KR20030012886A - Flexible resin pellet and process for producing the same - Google Patents

Abstract

The soft resin pellet of the present invention has a kinematic viscosity of 0.5 to 100,000 cSt at 25 ° C and a surface tension of 10 to 25 ° C on the surface of the soft resin pellet having a tensile modulus of 1600 MPa or less selected from (i) to (v). A liquid (for example, dimethylpolysiloxane) in the range of 50 dyne / cm and fine powder (for example, calcium stearate) having an average particle diameter of 50 µm or less are attached. Said soft resin pellets are (i) specific ethylene / alpha-olefin copolymer, (ii) specific propylene / alpha-olefin copolymer, (iii) ethylene, alpha-olefin of C3-C20, (non) conjugation Unsaturated olefin copolymer which becomes a polyene monomer, (iv) Vinyl acetate content 5-40 weight% of ethylene / vinyl acetate copolymer, (v) Cyclic olefin resin.

According to the present invention, a soft resin pellet having excellent non-tackiness, appearance, and handleability can be obtained as compared with conventional pelletized soft resins such as olefin copolymer rubber.

Description

Flexible resin pellet and its manufacturing method {FLEXIBLE RESIN PELLET AND PROCESS FOR PRODUCING THE SAME}

Olefin-based copolymer rubbers such as soft resins such as ethylene / propylene copolymer rubber and ethylene / propylene / diene copolymer rubber are usually supplied to the market in the form of blocks such as bales.

However, these block-like olefin copolymer rubbers have drawbacks such as trouble of taking out from the storage place, trouble of supply phase or transport to the molding apparatus, and poor metering.

Therefore, if the olefin copolymer rubber can be supplied to the market in the form of pellets, the above drawbacks are eliminated, and when kneading the olefin copolymer rubber with a compounding agent such as fillers, softeners and vulcanizing agents that are commonly used, The extruder has a high production efficiency instead of a mixer having a poor production efficiency, such as a short-barrier mixer, which has been used in the past, and has a great advantage of being able to produce compound rubber by supplying olefin copolymer rubber and compounding agent in pellet form. Can bring

However, even when the olefin copolymer rubber as described above is pelletized, since the olefin copolymer rubber itself has adhesiveness, it condenses in a block shape during pellet storage and loses its meaning as a pellet.

In addition, even when the ethylene / α-olefin copolymer elastomer having relatively low adhesion at room temperature is stored under a load or placed in a high temperature environment such as in summer, the pellets condense to form pellet products. There is a case where it loses its value.

Conventionally, as a method of reducing the surface tackiness of such sticky olefin copolymer rubber pellets or preventing pellets of olefin elastomers having relatively low stickiness at room temperature from condensing under load and / or at high temperature, A method is proposed. For example, the method of coating the surface of rubber pellets with silicone oil (Japanese Patent Application Laid-Open No. 48-47934), or inorganic powders such as talc, silica, calcium carbonate, or polyethylene powder as an anti-sticking agent, or pellets that are easily tackified by being embedded with polyethylene powder Methods of adhering powders are known.

However, the method of coating the surface of a rubber pellet or an elastomer pellet with silicone oil has the drawback that sufficient effect cannot be acquired with a sticky pellet. In the latter method, inorganic materials such as talc and silica are incompatible with the olefin copolymer rubber, and therefore, when these powders are adhered, they often adversely affect performance in the end use. In addition, in this method, in order to substantially prevent the condensation of the pellets, it is necessary to mix the anti-sticking agent powder with the pellet in the range of several to several ten percent, and when such an amount of the powder is mixed, the characteristics of the olefin copolymer rubber to be treated There is a flaw that is damaged. For example, when polyethylene powder is embedded in a pellet of olefin copolymer rubber, there is a drawback that the adhesion amount of polyethylene powder increases, causing deterioration of the rubbery property of the olefin copolymer rubber vulcanizate. This method also has the drawback of generating dustiness or the like on the surface of the pellets, which damages the appearance and deteriorates the handleability.

As an excellent anti-sticking method of these defect-free rubber pellets, the applicant has proposed a method of coating the rubber pellets with higher fatty acids and / or salts thereof (JP-A-56-136347). According to this method, the adhesiveness of a rubber pellet can be prevented and a rubber property is not impaired substantially.

However, Applicants can only stably attach higher fatty acids and / or their salts to the rubber pellets in a stable manner since the method described in this publication merely mixes the higher fatty acids and / or their salts and rubber. As a result, it was confirmed that blocking may also occur during storage after operations such as transportation and weighing of the rubber pellets.

Therefore, the present applicant further studies, and as a method of preventing the blocking of the rubber pellets in the storage, the olefin copolymer rubber pellets, fine powder carbon 12 to 30 fatty acids and / or salts thereof are 1 A method of producing a rubber sticky rubber pellet was proposed by mixing in the presence of ˜4 monovalent alcohols (JP-A-4-1011). Rubber pellets coated with the higher fatty acids and / or salts thereof obtained by this production method are filled with 25 kg bags after cargo transportation, and the bags are stacked in 10 steps and do not cause blocking even if left for one month. In this method, however, the powder comes out of the surface of the pellet, which may cause some difficulty in handling.

In recent years, the demand of the soft resin pellets which are excellent in non-tackiness and appearance, and is easy to handle is requested | required by the request of a user etc., compared with soft resin pellets, such as a conventional olefin copolymer rubber.

The present invention seeks to solve the problems associated with the prior art as described above. The soft resin pellets, which are superior in non-tackiness and appearance and are easier to handle than soft resin pellets such as conventional olefin copolymer rubbers, and their It is an object to provide a manufacturing method.

Disclosure of the Invention

The soft resin pellets according to the present invention

On the surface of the pellet of the soft resin (A) having at least one tensile modulus of elasticity (YM; ASTM D-658) selected from the group consisting of (i) to (v) below 1600 MPa,

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 dyne / cm,

At least one type of fine powder (C) having an average particle diameter of 50 µm or less is attached.

(i) an ethylene / α-olefin copolymer obtained by copolymerizing ethylene and at least one α-olefin having 3 to 20 carbon atoms,

(ii) a propylene / α-olefin copolymer obtained by copolymerizing propylene with at least one kind of carbon number 2 or 4-20 α-olefin,

(iii) Ethylene, at least 1 type of C3-C20 alpha olefin, and following formula

In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and at least one of R ¹ and R ² is a hydrogen atom. Unsaturated olefin copolymer obtained by random copolymerization of at least one monomer selected from the group consisting of polyene monomers,

(iv) an ethylene / vinylacetate copolymer having a vinylacetate content in the range of 5-40% by weight,

(v) cyclic olefin resin.

Such a soft resin pellet of the present invention is on the surface of the pellet of the soft resin (A), to the pellet (B) and 50 to 20,000 ppm by weight of the liquid (A) with respect to the pellet of the soft resin (A). 50 to 10,000 ppm by weight of the fine powder (C) may be attached.

Moreover, the manufacturing method of the soft resin pellets by this invention is

On the surface of the pellet of the soft resin (A) having at least one tensile modulus of elasticity (YM; ASTM D-658) selected from the group consisting of (i) to (v) below 1600 MPa,

At least one liquid (B) having a kinematic viscosity at 25 ° C. of 0.5 to 100,000 cSt (sent stock) and a surface tension at 25 ° C. of 10 to 50 dyne / cm;

It is characterized by adhering at least one kind of fine powder (C) having an average particle diameter of 50 µm or less.

(i) an ethylene / α-olefin copolymer obtained by copolymerizing ethylene and at least one α-olefin having 3 to 20 carbon atoms,

(ii) a propylene / α-olefin copolymer obtained by copolymerizing propylene with at least one kind of carbon number 2 or 4-20 α-olefin,

(iii) Ethylene, at least 1 type of C3-C20 alpha olefin, and following formula

In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and at least one of R ¹ and R ² is a hydrogen atom. Unsaturated olefin copolymer obtained by random copolymerization of at least one monomer selected from the group consisting of polyene monomers,

(iv) an ethylene / vinylacetate copolymer having a vinylacetate content in the range of 5-40% by weight,

(v) cyclic olefin resin.

The said soft resin (A) may contain unsaturated carboxylic acid or its derivative in the ratio of 0.01-30 weight% with respect to 100 weight% of soft resin (A).

In addition, the ethylene / α-olefin copolymer (i) is a modified ethylene / α- grafted with an unsaturated carboxylic acid or a derivative thereof in an unmodified ethylene / α-olefin copolymer (ia) at a ratio of 0.01 to 30% by weight. The olefin copolymer (ib) may be sufficient.

The propylene / α-olefin copolymer (ii) is a modified propylene / α- grafted with an unsaturated carboxylic acid or a derivative thereof in an unmodified propylene / α-olefin copolymer (ii-a) at a ratio of 0.01 to 30% by weight. An olefin copolymer (ii-b) may be sufficient.

