JP2013220992A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cosmetic excellent in rheological properties and stability when coated (hardly peeling-off property and the like) by finding out a component that exhibits the properties when used in combination with an oily agent such as silicone oil or the like.SOLUTION: A block copolymer having a specific high molecular weight ethylene polymer segment and a silicone segment is combined with an oily agent, preferably silicone oil or the like, or a cosmetic component to prepare a cosmetic. The ethylene polymer segment is derived from an olefin polymer having a double bond at one end thereof.

Description

  The present invention relates to a cosmetic using an oil and fat having a specific structure including a silicone structural unit.

In general, silicone oils are known to have high bond energy in the main chain, excellent heat resistance, acid resistance, weather resistance, etc., and low surface tension, releasability, lubricity, water repellency and the like. In addition, the intermolecular force is small, the main chain is flexible, the gas permeability is high, and it is physiologically inert, that is, it has characteristics such as low toxicity and low irritation.
Taking advantage of such characteristics, various silicone oils are used in a wide range of fields such as electrical appliances, electronics, automobiles, machinery, medicine, cosmetics, fibers, paper, pulp, and building materials. In particular, in the field of cosmetics, silicone oils such as dimethylpolysiloxane and cyclic silicone, which have no stickiness and high safety, are widely used as hair finishes and various cosmetic oils.
As described above, silicone oil is widely used for various applications such as industrial use, but its characteristics are reversed, and control of viscosity adjustment, uniformity of surface diffusion (for example, elongation as a cosmetic), etc. In reality, there are cases in which there are cases where restrictions are imposed on the material, and there are cases where the compatibility and stability with other materials are insufficient.

As a method of solving such a problem, as a method of adjusting viscosity, a method of gelling silicone oil by using a gelling agent having a polysiloxane structure has been proposed (for example, Patent Documents 1 to 3). . However, the gelling agent is insoluble in silicone oil and may not be sufficient for rheological properties.
On the other hand, a method using a compound having an organopolysiloxane structure having a saturated hydrocarbon group at the terminal of the silicone structure is also disclosed. (Patent Document 4)

JP 63-152308 A JP-A-1-190757, JP-A-1-207354 Japanese Patent No. 3274588

Although the above-mentioned Patent Document 4 is an effective method, the molecular weight of the saturated hydrocarbon group may not be sufficiently increased due to restrictions on the production method, and may be insufficient for controlling the rheological characteristics.
Therefore, this invention is providing the cosmetics containing the silicone oil excellent in rheological characteristics, such as viscosity adjustment and surface diffusivity.

As a result of intensive studies to achieve the above object, the present inventors have been able to impart thixotropic and extremely stable rheological properties to organopolysiloxanes having a structure having a saturated hydrocarbon group in the polysiloxane structure. As a result, the present inventors have found that the cosmetics containing this compound may have properties that are less sticky and more difficult to peel off, and have completed the present invention.
That is, the present invention
It was obtained by subjecting an ethylene polymer (A) having a vinyl group at the end satisfying the following (i) to (iv) to a hydrogen silicone (B) having one or more SiH bonds per molecule. A cosmetic comprising the block copolymer (C).
(I) an ethylene homopolymer or a copolymer obtained by copolymerizing ethylene and at least one olefin selected from α-olefins having 3 to 12 carbon atoms,
(Ii) having a vinyl group at one end of the molecule, the vinyl group content per molecule is 0.8 to 1.0,
(Iii) the melting point is 70 to 136 ° C.
(Iv) The weight average molecular weight is 1000 to 10,000.

In the cosmetic of the present invention, the ethylene polymer (A) preferably satisfies the following (i ′) to (iv ′).
(I ′) a copolymer of ethylene and propylene, the composition of propylene being 1 mol% or more and less than 30 mol%,
(Ii ′) has a vinyl group only at one end of the molecule, and the vinyl group content per molecule is 0.8 to 1.0,
(Iii ′) the melting point is 70 to 136 ° C.,
(Iv ′) The weight average molecular weight is 1000 to 10,000.

  In the cosmetic of the present invention, the block copolymer (C) has a triblock structure in which the ethylene polymer (A) and the hydrogen silicone (B) are (A)-(B)-(A). preferable.

  The cosmetic of the present invention preferably contains 5 to 95% by weight of the block copolymer (C) and 95 to 5% by weight of the oil (D).

  Since the cosmetic of the present invention contains an organosilicone compound having a high molecular weight hydrocarbon group structure, it can impart rheological properties with excellent thixotropic properties. For this reason, it is suitable for obtaining a cosmetic having excellent storage stability and operability and less stickiness. Further, the cosmetic of the present invention is expected to be excellent in stability after application to the skin or the like.

FIG. 1 is an optical micrograph of the composition of Example 7. FIG. 2 is an optical micrograph of the composition of Comparative Example 4.

  The cosmetic of the present invention is characterized by containing an organosilicone compound having a high molecular weight hydrocarbon group. Such an organosilicone compound is an addition reaction between an ethylene polymer (A) having a vinyl group at the terminal and a hydrogen silicone (B) having one or more Si-H bonds per molecule as shown below. It is a block copolymer (C) obtained by making it. Such a block copolymer (C) is demonstrated below.

  The hydrogen silicone compound (B) used in the present invention is a compound containing one or more SiH bonds per molecule. For example, it can be expressed as a hydrosilane compound having a structural unit represented by the formula (1).

—Si (R ¹ ) H—Y ¹ — (1)
In formula (1), R ¹ is a hydrogen atom, a halogen atom or a hydrocarbon group,
Y ¹ is O, S or NR ³⁰ (R ³⁰ is a hydrogen atom or a hydrocarbon group).

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, octyl group, decyl group and octadecyl group. Linear or branched alkyl groups such as cycloalkyl groups; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and norbornyl group; and arylalkyl groups such as benzyl group, phenylethyl group and phenylpropyl group.

Examples of the alkenyl group include a vinyl group, a propenyl group, and a cyclohexenyl group.
Examples of the aryl group include phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthryl group, and phenanthryl group.

  In addition, the above hydrocarbon group may contain one or more heteroatoms. Specific examples include groups in which at least one hydrogen of these groups is substituted with a group containing a halogen atom, oxygen, nitrogen, silicon, phosphorus, or sulfur.

The hydrogen silicone compound (B) used for this invention can also be illustrated as a structure of Formula (2).
_{^{R 22 - (Si (R 21}} ) H-Y 21) m -Z- (Y 22 -Si (R 23) H) n -R 24 (2)
In formula (2), R ²¹ and R ²³ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group,
R ²² and R ²⁴ are each independently a halogen atom or a hydrocarbon group,
Y ²¹ and Y ²² are each independently O, S or NR ³⁰ (R ³⁰ is a hydrogen atom or a hydrocarbon group);
m is 0 or 1,
n is 0 or 1;
When a plurality of R ²¹ , R ²³ , Y ²¹ and Y ²² are present, each group may be the same or different;
Z is a divalent group represented by the formula (3):
-Si (R ⁴¹ ) (R ⁴¹ )-(Y ²³ -Si (R ⁴¹ ) (R ⁴¹ )) _l- (3)
In the formula (3), R ⁴¹ is a hydrogen atom, a halogen atom or a hydrocarbon group, each R ⁴¹ may be the same or different, and Y ²³ is independently O, S or NR. ³⁰ (R ³⁰ is a hydrogen atom or a hydrocarbon group),
l is an integer of 0 to 10,000.
However, in the above formula (2), when m = n = 0, in formula (3), at least one R ⁴¹ is a hydrogen atom.

  In addition, the definition of the halogen atom and hydrocarbon group in Formula (2) and Formula (3) is the same as the definition in the said Formula (1).

  It is also a typical embodiment that the hydrocarbon group in the formulas (1), (2), and (3) consists only of carbon atoms and hydrogen atoms.

  In the present invention, the hydrogen silicone compound (B) preferably has 3 or more, more preferably 5 or more, and still more preferably 10 or more silicon atoms per molecule. Further, the preferable upper limit of the silicon atom content per molecule of the hydrogen silicone compound (B) is 10,000, more preferably 1,000, still more preferably 300, and particularly preferably 50 or less. . Cosmetics obtained by using the block copolymer (C) obtained from such a hydrogen silicone compound (B) have good rheological properties and fixing properties, and can suppress stickiness and peeling. I can do it.

  In the hydrogen silicone compound (B) used in the present invention, l in the above formula (3) is an integer of 0 to 10,000, and preferred upper and lower limits are m and n in the formula (2). A number determined from the value and the preferable number of silicon atoms can be mentioned.

  As the hydrogen silicone compound (B) used in the present invention, a compound having a structure in which m = n = 1 in the above formula (2), that is, having SiH groups at both ends is preferably used. In such a case, the block copolymer (C) described later often becomes a linear block copolymer, which is one of particularly preferred embodiments.

  As the hydrogen silicone compound (B) used in the present invention, a compound having a structure in which m = 1 in the above formula (2) and n = 0, that is, having a SiH group at one end is also a preferred embodiment.

Particularly preferable hydrogen silicone compounds (B) include compounds in which m = n = 1 in the above formulas (2) and (3), and R ²¹ , R ²³ and R ⁴¹ are all hydrocarbon groups. It is done. Another hydrogen silicone compound (B) that is particularly preferable is a compound in which m = 1 and n = 0 in the above formulas (2) and (3), and R ²¹ and R ⁴¹ are all hydrocarbon groups. Can be mentioned.

Specific examples of the hydrogen silicone compound (B) used in the present invention are shown below.
Examples of the hydrogen silicone compound (B) having one SiH group include, for example, a compound represented by the formula (2a), in which a part or all of the methyl groups in the formula (2a) are ethyl, propyl, phenyl Group, a compound substituted with a trifluoropropyl group, and the like.

_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) d -Si (CH 3) 3 (2a)
(In Formula (2a), d is an integer greater than or equal to 1, and an upper limit is 1000, for example, Preferably it is 300, More preferably, it is 50.)

More specific examples of such a compound include, but are not limited to, the following compounds.
_{C 4 H 9 - ((CH} 3) 2 SiO) 9 - (CH 3) 2 SiH
_{C 4 H 9 - ((CH} 3) 2 SiO) 65 - (CH 3) 2 SiH
As another example of the hydrogen silicone compound (B) having one SiH group, for example, a dimethylsiloxane-methylhydrogensiloxane copolymer represented by the formula (2b), a methyl group in the formula (2b), Examples thereof include compounds in which part or all of them are substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, or the like.

