derived from ethylene (a) and the content of the structural unit derived from polyolefin (b) having 3 to 20 carbon atoms, obtained by copolymerizing olefin (d). [(A) / (b)] is in the range of 100 to 60/40, and the iodine value is in the range of 0.5 to 50. The unsaturated olefin copolymer (iv) or a copolymer thereof. A modified unsaturated olefin copolymer (iv-b) obtained by grafting an unsaturated carboxylic acid or a derivative thereof to the polymer (iv), and having a tensile modulus at 23 ° C (YM; ASTM D-658). It is 1600 MPa or less, usually 1-1600 MPa, preferably 1-1200 MPa. As the aromatic vinyl compound (b) to be copolymerized with ethylene (a), specifically, a compound represented by the following general formula (I) is used.

In the formula, ¹ , R ² and R ³ may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. It is.

 n is an integer of 0-5, preferably 0-3.

 As the aromatic vinyl compound (b) as described above, specifically,

 Styrene;

 Mono- or polyalkylstyrene such as 0-methylstyrene, m-methylstyrene, p-methylstyrene, 0, P-dimethylstyrene, 0-ethylstyrene, m-ethylstyrene, P-ethylstyrene;

 Functional group-containing styrene derivatives such as methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, 0-chlorostyrene, P-chlorostyrene and divinylbenzene;

 Examples include 3-phenylpropylene, 4-phenylbutene, and a-methylstyrene. These aromatic vinyl compounds (b) can be used alone or in combination of two or more.

Specific examples of the non-conjugated polyene (c) include 1,4-pentane, 1,4-hexadiene, 4-methyl-1,5-heptadiene, 5-methylene-2-norbornene, -Ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 2,5-norbornadiene, 1,6-cyclooctadiene, 2-ethylene-2,5-norbornaje Gen compounds such as 2-isopropenyl-2,5_norbornadiene, dicyclopentene, 1,6-octane, 1,7-octane, tricyclopentene, etc. Examples include a non-conjugated triene or tetraene having a vinyl group, and a non-conjugated triene or tetraene having one 5-norbornene-2-yl group in one molecule.

 The total number of carbon atoms per molecule of the non-conjugated triene or tetraene (when two or more non-conjugated trienes or tetrane are contained, the average number of carbon atoms is not particularly limited, but is preferably Is preferably 9 to 30, more preferably 10 to 25, and particularly preferably 10 to 22. A non-conjugated triene or tetrane having carbon atoms in such a range is advantageous because it is easy to handle such as purification.

 Here, “triene” means a hydrocarbon compound having three carbon-carbon double bonds (C = C) in one molecule, and “tetraene” means one carbon-carbon double bond in one molecule. It means a hydrocarbon compound having four bonds. The carbon-carbon double bond includes a carbon-carbon double bond of a vinyl group and a carbon-carbon double bond of a 5-norbornene-2-yl group.

Non-conjugated trienes or tetrauranes include 3 (for triene) or 4 (for tetraene) carbon-carbon double bonds (including vinyl or 5-norbornene-2-yl) C = C), but the total number of hydrogen atoms directly bonded to carbon atoms adjacent to all carbon-carbon double bonds contained in one molecule of this non-conjugated triene or tetraurane is as follows: Usually, it is not particularly limited, but preferably 9 to 33, more preferably 12 to 33, and particularly preferably 14 to 33. It is preferable that the total number of hydrogen atoms be in such a range, since a copolymer having a high crosslinking reaction rate can be obtained. Note that this number of hydrogen atoms is used When the non-conjugated triene or tetraene is a mixture of two or more, the average is the number of these hydrogen atoms.

In the present invention, among the non-conjugated trienes or tetraenes, non-conjugated trienes or tetraenes in which a vinyl group or a 5-norporen-2-yl group is bonded to a methylene group (1-CH ₂ —) are preferred.

 Among such non-conjugated trienes or tetraenes, compounds represented by the following general formula (II-a) or the following general formula (Ill-a) are preferable.

 -(H-a) In the formula, p and q may be the same or different from each other and are 0 or 1 (however, p and q are not simultaneously 0).

 f is an integer of 0 to 5, preferably 0 to 2 (however, it is not 0 when p and Q are both 1).

 g is an integer of 1 to 6, preferably 1 to 3.