The unsaturated olefin copolymer (iii) is a modified unsaturated olefin copolymer obtained by grafting an unsaturated carboxylic acid or a derivative thereof in an unmodified unsaturated olefin copolymer (iii-a) at a ratio of 0.01 to 30% by weight. (iv-b) may be sufficient.

The ethylene / vinylacetate copolymer (iv) is a modified ethylene / vinylacetate copolymer obtained by grafting an unsaturated carboxylic acid or a derivative thereof at a ratio of 0.01 to 30% by weight to an unmodified ethylene / vinylacetate copolymer (iv-a). (iv-b) may be sufficient.

The cyclic olefin resin (v) may be a modified cyclic olefin resin obtained by grafting an unsaturated carboxylic acid or a derivative thereof in an amount of 0.01 to 30% by weight to an unmodified cyclic olefin resin.

As the liquid (B), dimethylpolysiloxane is particularly preferable.

As said fine powder (C), a fatty acid or fatty acid derivative is preferable, and stearic acid, erucic acid, oleic acid, itaconic acid, montanic acid, and these metal salts, amides, and esters are especially preferable.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, the soft resin pellet which concerns on this invention, and its manufacturing method are demonstrated concretely.

The soft resin pellets according to the present invention have at least one kind of liquid (B) having a kinematic viscosity at 25 ° C. and a surface tension at 25 ° C. on a pellet surface of a specific soft resin (A), and a specific average. At least one type of fine powder C having a particle size is attached.

In the method for producing a soft pellet of the present invention, at least one kind of liquid (B) having a kinematic viscosity at 25 ° C. and a surface tension at 25 ° C. on the surface of the pellet of the specific soft resin (A), By attaching at least one type of fine powder (C) having a specific average particle diameter, a soft resin pellet having excellent non-tackiness is obtained.

First, the soft resin pellets according to the present invention and the soft resin pellets (A), liquid (B) and fine powder (C) used in the method for producing soft resin pellets according to the present invention will be described.

Soft resin (A)

Tensile modulus (YM; ASTM D-658) of the soft resin (A) used in the present invention is 1600 MPa or less, usually 1 to 1600 MPa, preferably 1 to 150 MPa. Specific examples of such a soft resin (A) include ethylene / α-olefin copolymer (i), propylene / α-olefin copolymer (ii), unsaturated olefin copolymer (iii), ethylene / vinylacetate copolymer (iv And cyclic olefin resin (v). These soft resins (A) can be used individually or in combination of 2 or more types. Examples of such two or more combinations include

(1) a combination of an ethylene / α-olefin copolymer (i) and a propylene / αolefin copolymer (ii),

(2) a combination of an ethylene / α-olefin copolymer (i) and an unsaturated olefin copolymer (iii),

(3) a combination of an ethylene / α-olefin copolymer (i) and an ethylene / vinylacetate copolymer (iv),

(4) a combination of an ethylene / α-olefin copolymer (i) and a cyclic olefin resin (v),

(5) a combination of an ethylene / α-olefin copolymer (i), a propylene / α-olefin copolymer (ii)) and an unsaturated olefin copolymer (iii),

(6) a combination of an ethylene / α-olefin copolymer (i) with a propylene / α-olefin copolymer (ii) and an ethylene / vinylacetate copolymer (iv),

(7) a combination of an ethylene / α-olefin copolymer (i), a propylene / α-olefin copolymer (ii), and a cyclic olefin resin (v),

(8) a combination of an ethylene / α-olefin copolymer (i), an unsaturated olefin copolymer (iii) and an ethylene / vinylacetate copolymer (iv),

(9) a combination of an ethylene / α-olefin copolymer (i), an unsaturated olefin copolymer (iii) and a cyclic olefin resin (v),

(10) a combination of an ethylene / α-olefin copolymer (i), an ethylene / vinylacetate copolymer (iv) and a cyclic olefin resin (v),

(11) ethylene / α-olefin copolymer (i), propylene / α-olefin copolymer (ii), unsaturated olefin copolymer (iii), ethylene / vinylacetate copolymer (iv) and cyclic olefin resin ( v), and the like.

Hereinafter, resin of (i)-(v) which can be used as soft resin (A) used for this invention is demonstrated.

Ethylene / α-olefin copolymer (i)

The ethylene / α-olefin copolymer (i) used in the present invention is unsaturated to an ethylene / α-olefin copolymer (ia) obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms, or a copolymer (ia) thereof. It is a modified ethylene / alpha-olefin copolymer (ib) which grafted the carboxylic acid or its derivative (s), and tensile modulus (YM; ASTM D-658) is 1600 MPa or less, Usually, 1-1600 MPa, Preferably it is 1-150 MPa.

Specific examples of the α-olefin having 3 to 20 carbon atoms copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene , 1-dodecene, 1-hexadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 4-methyl-1-pentene and the like. These alpha-olefins are used individually or in combination of 2 or more types.

The ethylene / α-olefin copolymer (ia) contains a structural unit derived from ethylene in an amount of 50 to 96 mol% and a structural unit derived from an α-olefin having 3 to 20 carbon atoms in an amount of 4 to 50 mol%. It is desirable to do it.

The composition of the ethylene / α-olefin copolymer (ia) is a sample obtained by uniformly dissolving about 200 mg of the ethylene / α-olefin copolymer in 1 m1 of hexachlorobutadiene in a 10 mm φ sample tube. The measurement temperature is 120 ° C. and the measurement frequency is 25.05. ¹³ C-NMR spectra were measured under the conditions of MHz, spectral width 1500 Hz, pulse repetition time 4.2 sec, and pulse width 6 μsec.

The ethylene / α-olefin copolymer (ia) used in the present invention has a density (ASTM D1505) of 0.855 to 0.915 g / cm ³ , preferably 0.865 to 0.885 g / cm ^3, and melt flow rate (MFR; ASTM D1238, 190 ° C, load 2.16 kg) is preferably in the range of 0.01 to 200 g / 10 minutes, preferably 0.5 to 40 g / 10 minutes.

Specific examples of the ethylene / α-olefin copolymer (ia) include ethylene / propylene random copolymer, ethylene / 1-butene random copolymer, ethylene / propylene / 1-butene random copolymer, ethylene / 1-hexene random copolymer, Ethylene / 1-butene / 1-hexene random copolymer, an ethylene / 1-octene random copolymer, etc. are mentioned. You may use these copolymers together 2 or more types.

The ethylene / α-olefin copolymer (i-a) as described above can be produced by a conventionally known method using a vanadium catalyst, a titanium catalyst or a metallocene catalyst.

Further, in the present invention, the modified ethylene / α-olefin copolymer (ib) used as the ethylene / α-olefin copolymer (i) may be unsaturated carboxylic acid or derivative thereof (hereinafter unsaturated) in the ethylene / α-olefin copolymer (ia). Carboxylic acid and the like).

The amount of graft such as unsaturated carboxylic acid in the modified ethylene / α-olefin copolymer is 0.01 to 30% by weight, preferably 0.01 to 10% by weight, more preferably 100% by weight of ethylene / α-olefin copolymer before graft modification. Preferably it is 0.1 to 2 weight% of range.

Specific examples of the unsaturated carboxylic acid include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid ^TM (endo-cis-bicyclo [2.2.1] hept-5- Ene-2,3-dicarboxylic acid), and the like.

Moreover, as a derivative of an unsaturated carboxylic acid, the above-mentioned acid halide compound, an amide compound, an imide compound, an acid anhydride, an ester compound, etc. of the unsaturated carboxylic acid are mentioned, for example. Specific examples include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. In these, unsaturated dicarboxylic acid or its acid anhydride is preferable, and maleic acid, nadic acid ^TM, or these acid anhydride is especially preferable.

Further, the graft position of the unsaturated carboxylic acid or the like grafted onto the ethylene / α-olefin copolymer (ia) is not particularly limited, and the unsaturated carboxylic acid or the like may be added to any carbon atom of the ethylene / α-olefin copolymer (ia). It may be combined.

Graft modification by the unsaturated carboxylic acid etc. of the said ethylene / alpha-olefin copolymer (i-a) can be performed using a conventionally well-known graft polymerization method. For example, a method of melting the ethylene / α-olefin copolymer (ia) and adding unsaturated carboxylic acid or the like to perform graft polymerization, dissolving the ethylene / α-olefin copolymer (Ia) in a solvent, There is a method in which graft polymerization is performed by adding an unsaturated carboxylic acid or the like.

In these methods, when graft polymerization is carried out in the presence of a radical initiator, graft monomers 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 ethylene / α-olefin copolymer (i-a).

As such a radical initiator, an organic peroxide, an azo compound, etc. are used. Specific examples of such radical initiators include benzoyl peroxide, dichloro benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexine-3, 1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di (t-butylperoxide) hexyne-3, 2 , 5-dimethyl-2,5-di (t-butylperoxide) hexane, t-butylperbenzoate, t-butylperphenyl acetate, t-butylperisobutyrate, t-butylper-see-octoate, t-butylperpibarate, cumyl perpirate, t-butylperdiethyl acetate; Azobisisobutyronitrile, dimethyl azoisobutyrate, etc. are mentioned.