_{Si (CH 3) 3 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O -) - Si (CH 3) 3 (2b)
(In formula (2b), e is an integer of 0 or more, and the upper limit is, for example, 1000, preferably 300, and more preferably 50.)
The order in which the —Si (CH ₃ ) ₂ —O— units and the —SiH (CH ₃ ) —O— units are arranged is not particularly limited, and is statistically random regardless of whether they are block or disordered. It may be.

  More specific examples of such a compound include, but are not limited to, the following compounds.

_{Si (CH 3) 3 O-} SiH (CH 3) -O-Si (CH 3) 3
Examples of the hydrogen silicone compound (B) of the present invention include compounds having two or more SiH groups.

Examples of the hydrogen silicone compound (B) having two or more SiH groups include, for example, methyl hydrogen polysiloxane represented by the formula (2c), and part or all of the methyl groups in the formula (2c) are ethyl groups. , A propyl group, a phenyl group, a compound substituted with a trifluoropropyl group, and the like.
_{(CH 3) 3 SiO - (} - SiH (CH 3) -O-) f -Si (CH 3) 3 (2c)
(In formula (2c), f is an integer of 2 or more, and the upper limit is, for example, 1000, preferably 300, and more preferably 50.)
As another example of the hydrogen silicone compound (B) having two or more SiH groups, for example, a dimethylsiloxane-methylhydrogensiloxane copolymer represented by the formula (2d), a methyl group in the formula (2d) Examples thereof include compounds partially or wholly substituted with ethyl group, propyl group, phenyl group, trifluoropropyl group and the like.
_{(CH 3) 3 SiO - (} - Si (CH 3) 2 -O-) g - (- SiH (CH 3) -O-) h -Si (CH 3) 3 (2d)
(In the formula (2d), g is an integer of 1 or more, h is an integer of 2 or more, and the upper limit of the sum of g and h is, for example, 1000, preferably 300, and more preferably 50.)
In the formula (2d), the order in which the —Si (CH ₃ ) ₂ —O— unit and the —SiH (CH ₃ ) —O— unit are arranged is not particularly limited, and may be disordered even if it is blocky. Or statistically random.

  More specific examples of such a compound include, but are not limited to, the following compounds.

  Further examples of the hydrogen silicone compound (B) having two or more SiH groups include, for example, methyl hydrogen polysiloxane represented by the formula (2e), part or all of the methyl groups in the formula (2e) Are compounds substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, or the like.

_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) i -Si (CH 3) 2 H (2e)
(In formula (2e), i is an integer of 1 or more, and the upper limit is, for example, 1000, preferably 300, and more preferably 50.)
More specific examples of such a compound include, but are not limited to, the following compounds.

_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) 5 -Si (CH 3) 2 H
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) 8 -Si (CH 3) 2 H
HSi (CH ₃ ) ₂ O — (— Si (CH ₃ ) ₂ —O—) ₁₈ —Si (CH ₃ ) ₂ H
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) 80 -Si (CH 3) 2 H
HSi (CH ₃ ) ₂ O — (— Si (CH ₃ ) ₂ —O—) ₂₃₀ —Si (CH ₃ ) ₂ H
Further examples of the hydrogen silicone compound (B) having two or more SiH groups include, for example, methyl hydrogen polysiloxane represented by the formula (2f), a part or all of the methyl groups in the formula (2f) Are compounds substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, or the like.

_{HSi (CH 3) 2 O -} (- SiH (CH 3) -O-) j -Si (CH 3) 2 H (2f)
(In the formula (2f), j is an integer of 1 or more, and the upper limit is, for example, 1000, preferably 300, and more preferably 50.)
As another example of the hydrogen silicone compound (B) having two or more SiH groups, for example, a dimethylsiloxane-methylhydrogensiloxane copolymer represented by the formula (2g), a methyl group in the formula (2g) And compounds in which a part or all of these are substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, or the like.

_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) k - (- SiH (CH 3) -O-) l -Si (CH 3) 2 H (2g)
(In the formula (2g), k and l are each an integer of 1 or more, and the upper limit of the sum of k and l is, for example, 1000, preferably 300, and more preferably 50.)
Further, the order in which the —Si (CH ₃ ) ₂ —O— unit and the —SiH (CH ₃ ) —O— unit are arranged is not particularly limited, and is statistically random regardless of whether it is blocky or disordered. It may be.

  The weight average molecular weight determined by the GPC method of the ethylene polymer (A) of the present invention is 1,000 or more and 10,000 or less, and more preferably 1,500 or more and 8,000 or less. When the number average molecular weight is lower than the above lower limit, cosmetics containing the block copolymer (C) described later may have increased stickiness and insufficient rheological properties. On the other hand, when higher than the said upper limit, a characteristic will fall as silicone oil of a block copolymer (C), and the basic performance as cosmetics may be reduced. In the present invention, as will be described later, the number average molecular weight (Mn), the weight average molecular weight (Mw), and Mw / Mn are values in terms of polyethylene.

The following describes the ethylene polymer (A).
The ethylene polymer (A) has an ethylene polymer structure having a vinyl group at the terminal. However, a polymer obtained by copolymerizing one or more selected from olefins having 3 to 50 carbon atoms with ethylene may be used as long as it is within the object of the present invention. Specific examples of the olefin having 2 to 50 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 -Methyl-1-pentene, 3,4-dimethyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl-1-pentene, 3,4-dimethyl -1-hexene, 4-methyl-1-heptene, 3,4-dimethyl-1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene , Α-olefins such as vinylcyclohexane; olefins containing internal double bonds such as cis-2-butene and trans-2-butene; isobutene, 2-methyl-1-pente 2,4-dimethyl-1-pentene, 2,4-dimethyl-1-hexene, 2,4,4-trimethyl-1-pentene, 2,4-dimethyl-1-heptene, 2-methyl-1-butene 2-methyl-1-hexene, 2-methyl-1-heptene, 2-methyl-1-octene, 2,3-dimethyl-1-butene, 2,3-dimethyl-1-pentene, 2,3-dimethyl -1-hexene, 2,3-dimethyl-1-octene, 2,3,3-trimethyl-1-butene, 2,3,3-trimethyl-1-pentene, 2,3,3-trimethyl-1-hexene 2,3,3-trimethyl-1-octene, 2,3,4-trimethyl-1-pentene, 2,3,4-trimethyl-1-hexene, 2,3,4-trimethyl-1-octene, 2, , 4,4-trimethyl-1-hexene, 2,4,4-trimethyl-1-octene, 2-methyl-3-cyclohexyl-1-propylene, vinylidenecyclopentane, vinylidenecyclohexane, vinylidenecyclooctane, 2-methylvinylidenecyclopentane, 3-methylvinylidenecyclopentane, 4 -Vinylidene compounds such as methylvinylidenecyclopentane; styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, etc. Arylvinyl compounds; arylvinylidene compounds such as α-methylstyrene, α-ethylstyrene, 2-methyl-3-phenylpropylene; cyclobutene, cyclopentene, 1-methyl-1-cyclopentene, 3-methyl-1-cyclope N-ene, 2-methyl-1-cyclopentene, cyclohexene, 1-methyl-1-cyclohexene, 3-methyl-1-cyclohexene, 2-methyl-1-cyclohexene, cycloheptene, cyclooctene, norbornene, 5-methyl-2-norbornene , Tetracyclododecene, 5,6-dihydrodicyclopentadiene, 3a, 4,5,6,7,7a-hexahydro-1Hindene, tricyclo [6.2.1.0 ^2,7 ] undec-4-ene An aliphatic cyclic olefin containing an internal double bond such as cyclopentadiene and dicyclopentadiene; cyclopent-2-enylbenzene, cyclopent-3-enylbenzene, cyclohex-2-enylbenzene, cyclohex-3-enylbenzene, indene, 1,2-dihydronaphthalene, 1,4 Cyclic olefins containing aromatic rings such as dihydronaphthalene and 1,4-methino 1,4,4a, 9a tetrahydrofluorene; butadiene, isoprene, 4-methyl-1,3-pentadiene, 4-methyl-1,4-pentadiene 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, , 6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl Cyclic polyenes having two or more double bonds, such as -1,4,8-decatriene and Examples thereof include a chain polyene having two or more double bonds.

Moreover, the C3-C50 olefin may have a functional group containing atoms, such as oxygen, nitrogen, and sulfur. For example, unsaturated carboxylic acids such as acrylic acid, fumaric acid, itaconic acid, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, and sodium, potassium, lithium and zinc salts thereof Unsaturated carboxylic acid metal salts such as magnesium salt and calcium salt; Unsaturated carboxylic acid such as maleic anhydride, itaconic anhydride and bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride Acid anhydride: methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, isobutyl acrylate, acrylic acid-tert-butyl, acrylic acid-2-ethylhexyl, methacrylic acid Methyl, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacryl -Unsaturated carboxylic acid esters such as n-butyl, isobutyl methacrylate, tert-butyl methacrylate; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate Vinyl esters such as glycidyl acrylate, unsaturated glycidyl esters such as glycidyl methacrylate, monoglycidyl itaconate;
Halogenated olefins such as vinyl chloride, vinyl fluoride, 2-fluoropropylene, 2-chloropropylene and allyl fluoride; acrylonitrile, 2-cyanopropylene, 2-cyano-bicyclo [2.2.1] hept-5-ene Unsaturated cyano compounds such as methyl vinyl ether and ethyl vinyl ether; unsaturated amides such as acrylamide, methacrylamide and N, N-dimethylacrylamide;
Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; 2-aminopropylene, N- Examples include vinyl pyrrolidone and 2-hydroxymethylpropylene.

  In a preferred embodiment, the ethylene polymer (A) is a compound having a structure represented by the formula (4) and having a weight average molecular weight of 500 or more and 10,000 or less.

_{A-CH = CH 2 (4} )
Here, in formula (4), A is a polymer chain containing a structural unit selected from ethylene and, if necessary, one or more α-olefins having 3 to 50 carbon atoms.
In Formula (4), Preferably, the A part of the ethylene polymer (A) is an ethylene chain or a chain having a structural unit derived from ethylene and α-olefin. The α-olefin is preferably an α-olefin having 3 to 20 carbon atoms.