RR ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a carbon atom. An alkyl group having 1 to 3 atoms, more preferably R ¹ R, R ³ , R ^4. , R ⁵ and R ⁶ are hydrogen atoms, and R ⁷ is a hydrogen atom or a carbon atom having 1 to 3 carbon atoms. It is an alkyl group. R ⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. is there.

R ⁹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or — (CH ₂ ) _n —

Wherein n is an integer of 1 to 5, R ¹⁰ and R ¹¹ may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. And R ¹² represents an alkyl group having 1 to 5 carbon atoms), preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or 1 (CH ₂ ) n—CRio-CRUR ¹² (Where n is an integer from 1 to 3), R ^ID and R ¹¹ may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ¹² represents an alkyl group having 1 to 3 carbon atoms). However, when p and Q are both 1, R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

(Wherein, p, Q, f, g , Ri~R 9 are the same meaning as in the formula (ΙΙ-a).)

Specific examples of the non-conjugated triene or tetraene represented by the general formula (a-a) include the following compounds. CH ₃ CH ₃

6,10 "dimethyl-1,5-9-ndene, triene (DMUT)

 5,9-dimethyl-U, 8 "decatriene (DMDT)

C¾ CH ₃

HaC = CH-CH ₂ -CH2-CH = C-CHa-CH = C-CH3

6,9-dimethyl - ^1, 5, 8 - De force Toryen

CH ₃ CH ₃ CH ₃

¾ C = CH-C¾ -CH ₂ -CH = C-CH ₂ -C = C-CH ₃

6,8,9 ~ trimethyl, 5,8-de, power trien

 6,10,1¾-trimethyl-1,5,9,13-penta, katetraene

6 - Echiru - "10" methyl -I, ^5, 9 - © down, force Toryen

 4-ethylide, n-8,12-di, methyl-1,7,1

(EDT)

The non-conjugated triene or tetraene represented by the general formula (III-a) is specifically exemplified by a vinyl group of the compound exemplified as the non-conjugated triene or tetraene represented by the general formula (Π-a) Is substituted with a 5-norporen-2-yl group. Among the non-conjugated triene or tetrane represented by the general formula (式 -a), the non-conjugated triene or tetraene represented by the following general formula (IV-a) is preferable. The non-conjugated triene or tetraene is a compound in which p is 1 and Q is 0 in the non-conjugated triene or tetraene represented by the general formula (II-a).

 Further, among the non-conjugated triene or tetraene represented by the general formula (III-a), a non-conjugated triene or tetraene represented by the following general formula (V-a) is preferable. This non-conjugated triene or tetraene is a compound in which p is 1 and is 0 in the non-conjugated triene or tetraene represented by the general formula (I I I-a).

In the formula, f is an integer from 0 to 5, preferably an integer from 0 to 2.

 g is an integer of 1 to 6, preferably an integer of 1 to 3.

RR ² , R ⁵ , R ⁶ and R ⁷ may be the same or different from each other, and are the same as those in the above general formula (式 Ι-a), and preferably have a hydrogen atom or a group having 1 to 3 carbon atoms. Alkyl groups, more preferably RR ² , R ⁵ and R ⁶ are hydrogen atoms, and R ⁷ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁸ is the same as in the above formula (Π-a), and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

R ⁹ is the same as in the above formula (Π-a), and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

(In the formula, f, g, R ¹ , R ² , and R ^{5 to} R ⁹ have the same meanings as in the case of the general formula (IV-a).)

Specific examples of the non-conjugated triene or tetraene represented by the general formula (IV-a) include the following compounds.

1/72876

43

Ha OCH-CH2

- Echiride, down - ^1, 6 «Okutajen

CH ₃

 /

C2) E ₂ C = CH-CH _a -C-CH ₂ -CH = C

 II \

HC-CHa CH ₃

7-Methyl-ft-ethylene, 1,6-octane

7-methyl-4-Wechiride ,, emissions - 1, ⁶ - Nonajen

7 - Echiru 4 Echiride, down -1, ⁶ - Nonajen

CH ₃ CH ₃

 I /

(5) H ₂ C = CH-CH ₂ -C-CHa -C = C

 II \

HC-CHa CH ₃

6,7-v methyl- ^ ethylene-"Ι, ⁶ o-octane

6,7 Zomechiru - - Echirite ,, down - ^{1, 6-Nonajen}

Echiride, -1, 6-de, force, ene (8) H ₂ C = CH-CH ₂

 7-methyl-4-ethylen

 7-methyl-6-fu. Mouth pill-4 4 チ リ, ン 1,66 ク タ ク タ

H

 (10) ¾

 4-Echilide, N-I,?-Nonazyn

 8-Methyl-ethyl-1,1-nonazi, ene (EMN)