Among these, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di ( Dialkyl peroxides, such as t-butyl peroxy) hexane and 1, 4-bis (t-butyl peroxy isopropyl) benzene, are used preferably.

The reaction temperature of the graft polymerization reaction using the radical initiator as described above or the graft polymerization reaction performed without using the radical initiator is usually set to 60 to 350 ° C, preferably 150 to 300 ° C.

Propylene / α-olefin copolymers (ii)

The propylene / α-olefin copolymer (ii) used in the present invention is a propylene / α-olefin copolymer (ii-a) obtained by copolymerizing propylene with an α-olefin having 2 or 4 to 20 carbon atoms, or a copolymer thereof. (ii-a), a modified propylene / α-olefin copolymer (ii-b) grafted with an unsaturated carboxylic acid or a derivative thereof, and a tensile modulus (YM; ASTM D-658) of 1600 MPa or less, usually 1 to 1600 MPa, Preferably it is 1-150 Mpa.

Specific examples of the α-olefin having 2 to 4 carbon atoms or copolymerized with propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 Undecene, 1-dodecene, 1-hexadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 4-methyl-1- pentene, etc. are mentioned. These alpha-olefins are used individually or in combination of 2 or more types.

Propylene / α-olefin copolymer (ii-a) has 50 to 95 mol% of structural units derived from propylene, and 5 to 50 mol of structural units derived from α-olefins having 2 or 4 to 20 carbon atoms. It is preferable to contain in the amount of%.

The composition of the propylene / α-olefin copolymer (ii-a) measured a sample obtained by uniformly dissolving about 200 mg of the propylene / α-olefin copolymer in 1 m hexachlorobutadiene in a 10 mm phi sample tube at a measurement temperature of 120 ° C. ¹³ C-NMR spectra were obtained by measuring the frequency 25.05 MHz, spectrum width 1500 Hz, pulse repetition time 4.2 sec, and pulse width 6 μsec.

Propylene / α- olefin copolymer (ii-a) used in the present invention is the density (ASTM D1505) is 0.855 ~ 0.900g / cm ^3, preferably 0.855 ~ 0.885g / cm ^3, a melt flow rate (MFR; ASTM D1238, 190 ° C, load 2.16 kg) is preferably in the range of 0.01 to 200 g / 10 minutes, preferably 0.1 to 40 g / 10 minutes.

In addition, the stereoregularity of polypropylene may be any of syndiotactic, isotactic, and atactic.

Specific examples of the propylene / α-olefin copolymer (ii-a) include propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / ethylene / 1-butene copolymer, propylene / ethylene / 1-octene copolymer, and the like. Can be mentioned. You may use these copolymers together 2 or more types.

The above propylene / α-olefin copolymer (ii-a) can be produced by a conventionally known method using a vanadium catalyst, a titanium catalyst or a metallocene catalyst.

In addition, the modified propylene / α-olefin copolymer (ii-b) used in the present invention as the propylene / α-olefin copolymer (ii) is an unsaturated carboxylic acid or derivative thereof in the propylene / α-olefin copolymer (ii-a). (Hereinafter referred to as unsaturated carboxylic acid, etc.) is a soft resin.

The unsaturated carboxylic acid or the like used in the production of the modified propylene / α-olefin copolymer (ii-b) is the same compound as the unsaturated carboxylic acid or the like used in the production of the modified ethylene / α-olefin copolymer (i-b).

The amount of grafts such as unsaturated carboxylic acid in the modified propylene / α-olefin copolymer (ii-b) is 0.01 to 30% by weight relative to 100% by weight of the propylene / α-olefin copolymer (ii-a) before graft modification. Preferably it is 0.01-10 weight%, More preferably, it is the range of 0.1-2 weight%.

In addition, graft positions, such as unsaturated carboxylic acid grafted to the propylene / alpha-olefin copolymer (ii-a), are not specifically limited, Unsaturated carboxylic acid etc. are arbitrary of a propylene / alpha-olefin copolymer (ii-a) It is good to be bonded to the carbon atom of.

Graft modification by the unsaturated carboxylic acid etc. of the said propylene / alpha-olefin copolymer (ii-a) can be performed using a conventionally well-known graft polymerization method.

For example, a method of melting a propylene / α-olefin copolymer (ii-a) and adding unsaturated carboxylic acid or the like to perform graft polymerization, and dissolving the propylene / α-olefin copolymer (ii-a) in a solvent Then, there is a method of performing graft polymerization by adding an unsaturated carboxylic acid or the like thereto.

In these methods, when graft polymerization is carried out in the presence of a radical initiator, graft monomers 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 propylene / α-olefin copolymer (ii-a).

As such a radical initiator, an organic peroxide, an azo compound, etc. are used. As a specific example of such a radical initiator, the compound enumerated as a specific example of the radical initiator used at the time of manufacture of said modified ethylene / alpha-olefin copolymer (i-b) is 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 to 60 to 350 ° C, preferably 150 to 300 ° C.

Unsaturated olefinic copolymers (iii)

The unsaturated olefin copolymer (iii) used in the present invention is an unsaturated olefin copolymer obtained by random copolymerization of ethylene, an α-olefin having 3 to 20 carbon atoms, and a conjugated diene monomer and / or a nonconjugated polyene monomer. (iii-a) or a modified unsaturated olefin copolymer (iii-b) obtained by grafting an unsaturated carboxylic acid or a derivative thereof to copolymer (iii-a), wherein tensile modulus (YM; ASTM D-658) is 1600 MPa or less, Usually, it is 1-1600 MPa, Preferably it is 1-150 MPa.

The alpha -olefin is not particularly limited as long as it is in the range of 3 to 20 carbon atoms, and may be linear or have a branch.

Specific examples of such α-olefins are propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl- 1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1- Heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1 -Nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like. Among them, propylene, 1-butene, 1-hexene, 1-octene and 1-decene are preferably used.

These alpha-olefins can be used individually by 1 type or in combination of 2 or more types.

The conjugated diene monomer is represented by the following formula.

In the above formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and at least one of R ¹ and R ² is a hydrogen atom.

Specific examples of such conjugated diene monomers include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1-phenyl-1,3- Butadiene, 1-phenyl-2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1 , 3-butadiene, 2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and the like. Among these, 1,3-butadiene and isoprene are especially preferable at the point which is excellent in copolymerizability. A conjugated diene monomer can be used individually or in combination of 2 or more types.

In addition, specific examples of the nonconjugated polyene monomer include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, 4,8-dimethyl-1,4,8 -Decatriene, 4,8-dimethyl-1,4,9-decatriene, 4,9-dimethyl-1,4,9-decatene, 5,9-dimethyl-1,4,9-deca Triene, 5,9-dimethyl-1,4,9-decatene, 5-vinyl-1,6-octadiene, and the like. Preferred nonconjugated polyene monomers include aliphatic polyene compounds.

The unsaturated olefin copolymer (iii-a) has a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a structural unit derived from a (non) conjugated polyene monomer, respectively. They are arranged at random and bound, have a double bond structure attributable to the (non) conjugated polyene monomer, and the main chain has a substantially linear structure.

This unsaturated olefin copolymer (iii-a) has a substantially linear structure and does not substantially contain a gel crosslinked polymer because the copolymer is dissolved in an organic solvent and substantially contains no insoluble content. It can be confirmed by. For example, when measuring intrinsic viscosity [(eta)], the copolymer can be confirmed by melt | dissolving completely in decalin at 135 degreeC.

The unsaturated olefin copolymer (iii-a) used in the present invention has a molar ratio (ethylene / α-olefin) of a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms. 1-40 / 60, Preferably it is 95 / 5-50 / 50, More preferably, it is the range of 90 / 10-55 / 45.

Unsaturated olefin copolymer (iii-a) used in the present invention, the density (ASTM D1505) is 0.855 ~ 0.880g / cm ^3, preferably 0.855 ~ 0.875g / cm ^3, Mooney viscosity (ML _{1+ 4} (100 degreeC)) is 1-99, Preferably it is the range of 5-98.

As for the unsaturated olefin type copolymer (iii-a), intrinsic viscosity [(eta)] measured in 135 degreeC decalin is 0.1-10d1 / g normally, Preferably it is the range of 1.0-7.0d1 / g. Intrinsic viscosity [η] is a measure of the molecular weight of the unsaturated olefin copolymer (iii).

In addition, the unsaturated olefin copolymer (iii-a) preferably has an iodine value of 1 to 50, preferably 3 to 50, and more preferably 5 to 40. In the present invention, at least one of the molar ratio, intrinsic viscosity [η] and iodine value of each constituent unit of the unsaturated olefin copolymer (iii-a) is preferably in the above range, more preferably two or more in the above range. It is preferable that especially the molar ratio, intrinsic viscosity [], and iodine value of each structural unit are in the said range.