  As a preferable aspect among the above, A of the ethylene polymer (A) represented by the formula (4) is a chain composed only of an α-olefin having 2 to 50 carbon atoms. More preferably, A in the ethylene polymer (A) is a chain composed of only an α-olefin having 2 to 20 carbon atoms. More preferably, A in the ethylene polymer (A) is a chain composed only of ethylene.

  In the ethylene polymer (A) represented by the formula (4), the structural unit derived from ethylene is in the range of 81 to 100 mol%, and the structural unit derived from the α-olefin having 3 to 20 carbon atoms is in the range of 0 to 19 mol%. An ethylene / α-olefin copolymer is desirable. More preferably, it is an ethylene / α-olefin copolymer having a constitutional unit derived from ethylene of 90 to 100 mol% and a constitutional unit derived from α-olefin having 3 to 20 carbon atoms in the range of 0 to 10 mol%. desirable. In particular, it is preferable that the structural unit derived from ethylene is 100 mol%.

  Further, the ethylene polymer (A) represented by the formula (4) has a molecular weight distribution (ratio of weight average molecular weight to number average molecular weight, Mw / Mn) measured by gel permeation chromatography (GPC) of 1.1. It is preferable that it exists in the range of -3.0, and a more preferable minimum is 1.2. On the other hand, a more preferable upper limit is 2.7, further 2.5, and particularly 2.3.

The ethylene polymer (A) represented by the formula (4) preferably has a weight average molecular weight (Mn) in the range of 1,000 to 10,000, and preferably 1,200 to 9,000. More preferably, it is 1,500 or more and 8,000 or less.
The ethylene polymer (A) represented by the formula (4) preferably has a melting point of 70 ° C. or higher and 130 ° C. or lower.
More preferably, the vinyl group of the ethylene polymer (A) represented by the formula (4) is preferably present at the end of the main chain, and more preferably the vinyl group is present only at the end of the main chain.

In addition, it can confirm that a vinyl group exists in the terminal of a principal chain, for example using ¹³ CNMR and ¹ HNMR. For example, when A is an ethylene homopolymer, a method of confirming that tertiary carbon is not detected by ¹³ CNMR and hydrogen of a vinyl group is detected by ¹ HNMR can be mentioned. ^{Even in 1} HNMR alone, the structure can be confirmed by assigning each detected proton peak. For example, in the compound synthesized in Synthesis Example 1, the peak of chemical shift 0.81 ppm having a proton integral value of 3 is a methyl group at one end, and the peak of chemical shift 1.10-1.45 ppm is the main chain. The peak of 1.93 ppm chemical shift with methylene group and proton integral value of 2 is 4.80, 4.86, 5.60-5.72 ppm with methylene group adjacent to the terminal vinyl group and proton integral value of 1, respectively. Is attributed to the terminal vinyl group and no other unidentified peak exists, so that it can be confirmed that A is an ethylene homopolymer and has a structure containing a vinyl group only at the terminal. As another method, by utilizing the fact that the hydrogen of the vinyl group present at the end of the main chain is shorter in the relaxation time in ¹ HNMR measurement than the hydrogen of the vinyl group present in the side chain, It can also be determined by a method of comparing the relaxation time with hydrogen of the vinyl group of the polymer having a vinyl group.

In some cases, the chemical shift in ¹ HNMR of the vinyl group in the side chain can be determined by utilizing the fact that the magnetic field shifts lower than the vinyl group present at the terminal.

When the ethylene polymer (A) represented by the formula (4) contains a vinyl group only at the end of the main chain, the terminal unsaturation ratio (VE described later) calculated by ¹ H-NMR is 60. It is desirable that the amount be from mol% to 100 mol%. One of the more preferable embodiments is one in which the terminal unsaturation calculated by ¹ H-NMR is 80 mol% or more and 99.5 mol% or less, more preferably 90 mol% or more and 99 mol% or less.

  As a preferable method for obtaining the ethylene polymer (A) represented by the formula (4) of the present invention, a transition metal compound represented by the following formula (I), formula (II), or formula (III): (A) and (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with the transition metal compound (A) to form an ion pair. Examples thereof include a method obtained by polymerizing or copolymerizing at least one selected from olefins having 2 to 50 carbon atoms with the catalyst (B) comprising one compound.

Transition metal compound represented by formula (I)

(In the formula (I), M represents a transition metal atom of groups 4 to 5 in the periodic table. M represents an integer of 1 to 4. R ⁵¹ represents a linear hydrocarbon group having 1 to 5 carbon atoms ( C _{n ′} H _{2n ′ + 1} , n ^′ = 1 to 5) or a hydrogen atom, R ^{52 to} R ⁵⁶ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group or a heterocyclic group. Indicates a compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of these are linked to each other In addition, when m is 2 or more, two of the groups represented by R ^{52 to} R ⁵⁶ may be linked, and n is the valence of M. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, A nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. A plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.)

Transition metal compound represented by formula (II)

(In formula (II), M represents a transition metal atom of Groups 4 to 5 of the periodic table. M represents an integer of 1 to 4. R ⁶¹ has one or more substituents. R ^{62 to} R ⁶⁶ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, or a heterocyclic compound residue. , An oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these are linked to each other to form a ring In addition, when m is 2 or more, two groups out of the groups represented by R ^{62 to} R ⁶⁶ may be linked, and n is a number that satisfies the valence of M. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, or a nitrogen-containing group. An organic group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. And a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.)

Transition metal compound represented by formula (III)

(In formula (III), M represents a transition metal atom of Groups 4 to 5 of the periodic table. M represents an integer of 1 to 4. R ⁷¹ has one or more substituents. And a bicyclic hydrocarbon group sharing at least one or more carbon atoms having 4 to 20 carbon atoms, R ^{72 to} R ⁷⁶ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a carbon atom; 2 represents a hydrogen group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group. Two or more of them may be connected to each other to form a ring, and when m is 2 or more, two of the groups represented by R ^{72 to} R ⁷⁶ may be connected. Is a number satisfying the valence of M, and X is a hydrogen atom, halogen atom, carbonization Hydrogen group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin-containing group When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.)
Moreover, when A consists only of the structural unit derived from ethylene, and when it consists only of the structural unit derived from propylene, it can also be produced by the following method.

(Polyolefin having ethylene homopolymer chain)
(E1) A polyolefin polymer chain having an ethylene homopolymer chain can also be produced, for example, by the following method.
(A) A transition metal compound having a salicylaldoimine ligand as shown in JP 2000-239312 A, JP 2001-27331 A, JP 2003-73412 A, or the like is used as a polymerization catalyst. Polymerization method.
(B) A polymerization method using a titanium-based catalyst comprising a titanium compound and an organoaluminum compound.
(C) A polymerization method using a vanadium catalyst comprising a vanadium compound and an organoaluminum compound.
(D) A polymerization method using a Ziegler-type catalyst comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane).

(Olefin / polyene copolymer)
Examples of the ethylene polymer (A) of the present application include (Z) a copolymer of ethylene and polyene. Of course, the copolymer which also contains the above-mentioned C3-C50 alpha olefin may be sufficient. The α-olefin is more preferably an α-olefin having 3 to 12 carbon atoms.

  Examples of the α-olefin having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1. -Pentene, 1-octene, 1-decene, 1-dodecene and the like. Among these, preferably an α-olefin having 3 to 10 carbon atoms, more preferably an α-olefin having 3 to 8 carbon atoms, particularly preferably propylene, 1-butene, 1-hexene, 4-methyl-1- Penten.

  Polyenes include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1, 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylnorbornene (5-vinylbicyclo [2.2.1] hept-2-ene ), Dicyclopentadiene, 2-methyl-1,4-hexadiene, 2-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, Examples include conjugated polyenes such as 5,9-dimethyl-1,4,8-decatriene and non-conjugated polyenes. Among these, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, butadiene, isoprene, 2-methyl-1,4-hexadiene or 2-methyl-1,6-octadiene is preferable. Since vinyl norbornene has a bulky skeleton, it has a rigid structure even at a low density, so it can be introduced as appropriate in consideration of differences in the area used as cosmetics and the assumed operating temperature described later. . .

  (I) The copolymer of ethylene and polyene is preferably the following copolymer (Z1). That is, (Z1) is selected from a copolymer of ethylene and polyene as described above, or a copolymer of at least one α-olefin and polyene selected from ethylene and an α-olefin having 3 to 12 carbon atoms. At least one selected from the above.

  The ethylene-polyene copolymer (Z) used in the present invention contains a structural unit derived from polyene in a proportion of 0.01 to 6.0 mol%, preferably 0.1 to 4.0 mol%. Is desirable. When the ethylene / polyene copolymer (Z) contains a structural unit derived from an α-olefin having 3 to 12 carbon atoms, the content is 0.01 to 15 mol%, preferably 0.1. -12 mol% is desirable.

  When the ethylene-polyene copolymer (Z) used in the present invention contains structural units derived from polyene in a proportion within the above range, the polymerization activity is also moderately high.

  Further, when a structural unit derived from an α-olefin having 3 to 12 carbon atoms is introduced, the melting point of the ethylene / polyene copolymer (Z) can be controlled. This is a useful method for product development in consideration of the area where the cosmetics described below are used, the operating temperature, and the like.

  (Z2) The ethylene-polyene copolymer (Z) used in the present invention has an average of 0.5 to 3.0 / molecule, preferably 0.5 to 2.0 / molecule, more preferably 1.0. It is desirable to have an unsaturated group content in the range of ~ 2.0 / molecule, particularly preferably 1.0-1.9, particularly preferably 1.0-1.5. When the unsaturated group content in the ethylene / polyene copolymer (Z) is within the above range, a block polymer having a structure in which silicone is added to the ethylene / polyene copolymer (Z) can be easily obtained in a high yield. Therefore, the obtained block copolymer (C) is expected to exhibit high performance as a cosmetic.

The unsaturated group content of the ethylene / polyene copolymer (Z) is measured as follows. ^The number M of unsaturated groups per 1,000 carbons can be obtained by comparing the peak area of the unsaturated portion carbon by ¹³ C-NMR with the peak area of all carbon. The unsaturated group content per molecule can be calculated by Mn × M / 14,000 using the number average molecular weight Mn.