(12) H ₂ C = CH-CH ₂

ェ チ リ ン ゥ 7 7 7 7 7 CH ₃

Π 3) H ₂ C = CIi-CH ₂ -C-CH2 -CHa ^ CH-C,

 II \

 HC-CHa CHa-CHa-CHa

 8-Methyl-H-Echirite, n-"!, 7-ende, power gen

CH ₃ CH ₃

 () H20CH-CH2-C-CH2-CH2-C = C,

 II \

HC-CH ₃ CH ₃

 7, 8-dimethyl-U-ethylenite, n-1,7-nonazi, ene

CH ₃ CH ₃

 I /

(15) H ₂ C = CH-C¾ -C-CH2 -CH2-C = C

 I! \

HC-CHa C ₂ Hs

 7,8-dimethyl-4-ethylidene, n, 7-diene

CH ₃ CHa

 I /

(16) ¾ C = CH-CH ₂ -C-CHa -CH ₂ -C = C

_{HC-CH 3 CH2-CH2-} CH3 7,8- di Chill - Echirite, - ^1, 7-© down force Jen

(17) Ha OCH-CH2

8-methyl-7-ethyl-4-ethylidene, -1, 7-pan (18)

7,8-di, Echiru - ^ Echiri Hmm ^1, 7 - Kajen

 9-methyl-4-ethylidene-1,8-kajen

β, 9-ν methyl - 4 - Echirite ,, down - ^1, 8 "Kaji, E down

(21) Ha C = CH-CH _a

10-methyl-4 - Echiride ^x emissions -1, 9 - Unte ', Chikaraji, E down

9, "10"'Dimethyl ^ -ethylide, n-1,9-pentene, (23) H2O H-CH2-C-CH2-CH2-CH2-CH2-CH2-CH ^ C,

 I! \

 HC-CH3 C¾

1-Methyl- -ethylene- ¹ , ¹⁰ >

CH ₃ CHa

 I /

(21 | H2 C = CH-CH ₂ -C-CHz -CH2 -CH ₂ -CH ₂ -CHa -C = C

 II \

HC-CH3 CH ₃

 10 1 ,,--,,

 , U-dityl-4-ethylitite, n-I O-, te, 'ジ ェ ン The non-conjugated triene or tetraene represented by the general formula (V-a) is specifically represented by the general formula (IV Examples thereof include compounds in which the vinyl group of the compound exemplified as the non-conjugated triene or tetraene represented by -a) is replaced with a 5-norbornene-2-yl group.

 In the present invention, the non-conjugated polyene (c) is more preferably a compound represented by the general formula (II-a), and more preferably a compound represented by the general formula (IV-a). Particularly preferred.

 The non-conjugated triene or tetraene may be a mixture of a trans form and a cis form, or may be a trans form alone or a cis form alone.

 These non-conjugated polyenes (c) can be used alone or in combination of two or more.

Non-conjugated trienes or tetranes represented by the general formula (II-a) or (ΙΠ-a) are described in, for example, EP 0 916 354 A1 and WO 966 ノ 21050 Can be prepared by a conventionally known method as described in (1). These non-conjugated polyenes (c) can be used alone or in combination of two or more.

 Examples of the hypoolefin (d) having 3 to 20 carbon atoms which may constitute the unsaturated olefin copolymer (iv) include propylene, arbutene, 1-pentene and arbor. Xen, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethylpentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl- Trihexene, 4,4-dimethyltripentene, 4-ethyl-trihexene, 3-ethyltrihexene, trioctene, tridecene, tridodecene, tritetradecene, trihexadecene, trioctadecene, trioctene Examples include eicosene, 9-methyl-tridecene, 1-methyl-to-dodecene, and 12-ethyl-to-tetradecene. Of these, a olefin having 4 or more carbon atoms is preferred, and tobutene, trihexene, trioctene and tridecene are particularly preferred. These free fins

One type can be used alone, or two or more types can be used in combination.

