JP3331673B2 - Cyclic polyolefin resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cyclic polyolefin resin composition useful as a molding material.

[0002]

2. Description of the Related Art Cyclic polyolefin resins have high transparency,
Excellent in heat resistance, solvent resistance, dielectric properties and various mechanical properties, etc., automotive parts, machine housings, machine parts,
It is known as a useful material for various uses such as gaskets for construction materials, waterproof sheets for civil engineering or construction, industrial hoses and tubes, housings for home appliances, bags, sports goods, office supplies, and the like (Japanese Patent Laid-Open No. 4-356554, etc.). ).

[0003] However, the resin has low impact resistance and low flexibility at low temperatures, and thus tends to be restricted particularly in use in cold regions. In addition, since it does not have the characteristics of a polyvinyl chloride resin-based elastomer or a soft vinyl chloride resin, it is particularly suitable for interior and exterior of automobiles and vehicles, electric wires and home appliances, civil engineering, construction, building materials, hoses and tubes, etc. Although there is still room for improvement as a material for various applications, no effective means for improvement have been known so far.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a cyclic polyolefin resin composition having good low-temperature impact resistance, flexibility, processability and gasoline resistance and improved fluidity. I do.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, the desired effects have been obtained by blending an ester compound having a specific structure with a cyclic polyolefin resin. The inventors have found that the present invention can be obtained, and have completed the present invention based on such findings.

That is, the cyclic polyolefin resin composition according to the present invention is represented by the general formula (1), the general formula (2), the general formula (3) or the general formula (4) with respect to the cyclic polyolefin resin. at least one kind of ester compounds (hereinafter collectively referred to as "ester".) cyclic polyolefin resin composition der characterized by comprising blending that
Therefore, the compounding amount of the ester compound is
0.2 to 100 parts by weight based on 100 parts by weight of resin
However, in the case of the ester compound represented by the general formula (1),
6 to 100 parts by weight].

[0007]

Embedded image [In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 5 to 35 carbon atoms. R ² represents a linear or branched alkyl or alkenyl group having 6 to 28 carbon atoms. ]

[0008]

Embedded image [In the formula, R ³ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched alkenyl group having 2 to 10 carbon atoms. R ⁴ represents a linear or branched alkyl or alkenyl group having 6 to 28 carbon atoms. ]

[0009]

Embedded image [Wherein, R ⁵ , R ⁶ and R ⁷ are the same or different and each represent a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a linear or branched chain having 2 to 5 carbon atoms. Alkenyl group or endomethylene group. R ⁸ and R ⁹ are the same or different and each represent a linear or branched alkyl or alkenyl group having 6 to 28 carbon atoms. ]

[0010]

Embedded image [Wherein, R ¹⁰ , R ¹¹ and R ¹² are the same or different and each represent a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched chain having 2 to 5 carbon atoms. Alkenyl group or endomethylene group. R ¹³ and R ¹⁴ are the same or different and each represent a linear or branched alkyl or alkenyl group having 6 to 28 carbon atoms. ]

The method for producing the present ester is not particularly limited, and any conventionally known operation can be employed.
As a general method, there is a method in which a predetermined mono- or dicarboxylic acid or an acid anhydride thereof and a predetermined aliphatic alcohol are esterified without removing a reaction product water in the absence of a catalyst or in the presence of a catalyst. Hereinafter, each group will be described in detail.

The ester represented by the general formula (1) is easily synthesized by subjecting a predetermined aliphatic monocarboxylic acid and an aliphatic alcohol to an esterification reaction according to a conventional method.

Examples of the aliphatic monocarboxylic acid include saturated or unsaturated fatty acids having 6 to 36 carbon atoms, more preferably saturated or unsaturated fatty acids having 8 to 24 carbon atoms. If the fatty acid has less than 6 carbon atoms, the compatibility with the cyclic polyolefin-based resin is reduced and bleeding is liable to occur. Conversely, if the fatty acid has more than 36 carbon atoms, the gasoline resistance is reduced, which is not preferable.

Preferred aliphatic monocarboxylic acids according to the present invention include octylic acid, 2-ethylhexanoic acid, nonanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, and behen. Acid, oleic acid, linoleic acid, linolenic acid,
Examples thereof include dimer acid, and particularly, 2-ethylhexanoic acid,
Nonanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid and the like are recommended.