The unsaturated olefin copolymer (iii-a) preferably has a melting point (Tm) measured by DSC of preferably 110 ° C. or lower, more preferably 70 ° C. or lower, and even more preferably 40 ° C. or lower. Preferably the glass transition temperature (Tg) measured by DSC is 25 degrees C or less, More preferably, it is 10 degrees C or less, More preferably, it is 0 degrees C or less. Moreover, it is preferable that the value of Mw / Mn measured by GPC is three or less.

Melting | fusing point (Tm) and glass transition temperature (Tg) of an unsaturated olefin type copolymer (iii-a) were calculated | required by the following method.

That is, the endothermic curve of DSC is calculated | required, and let temperature of the largest peak position be melting | fusing point (Tm).

The measurement is to fill the sample in an aluminum pan, raise the temperature to 200 ° C. at 10 ° C./min, hold for 5 minutes at 200 ° C., then lower the temperature to -150 ° C. at 20 ° C./min, and then increase the temperature to 10 ° C./min. It calculated | required from the endothermic curve at the time.

In addition, Mw / Mn of an unsaturated olefin type copolymer (iii-a) was measured at 140 degreeC with o-dichlorobenzene solvent using GPC (gel permeation chromatography).

The unsaturated olefin copolymer (iii-a) used in the present invention may be a so-called oil-extended rubber, i.e., a rubber that is passed through a softener such as a conventionally known mineral oil softener.

Specific examples of the unsaturated olefin copolymer (iii-a) used in the present invention include ethylene / propylene / 1,3-butadiene copolymer, ethylene / propylene / isoprene copolymer, ethylene / propylene / 5-ethylidene-2 EPDM such as norbornene copolymer rubber, dielectric ethylene / propylene / 1,3-butadiene copolymer, dielectric ethylene / propylene / isoprene copolymer, dielectric ethylene / propylene / 5-ethylidene-2-norbornene copolymer Dielectric EPDM, such as rubber | gum, etc. are mentioned.

The unsaturated olefin copolymer (iii-a) described above is a vanadium-based or metal-conjugated ethylene, an α-olefin having 3 to 20 carbon atoms, and a conjugated diene monomer and / or a nonconjugated polyene represented by the above formula. It is obtained by copolymerization, preferably random copolymerization, in the presence of a sen catalyst.

Details of the method for producing the unsaturated olefin copolymer (iii-a) used in the present invention and the metallocene catalyst used for the production method are described in Japanese Patent Application Laid-Open No. 11-228743.

In addition, the modified unsaturated olefin copolymer (iii-b) used in the present invention as the unsaturated olefin copolymer (iii) is an unsaturated carboxylic acid or a derivative thereof (hereinafter, It is a soft resin grafted with unsaturated carboxylic acid etc.).

The unsaturated carboxylic acid or the like used in the production of the modified unsaturated olefin copolymer (iii-b) is the same compound as the unsaturated carboxylic acid or the like used in the production of the modified ethylene / α-olefin copolymer (i-b).

The amount of grafts such as unsaturated carboxylic acid in the modified unsaturated olefin copolymer (iii-b) is preferably 0.01 to 30% by weight relative to 100% by weight of the unsaturated olefin copolymer (iii-a) before graft modification. Is 0.01 to 10 weight%, More preferably, it is the range of 0.1 to 2 weight%.

In addition, the graft position of the unsaturated carboxylic acid or the like grafted to the unsaturated olefin copolymer (iii-a) is not particularly limited, and the unsaturated carboxylic acid or the like is any carbon atom of the unsaturated olefin copolymer (iii-a). It is good to be coupled to.

Graft modification by the unsaturated carboxylic acid etc. of the said unsaturated olefin type copolymer (iii-a) can be performed using a conventionally well-known graft polymerization method.

For example, a method of melting the unsaturated olefin copolymer (iii-a), adding unsaturated carboxylic acid and the like to perform graft polymerization, dissolving the unsaturated olefin copolymer (iii-a) in a solvent, There is a method in which graft polymerization is performed by adding an unsaturated carboxylic acid or the like.

In these methods, when graft polymerization is carried out in the presence of a radical initiator, graft monomers 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 (iii-a).

As such a radical initiator, an organic peroxide, an azo compound, etc. are used. As a specific example of such a radical initiator, the compound enumerated as a specific example of the radical initiator used at the time of manufacture of said modified ethylene / alpha-olefin copolymer (i-b) is 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 to 60 to 350 ° C, preferably 150 to 300 ° C.

Ethylene / vinylacetate copolymer (iv)

The ethylene / vinylacetate copolymer (iv) used in the present invention is unsaturated carboxylic acid or derivative thereof in the ethylene / vinylacetate copolymer (iv-a) obtained by copolymerizing ethylene and vinyl acetate, or the copolymer (iv-a). As a modified ethylene / vinylacetate copolymer (iv-b) obtained by grafting, the tensile modulus (YM; ASTM D-6588) is 1600 MPa or less, usually 1 to 1600 MPa, preferably 1 to 150 MPa.

The ethylene / vinylacetate copolymer (iv-a) used in the present invention has a vinyl acetate content of 5 to 40% by weight, preferably 10 to 35% by weight. In addition, this ethylene / vinylacetate copolymer (iv-a) generally has a melt flow rate (ASTM D1238, 190 ° C., 2.16 kg load) of 0.1 to 50 g / 10 minutes, preferably 0.3 to 30 g / 10 minutes. Range.

In addition, the modified ethylene / vinylacetate copolymer (iv-b) used as the ethylene / vinylacetate copolymer (iv) in the present invention is an unsaturated carboxylic acid or derivative thereof (hereinafter, referred to as ethylene / vinylacetate copolymer (iv-a)). It is a soft resin grafted with unsaturated carboxylic acid etc.).

The unsaturated carboxylic acid or the like used in the production of the modified ethylene / vinylacetate copolymer (iv-b) is the same compound as the unsaturated carboxylic acid or the like used in the production of the modified ethylene / α-olefin copolymer (i-b).

The amount of graft, such as unsaturated carboxylic acid, in the modified ethylene / vinylacetate copolymer (iv-b) is preferably 0.01 to 30% by weight relative to 100% by weight of ethylene / vinylacetate copolymer (iv-a) before graft modification. Is 0.1 to 10 weight%, More preferably, it is 0.1 to 2 weight% of range.

Further, the graft position of the unsaturated carboxylic acid or the like grafted onto the ethylene / vinylacetate copolymer (iv-a) is not particularly limited, and the unsaturated carboxylic acid or the like may be any carbon atom of the ethylene / vinylacetate copolymer (iv-a). It is good to be coupled to.

Graft modification by the unsaturated carboxylic acid etc. of the said ethylene / vinyl acetate copolymer (iv-a) can be performed using a conventionally well-known graft polymerization method.

For example, a method of melting ethylene / vinylacetate copolymer (iv-a), adding unsaturated carboxylic acid or the like to perform graft polymerization, dissolving ethylene / vinylacetate copolymer (iv-a) in a solvent, There is a method in which graft polymerization is performed by adding an unsaturated carboxylic acid or the like.

In these methods, when graft polymerization is carried out in the presence of a radical initiator, graft monomers 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 ethylene / vinylacetate copolymer (iv-a).

An organic peroxide, an azo compound, etc. are used as such a radical initiator. As a specific example of such a radical initiator, the specific example of the radical initiator used at the time of preparation of the said modified ethylene / alpha-olefin copolymer (ib) is mentioned. The listed compounds 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 to 60 to 350 ° C, preferably 150 to 300 ° C.

Cyclic olefin resin (v)

As cyclic olefin resin (v) used for this invention, for example

(a-1) Ethylene / cyclic olefin random copolymer obtained by copolymerizing ethylene and cyclic olefin represented by following formula (I) or (II),

(a-2) Ring-opening polymer or copolymer of cyclic olefin represented by the following formula (I) or (II),

(a-3) hydride of the ring-opening polymer or copolymer of (a-2), or

(a-4) Graft modified product of (a-1), (a-2) or (a-3)

The tensile modulus (YM; ASTM D-658) is 1600 MPa or less, usually 1 to 1600 MPa, preferably 2 to 150 MPa.

First, the cyclic olefin represented by general formula (I) or (II) which is a monomer used in order to manufacture cyclic olefin resin used for this invention is demonstrated.

The cyclic olefin used for manufacture of cyclic olefin resin can be represented by following formula (I) or (II).

In said formula (I), n is 0 or 1, m is 0 or a positive integer, and k is 0 or 1. When k is 1, R ^a and R ^b are each independently the following atom or hydrocarbon group, and when k is 0, each bond is bonded to form a five-membered ring.

R ¹ to R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group.