  In the present invention, the number M of unsaturated groups per 1,000 carbon is 1.4 to 105, preferably 1.4 to 70, and more preferably 2.8 to 70.

(Z3) The ethylene / polyene copolymer (Z) used in the present invention has a density measured by a density gradient tube method of preferably 870 kg / m ³ or more, more preferably 890 kg / m ³ or more, further preferably 910 kg / m ³ or more. On the other hand, it is preferably 980 kg / m ³ or less, more preferably 970 kg / m ³ or less, and still more preferably 960 kg / m ³ or less. When the density of the ethylene-polyene copolymer (Z) is within the above range, the movement of the segment derived from the hydrogen silicone compound (B) is effectively suppressed in the normal use range as a cosmetic. Rheological properties can be developed.

  (Z4) The ethylene-polyene copolymer (Z) used in the present invention has a melting point measured by a differential scanning calorimeter (DSC) of 70 ° C or higher, preferably 80 ° C or higher, more preferably 90 ° C or higher, particularly preferably. It is desirable that the temperature is 100 ° C. or higher and 130 ° C. or lower, preferably 125 ° C. or lower, more preferably 120 ° C. or lower. When the melting point of the ethylene-polyene copolymer (Z) is within the above range, there is little tackiness and excellent dispersibility in the resin, so that a molded body having excellent scratch resistance and stain resistance can be obtained. Can do.

  (Z5) The ethylene-polyene copolymer (Z) used in the present invention has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 400 to 5,000, preferably 400 to 4000, more preferably. Is preferably in the range of 400 to 3000, particularly preferably in the range of 1,500 to 2,500. When the Mn of the ethylene-polyene copolymer (Z) is within the above range, there is little tackiness and excellent dispersibility in the resin, so that a molded article having excellent scratch resistance and stain resistance can be obtained. Can do.

  (Z6) The ethylene-polyene copolymer (Z) used in the present invention has a ratio (Mw / Mn) of weight average molecular weight to number average molecular weight measured by GPC of 4.0 or less, preferably 3.5 or less. More preferably it is 3.0 or less.

  In addition, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are polystyrene conversion values measured by gel permeation chromatography (GPC). Here, the measurement by GPC is performed under the conditions of temperature: 140 ° C. and solvent: orthodichlorobenzene.

  (Z7) The ethylene-polyene copolymer (Z) used in the present invention has a penetration hardness of 15 dmm (1 dmm = 0.1 mm) or less, preferably 10 dmm or less, more preferably 3 dmm or less, particularly preferably 1 dmm or less. It is desirable. The penetration hardness can be measured according to JIS K2207. When the penetration hardness of the ethylene / polyene copolymer (Z) is within the above range, a molded article having excellent scratch resistance and stain resistance can be obtained.

The ethylene-polyene copolymer (Z) according to the present invention comprises (Z2) unsaturated group content, (Z3) density, (Z4) melting point, (Z5) number average molecular weight (Mn), (Z6) Mw / It is desirable to satisfy one or more of the conditions of Mn (Mw: weight average molecular weight) and (Z7) penetration hardness, more preferably two or more, and still more preferably three or more. It is even more preferable that the above is satisfied, it is particularly preferable that five or more are satisfied, and it is particularly preferable that all six are satisfied. For example particularly preferred embodiment is 0.5 to 3.0 groups / molecule unsaturated group content (Z2-1), (Z3-1) density of 870~980kg / ^{m 3,} (Z4-1 ) Melting point is 70 to 130 ° C., (Z5-1) number average molecular weight (Mn) is 400 to 5,000, and (Z6-1) Mw / Mn (Mw: weight average molecular weight) is 4.0 or less. More preferably, in addition to these five (Z7-1), the penetration hardness satisfies 15 dmm or less.

The ethylene-polyene copolymer (Z) according to the present invention is copolymerized using vinyl norbornene (5-vinylbicyclo [2.2.1] hept-2-ene) as a polyene. In this case, the ethylene-polyene copolymer has the above-mentioned (Z2) unsaturated group content, (Z3) density, (Z4) melting point, (Z5) number average molecular weight (Mn), (Z6) Mw / Mn (Mw: (Weight average molecular weight), (Z7) It is desirable to satisfy at least one of the conditions of penetration hardness, more preferably at least 2, more preferably at least 3, more preferably at least 4. Is more preferable, it is particularly preferable that 5 or more are satisfied, and it is particularly preferable that all 6 are satisfied. For example particularly preferred embodiment is 0.5 to 2.0 groups / molecule is (Z2-2) unsaturated group content, (Z3-2) density of 890~980kg / ^{m 3,} (Z4-2 ) Melting point is 80 to 130 ° C., (Z5-2) number average molecular weight (Mn) is 400 to 5,000, and (Z6-2) Mw / Mn (Mw: weight average molecular weight) is 4.0 or less. More preferably, in addition to these five, (Z7-2) those satisfying a penetration hardness of 15 dmm or less are mentioned.

  The ethylene-polyene copolymer (Z) as described above is composed of, for example, a metallocene compound of a transition metal selected from Group 4 of the periodic table and an organoaluminum oxy compound and / or an ionized ionic compound as follows. It can manufacture using a system catalyst. Suitable metallocene catalysts in the present invention include Japanese Patent Application Laid-Open No. 2001-002731 or PCT applications already published internationally, WO / 2007/114102, WO / 2007/1055483, WO / 2007/114409, WO / 2007 / For example, (A) transition metal metallocene compounds selected from Group 4 of the periodic table, (B) (b-1) organoaluminum oxy compounds, (b-2) metallocene compounds (A) And an olefin polymerization catalyst comprising at least one compound selected from a compound that forms an ion pair by reacting with (b-3) an organoaluminum compound.

Specific examples of (A) metallocene compounds of transition metals selected from Group 4 of the periodic table used in the present invention include bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (1-Methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, dimethyl ((t-butylamide) (tetramethyl-η ⁵ -Cyclopentadienyl) silane) titanium dichloride and the like.

  Further, (B) (b-1) an organoaluminum oxy compound, (b-2) a compound that reacts with a metallocene compound (A) to form an ion pair and (b-3) an organoaluminum compound used in the present invention. Specific examples of at least one selected compound include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3 , 5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, trimethylaluminum, triisobutylaluminum and the like.

  In the present invention, the case where the ethylene polymer (A) is represented by the formula (4) is particularly preferable because it is excellent in wear resistance and stain resistance and has little bleeding from the surface of the molded body.

Although the block copolymer (C) used in the present invention can be produced by any method, it is preferably obtained by sequentially performing the following [Step 1] and [Step 2]. It is a block copolymer (C) or a derivative thereof, or a mixture thereof.
[Step 1] A step of mixing and stirring the hydrogen silicone compound (B) and the transition metal halide, filtering the obtained suspension solution to obtain a transition metal catalyst composition (D) as a filtrate,
[Step 2] A reaction between the ethylene polymer (A) and the hydrogen silicone compound (B) in the presence of the transition metal catalyst composition (D) obtained in the above [Step 1] (however, the above hydrogen silicone compound) (B) except that one having two or more SiH groups per molecule and the ethylene polymer (A) having an average of 2.0 or more vinyl groups per molecule are excluded) Process.

Below, the example of the manufacturing method of a block copolymer (C) is explained in full detail.
[Step 1]: Step of obtaining a transition metal catalyst composition (D) In [Step 1], the hydrogen silicone compound (B) and the transition metal halide are mixed and stirred, and the resulting suspension solution is filtered. A transition metal catalyst composition (D) is obtained as a filtrate.

  The halogenated transition metal is a halide of a transition metal from Group 3 to Group 12 of the periodic table, and preferably from Group 8 to Group 10 of the periodic table from the viewpoint of availability and economy. More preferred are halides of platinum, rhodium, iridium, ruthenium, osmium, nickel and palladium. More preferred is a platinum halide. Further, it may be a mixture of two or more transition metal halides.

  Examples of the halogen of the halogenated transition metal include fluorine, chlorine, bromine, and iodine. Among these, chlorine is preferable from the viewpoint of easy handling.

  Specific examples of the transition metal halide used in [Step 1] include platinum dichloride, platinum tetrachloride, platinum dibromide, platinum diiodide, rhodium trichloride, rhodium tribromide, rhodium triiodide, three Iridium chloride, iridium tetrachloride, iridium tribromide, iridium triiodide, ruthenium trichloride, ruthenium tribromide, ruthenium triiodide, osmium trichloride, osmium tribromide, osmium triiodide, nickel dichloride, two Examples thereof include nickel fluoride, nickel dibromide, nickel diiodide, palladium dichloride, palladium dibromide, and palladium diiodide. Of these, platinum dichloride, palladium dichloride, ruthenium trichloride, rhodium trichloride, and iridium trichloride are preferred, and platinum dichloride is most preferred.

  The halogenated transition metal used in [Step 1] is usually a powdery solid, and the particle size is preferably 1000 μm or less, more preferably 500 μm or less. As the particle size increases, the preparation time of the transition metal catalyst composition (D) becomes longer.

  The amount of the hydrogen silicone compound (B) and the transition metal halide used in [Step 1] is not particularly limited as long as the amount of the hydrogen silicone compound (B) is 1 equivalent or more with respect to the halogenated transition metal. Is 2 equivalents or more. When the amount of the hydrogen silicone compound (B) is small, stirring necessary for preparing the transition metal catalyst composition (D) becomes difficult.

  The mixing and stirring of the hydrogen silicone compound (B) and the transition metal halide in [Step 1] is not limited as long as this is possible, but the transition metal halide is placed in a reaction vessel equipped with a stirrer under a nitrogen stream. Is added in an appropriate amount, and the hydrogen silicone compound (B) is added thereto and stirred. In the case of a small amount, a stirrer chip may be put in a sample tube and charged in the same manner and stirred.

  The mixing and stirring time of the hydrogen silicone compound (B) and the transition metal halide is usually 10 hours or more, preferably 20 hours or more, more preferably 60 hours or more, and further preferably 80 hours or more. is there. If the reaction time is short, the production rate of the isomeric vinylene derivative which is an impurity in the block copolymer (C) obtained in the next [Step 2] increases, which is not preferable. Although there is no particular upper limit for the mixing and stirring time, it is generally within one month from an economical viewpoint.