 The unsaturated olefin-based copolymer (iv) is composed of a structural unit derived from ethylene (a), a structural unit derived from an aromatic vinyl compound (b), and a non-conjugated polyene.

The structural units derived from (c) and, if necessary, the structural units derived from the olefins having 3 to 20 carbon atoms (d) are randomly arranged and bonded to form a non-conjugated polyene (c) The main chain is a copolymer having a substantially linear structure while having a branched structure caused by the above. The fact that the copolymer has a substantially linear structure and does not substantially contain a gel-like crosslinked polymer means that the copolymer is soluble in an organic solvent and contains substantially no insoluble matter. Can be confirmed by For example, when the intrinsic viscosity [77] is measured, it can be confirmed by completely dissolving the copolymer in decalin at 135 ° C. The unsaturated olefin copolymer (iv) has a molar ratio of a structural unit derived from ethylene (a) to a structural unit derived from hypoolefin (d) having 3 to 20 carbon atoms (ethylene olefin). (Olefin) is in the range of 100/0 to 60/40, preferably 100Z0 to 70Z30, more preferably 100Ζ0 to 80Ζ20, and the structural unit derived from ethylene (a) and the carbon having 3 to 20 carbon atoms. And the total amount of structural units derived from olefins (d) and aromatic vinyl compounds

the molar ratio of constituent units derived from (b) (ethylene + Fei - Orefin Z aromatic vinyl compound) is 90 / ^/ 10-50 Bruno 50, preferably 85Z15～55Z4 5, preferably from 80Z20～60 / 40 Is desirable.

 The iodine value of the unsaturated olefin copolymer (iv) is usually in the range of from 0.5 to 50, preferably from 3 to 50, and more preferably from 4 to 40. The unsaturated olefin copolymer (iv) preferably has a crystallinity calculated from the peak of the melting point measured by a differential scanning calorimeter of 15% or less, preferably 10% or less. The intrinsic viscosity [] measured in decalin solution at 135 ° C is 0 :! It is desirably in the range of ~ 10 d1 Zg, preferably 1-5 d1.

The unsaturated olefin copolymer (iv) used in the present invention has an aromatic vinyl compound (b) in which the proportion of structural units constituting a continuous chain structure in which two or more continuous structural units are aromatic is It is desirable that the content is 1% or less, preferably 0.1% or less, based on the structural unit derived from the vinyl compound (b). The content of a chain structure in which two or more structural units derived from the aromatic vinyl compound (b) are continuous can be determined by ¹³ C-NMR.

 In such unsaturated olefin copolymer (iv), non-conjugated

When (c) is represented by the general formula (ΙΙ-a), the unsaturated oligomer In the polymer (iv), the structural unit derived from the non-conjugated triene or tetraene has a structure represented by the following general formula (II-b).

 (II-b)

(Wherein, p, q, f, g , R 'R 9 are the same meaning as in the formula (II- a).)

 When the non-conjugated polyene (c) is represented by the above general formula (ΙΠ-a), the structural unit derived from the non-conjugated triene or tetrane in the unsaturated olefin copolymer (iv) is It has a structure represented by the following general formula (III-b).

 -(ΠΙ-b)

(Wherein, p, q, f, g , R 'R 9 are the same meaning as in the formula (ΙΙ-a).)

Further, when the non-conjugated polyene (c) is represented by the general formula (IV-a), the non-conjugated triene or tereene may be contained in the unsaturated olefin copolymer (iv). Structural units derived from Traen have a structure represented by the following general formula (IV-b).

(In the formula, f, g, RR ² , and R ^{5 to} R ⁹ have the same meanings as in the above formula (IV-a).)

 When the non-conjugated polyene (c) is represented by the general formula (Va), the structural unit derived from the non-conjugated triene or tetrane in the unsaturated olefin copolymer (iv) is as follows: It has a structure represented by the general formula (V-b).