The halogen atom here is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Moreover, as a hydrocarbon group, respectively independently, a C1-C20 alkyl group, a C3-C15 cycloalkyl group, and an aromatic hydrocarbon group are mentioned normally. More specifically, the alkyl group includes methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group, and the like, and cycloalkyl group includes cyclohexyl group These etc. are mentioned, As an aromatic hydrocarbon group, a phenyl group, a naphthyl group, etc. are mentioned. These hydrocarbon groups may be substituted with halogen atoms.

In formula (I), R ¹⁵ to R ¹⁸ may be bonded to each other (joint together) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring formed in this manner may have a double bond. Specific examples of the monocyclic or polycyclic ring formed here are shown below.

In the above examples, the carbon atoms numbered 1 or 2 represent carbon atoms to which R ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) are bonded in Formula (I), respectively.

R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of the alkylidene group include ethylidene group, propylidene group and isopropylidene group.

In the formula (II), p and q are 0 or a positive integer, and r and s are 0, 1 or 2.

And R ²¹ to R ³⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

The halogen atom is the same as the halogen atom in the formula (I).

Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C1-C20 halogenated alkyl group, a C3-C15 cycloalkyl group, or an aromatic hydrocarbon group are respectively independently mentioned. More specifically, the alkyl group includes methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group, and the like, and cycloalkyl group includes cyclohexyl group The aromatic hydrocarbon group includes an aryl group and an aralkyl group, specifically, a phenyl group, tolyl group, naphthyl group, benzyl group and phenyl ethyl group. As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned.

These hydrocarbon groups and alkoxy groups may be substituted with fluorine, chlorine, bromine or iodine atoms.

The carbon atom to which R ²⁹ and R ³⁰ are bonded, the carbon atom to which R ³³ is bonded, or the carbon atom to which R ³¹ is bonded, may be bonded directly or through an alkylene group having 1 to 3 carbon atoms. In other words, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ²⁹ and R ³³ or the groups represented by R ³⁰ and R ³¹ are mutually covalent with each other to form a methylene group (-CH _2- ) may form a group in which the alkylene (-CH ₂ CH ₂ - -) or propylene group _{(-CH 2 CH 2 CH 2)} .

When r = s = 0, R ³⁵ and R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Examples of the monocyclic or polycyclic aromatic ring in this case include groups in which R ³⁵ and R ³² further form an aromatic ring when r = s = 0 as described below.

Here, q is the same as q in General formula (II).

The cyclic olefin represented by general formula (I) or (II) as mentioned above is illustrated below more specifically.

Examples of the cyclic olefin forming the cyclic olefin resin (v) include

Bicyclo [2.2.1] -2-heptene (= norbornene) represented by the formula (wherein, the numbers 1 to 7 represent the position number of carbon) and derivatives in which the hydrocarbon group is substituted for this compound. Can be.

Examples of the hydrocarbon group include 5-methyl, 5,6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5-methyl-5-phenyl, 5 -Benzyl, 5-tolyl, 5- (ethylphenyl), 5- (isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- (Anthryl), group like 5, 6- diphenyl can be illustrated.

Further derivatives include cyclopentadiene-acenaphthylene adducts,

1,4-methano-1,4,4a, 9a-tetrahydrofluorene,

Bicyclo [2.2.1] -2-heptene derivatives, such as 1, 4- methano- 1,4,4a, 5, 10, 10a- hexahydroanthracene, can be illustrated.

In addition,

Tricyclo [4.3.0.1 ^2,5 ] -3-decene,

2-methyltricyclo [4.3.0.1 ^2.5 ] -3-decene,

5-methyl-tricyclo [4.3.0.1 ^2,5] -3- decene such as tricyclo [4.3.0.1 ^2,5] -3- decene derivative,

Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,

10-methyl-tricyclo [4.4.0.1 ^2,5] -3- undecyl tricyclo such sen [4.4.0.1 ^2,5] -3- undecene derivative,

Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (wherein the numbers 1 to 12 represent the position number of carbon) represented by And compounds in which at least some of the hydrogen atoms are substituted with other atoms.

Wherein as a hydrocarbon group or a substituted atom, 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2 , 10-dimethyl, 8,9-dimethyl, 8-ethyl-9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl-9-ethyl, 9-isobutyl-2, 7-dimethyl, 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,12-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8 -Ethylidene-9-methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-n-propylidene, 8-n-propylidene- 9-methyl, 8-n-propylidene-9-ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene- 9-methyl, 8-isopropylidene-9-ethyl, 8-isopropylidene-9-isopropyl, 8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8 , 9-dichloro, 8-phenyl, 8-methyl-8-phenyl, 8-benzyl, 8-tolyl, 8- (ethylphenyl), 8- (this Propylphenyl), 8,9-diphenyl, 8- (biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8- (antryl), 5,6-diphenyl Group or atom, etc. can be illustrated.

In addition, tetracyclo [4.4.0.1 ^2,5, 1 ^7,10] -3- dodecene derivative,

^Pentacyclo [6.5.1.1 ^3,6 .0 ^{2,7 9,13} ] -4- ^pentadecene and derivatives thereof,

Pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] -3- ^pentadecene and derivatives thereof,

Pentacyclo [8.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] -3-hexadecene and its derivatives,

^Pentacyclo [6.6.1.1 ^3,6 .0 ^{2,7 9,14} ] -4-hexadecene and its derivatives,

Hexahydro cyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] -4- hepta-decene and derivatives thereof,

Cyclo hepta ^{[8.7.0.1 2,9 .1 4,7 .1 11,17 .O} 3,8 .0 12,16] -5- eicosene and its derivatives,

Heptacyclo [8.7.0.1 ^3,6 .1 ^10,17 .1 ^12,15 .0 ^2,7 .0 ^11,16 ] -4-eicosene and its derivatives,

Heptacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^11,18 .O ^3,8 .0 ^12,17 ] -5- ^heneicosene and derivatives thereof,

Octacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17 ] -5- ^docosene and derivatives thereof,

Na and the like cyclo ^{[10.9.1.1 4,7 .1 13,20 .1 15,18 .0} 2,10 .O 3,8 .0 12,21 .0 14,19] -5- penta Hill and its derivatives Can be mentioned.

Although the specific example of the cyclic olefin represented by general formula (I) or general formula (II) which can be used by this invention is the same as the above, About the specific structure of these compounds, Unexamined-Japanese-Patent No. 7-145213 regarding the applicant's application It is shown by Paragraph No. [0032]-[0054] of the publication, and what is illustrated here also in this invention can be used as cyclic olefin in this invention.

The cyclic olefin represented by general formula (I) or (II) as described above can be produced by Diels Alder reaction with cyclopentadiene and olefins having a corresponding structure.

These cyclic olefins can be used individually or in combination of 2 or more types.

As the cyclic olefin resin used in the present invention, the cyclic olefin represented by the above general formula (I) or (II) is used. For example, Japanese Patent Application Laid-Open No. 60-168708, No. 61-120816, No. 61- According to the method proposed by the applicant in the publications of 115912, 61-115916, 61-271308, 61-272216, 62-252406 and 62-252407, It can manufacture.

The ethylene / cyclic olefin random copolymer (a-1) is a copolymer in which ethylene and the cyclic olefin are bonded randomly, and the proportion of structural units derived from ethylene is usually 20 to 95 mol%, preferably 30 to 90 mol%. And the structural unit guide | induced from cyclic olefin is 5 to 80 mol% normally, Preferably it contains 10 to 70 mol% ratio. In addition, the composition ratio of the structural unit derived from ethylene and the structural unit derived from cyclic olefin is measured by ¹³ C-NMR.

In this ethylene / cyclic olefin random copolymer (a-1), structural units derived from ethylene and structural units derived from cyclic olefins are randomly arranged and bonded, and have a substantially linear structure. This copolymer is substantially linear and does not have a gel-like crosslinked structure can be confirmed by the fact that this solution does not contain an insoluble content when dissolved in an organic solvent. For example, when measuring intrinsic viscosity [(eta)], this copolymer can be confirmed by melt | dissolving completely in decalin at 135 degreeC.

In the ethylene / cyclic olefin random copolymer (a-1) used in the present invention, at least some of the cyclic olefins represented by the formula (I) or (II) are represented by the following formula (III) or (IV). It is thought to constitute the unit.

In the formula (III), n, m, k and R ¹ to R ¹⁸ and R ^a and R ^b are the same as in general formula (I).

In the formula (IV), p, q, r, s and R ²¹ to R ³⁹ are the same as those in general formula (II).

In addition, the ethylene / cyclic olefin random copolymer (a-1) used for this invention may have a structural unit derived from the other copolymerizable monomer as needed in the range which does not impair the objective of this invention.