The ester represented by the general formula (2) is easily synthesized by subjecting a predetermined aromatic monocarboxylic acid and an aliphatic alcohol to an esterification reaction according to a conventional method.

As the aromatic monocarboxylic acid, benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-
Examples thereof include methylbenzoic acid, o-ethylbenzoic acid, m-ethylbenzoic acid, and p-ethylbenzoic acid.

The ester represented by the general formula (3) is easily synthesized by subjecting a predetermined alicyclic unsaturated dicarboxylic acid or its anhydride and an aliphatic alcohol to an esterification reaction according to a conventional method.

Examples of the alicyclic unsaturated dicarboxylic acid or anhydride thereof include tetrahydrophthalic acid, methyltetrahydrophthalic acid, dimethylbutenyltetrahydrophthalic acid, nadic acid, methylnadic acid, methylhymic acid and their acids. Examples thereof include anhydrides, isomers thereof (including geometric isomers and structural isomers), acid anhydrides obtained by the reaction of decatrienes such as allocymene and α-terpinene with maleic anhydride, and free carboxylic acids thereof. You.

The ester represented by the general formula (4) is easily synthesized by subjecting a predetermined alicyclic saturated dicarboxylic acid or an acid anhydride thereof to an aliphatic alcohol by an esterification reaction according to a conventional method. Further, it can also be obtained by subjecting the ester represented by the general formula (3) to nuclear hydrogenation.

Examples of the alicyclic saturated dicarboxylic acid or its anhydride include hexahydrophthalic acid, methylhexahydrophthalic acid, hydrogenated nadic acid, hydrogenated methylnadic acid, their acid anhydrides and isomers thereof. (Including geometric isomers).

The aliphatic alcohol used as the alcohol component of each ester according to the present invention has 6 to 6 carbon atoms.
It is a saturated or unsaturated aliphatic alcohol having 28, more preferably an aliphatic alcohol having 8 to 24 carbon atoms.
If the alcohol has less than 6 carbon atoms, the compatibility with the cyclic polyolefin resin decreases, and bleeding tends to occur. Conversely, an alcohol having more than 28 carbon atoms decreases gasoline resistance, which is not preferable.

Preferred aliphatic alcohols according to the present invention include heptanol, 2-ethylhexanol, n-
Octanol, isononanol, 3,5,5-trimethylhexanol, n-decanol, isodecanol, undecanol, dodecanol, tridecyl alcohol,
Alfort 610 (manufactured by Vista Chemical Far East), Lineball 79, 911 (manufactured by Shell Chemical), Diamond Doll 79, 911, 11, 11
(Manufactured by Mitsubishi Kasei), myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol,
Oleyl alcohol and dimerized alcohol obtained by the Garbet reaction of these alcohols are exemplified.

Examples of the esterification catalyst selectively applied in the above esterification include acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, paratoluenesulfonic acid, methanesulfonic acid, and alkylsulfuric acid, aluminum sulfate, lithium fluoride, and chloride. Metal salts such as potassium, cesium chloride, calcium chloride, iron chloride, and aluminum phosphate, ZnO ₂ / C, SnO,
Metal oxides such as SiO ₂ —TiO ₂ , ZnO, Fe ₂ O ₃ , heteropolyacid, Al ₂ O ₃ —KOH—LiOH, Al ₂ O ₃
Alumina-alkali composite systems such as NaOH, mordenite, natural and synthetic zeolites such as decationized Y zeolite, solid superacids such as SO ₄ ²⁻ / ZnO ₂ , SO ₄ ²⁻ / TiO ₂ , cation exchange resins, Examples include ion exchange resins such as anion exchange resins, tetraalkyl titanates and polymers thereof, and organic metals such as Bu ₂ Sn (OBu) OB (OBu) ₂ and stannous oxalate.

The post-treatment after completion of the esterification reaction includes:
Although not particularly limited, for example, a method of removing excess alcohol from the system, neutralizing, washing with water, and finally purifying the ester may be mentioned. In addition, it is also possible to use the ester according to the present invention simply by distilling excess alcohol out of the system without purification.