CH ⁹

 c¾

 (V-b)

(In the formula, f, g, RR ² , and R ^{5 to} R ⁹ have the same meanings as in the case of the general formula (IV-a) ′.) The fact that the structural unit derived from the non-conjugated polystyrene (c) has the above-mentioned structure in the unsaturated olefin-based copolymer (iv) means that the ¹³ C—NMR spectrum of the copolymer Can be confirmed by measuring

 The unsaturated olefin copolymer (iv-a) as described above can be prepared by reacting ethylene (a) with an aromatic vinyl compound (b) in the presence of, for example, a metamouth catalyst for olefin polymerization. It can be prepared by copolymerizing the conjugated polyene (c) and, if necessary, a hypoolefin (d) having 3 to 20 carbon atoms. The details of the method for producing the unsaturated olefin copolymer (iv-a) are described in JP-A-10-273565.

 Further, the modified unsaturated olefin copolymer (iv-b) used as the unsaturated olefin copolymer (iv) in the present invention is an unsaturated olefin copolymer.

It is a soft resin obtained by grafting an unsaturated carboxylic acid or a derivative thereof (hereinafter referred to as an unsaturated carboxylic acid, etc.) to (iv-a).

 Unsaturated carboxylic acids and the like used in the production of the modified unsaturated olefin copolymer (iv-b) include a modified ethylene-olefin-aromatic vinyl compound copolymer (i-l-b) Is the same compound as the unsaturated carboxylic acid used in the production of

 The amount of the unsaturated carboxylic acid and the like in the modified unsaturated olefin copolymer (iv-b) was calculated based on 100% by weight of the unsaturated olefin copolymer (iv-a) before the graft modification. It is in the range of 0.01 to 30% by weight, preferably 0.01 to 10% by weight, and more preferably 0.1 to 2% by weight.

The graft modification of the unsaturated olefin copolymer (iv-a) with an unsaturated carboxylic acid or the like can be performed by a conventionally known graft polymerization method. For example, a method of melting an unsaturated olefin copolymer (iv-a) and adding an unsaturated carboxylic acid or the like to carry out graft polymerization, using an unsaturated olefin copolymer (iv-a) as a solvent There is a method of dissolving and adding an unsaturated carboxylic acid or the like to carry out graft polymerization.

 In these methods, when the graft polymerization is performed in the presence of a radical initiator, the graft monomer such as the unsaturated carboxylic acid can be efficiently graft-polymerized. In this case, the radical initiator is usually used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the unsaturated olefin copolymer (iv-a).

 Organic radicals, azo compounds and the like are used as such radical initiators. Specific examples of such a radical initiator include the specific examples of the radical initiator used in the production of the above-mentioned modified ethylene / hydroxyolefin / aromatic vinyl compound copolymer (i-111b). The compounds listed as are mentioned. The reaction temperature of the graft polymerization reaction using a radical initiator or the graft polymerization reaction performed without using a radical initiator is usually set in the range of 60 to 300 ° C, preferably 80 to 230 ° C. Is done.

 Liquid (B)

The liquid (B) used in the present invention has a kinematic viscosity at 25 ° C. (JIS K-2283) of 0.5 to: L 00,000 cSt, preferably 100 to 5,000 cSt, and Preferably 200 to 1,000 cSt, and a surface tension at 25 ° C (measured by a capillary rising method) of 10 to 50 dyne Z cm, preferably 10 to 40 dyne / cm, more preferably 10 to 40 dyne Z / cm. It is in the range of ~ 30 dy ne / cm. As such a liquid (B), an organosilicon compound is desirable, and specific examples thereof include silicone oil, glycol, mineral oil, and higher alcohols. Silico Specific examples of the vegetable oil include polysiloxane RSIs having a repeating unit represented by the following formula.

 1 •

 o

 R

In the above formula, R and R ′ each independently represent an alkyl group, an aryl group, or a group in which a hydrogen atom of these groups is substituted by a halogen atom or the like. R and R 'may be the same group or may be different. Further, a part of R and R 'may be substituted with a hydroxyl group or an alkoxy group.

 Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. Specific examples of the aryl group include a phenyl group and a tolyl group.

 Specific examples of the halogen atom include atoms of fluorine, chlorine, bromine, and iodine.

 Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

 Among such polysiloxanes, dimethylpolysiloxane is particularly preferably used.

 In the present invention, the liquid (B) as described above can be used alone or in combination of two or more.