  The temperature of mixing and stirring the hydrogen silicone compound (B) and the transition metal halide is not particularly limited as long as it is not higher than the boiling point of the hydrogen silicone compound (B), but is usually in the range of 0 to 50 ° C., preferably 10 It is the range of -30 degreeC. In addition, the pressure can be usually performed at normal pressure, but can be performed under pressure or under reduced pressure as necessary.

  In [Step 1], a solvent may be used as necessary. As the solvent to be used, a solvent inert to the raw material hydrogen silicone compound (B) and the transition metal halide can be used. Specific examples of the solvent that can be used include aliphatic hydrocarbons such as n-hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, acetone, Examples include ketones such as methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, and methyl propyl ketone; ethers such as tetrahydrofuran and 1,4-dioxane; halogenated hydrocarbons such as chloroform, dichloroethane, trichloroethane, tetrachloroethane, and perchloroethane. . Of these, aromatic hydrocarbons such as toluene and xylene are particularly preferable.

  When the solvent is used, the amount of the solvent used affects the solubility of the raw material, but is preferably 100 times by mass or less, more preferably 20 times by mass or less with respect to the raw material. In the present invention, it is most preferable to carry out without solvent.

  Next, the suspended solution obtained by the reaction is filtered to remove solids, and a transition metal catalyst composition (D) is obtained as a filtrate. There is no restriction | limiting in particular as a filtration method, General methods, such as natural filtration, pressure filtration, and reduced pressure filtration, can be used. There is no restriction | limiting in particular as a filter used by filtration, The membrane filter made from a cellulose filter paper, a glass fiber filter, a fluororesin, or a cellulose acetate etc. can be used suitably. Among these, it is preferable to use a fluororesin membrane filter in view of uniformity of pore diameter, low hygroscopicity, chemical stability, and the like. The filter used for filtration is preferably an eye filter smaller than 10 μm, and more preferably an eye filter of 1 μm or less. If a larger filter than this is used, the solid content of the unreacted transition metal halide is mixed in the catalyst and the catalyst becomes heterogeneous, which increases the amount of vinylene derivative that is an impurity of the synthesis target. Cause. Further, during filtration, the solid content can be washed using the above-mentioned solvent.

  The solid content removed by filtration, that is, the amount of the unreacted transition metal halide is usually 50% by weight or less, preferably 10% by weight or less based on the amount of the transition metal halide used. The reaction rate of the transition metal halide can be adjusted mainly by changing the preparation time.

  The transition metal catalyst composition (D) thus prepared can be used as it is in the next [Step 2], but after removing the solvent, concentrating and diluting, if necessary, [ It can also be used in Step 2]. Further, the hydrogen concentration of the hydrogen silicone compound (B) can be further diluted to adjust the catalyst concentration.

Instead of carrying out [Step 1], a commercially available transition metal catalyst, for example, platinum alone (platinum black), chloroplatinic acid, platinum-olefin complex, platinum-alcohol complex, or a platinum carrier on a carrier such as alumina or silica. Although what was carry | supported is mentioned, You may use this for [process 2].
[Step 2]: A step of reacting the ethylene polymer (A) with the hydrogen silicone compound (B).

  In [Step 2], the ethylene polymer (A) and the hydrogen silicone compound (B) are reacted in the transition metal catalyst composition (D) obtained in [Step 1] (provided that the hydrogen Except when the one having two or more SiH groups per molecule as the silicone compound (B) and the one having an average of 2.0 or more vinyl groups per molecule as the ethylene polymer (A) are excluded. ), And a block copolymer (C) is obtained.

  The hydrogen silicone compound (B) used in [Step 2] may be different from the hydrogen silicone compound (B) used in [Step 1], but preferably used in [Step 1]. Use the same one.

  The amount ratio when the ethylene polymer (A) and the hydrogen silicone compound (B) are reacted varies depending on the purpose, but the vinyl group in the ethylene polymer (A) and the Si in the hydrogen silicone compound (B). The equivalent ratio to the —H bond is in the range of 0.01 to 10 equivalent times, preferably in the range of 0.1 to 2 equivalent times. Here, the amount of the hydrogen silicone compound (B) is the total amount of the portion used in [Step 1] and included in the transition metal catalyst composition (D) and the portion newly added in [Step 2]. is there. When the total amount of the hydrogen silicone compound (B) required in [Step 1] is used, the [Step 2] can be carried out without adding the hydrogen silicone compound (B).

The reaction between the ethylene polymer (A) and the hydrogen silicone compound (B) is performed in the presence of the transition metal catalyst composition (D) prepared in [Step 1]. The quantitative ratio of the transition metal catalyst composition (D) and the ethylene polymer (A) is the equivalent ratio of the vinyl group in the ethylene polymer (A) and the transition metal content in the transition metal catalyst composition (D). It is in the range of 10 ⁻¹⁰ to 10 ⁻¹ equivalent times, preferably in the range of 10 ⁻⁷ to 10 ⁻³ equivalent times.

  As a reaction method in the reaction between the ethylene polymer (A) and the hydrogen silicone compound (B), the reaction may be finally performed, and the method is not limited. For example, the reaction is performed as follows. An ethylene polymer (A) is charged into a reaction vessel, and a hydrogen silicone compound (B) and a transition metal catalyst composition (D) are charged under a nitrogen atmosphere. The reactor is set and stirred in an oil bath whose internal temperature has been raised to the melting point of the ethylene polymer (A) in advance. After the reaction, the oil bath is removed and the mixture is cooled to room temperature, and the resulting reaction mixture is taken out in a poor solvent such as methanol or acetone and stirred for 2 hours. Thereafter, the obtained solid is collected by filtration, washed with the above poor solvent, and dried under reduced pressure at 60 ° C. and 2 hPa or less to obtain the desired product.

  The reaction between the ethylene polymer (A) and the hydrogen silicone compound (B) in [Step 2] preferably has a reaction temperature in the range of 100 to 200 ° C. From the melting point of the ethylene polymer (A) to be reacted. It is more preferable to carry out at a high temperature. A reaction temperature lower than 100 ° C. is not preferable because the reaction efficiency may be lowered. In addition, the pressure can be usually performed at normal pressure, but can be performed under pressure or under reduced pressure as necessary.

  In [Step 2], a solvent may be used as necessary. As the solvent to be used, those inert to the raw hydrogen silicone compound (B) and the ethylene polymer (A) can be used. When making it react under a normal pressure, it is preferable to use what has a boiling point more than melting | fusing point of the ethylene polymer (A) to react. Specific examples of the solvent that can be used include aliphatic hydrocarbons such as n-hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, acetone, Examples include ketones such as methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, and methyl propyl ketone; ethers such as tetrahydrofuran and 1,4-dioxane; halogenated hydrocarbons such as chloroform, dichloroethane, trichloroethane, tetrachloroethane, and perchloroethane. . Of these, aromatic hydrocarbons such as toluene and xylene are particularly preferable.

  In the case of using a solvent, the amount of the solvent used affects the solubility of the raw material, but is preferably 100 times by weight or less, more preferably 20 times by weight or less with respect to the raw material. In the present invention, it is most preferable to carry out without solvent.

  As described above, the structural unit represented by the formula (1) is contained by reacting the ethylene polymer (A) with the hydrogen silicone compound (B) in the presence of the transition metal catalyst composition (D). A reaction mixture containing the block copolymer (C) is obtained.

  The reaction mixture containing the block copolymer (C) after the reaction contains, in addition to the block copolymer (C), an unreacted ethylene polymer (A) and a vinylene derivative as a by-product. . In some cases, an unreacted hydrogen silicone compound (B) may be contained.

  The ratio of the structure derived from the structural unit represented by the formula (1) in the block copolymer (C) is not particularly limited as long as the target function of the block copolymer (C) is expressed. Usually, it is 5-99 weight%, Preferably it is 10-95 weight%. If the structural unit is in this range, functions such as thixotropy, stickiness resistance, and silicone and other solvent mixing properties can be expressed.

  In the above method, since the very high activity and high selectivity transition metal catalyst composition (D) obtained in [Step 1] is used, the ethylene polymer (A) and hydrogen silicone in [Step 2] are used. The reaction with the compound (B) proceeds efficiently. For this reason, the reaction rate of the double bond of the ethylene polymer (A) is usually 90% or more, preferably 95% or more, and the amount of vinylene derivative produced as a by-product depends on the block copolymer (C). On the other hand, it is usually 10% by weight or less, preferably 5% by weight or less.

  If the method as described above is used, the molecular weight of the ethylene polymer (A) can be freely controlled, and many segments derived from the ethylene polymer (A) can be introduced into the hydrogen silicone (B). Is possible. For this reason, block copolymers (C) having various structures can be produced. This is considered to be a significant advantage in the cosmetics field, where fine adjustments are often required due to various factors such as region, season, and people.

  The block copolymer (C) can be removed from the reaction mixture by reprecipitation in a poor solvent or by sludgeing. The poor solvent is not particularly limited as long as the solubility of the block copolymer (C) is small, and can be appropriately selected. Specific examples of the poor solvent include acetone, methanol, ethanol, n-propanol, isopropanol, acetonitrile, ethyl acetate, n-hexane, and n-heptane. Among these, acetone and methanol are preferable.

  Specific examples of the ethylene polymer (A) used in the present invention include the compound represented by the formula (4) or the ethylene / polyene copolymer (Z) as described above.

_{A-CH = CH 2 (4} )
(In Formula (4), A is a polymer chain containing a structural unit derived from one or more α-olefins having 2 to 50 carbon atoms.)
When ethylene polymer (A) is a compound represented by Formula (4), the structure (structure 4-1) in which A consists only of C2-C20 alpha olefin is preferable.

More preferably, the ethylene polymer (A) has a structure (structure 4-2) in which —CH═CH ₂ is present at the end of the polymer main chain.

Still more preferably, the ethylene polymer (A) has a structure (structure 4-3) in which —CH═CH ₂ is present only at the terminal of the polymer main chain.

Still more preferably, the ethylene polymer (A) has a structure (structure 4-4) in which A is composed only of an α-olefin having 2 to 20 carbon atoms, and —CH═CH ₂ is present at the end of the polymer main chain. A combination of structure 4-1 and structure 4-2).