Such other monomers include olefins other than the above ethylene or cyclic olefins, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1 -Pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl Straight chains such as -1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene; Branched α-olefins having 3 to 20 carbon atoms;

Cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene and cyclooctene, 3a, 5,6,7a-tetrahydro Cycloolefins such as -4,7-methano-1H-indene;

1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene and 5-vinyl-2-norbornene Non-conjugated dienes, such as these, are mentioned.

These other monomers can be used individually or in combination. In the ethylene / cyclic olefin random copolymer (a-1), the structural unit derived from other monomers as described above may usually be contained in an amount of 20 mol% or less, preferably 10 mol% or less.

The ethylene / cyclic olefin random copolymer (a-1) used in the present invention can be produced by the production method disclosed in the above publication using ethylene and a cyclic olefin represented by formula (I) or (II). Among these, it is preferable to perform this copolymerization in a hydrocarbon solvent and to prepare an ethylene / cyclic olefin random copolymer (a-1) using a catalyst formed from a soluble vanadium compound and an organoaluminum compound in the hydrocarbon solvent as a catalyst. .

In this copolymerization reaction, a solid Group 4 metallocene catalyst may also be used. The solid group IV metallocene catalyst is a catalyst comprising a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organoaluminumoxy compound, and an organoaluminum compound blended as necessary. The transition metal of Group 4 is zirconium, titanium or hafnium, and these transition metals have a ligand containing at least one cyclopentadienyl skeleton. Here, examples of the ligand containing a cyclopentadienyl skeleton include a cyclopentadienyl group or indenyl group, tetrahydroindenyl group, and fluorenyl group in which an alkyl group may be substituted. These groups may be bonded via another group such as an alkylene group. In addition, ligands other than the ligand containing a cyclopentadienyl skeleton are an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a halogen, etc.

Moreover, the organoaluminumoxy compound and organoaluminum compound can use what is normally used for manufacture of an olefin resin. Such solid group IV metallocene catalysts are described in, for example, Japanese Patent Laid-Open Nos. 61-221206, 64-106, and Japanese Patent Laid-Open No. 2-173112.

In the ring-opening polymer or ring-opening copolymer (a-2) of the cyclic olefin, at least some of the cyclic olefins represented by the formula (I) or (II) constitute a repeating unit represented by the following formula (V) or (VI) I think.

In formula (V), n, m, k and R ¹ to R ¹⁸ and R ^a and R ^b are the same as in formula (I).

In formula (VI), p, q, r, s and R ²¹ to R ³⁹ are the same as in formula (II).

Such a ring-opening polymer or ring-opening copolymer can be produced by the production method disclosed in the above publication, and can be produced, for example, by polymerizing or copolymerizing the cyclic olefin represented by Formula (I) in the presence of a ring-opening polymerization catalyst. have.

Such ring-opening polymerization catalysts include metals such as ruthenium, rhodium, palladium, osmium, indium or platinum, halides, nitrates or acetylacetone compounds and catalysts consisting of reducing agents or metals such as titanium, palladium, zirconium or molybdenum A catalyst composed of a halide or acetylacetone compound and an organoaluminum compound can be used.

The hydride (a-3) of the ring-opening polymer or copolymer used in the present invention is obtained by hydrogenating the ring-opening polymer or copolymer (a-2) obtained as described above in the presence of a conventionally known hydrogenation catalyst.

In the hydride (a-3) of this ring-opening polymer or copolymer, at least some of the cyclic olefins represented by the formula (I) or (II) are represented by the following formula (VII) or (VII). It is thought to have.

In formula (VII), n, m, k and R ¹ to R ¹⁸ and R ^a and R ^b are the same as in formula (I).

In formula (VIII), p, q, r, s, R ²¹ to R ³⁹ are the same as in formula (II).

The graft modified product (a-4) of the cyclic olefin resin is a graft modified product of the ethylene / cyclic olefin random copolymer (a-1), a ring-opened polymer or copolymer (a-2) of the cyclic olefin. Graft modified products or graft modified products of the hydride (a-3) of the ring-opening polymer or copolymer.

As this modifier, an unsaturated carboxylic acid or its derivative (unsaturated carboxylic acid, etc.) is usually used. Specific examples of the unsaturated carboxylic acid used herein include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid and endo-cis-bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxylic acid (Nadic acid ^TM ) is mentioned. In addition, examples of derivatives of unsaturated carboxylic acids include unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and ester compounds of unsaturated carboxylic acids.

Specific examples of the derivative of the unsaturated carboxylic acid include maleic anhydride, citraconic anhydride, maleyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like.

Among these modifiers, α, β-unsaturated dicarboxylic acids and α, β-unsaturated dicarboxylic acid anhydrides such as maleic acid, nadic acid ^TM and anhydrides of these acids are preferably used. These modifiers can also be used in combination of 2 or more type.

The amount of grafts such as unsaturated carboxylic acid in the graft modified product of the cyclic olefin resin used in the present invention is 0.01 to 30% by weight, preferably 0.1 to 10% by weight relative to 100% by weight of the cyclic olefin resin before the graft. More preferably, it is 0.1 to 2 weight% of range.

The graft modified product of such a cyclic olefin resin can be prepared by blending a modifier with a cyclic olefin resin so as to have a desired graft amount and graft polymerizing it to prepare a modified product having a high modification rate in advance. It can also manufacture by mixing this modified thing and unmodified cyclic olefin resin.

In order to obtain the graft modified product of the cyclic olefin resin and the cyclic olefin resin including the modifier, a conventionally known method for modifying the polymer can be widely applied. For example, the graft modified product may be prepared by adding a modifier to a cyclic olefin resin in a molten state to perform graft polymerization (reaction), or by adding a modifier to a solvent solution of a cyclic olefin resin to perform graft reaction. You can get it.

Such graft reaction is normally performed at the temperature of 60-350 degreeC.

The graft reaction can also be carried out in the presence of radical initiators such as organic peroxides and azo compounds.

In the present invention, as the cyclic olefin resin (v), any one of the above-mentioned (a-1), (a-2), (a-3) and (a-4) can be used alone, and these It can also be used in combination.

Such cyclic olefin resin (v) has a melt flow rate (MFR; ASTM D1238, 260 ° C, 2.16 kg load) of usually 0.1 to 60 g / 10 minutes, preferably 2 to 50 g / 10 minutes, more preferably 10 to The range of 30 g / 10 minutes is good.

Liquid (B)

The liquid (B) used in the present invention has a kinematic viscosity at 25 ° C. (JISE-2283) of 0.5 to 100,000 cSt, preferably 100 to 5,000 cSt, more preferably 200 to 1,000 cSt, and the surface at 25 ° C. The tension (measured by the capillary rise method) is in the range of 10 to 50 dyne / cm, preferably 10 to 40 dyne / cm, more preferably 10 to 30 dyne / cm. Specifically as such a liquid (B), silicone oil, glycol, mineral oil, higher alcohol, etc. are mentioned. Specific examples of the silicone oil include polysiloxanes having a repeating unit represented by the following formula.

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

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group and the like.

Specific examples of the aryl group include a phenyl group, tolyl group and the like.

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

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

Among these polysiloxanes, especially dimethylpolysiloxane is used preferably.

In the present invention, the above-mentioned liquid (B) can be used alone or in combination of two or more thereof as a mixed solution.

Differential (C)

The fine particle (C) used in the present invention has an average particle diameter of 50 µm or less, usually 0.1 to 50 µm, preferably 1 to 30 µm, and more preferably 1 to 25 µm. The average particle diameter was calculated | required by SEM (scanning electron microscope) or optical microscope observation.

The fine powder (C) preferably used in the present invention is specifically an inorganic filler, an organic filler, a fatty acid or a fatty acid derivative.

Specific examples of the inorganic filler include silica, silica alumina, diatomaceous earth, alumina, calcium carbonate, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, boron hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate Barium carbonate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide and the like. These inorganic fillers can be used individually by 1 type or in combination of 2 or more types.

Fatty acids preferably used in the present invention are usually saturated or unsaturated higher fatty acids having 12 to 30 carbon atoms, specifically, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, behenic acid, oleic acid, and linolenic acid. , α-eostearic acid, β-eostearic acid, α-linolenic acid and the like. Among them, stearic acid is preferable.

In addition, the fatty acid derivatives preferably used in the present invention include salts of the higher fatty acids, specifically sodium salts, potassium salts, magnesium salts, calcium salts, zinc salts, aluminum salts, iron salts, lithium salts, etc. of the higher fatty acids. Can be mentioned. Among them, stearate is preferable. Moreover, higher fatty acid amide, ester, etc. are mentioned as a higher fatty acid derivative. Among them, stearic acid, erucic acid, oleic acid, itaconic acid, amide of montanic acid, and esters are preferable.

Such fatty acids or fatty acid derivatives may be used alone or in combination of two or more.

Method of Making Pellets

The soft resin pellet according to the present invention is obtained by attaching the liquid (B) and the fine powder (C) to the pellet surface of the soft resin (A). In the method for producing a soft resin pellet of the present invention, the pellets of the soft resin (A) and the liquid (B) are mechanically mixed to attach the liquid (B) to the surface of the pellet, and then the fine powder (C) on the pellet surface. ) Is preferably applied by burying them).