Fine powder (C) The fine powder (C) used in the present invention is at least one kind of organic fine powder or silica fine powder, and has an average particle size of 50 m or less, usually 0.1 to 50 m, preferably 1 to 50 m. 30 μm, more preferably in the range of 1-25 jum. The average particle size was determined by SEM (scanning electron microscope) or optical microscope observation.

 Examples of the organic fine powder preferably used in the present invention include fine powders of higher fatty acids or higher fatty acid derivatives.

 The higher fatty acid preferably used in the present invention is usually a saturated or unsaturated higher fatty acid having 12 to 30 carbon atoms. Specifically, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid , Behenic acid, oleic acid, linoleic acid, and hy-eleostearic acid; 8-eleostearic acid and hy-linoleic acid. Among them, stearic acid is preferred.

 The higher fatty acid derivatives preferably used in the present invention include salts of the above-mentioned higher fatty acids, specifically, sodium, potassium, magnesium, calcium, zinc, and aluminum salts of the higher fatty acids. Iron salts, lithium salts and the like. Among them, stearates are preferred. In addition, higher fatty acid derivatives, higher fatty acid amides, esters and the like can also be mentioned. Among these, amides and esters of stearic acid, erlic acid, oleic acid, itaconic acid and montanic acid are preferred.

 The above higher fatty acids or higher fatty acid derivatives can be used alone or as a mixture of two or more.

 Coating method

In the method for producing a resin pellet having excellent non-adhesiveness according to the present invention, the surface of a pellet of the resin (A) is coated with the liquid (B) and the fine powder (C). Such coating methods include, for example, (1) The resin (A) pellets and the liquid (B) are mechanically mixed by an ordinary method to adhere the liquid (B) to the pellet surface, and then the fine powder is applied to the pellet surface.

(C) and coat the surface of resin (A) pellets with liquid (B) and fine powder (C), or

 (2) Using an extruder with a so-called underwater cut type pelletizer, add the liquid (B) and a conventionally known surfactant (for example, soap) to water in which the liquid (B) is finely dispersed. The resin (A) in a molten state is extruded by an extruder and pelletized, so that the liquid (B) adheres to the surface of the pellet, and then the fine powder (C) is dusted on the surface of the pellet. There is a method of coating the surface of resin (A) pellets with liquid (B) and fine powder (C).

 In the above method (1), the amount of the liquid (B) adhering to the surface of the resin (A) pellet is usually 50 to 20,000 weight 111, preferably 500 to the resin (A) pellet. Desirably, it is 55,000 weight ppm. In addition, the amount of fine powder (C) attached to the surface of the resin (A) pellet is usually 50 to 10,000 ppm by weight, preferably 500 to 5,000 ppm by weight, based on the resin (A) pellet. It is desirable.

 In the above method (2), the concentration of the liquid (B) in water is usually 500 to 10,000 weight ppm, preferably 500 to 5,000 ppm by weight. The surfactant is used in an amount of usually 1 to 100 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the liquid (B). When the surfactant is used in the above ratio, the liquid (B) can be finely dispersed in water.

In the above method (2), the amount of the liquid (B) adhered to the surface of the resin (A) pellets is usually 50 to 20,000 weight 1) 111, preferably 50 to 20,000 weight per resin (A) pellets. More preferably, it is 50 to 5,000 weight ppm. The amount of fine powder (C) adhering to the surface of the resin (A) pellet is usually 50 to 10,000 pp, preferably 500 to 5,000 ppm by weight, based on the resin (A) pellet. Desirably. The invention's effect

 According to the present invention, it is possible to prepare a resin pellet which is more excellent in non-adhesiveness (pellet blocking resistance) and more excellent in appearance and handleability than a conventional resin pellet such as an olefin copolymer rubber. .

Example

 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples.

 The pellet blocking test in the examples and the like of the present invention was performed according to the following method.

 [Pellet blocking test]

 Place 60 g of a sample pellet (average weight of one pellet: about 35 mg) in a 12 Omm 210 mm polyethylene bag, fold the bag into three, and close the opening of the bag with cellophane adhesive tape.

Then, in an atmosphere of 40 ° C, the three-fold bags obtained as described above are stacked in two layers, a load of 90 gZcm ² is applied thereon, and the state is maintained for 24 hours. The bag was opened, the pellets were taken out, and the pellets were observed for non-adhesion, and evaluated by the following 10-point method.