Still more preferably, the ethylene polymer (A) has a structure (structure 4-5) in which A is composed only of an α-olefin having 2 to 20 carbon atoms, and —CH═CH ₂ is present only at the terminal of the polymer main chain. ) (Combination of structure 4-1 and structure 4-3).

  When the ethylene polymer (A) is (Z), a structure using vinyl norbornene as the polyene is more preferable.

  As described above, the hydrogen silicone compound (B) of the present invention specifically has a structure of the formula (2). Among them, preferable hydrogen silicone compounds (B) in the case where the ethylene polymer (A) is represented by the formula (4) and the case where it has the structure of (Z) are as follows.

When the ethylene polymer (A) is represented by the formula (4), the hydrogen silicone compound (B) is preferably a structure (structure 2-1) in which m = n = 1 in the formula (2). Is more preferably a structure (structure 2-2) in which all of R ⁴¹ in Z in the formula (2) are selected from a hydrocarbon group and a halogen (that is, R ⁴¹ is preferably not a hydrogen atom).

In the case where the ethylene polymer (A) is (Z) and there are, for example, two or more vinyl groups on average per molecule, the hydrogen silicone compound (B) is represented by the formula (2) In the formula (2), and R ⁴¹ in Z in the formula (2) is a structure selected from a hydrocarbon group and a halogen (structure 2-3), or in the formula (4) A compound having a structure (structure 2-4) in which m = 0 and n = 0 and only one of R ⁴¹ in Z in formula (2) is a hydrogen atom is preferable.

  Further, when the ethylene polymer (A) has an average of less than two vinyl groups per molecule, the hydrogen silicone compound (B) may be SiH as in the above structures 2-3 and 2-4. In addition to a compound having one group per molecule, it is also possible to use a compound having two or more Si-H bonds per molecule. For example, the above structure 2-1 and structure 2-2 may be adopted. .

  The block copolymer (C) is presumed to have a structure represented by, for example, formulas (5) to (8). Of course, the combination of the hydrogen silicone compound (B) and the ethylene polymer (A) is not limited to these examples.

(M, n, o, p, q in the above formulas represent an integer of 1 or more.)
Below, a particularly preferable aspect and the reason for the estimation will be described. Hereinafter, the part derived from the ethylene polymer (A) may be referred to as “polyolefin chain”, and the part derived from the hydrogen silicone compound (B) may be referred to as “silicon-containing compound chain”. When the ethylene polymer (A) has the structure represented by the formula (4), particularly the structure (4-5) and the hydrogen silicone compound (B) has the structure (2-2), the block copolymer ( C) is considered to have a structure like a block copolymer in which (polyolefin chain)-(silicon-containing compound chain)-(polyolefin chain) are bonded in this order. Specifically, the compound which has a presumed structure like above-mentioned Formula (5) can be illustrated.

  The ethylene polymer (A) has the structure (4-5) and the hydrogen silicone compound (B) has the structure (2-1), and the hydrogen silicone compound (B) has 3 SiH groups. In the case of having more than one, the block copolymer (C) has a block structure in which (polyolefin chain)-(silicon-containing compound chain)-(polyolefin chain) are bonded in this order. It is believed that structures can be included where the chains are grafted together.

  When the ethylene polymer (A) has the structure (4-5) and the hydrogen silicone compound (B) has the structure (2-3) and the structure (2-4), the block copolymer (C) Specifically, it can be considered that the structures of the above formulas (6) and (8) are taken.

Further, the ethylene polymer (A) has the structure (4-5), and the hydrogen silicone compound (B) is represented by the formula (2) where m = 0, n = 0, and Z is (—SiH (CH ₃ ) O—. ) ₆ -Si (CH ₃ ) ₂ O—Si (C ₆ H ₅ ) ₂ —, it is considered that it may take the form of formula (7).

  Further, when the ethylene polymer (A) is (Z) and the hydrogen silicone compound (B) has the structure (2-3), the block copolymer (C) is converted to (silicone-containing compound) in (polyolefin chain). It is thought that the structure of the formula (9) is obtained by grafting the chain).

  The block copolymer (C) having such a structure is derived from the hydrogen silicone compound (B) by agglomeration, amorphization and the like of segments derived from the ethylene polymer (A) having a relatively high molecular weight. The chain movement can be effectively suppressed. In particular, the effect is high in a state close to a stationary state where substantially no shear is applied. Therefore, it is considered that the cosmetic containing the block copolymer (C) of the present invention can effectively suppress stickiness even in a small amount and exhibits excellent fixability. On the other hand, when the cosmetic containing the block copolymer (C) is applied, that is, in a situation where shearing is applied, the ethylene polymer (A) segment is easily unraveled and the kinematic viscosity is liable to decrease. In addition to the molecular weight of the ethylene polymer (A), this property can be appropriately controlled by introducing a copolymer structure in which the ethylene polymer (A) includes a structure derived from an α-olefin such as propylene. That is, in the present invention, the ethylene polymer (A) may preferably have an embodiment in which a structural unit derived from an α-olefin having 3 to 50 carbon atoms is present.

  The above properties of the block copolymer (C) used in the present invention can be confirmed using a rheometer. Specifically, the viscosity in the step of increasing the shear rate from 1 / s to 100 / s in 60 seconds can be measured and expressed. That is, the relationship between the initial viscosity: Vi and the viscosity at the maximum shear rate: V100 is such that the Vi / V100 ratio is preferably 3-20, more preferably 3-15, and still more preferably 5-12.

  In the present invention, the above evaluation can be measured with a Visco Analyzer manufactured by REOLOGICA.

The block copolymer (C) used in the present invention can be used alone, but if necessary, other components such as carnauba wax, beeswax, candelilla wax, paraffin wax, microcrystalline wax , Various waxes such as montan wax, ozokerite, ceresin, polyethylene wax, Fischer-Tropsch wax, ethylene propylene copolymer; and oil gelling agents such as 12-hydroxystearic acid, metal soap, and sucrose fatty acid ester. Specifically, it is 5-1000 weight part with respect to 100 weight part of block copolymers (C).
Moreover, when forming cosmetics using the block copolymer of this invention, oil agents (E), such as silicone oil, can be used together. When the oil agent is added, the ratio of the block copolymer (C) to the oil agent (E) is such that the ratio of block copolymer (C) / oil agent (E) is 5/95 to 95/5, preferably The ratio is 10/90 to 90/10, more preferably 30/70 to 70/30.

  The cosmetic of the present invention is characterized by containing the block copolymer (C). The block copolymer (C) used in the present invention is preferably 0.1 to 100% by weight, particularly 2 to 70% by weight, more preferably 10 to 70% by weight, with the total cosmetic as 100% by weight. .

  As the silicone oil preferably used as the oil agent (E) in the present invention, known silicone oils used in cosmetics can be used without limitation. Further, it is preferably a liquid silicone oil during use, transportation, storage, and the like. Specific examples include dimethylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylethylpolysiloxane, and the like. These silicone oils can be used singly or in combination of two or more, and it is preferable to blend 1 to 99% by weight, particularly 10 to 90% by weight, in the total composition.

  The cosmetics of the present invention include oils, waxes, powders, pigments, dyes, fragrances, surfactants, preservatives, drugs, moisturizers, additives within the qualitative and quantitative ranges that do not impair the object of the present invention. A sticky agent, a cosmetic ingredient, water and the like can be blended.

The cosmetic of the present invention can be produced according to a usual method, and can be in any form such as a stick, paste, cream, gel, and liquid. Also, oily solid cosmetics such as makeup cosmetics such as foundations, lipsticks, blushers, eyebrows, eye shadows, eyeliners, etc .; emulsified cosmetics such as emulsions and creams; liquid cosmetics such as lotions and cleansing oils, etc. can do.
In the case of making a foundation, makeup cosmetics, etc., it is produced by mixing and dispersing the cosmetic powder in the cosmetic of the present invention, and solidifying and molding it. Moreover, these oil phases can also be emulsified and used together with a suitable aqueous phase. As the powder used here, known pigments commonly used in cosmetics can be used. For example, extender pigments such as talc, sericite, mica, kaolin, silica, nylon powder, polyethylene powder, cellulose powder; carbon black And coloring agents such as titanium oxide, iron oxide, zinc oxide, ultramarine, bitumen, chromium oxide, organic tar dyes, lakes and the like; and composite pigments such as mica titanium and iron oxide coated mica. In addition, those obtained by surface-treating these pigments with silicone, higher fatty acid, higher alcohol, fatty acid ester, metal soap, amino acid, alkyl phosphate, or the like, or those encapsulated in organic or inorganic microcapsules can also be used. These pigments can be used alone or in combination of two or more, preferably 0.1 to 90% by weight, more preferably 1 to 80% by weight, especially 5 to 70% by weight in the total composition. It is preferable to do this.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

(Measurement and calculation method)
The yield, conversion rate and isomerization rate were measured and calculated by the methods described below.

(Measurement and calculation method of yield, conversion rate, isomerization rate, terminal unsaturation rate, number of double bonds per 1000 carbon atoms by NMR analysis)
The yield, conversion rate, isomerization rate, terminal unsaturation rate, and number of double bonds per thousand carbons of the silylated polyolefin are determined by ¹ H-NMR. The NMR measurement in the present invention is carried out under the following conditions.
[ ¹ H-NMR]
An ECX400 nuclear magnetic resonance apparatus manufactured by JEOL Ltd. was used, and deuterated orthodichlorobenzene, deuterated chloroform, and deuterated benzene were appropriately used as solvents. The sample concentration was 20 mg / 0.6 mL, and the measurement temperature was appropriately selected from room temperature to 120 ° C.
The observation nucleus is ¹ H (400 MHz), the sequence is a single pulse, the pulse width is 5.12 μs (45 ° pulse), the repetition time is 7.0 seconds, the number of integration is 500 times or more, and 7.10 ppm is the standard for chemical shift Measured as a value. Peaks such as ¹ H derived from a vinyl group or a methyl group were assigned by a conventional method.