Examples of methods for producing such pellets

(1) The soft resin (A) pellets and the liquid (B) are mechanically mixed by a conventional method to adhere the liquid (B) to the pellet surface, and then the fine powder (C) is buried on the pellet surface, Method of adhering liquid (B) and fine powder (C) to the surface of soft resin (A) pellet, or

(2) Extruder in water in which liquid (B) is undispersed by adding liquid (B) and a conventionally known surfactant (for example, soap), using an extruder with a so-called underwater cut pelletizer. By extruding and pelletizing the soft resin (A) which has become a molten state in the furnace, the liquid (B) adheres to the pellet surface, and then the fine powder (C) is buried in the pellet surface, and the soft resin (A) There is a method of adhering the liquid (B) and the fine powder (C) to the surface of the pellet.

In this manner, the surface of the soft resin (A) pellet is coated with the liquid (B) and the fine powder (C).

In the method (1), the liquid (B) adhesion amount on the surface of the soft resin (A) pellet is usually 50 to 20,000 weight ppm, preferably 100 to 2,000 weight ppm, relative to the soft resin (A) pellet. . In addition, the amount of fine powder (C) adhesion to the surface of the flexible resin (A) pellet is usually 50 to 10,000 ppm by weight, preferably 500 to 5,000 ppm by weight, with respect to the soft resin (A) pellet.

In the method (2), the concentration of the liquid (B) in water is preferably 500 to 50,000 ppm by weight, 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). If surfactant is used in the above ratio, liquid B can be disperse | distributed in water.

In the above method (2), the amount of adhesion of the liquid (B) to the surface of the soft resin (A) pellet is usually 50 to 20,000 ppm by weight, preferably 100 to 2,000 ppm by weight, with respect to the soft resin (A) pellet. do. In addition, the amount of fine powder (C) adhesion to the surface of the soft resin (A) pellet is usually 50 to 10,000 ppm by weight, preferably 500 to 5,000 ppm by weight, with respect to the soft resin (A) pellet.

It is preferable that the surface of the flexible resin pellet of this invention has a structure in which the fine powder (C) disperse | distributes and exists in the liquid (B) layer with which at least one part was attached. This can be judged by the naked eye, for example.

In the flexible resin pellet of the present invention, the liquid (B) is preferably attached to the entire surface of the flexible resin (A) pellet. This can be judged by the naked eye, for example.

ADVANTAGE OF THE INVENTION According to this invention, the soft resin pellet which is superior to non-adhesive property (pellet blocking property), and is also excellent in appearance and handling compared with soft resin pellets, such as conventional olefin copolymer rubber, can be provided.

The present invention relates to a soft resin pellet having excellent non-tackiness and appearance, and a manufacturing method thereof.

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these Examples.

The pellet blocking test in the Example etc. of this invention was performed according to the following method.

[Pellet Blocking Test]

60 g of sample pellets (average weight of one pellet: about 35 mg) were put into a 120 mm x 210 mm polyethylene bag, and the bag was folded three times and the opening of the bag was sealed with a cellophane adhesive tape.

Next, under the atmosphere of 40 ° C., two stacks of the three folded bags obtained as described above were loaded, a load of 90 g / cm ² was placed thereon, the state was maintained for 24 hours, and then the three folded bags were opened. Pellets were taken out. The non-tackiness of this pellet was observed and evaluated by the following 10-point method.

<Rate of non-adhesiveness of pellet>

10 --- no blocking

7 --- stuck pellets collapse into their own weight

5 --- Sticky pellets disintegrate easily by hand

3 --- collapsed only by pushing the adherent pellets by hand

1 --- Pellets stick together to form bales

In addition, the appearance of the pellets was visually observed and evaluated according to the following criteria.

<Appearance>

Good (O): No powder coming out (can't determine whether fine powder (C) is added visually)

Poor (×): powder comes out (visually, it can be determined that fine powder (C) is added.)

In addition, in Example etc., the quantification of the silicone oil and calcium stearate adhering to the pellet surface was performed as follows.

<Quantification of silicone oil>

After washing a predetermined amount of pellets with methyl isobutyl ketone (MIBK) which is a solvent which melt | dissolves a silicone oil, the washing | cleaning liquid was collect | recovered. Subsequently, fluorescence X-ray analysis was performed on the collected washing liquid, and the amount of silicone oil was determined from the X-ray intensity of Si and the calibration curve of the silicone oil prepared in advance.

<Quantification of the amount of calcium stearate>

Fluorescence X-ray analysis was performed on a predetermined amount of pellets, and the amount of calcium stearate was determined from the X-ray intensity of Ca and the calibration curve of calcium stearate prepared in advance.

The amount of silicon oil and amount of calcium stearate are 100 g of pellets washed with methanol, and then all of the washing liquid is recovered. Then, the methanol component is removed from the washing liquid using an evaporator to remove silicon and calcium in the residue. It can also be quantified by the method of performing metal analysis.

Example 1

Using a single screw extruder, ethylene / 1-butene copolymer (EBR) [density (ASTM D1505) = 0.865 g / cm ³ , MFR (ASTM D1238, 190 ° C., load 2.16 kg) = 4 g / 10 min, ethylene content = 100 parts by weight of a pellet prepared by kneading 82 mol% and tensile modulus of elasticity (YM) = 9.5 MPa] at 200 ° C., and silicone oil (trade name SH200, manufactured by Toray Dou Corning Corporation; Dynamic viscosity (20 degreeC) = 500 cSt, surface tension (20 degreeC) = 20 dyne / cm] 0.1 weight part was mechanically mixed using the Henschel mixer.

Subsequently, the entire amount of the soft resin pellets with silicon oil attached to the surface obtained as described above and 0.35 parts by weight of calcium stearate having an average particle diameter of 20 µm were mechanically mixed using a Henschel mixer.

The adhesion amount of the silicone oil in the pellet obtained as mentioned above was 990 weight ppm. In addition, the adhesion amount of the calcium stearate in the obtained pellet was 3,350 weight ppm.

Next, using this soft resin pellet, the pellet blocking test was performed in accordance with the said method.

The results are shown in Table 1.

Comparative Example 1

In Example 1, it carried out similarly to Example 1 except not having performed mechanical mixing of a soft resin pellet, a silicone oil, and calcium stearate.

The results are shown in Table 1.

Comparative Example 2

In Example 1, it carried out similarly to Example 1 except not having performed mechanical mixing of a soft resin pellet and calcium stearate.

The results are shown in Table 1.

Comparative Example 3

In Example 1, it carried out similarly to Example 1 except not having performed mechanical mixing of a soft resin pellet and silicone oil.

The results are shown in Table 1.

Example 2

Using a single screw extruder, propylene / ethylene copolymer (PER) [density (ASTMD1505) = 0.858 g / cm ³ , MFR (ASTM D1238, 190 ° C., load 2.16 kg) = 2 g / 10 min, propylene content = 60 mol% , 100 parts by weight of pellets prepared by kneading tensile modulus (YM) = 3.5 MPa] at 200 ° C., and silicone oil [trade name SH200, manufactured by Toray Dou Corning Corporation; Dynamic viscosity (20 degreeC) = 500 cSt, surface tension (20 degreeC) = 20 dyne / cm] 0.1 weight part was mechanically mixed using the Henschel mixer.

Subsequently, the entire amount of the soft resin pellets with silicon oil attached to the surface obtained as described above and 0.35 parts by weight of calcium stearate having an average particle diameter of 20 µm were mechanically mixed using a Henschel mixer.

The adhesion amount of the silicone oil in the pellet obtained as mentioned above was 980 weight ppm. In addition, the adhesion amount of the calcium stearate in the obtained pellet was 3,400 weight ppm.

Next, using this soft resin pellet, the pellet blocking test was performed in accordance with the said method.

The results are shown in Table 1.

Comparative Example 4

In Example 2, it carried out similarly to Example 2 except not having performed mechanical mixing of a soft resin pellet and calcium stearate.

The results are shown in Table 1.

Comparative Example 5

In Example 2, it carried out similarly to Example 2 except not having performed mechanical mixing of a soft resin pellet and silicone oil.

The results are shown in Table 1.

Example 3

Using a single screw extruder, a dielectric ethylene / propylene / 5-ethylidene-2-norbornene copolymer (dielectric EPDM) [density (ASTM D1505) = 0.87 g / cm ³ , pattern viscosity [ML _{1 + 4} (100 ° C.) )] = 74, intrinsic viscosity measured in 135 ° C decalin solvent = 3dl / g, ethylene / propylene / 5-ethylidene-2-norbornene (molar ratio) = 78 / 15.8 / 6.2mol%, iodine value = 13 , Tensile modulus (YM) = 2 MPa, dielectric constant = 40 phr, softener: 100 parts by weight of a pellet produced by kneading a trade name W-380, manufactured by Idemitsu Seki Yugakaku Co., Ltd. at 200 ° C., and a silicone oil [trade name SH200, Manufactured by Toray Dou Corning; Dynamic viscosity (20 degreeC) = 500 cSt, surface tension (20 degreeC) = 20 dyne / cm] 0.1 weight part was mechanically mixed using the Henschel mixer.