 <Non-stickiness rating of pellets>

1 0 ... No blocking 7 ······················································································ /

 5 ······················································································ /

 3 ...

 1 ················· Pellet is veiled

 Further, the appearance of the pellet was visually observed, and evaluated by the following 〇 and X.

<Appearance>

 〇: No dusting (It is not possible to visually determine whether fine powder (C) has been added.)

 X: With dusting (It can be visually determined that fine powder (C) has been added.)

 In addition, in Examples and the like, the amounts of silicone oil and calcium stearate adhering to the pellet surface were determined as follows.

 That is, after washing 100 g of the pellet with methanol, all the washing liquid was recovered. Next, the methanol component was removed from the washing solution using an evaporator, and the residual silicon and calcium were analyzed for metals. The amount of adhesion between silicone oil and calcium stearate was calculated from the residual metal salt.

Example 1

Using a single screw extruder, ethylene-styrene copolymer (ESRC) [styrene content = 36.9 mol%, ethylene content 63.1 mol%, MFR (ASTM d 1238, 190 ° C, load 2.16 kg) = 100 parts by weight of a pellet prepared by kneading lg / 10 minutes, tensile modulus (YM) = 7. OMPa] at 200 ° C, and silicone oil [SH200, manufactured by Dow Corning Toray Co .; kinematic viscosity (20 ° C) = 500 cSt, surface tension (20 ° C) = 20 dyn eZcm] and 0.1 part by weight were mechanically mixed using a Henschel mixer. Next, the total amount of the resin pellet having silicone oil adhered to the surface obtained above and 3,500 parts by weight of calcium stearate having an average particle size of 2 Oim were mechanically mixed using a Henschel mixer. Was mixed.

 The amount of silicone oil deposited on the pellets obtained as described above was 980 weight ppm. The amount of calcium stearate adhering to the obtained pellets was 3,450 weight ppm.

 Next, a pellet blocking test was performed using the resin pellets according to the above method.

 Table 1 shows the results.

Comparative Example 1

 Example 1 was carried out in the same manner as in Example 1 except that the resin pellet was not mechanically mixed with the silicone oil and calcium stearate. The results are shown in Table 1.

Comparative Example 2

 In Example 1, mechanical mixing of 100 parts by weight of resin pellets and 0.05 part by weight of silicone oil was performed to attach silicone oil to the surface of the resin pellet, and mechanical mixing of the pellet with calcium stearate was performed. The procedure was performed in the same manner as in Example 1 except that the mixing was not performed.

 The results are shown in Table 1.

Comparative Example 3

 Example 1 was carried out in the same manner as in Example 1 except that the resin pellet and calcium stearate were not mechanically mixed.

 The results are shown in Table 1.

Comparative Example 4 Example 1 was carried out in the same manner as in Example 1 except that the mechanical mixing of the resin pellet and the silicone oil was not performed.

 The results are shown in Table 1.

Comparative Example 5 In Example 1, 100 parts by weight of resin pellets and 0.5 part by weight of silicone oil were mechanically mixed to adhere silicone oil to the surface of a resin pellet, and the pellet was mixed with calcium stearate. The procedure was performed in the same manner as in Example 1 except that mechanical mixing was not performed.

 The results are shown in Table 1. Table 1-Oil Silicone oil Stearic acid Ca Blocking Appearance

 [Weight ρρπΰ [Weight ppm]

 Example 1 ESRC 980 3,450 5 比較 Comparative example 1 ES C 0 0 1 比較 Comparative example 2 ESRC 950 0 1 比較 Comparative example 3 ESRC 960 0 1 比較 Comparative example 4 ESRC 0 3,400 5 X Comparative example 5 ESRC 4 , 600 0 1 〇

Claims

The scope of the claims

 1. At least one resin selected from the group consisting of the following (i) to (iv) and having a tensile modulus at 23 ° C (YM; ASTM D-658) of 1600 MPa or less (A) At least one liquid whose kinematic viscosity at 25 ° C is 0.5 to 100,000 cSt and surface tension at 25 ° C is in the range of 10 to 50 dyne cm (B) A resin pellet having excellent non-adhesiveness, characterized by being coated with at least one kind of organic fine powder or fine powder (C) comprising silica fine powder having an average particle size of 5 or less;

 (i) (1) (a) at least one aromatic vinyl or vinylidene monomer

 One or

 (b) at least one hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer, or

 (c) 1 to 99 mol% of polymer units derived from a combination of at least one aromatic vinyl or pinylidene monomer and at least one binder aliphatic or cycloaliphatic vinyl or vinylidene monomer; and ) 99-1 mol% of polymer units derived from ethylene, or at least one olefin having 3 to 20 carbon atoms or a combination thereof.