  Yield is the ratio of the number of moles of the silylated polyolefin obtained relative to the number of moles of the vinyl group-containing compound as the raw material, and the conversion ratio is the ratio of the same number of moles consumed per mole of the vinyl group-containing compound as the raw material Is the ratio of the number of moles of vinylene produced to the number of moles of the vinyl group-containing compound of the raw material, and the terminal unsaturation is the main chain with respect to the total of the terminal vinyl group and terminal methyl group of the main chain of the vinyl group-containing compound as the raw material The ratio of terminal vinyl groups, the number of vinyl groups per thousand carbons, is defined as the ratio of the number of vinyl groups to the number of carbons derived from the number of protons corrected to the number of vinyl groups per thousand carbons. The terminal unsaturation rate and the number of vinyl groups per thousand carbons are generally applied to the vinyl group-containing compound as a raw material, but in cases where hydrosilylation is insufficient, etc., an indicator of the remaining amount of unreacted raw material May also be applied to silylated polyolefins. For example, a peak (C) of 6 protons of ethoxy group methylene of a silylated polyolefin obtained by hydrosilylating a main chain terminal vinyl group-containing compound consisting only of ethylene with triethoxysilane is 3.8 ppm, an isomerized vinylene group A peak (D) of 2 protons is observed at 5.4 ppm. When hydrosilylation is not sufficient, the peak (E) for two protons of the unreacted vinyl group is observed at 4.8 to 5.1 ppm, and the peak (F) for one proton is observed at 5.6 to 5.8 ppm. The As for the raw material vinyl group-containing compound, the main chain methylene (G) for two protons was observed at 1.0 to 1.5 ppm, and the one having no vinyl group at the end of the main chain was terminal methyl (H ) Is observed at 0.8 ppm. Furthermore, the peak (I) for two protons on the carbon adjacent to the double bond is observed at 1.9 ppm.

  If the peak areas of each peak (C), (D), (E), (F), (G), (H) and (I) are respectively SC, SD, SE, SF, SG, SH and SI , Yield (YLD (%)), conversion rate (CVS (%)), isomerization rate (ISO (%)), terminal unsaturation rate (VE (%)), number of double bonds per thousand carbons ( VN (pieces / 1000 C)) is calculated by the following formula.

YLD (%) = (SC / 3) / (SC / 3 + SD + SE) × 100
CVS (%) = {1-SE / (SC / 3 + SD + SE)} × 100
ISO (%) = SD / (SC / 3 + SD + SE) × 100
VE (%) = SE / (SE / 2 + SH / 3) × 100
VN (pieces / 1000C) = (SE + SF) / 3 × 1000 / {(SD + SE + SF + SG + SH + SI) / 2}

[ ¹³ C-NMR]
Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of orthodichlorobenzene / heavy benzene (80/20 vol%) as a solvent, sample concentration 55 mg / 0.6 mL, measuring temperature 120 ° C., observation nucleus ¹³ C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45 ° pulse), repetition time is 5.5 seconds, integration number is 10,000 times or more, 27.50 ppm as standard for chemical shift Measured as a value.
Methylene carbon, methine carbon, and methyl carbon were assigned, and the contents of ethylene and propylene were calculated by a conventional method.

(Molecular weight of polymer)
The molecular weight was determined by the GPC method under the following conditions.

Liquid chromatograph: Alliance GPC 2000 model equipment manufactured by Waters Column: TSKgel GMH6-HT × 2 and GMH6-HTL × 2 manufactured by Tosoh Corporation were connected in series.

Mobile phase medium: o-dichlorobenzene (containing 0.025% stabilizer)
Flow rate: 1.0 ml / min Measurement temperature: 140 ° C
Method for preparing calibration curve: Sample concentration using standard polystyrene sample: 0.15% (w / v)
Sample solution volume: 500 μl
Standard sample for calibration curve creation: monodisperse polystyrene manufactured by Tosoh Corporation

[Melting point of polymer (Tm)]
The melting point (Tm) of the polymer in the present invention was measured by a differential scanning calorimeter (DSC) using a DSC220C apparatus manufactured by Seiko Instruments Inc. Samples 7-12 mg were sealed in an aluminum pan and heated from room temperature to 200 ° C. at 10 ° C./min. The sample was held at 200 ° C. for 5 minutes to completely melt all crystals and then cooled to −50 ° C. at 10 ° C./min. After 5 minutes at −50 ° C., the sample was heated a second time to 200 ° C. at 10 ° C./min. In this second heating test, the peak temperature was adopted as the melting point (Tm-II).

(Viscoelasticity measurement: shear rate 1 / s to 100 / s)
Using a Visco Analyzer manufactured by REOLOGICA, the shear rate was increased from the initial value 1 / s to 100 / s. The viscosity of 1 / s Vi (Pa · s ), the viscosity at 100 / s and _V 100 (Pa · s), to calculate the value of Vi _{/ V 100.}

[Synthesis Example 1]
(Synthesis of polyethylene having a vinyl group at one end)
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 3.89 g (15.0 mmol) of 3-cumyl-5-methylsalicylaldehyde, 30 ml of toluene and 1.75 g of methylamine (40% aqueous solution, 22.5 mmol). And stirred at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 3.87 g (yield 97%) of a yellow oily compound (L-1).

¹ H-NMR (CDCl ₃ ): 1.69 (s, 6H), 2.34 (s, 3H), 3.33 (s, 3H), 6.93-7.29 (m, 7H), 8 .21 (s, 1H), 13.5 (s, 1H)
A 100 ml reactor thoroughly dried and purged with argon was charged with 1.12 g (4.00 mmol) of the compound (L-1) obtained above and 25 ml of diethyl ether, cooled to −78 ° C. and stirred. To this, 2.58 ml of n-butyllithium (n-hexane solution, 1.55M, 4.00 mmol) was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 2 hours. The mixture was further stirred for 3 hours to prepare a lithium salt. This solution was added dropwise to 25 ml of a tetrahydrofuran solution containing 0.76 g (2.00 mol) of ZrCl ₄ (THF) ₂ complex cooled to −78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. Furthermore, after stirring at room temperature for 12 hours, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 50 ml of methylene chloride, and insoluble matters were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with n-hexane and dried under reduced pressure to obtain 1.10 g (yield 79%) of yellow powdered compound (Ia).

¹ H-NMR (CDCl ₃ ): 0.86-1.91 (m, 18H), 2.35 (s, 6H), 6.92-7.52 (m, 14H), 7.78 (s, 2H)

A stainless steel autoclave with an internal volume of 2000 ml sufficiently purged with nitrogen was charged with 1000 ml of heptane at room temperature, and the temperature was raised to 150 ° C. Subsequently, the inside of the autoclave was pressurized to 30 kg / cm ² G with ethylene to maintain the temperature. A hexane solution of MMAO (manufactured by Tosoh Finechem) (0.5 mmol (0.5 mmol) in terms of aluminum atom) was injected, and then 0.5 ml of a toluene solution of compound Ia (0.0002 mmol / ml) (0.0001 mmol) was injected to initiate the polymerization. After carrying out the polymerization at 150 ° C. for 30 minutes in an ethylene gas atmosphere, the polymerization was stopped by press-fitting a small amount of methanol. The obtained polymer solution was added to 3 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours.

^{From the 1} H-NMR measurement, it is clear that the obtained polymer is a homopolyethylene and contains a double bond only at one end, and the integral value SH = From 3.00, the integration value SE of the vinyl group SE = 1.92, the terminal unsaturation rate (VE) was 98%. The ¹ H-NMR measurement results and physical properties of this single terminal double bond-containing ethylene polymer (A-1) (single) were as follows.

¹ H-NMR: δ (C ₆ D ₆ ): 0.81 (t, 3H, J = 6.9 Hz), 1.10-1.45 (m), 1.93 (m, 2H), 4. 80 (dd, 1H, J = 9.2, 1.6 Hz), 4.86 (dd, 1H, J = 17.2, 1.6 Hz), 5.60-5.72 (m, 1H)
Melting point (Tm) 117 ° C
Mw = 1900, Mw / Mn = 2.24 (GPC)
Terminal unsaturation rate 98%
The results are summarized in Table 1.

[Synthesis Example 2]
The methylamine used in Synthesis Example 1 was replaced with the same molar amount of ethylamine, and a zirconium complex compound (Ib) was synthesized in the same manner as in Synthesis Example 1.

  Further, ethylene polymerization was carried out in the same manner as in Synthesis Example 1 using Ib, and the physical properties of the one-end vinyl group-containing ethylene polymer (A-2) (single) were as follows.

Melting point (Tm) 128 ° C
Mw = 4770, Mw / Mn = 2.25 (GPC)
Terminal unsaturation 97%
The results are summarized in Table 1.

[Synthesis Example 3]
(Synthesis of ethylene / propylene copolymer having a vinyl group at one end)
In the same manner as in Synthesis Example 1, 3-cumyl-5-methylsalicylaldehyde used in Synthesis Example 1 was changed to the same molar amount of 3-adamantyl-5-methoxysalicylaldehyde, methylamine was changed to the same molar amount of cyclopentylamine. The mixture was stirred and stirred at room temperature for 1.5 hours. The reaction solution was concentrated under reduced pressure to obtain 3.45 g (yield 97%) of a yellow solid compound (L-3).

¹ H-NMR (CDCl ₃ ): 1.5-2.2 (m, 24H), 3.76 (s, 3H), 6.49 (s, 1H), 6.89 (s, 1H), 8 .29 (s, 1H), 13.6 (s, 1H).
In a 100 ml reactor sufficiently dried and purged with argon, 1.43 g (4.00 mmol) of the compound (L-3) obtained above, 15 ml of diethyl ether and 15 ml of tetrahydrofuran were charged, cooled to −78 ° C. and stirred. To this, 2.56 ml of n-butyllithium (n-hexane solution, 1.56M, 4.00 mmol) was added dropwise over 5 minutes, stirred at the same temperature for 2 hours, and then slowly warmed to room temperature. The mixture was further stirred for 3 hours to prepare a lithium salt. This solution was added dropwise to 25 ml of a tetrahydrofuran solution containing 0.76 g (2.00 mol) of ZrCl ₄ (THF) ₂ complex cooled to −78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. Furthermore, after stirring at room temperature for 12 hours, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 50 ml of methylene chloride, and insoluble matters were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with n-hexane and dried under reduced pressure to obtain 519 mg (yield 30%) of compound (Ic) as a yellow powder.

¹ H-NMR (CDCl ₃ ): 1.2-2.5 (m, 48H), 3.80 (s, 6H), 6.61 (s, 2H), 7.13 (s, 2H), 8 .23 (s, 2H).