Subsequently, the entire amount of the soft resin pellets with silicon oil attached to the surface obtained as described above and 0.35 parts by weight of calcium stearate having an average particle diameter of 20 µm were mechanically mixed using a Henschel mixer.

The adhesion amount of the silicone oil in the pellet obtained by making it above was 950 weight ppm. In addition, the adhesion amount of calcium stearate in the obtained pellet was 3,200 weight ppm.

Next, using this soft resin pellet, the pellet blocking test was performed in accordance with the said method.

The results are shown in Table 1.

Comparative Example 6

In Example 3, it carried out similarly to Example 3 except not having performed mechanical mixing of a soft resin pellet and calcium stearate.

The results are shown in Table 1.

Comparative Example 7

In Example 3, it carried out similarly to Example 3 except not having performed mechanical mixing of a soft resin pellet and silicone oil.

The results are shown in Table 1.

Example 4

Ethylene / 1-octene copolymer (E0R) [density (ASTM D1505) = 0.87 g / cm ³ , MFR (ASTM D1238, 190 ° C., load 2.16 kg) = 2 g / 10 min, ethylene content as a soft resin for pellet formation 85 mol% and tensile modulus (YM) = 8 MPa] were prepared.

This ethylene / 1-octene copolymer (E0R) was fed to an extruder with a pelletizer. This ethylene / 1-octene copolymer (E0R) is melt-extruded at a rate of 5 tons / h into a circulation box in which circulating cooling water flows at a flow rate of 140 tons / h, wherein the melt-extruded resin is rotated by a rotary cutter. It was continuously cut into pellets. The resulting soft resin pellets were transferred to a centrifugal dehydrator. In addition, the circulation cooling water introduced into the circulation box was adjusted to a temperature of 5 ° C. for the purpose of preventing blocking of the soft resin. Furthermore, in the circulating cooling water for the same purpose, silicone oil [trade name SH200, manufactured by Toray Dou Corning; Dynamic viscosity (20 degreeC) = 500 cSt, surface tension (20 degreeC) = 20 dyne / cm] is added at a speed | rate of 10 kg / h, and also surfactant (manufactured by Asahi Denka Co., Ltd.) for the purpose of disperse | distributing this silicone oil, Bulronick F108] was added at a rate of 120 g / h.

Then, after separating the soft resin pellets and water using a centrifugal dehydrator, the pellets were returned to a Henschel mixer, where they were mixed with 3,500 ppm by weight of calcium stearate.

The adhesion amount of the silicone oil in the pellet obtained as mentioned above was 1,100 weight ppm. In addition, the adhesion amount of the calcium stearate in the obtained pellet was 3,000 ppm by weight.

Next, using this soft resin pellet, the pellet blocking test was performed in accordance with the said method. The result of the blocking test using this pellet was a grade 7, and since the appearance was not observed, powdery appearance was favorable.

The results are shown in Table 1.

In the pellets obtained in Examples 1 to 4, silicone oil is attached to the entire surface of the pellets. In the silicone oil, it was visually confirmed that calcium stearate was dispersed and present.

TABLE 1

Soft resin Silicone Oil (Weight ppm) Calcium Stearate (weight ppm) Blocking test result Exterior Example 1 EBR 990 3350 7 O Comparative Example 1 EBR 0 0 3 O Comparative Example 2 EBR 980 0 5 O Comparative Example 3 EBR 0 3350 5 × Example 2 EBR 980 3400 5 O Comparative Example 4 EBR 980 0 One O Comparative Example 5 EBR 0 3300 3 × Example 3 Oilfield EPDM 950 3200 5 O Comparative Example 6 Oilfield EPDM 960 0 One O Comparative Example 7 Oilfield EPDM 0 3250 3 × Example 4 EOR 1100 3000 7 O

Claims (12)

On the surface of the pellet of the soft resin (A) having at least one tensile modulus of elasticity (YM; ASTM D-658) selected from the group consisting of (i) to (v) below 1600 MPa, 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 dyne / cm, At least one kind of fine powder (C) having an average particle diameter of 50 µm or less attached thereto; (i) an ethylene / α-olefin copolymer obtained by copolymerizing ethylene and at least one α-olefin having 3 to 20 carbon atoms, (ii) a propylene / α-olefin copolymer obtained by copolymerizing propylene with at least one kind of carbon number 2 or 4-20 α-olefin, (iii) Ethylene, at least 1 type of C3-C20 alpha olefin, and following formula [Wherein, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and at least one of R ¹ and R ² is a hydrogen atom] Unsaturated olefin copolymers obtained by random copolymerization of at least one monomer selected from the group consisting of conjugated diene monomers and non-conjugated polyene monomers represented by (iv) an ethylene / vinylacetate copolymer having a vinylacetate content in the range of 5-40% by weight, (v) cyclic olefin resin. The method of claim 1, On the surface of the pellet of the soft resin (A), 50 to 20,000 ppm by weight of the powder (B) and 50 to 10,000 ppm by weight of the fine resin (A) with respect to the pellet of the soft resin (A) Soft resin pellets to which (C) adheres. On the surface of the pellet of the soft resin (A) having at least one tensile modulus of elasticity (YM; ASTM D-658) selected from the group consisting of (i) to (v) below 1600 MPa, 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 dyne / cm, At least one kind of fine powder (C) having an average particle diameter of 50 µm or less is adhered; (i) an ethylene / α-olefin copolymer obtained by copolymerizing ethylene and at least one α-olefin having 3 to 20 carbon atoms, (ii) a propylene / α-olefin copolymer obtained by copolymerizing propylene with at least one kind of carbon number 2 or 4-20 α-olefin, (iii) Ethylene, at least 1 type of C3-C20 alpha olefin, and following formula [Wherein, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and at least one of R ¹ and R ² is a hydrogen atom] Unsaturated olefin copolymer obtained by random copolymerization of at least one monomer selected from the group consisting of conjugated diene monomers and non-conjugated polyene monomers, (iv) an ethylene / vinylacetate copolymer having a vinylacetate content in the range of 5-40% by weight, (v) cyclic olefin resin. The method of claim 3, The said soft resin (A) contains unsaturated carboxylic acid or its derivative in the ratio of 0.01-30 weight% with respect to 100 weight% of soft resin (A), The manufacturing method of the soft resin pellets characterized by the above-mentioned. The method of claim 3, Modified ethylene / α-olefin air in which the ethylene / α-olefin copolymer (i) is grafted with unsaturated carboxylic acid or derivative thereof in an unmodified ethylene / α-olefin copolymer (ia) at a ratio of 0.01 to 30% by weight. It is a coalescence (ib), The manufacturing method of soft resin pellets characterized by the above-mentioned. The method of claim 3, Modified propylene / α- wherein the propylene / α-olefin copolymer (ii) is grafted with unsaturated carboxylic acid or derivative thereof in an unmodified propylene / α-olefin copolymer (ii-a) at a ratio of 0.01 to 30% by weight. It is an olefin copolymer (ii-b), The manufacturing method of soft resin pellets characterized by the above-mentioned. The method of claim 3, Modified unsaturated olefin copolymer in which the unsaturated olefin copolymer (iii) is grafted an unsaturated carboxylic acid or a derivative thereof in an unmodified unsaturated olefin copolymer (iii-a) at a ratio of 0.01 to 30% by weight. (iii-b). The method for producing a soft resin pellet. The method of claim 3, Modified ethylene / vinylacetate copolymer in which the ethylene / vinylacetate copolymer (iv) is grafted with unsaturated carboxylic acid or derivative thereof in an unmodified ethylene / vinylacetate copolymer (iv-a) at a ratio of 0.01 to 30% by weight. It is (iv-b), The manufacturing method of soft resin pellets characterized by the above-mentioned. The method of claim 3, Said cyclic olefin resin (v) is modified cyclic olefin resin which grafted unsaturated carboxylic acid or its derivative in 0.01-30 weight% to unmodified cyclic olefin resin, The manufacturing method of the soft resin pellet characterized by the above-mentioned. . The method of claim 3, The method for producing a flexible resin pellet, wherein the liquid (B) is dimethylpolysiloxane. The method of claim 3, Said fine powder (C) is a fatty acid or its fatty acid derivative, The manufacturing method of the soft resin pellet characterized by the above-mentioned. The method of claim 11, The fatty acid or fatty acid derivatives thereof are stearic acid, erucic acid, oleic acid, itaconic acid, montanic acid, and metal salts, amides, esters thereof.