Consisting of a substantially random interpolymer

(ii) A hydrogenated product of a copolymer obtained by random copolymerization of an aromatic vinyl compound and a conjugated gen, and is derived from a structural unit derived from a conjugated gen and a vinyl or aromatic vinyl compound. A hydrogenated random copolymer whose constituent units have a hydrogenation ratio of 90% or more, (iii) a hydrogenated product of a copolymer obtained by block copolymerization of an aromatic vinyl compound and a conjugated gen, wherein the structural unit is derived from a conjugated gen and a structural unit derived from an aromatic or vinyl compound. A hydrogenated block copolymer having a unit hydrogenation rate of 90% or more,

 (iv) obtained by copolymerizing ethylene (a), an aromatic vinyl compound (b), a non-conjugated polyene (c), and optionally a olefin having 3 to 20 carbon atoms (d); The molar ratio between the content of the structural unit derived from a) and the content of the structural unit derived from hypoolefin having 3 to 20 carbon atoms (d) [(a) /

(d)] is in the range of 100/0 to 6040, and the iodine value is in the range of 0.5 to 50.

2. at least one kind of 2 selected from the group consisting of (i) to (iv),

The kinematic viscosity at 25 ° C of 0.5 to 100,000 cS is applied to the pellet surface of resin (A) whose tensile modulus at 3 ° C (YM; ASTM D-658) is 160 OMPa or less. at least one type of liquid (B) with a surface tension at 25 ° C in the range of 10 to 50 dyneZcm and at least one type of organic fine powder with an average particle size of 50 jum or less 2. The method for producing a resin pellet having excellent non-adhesiveness according to claim 1, wherein a fine powder (C) comprising silica fine powder is coated.

3. The interpolymer (i) power 1 to 99 mol% of a polymer unit derived from at least one aromatic vinyl or vinylidene monomer, and at least one of 3 to 20 carbon atoms. 3. The method for producing a resin bellet according to claim 2, wherein the polymer derived from the olefin is a substantially random interpolymer composed of 99 to 1 mol% of one unit.

4. The interpolymer (i) polymer units derived from styrene;! -99 mol%, and derived from ethylene or a combination of ethylene and at least one type of olefin having 3 to 10 carbon atoms. The method for producing a resin pellet according to claim 2, wherein the resin pellet is a substantially random interpolymer composed of 99 to 1 mol% of a polymer unit.

5. The interpolymer (i) is a pseudo-random interpolymer composed of 1 to 65 mol% of a polymer unit derived from styrene and 99 to 35 mol% of a polymer unit derived from ethylene. 3. The method for producing a resin pellet according to claim 2, wherein:

6. The interpolymer (U is a polymer unit derived from styrene;! To 65 mol%, and a polymer unit derived from ethylene and at least one a-olefin having 3 to 20 carbon atoms. 3. The method for producing a resin belt according to claim 2, wherein the resin belt is a pseudo-random polymer composed of up to 35 mol%.

7. The resin (A) is characterized in that the resin (A) contains 0.01 to 30% by weight of an unsaturated carboxylic acid or a derivative thereof with respect to 100% by weight of the resin (A). A method for producing the resin pellet according to claim 2.

8. The method for producing a resin pellet according to claim 2, wherein the liquid (B) is an organosilicon compound.

9. The method for producing a resin pellet according to claim 8, wherein the organosilicon compound is dimethylpolysiloxane.

10. The method for producing a resin bellet according to claim 2, wherein the fine powder (C) is an organic fine powder comprising a higher fatty acid or a higher fatty acid derivative.

11. The method according to claim 10, wherein the higher fatty acid or higher fatty acid derivative is stearic acid, erlic acid, oleic acid, itaconic acid, montanic acid, or a metal salt, amide or ester thereof. Production method of resin pellets.