A glass polymerization vessel having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene at room temperature and heated to 25 ° C. Subsequently, the temperature was maintained while flowing a mixed gas of ethylene 100 L / h and propylene 100 L / h into the polymerization vessel. 3.8 ml (3.8 mmol) of MMAO (manufactured by Tosoh Finechem) in hexane (1.00 mmol / ml of aluminum atom equivalent) was injected, and then 4.0 ml of a toluene solution of compound Ic (0.002 mmol / ml) (0.008 mmol) was added to initiate the polymerization. After carrying out the polymerization at 25 ° C. for 30 minutes, the polymerization was stopped by adding a small amount of methanol. The obtained polymer solution was added to 3 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours.

^{From the 1} H-NMR measurement, the terminal unsaturated ratio (VE) of the ethylene / propylene copolymer having a vinyl group at one end was estimated to be 82%, and the ethylene / propylene composition was estimated to be 82/12 (mol%). It was lost. The ¹ H-NMR measurement results and physical properties of this single-end double bond-containing ethylene polymer (A-3) (single) were as follows.

¹ H-NMR: δ (tetrachloroethane-d2): 0.8-0.9 (m), 1.10-1.45 (m), 2.0-2.1 (m), 4.91- 5.03 (m, 2H), 5.70-5.93 (m, 1H)
Melting point (Tm) 111 ° C
Mw = 7100, Mw / Mn = 7.8 (GPC)
Terminal unsaturation rate 82%
The results are summarized in Table 1.

[Synthesis Example 4]
(Preparation of platinum catalyst composition (D-1))
In a 50 ml sample tube containing a magnetic stirrer chip, 0.50 g of platinum chloride (II) was added to hydrosilane A having the following structure (HS (A), manufactured by Momentive Performance Materials Japan GK, product number: XF40-C2195). (10 ml) and suspended at room temperature under a nitrogen stream. After stirring for 190 hours, about 0.4 ml of the reaction solution was collected with a syringe, filtered using a 0.45 μm PTFE filter, and the filtrate was collected in a 10 ml sample tube. A platinum catalyst having a platinum concentration of 3.8% by weight A composition (D-1) was obtained.
Hydrosilane A (HS (A)): HSi (CH ₃ ) ₂ O — (— Si (CH ₃ ) ₂ —O—) ₁₈ —Si (CH ₃ ) ₂ H

[Synthesis Example 5]
(Preparation of platinum catalyst composition (D-2))
In a 50 ml sample tube containing a magnetic stirrer chip, 0.50 g of platinum (II) chloride was added to the hydrosilane A (HS (A), manufactured by Momentive Performance Materials Japan GK, product number: XF40-C2195) (10 ml). ) And stirred at room temperature under a nitrogen stream. After stirring for 190 hours, about 0.4 ml of the reaction solution was collected with a syringe, filtered using a 0.45 μm PTFE filter, and the filtrate was collected in a 10 ml sample tube. A platinum catalyst having a platinum concentration of 3.8% by weight A composition (D-2) was obtained.

[Synthesis Example 6]
(Preparation of platinum catalyst composition (D-3))
In a 50 ml sample tube containing a magnetic stirrer chip, 0.50 g of platinum (II) chloride was added to the hydrosilane A (HS (A), manufactured by Momentive Performance Materials Japan GK, product number: XF40-C2195) (10 ml). ) And stirred at room temperature under a nitrogen stream. After stirring for 190 hours, about 0.4 ml of the reaction solution was collected with a syringe, filtered using a 0.45 μm PTFE filter, and the filtrate was collected in a 10 ml sample tube. A platinum catalyst having a platinum concentration of 3.8% by weight A composition (D-3) was obtained.

[Synthesis Example 7] Synthesis of triblock copolymer (C-1) (Introduction of polyethylene having terminal vinyl group into hydrosilane-1)
A 300 ml separable flask was charged with 22.0 g (9.3 mmol) of the one-end vinyl group-containing ethylene polymer (A-2) obtained in [Synthesis Example 2], and hydrosilane C (Guerest) under a nitrogen atmosphere. 85.0 g (5.0 mmol; equivalent to 10.0 mmol as a Si-H group) manufactured by Co., Ltd. was suspended in 28 g of toluene, and the platinum catalyst composition prepared in [Synthesis Example 4] was suspended in the hydrosilane C. 350 μl (3.3 × 10 ⁻⁴ mmol in terms of Pt) diluted with 200 times was charged. The reactor was set in an oil bath that had been heated to an internal temperature of 150 ° C. in advance, and stirred. The polymer melted after about 5 minutes. Next, toluene was allowed to flow out while circulating nitrogen, cooled after 2 hours, and dried under reduced pressure of 80 ° C. and 2 hPa or less to obtain 104.7 g of a white waxy triblock copolymer (C-1). It was. As a result of NMR analysis, the obtained silylated polyolefin (C-1) had a yield of 46%, an olefin conversion rate of 50%, and an isomerization rate of 4%.

[Synthesis Example 8] Synthesis of triblock copolymer (C-2) (Introduction of polyethylene having terminal vinyl group into hydrosilane-2)
A 300 ml separable flask was charged with 35.0 g (32.3 mmol) of the one-end vinyl group-containing ethylene polymer (A-1) obtained in [Synthesis Example 1], and Hydrosilane B (Gerest Co., Ltd.) under a nitrogen atmosphere. Manufactured product No. DMS-H21) 75.0 g (17.0 mmol; equivalent to 34.0 mmol as Si-H group) was suspended in 28 g of toluene, and the platinum catalyst composition prepared in [Synthesis Example 4] 350 μl (3.3 × 10 ⁻⁴ mmol in terms of Pt) was charged. The reactor was set in an oil bath that had been heated to an internal temperature of 150 ° C. in advance, and stirred. The polymer melted after about 5 minutes. Next, toluene was allowed to flow out while circulating nitrogen, cooled after 2 hours, and dried under reduced pressure of 80 ° C. and 2 hPa or less to obtain 104.3 g of a white waxy triblock copolymer (C-2). It was. As a result of NMR analysis, the obtained triblock copolymer (C-2) had a quantitative olefin conversion, yield of 96%, and isomerization of 4%.

[Synthesis Example 9] Synthesis of triblock copolymer (C-3) (Introduction of polyethylene having terminal vinyl into hydrosilane-3)
One-end vinyl group-containing ethylene polymer (A-1) was replaced with 30.0 g (8.4 mmol) of the one-end vinyl group-containing ethylene / propylene copolymer (A-3) of [Synthesis Example 3], and the hydrosilane A 7.0 g. (4.4 mmol; equivalent to 8.8 mmol as Si—H group), a white solid triblock copolymer (C-3) 36. in the same manner as in Synthesis Example 7 except that the hydrosilane to be diluted was replaced with hydrosilane A. 2 g was obtained. As a result of NMR analysis, the obtained silylated polyolefin (C-3) had a yield of 100%, the olefin conversion rate was quantitative, the yield was 100%, and there was no isomerization.

[Examples 1-8], [Comparative Examples 1-4]
Triblock copolymers (C-1) to (C-3), the raw material polyethylene wax (A-2), and the hydrosilane A as an oil agent were mixed in the eggplant flask at the composition ratios shown in Tables 2 and 3. Then, melt mixing was performed in a 150 ° C. oil bath. About each composition, the shape retention property, glossiness, and stickiness when thinly apply | coated on the glass base | substrate were evaluated on the following reference | standard. The results are shown in Tables 2 and 3.
Shape retention (visual evaluation)
○ Visually in a solid state and excellent in shape retention. △ Partially solid state but in shape retention. × Visually oily and poor in shape retention.

Luster (visual evaluation)
○ Excellent gloss feeling △ Glossy feeling is maintained × Glossy feeling is bad

Stickiness (feel when touched by hand)
○ There is little stickiness △ There is a little sticky feeling × Stickiness

In the triblock copolymers shown in Examples 1 to 3, viscoelasticity measurement shows that the viscosity change (Vi / V ₁₀₀ ) accompanying the change in shear rate is large and the thixotropic property is larger. In addition, these triblock copolymers not only have shape-retaining properties alone, but also are superior in gloss and tackiness compared to silicone alone or a mixture of PE wax and silicone shown in Comparative Examples 1 to 4. Furthermore, in Examples 4-7, the composition with silicone is evaluated as an oil agent. These mixtures not only showed thixotropic properties, but also showed excellent shape retention, gloss and stickiness. Such excellent properties reflect the excellent compatibility with the silicone used as the oil. FIG. 1 shows an optical micrograph of the triblock copolymer / silicone composition shown in Example 7, and FIG. 2 shows an optical micrograph of the PE wax / silicone composition of Comparative Example 4.

  As is apparent from the optical micrograph, the triblock copolymer of the present invention has not only the properties shown in the examples but also the texture and glossiness because the PE crystal parts contained therein are more finely and uniformly dispersed. Excellent performance required for cosmetics.

Claims (4)

It was obtained by subjecting an ethylene polymer (A) having a vinyl group at the end satisfying the following (i) to (iv) to a hydrogen silicone (B) having one or more SiH bonds per molecule. A cosmetic comprising a block copolymer (C).
(I) an ethylene homopolymer or a copolymer obtained by copolymerizing ethylene and at least one olefin selected from α-olefins having 3 to 12 carbon atoms,
(Ii) having a vinyl group at one end of the molecule, the vinyl group content per molecule is 0.8 to 1.0,
(Iii) the melting point is 70 to 136 ° C.
(Iv) The weight average molecular weight is 1000 to 10,000. The cosmetic according to claim 1, wherein the ethylene polymer (A) satisfies the following (i ') to (iv').
(I ′) a copolymer of ethylene and propylene, the composition of propylene being 1 mol% or more and less than 30 mol%,
(Ii ′) has a vinyl group only at one end of the molecule, and the vinyl group content per molecule is 0.8 to 1.0,
(Iii ′) the melting point is 70 to 136 ° C.,
(Iv ′) The weight average molecular weight is 1000 to 10,000. The block copolymer (C) contains an ethylene polymer (A) and a hydrogen silicone (B) characterized by having a triblock structure of (A)-(B)-(A). The cosmetic according to claim 1, wherein the cosmetic is characterized by the following. 4. A cosmetic comprising 5 to 95% by weight of the block copolymer (C) according to claim 1 and 95 to 5% by weight of an oil (D).

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