The kind of the present ester to be mixed with the cyclic polyolefin resin is appropriately selected according to the intended properties. For example, when the main purpose is to improve cold resistance and impact resistance, an ester compound represented by the general formula (1) is recommended. When the main purpose is to improve compatibility with a resin, An ester compound represented by the general formula (2) is recommended. In addition, when the main purpose is to provide balanced performance as a soft product and excellent breaking strength, an ester compound represented by the general formula (3) or (4) is recommended. Furthermore, when the main purpose is to improve weather resistance,
Among the ester compounds represented by the general formula (1) or (4), compounds in which R ² in the general formula (1) and R ¹³ and R ¹⁴ in the general formula (4) are alkyl groups are particularly recommended. You.

The cyclic polyolefin-based resin according to the present invention is a generic name of a polymer composed of a monomer unit of a polymerizable cyclic olefin having an ethylenic double bond in a ring. Olefin-based copolymers, ring-opened polymers of cyclic olefins, ring-opened polymers of two or more cyclic olefins and the above polymers and various rubbery polymers, amide-based polymers and ester-based polymers,
A polymer blend with an elastic elastomer or the like is exemplified. Such polymers are described, for example, in JP-A-60-16870.
No. 8, JP-A-61-120816, JP-A-62-25
2406 No., JP-A-2-167318, JP-4- 3
No. 56554 and the like.

Typical cyclic olefins constituting the above-mentioned cyclic olefin ring-opening polymer and cyclic olefin copolymer include 1,4,5,8 produced by condensing norbornenes and cyclopentadiene. -Dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalenes, hexacyclo [6.6.1.1.1.1.
0] Heptadecene-4, 6-ethylbicyclo [2.2.1] hept-2-ene synthesized from ethylene and cyclopentadiene, and the like.

The above-mentioned cyclic polyolefin-based resin may be used by blending another resin with a polymer to form an alloy.

The polymer that can be blended is not specified, and specific examples include natural rubber, styrene butadiene rubber, butadiene rubber, isoprene rubber, ethylene propylene copolymer, ethylene propylene diene terpolymer, nitrile butadiene rubber, and chloroprene rubber. , Rubbery polymers such as butyl rubber, urethane rubber and silicone rubber, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 1
2, amide-based polymers such as copolymerized nylon, nylon MXD6, and modified polyamide 6T, and ester-based polymers such as polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene isophthalate, polytetramethylene sebacate, and polypropylene adipate. Can be

Further, olefin elastomers represented by partially crosslinked ethylene α-olefin rubber / polypropylene, polybutadiene or polyisoprene /
Styrene elastomer represented by polystyrene,
Polytetramethylene oxide glycol / polybutylene terephthalate copolymer, polyester elastomer represented by polycaprolactone / polybutylene terephthalate, polyamide elastomer represented by polyamide resin / polyalkylene glycol copolymer, syndiotactic It is also possible to blend elastic elastomers such as thermoplastic elastomers such as polybutadiene elastomers of 1,2-polybutadiene and thermosetting elastomers such as polyurethane elastomers and silicone elastomers.

The amount of the present ester in the cyclic polyolefin-based resin is not particularly limited as long as a predetermined effect can be obtained, but the following range is recommended depending on the structure of the present ester and the main purpose of the resin. That is, when the chain ester represented by the general formula (1) is applied to 100 parts by weight of the resin, the amount is about 6 to 100 parts by weight, more preferably about 6 to 60 parts by weight, and the general formula ( 2),
When the ester having a 6-membered ring represented by (3) and (4) is used, the amount is 0.2 to 100 parts by weight, more preferably about 1 to 60 parts by weight. If the amount is less than each of the above amounts, it is difficult to obtain a predetermined modifying effect. Conversely, if the amount exceeds the above amount, a remarkable increase in the effect cannot be expected, and bleeding increases, which is not preferable.

On the other hand, a recommended example of the compounding amount according to the main purpose is shown below. That is, flexibility, cold resistance, in a soft compound for the purpose of improving impact resistance, about 5 to 60 parts by weight,
In a hard compound for the purpose of improving workability and impact resistance, the content is about 0.2 to 5 parts by weight.

In a system containing a filler such as calcium carbonate, glass mat, titanium oxide, clay, carbon black, talc, antimony oxide, aluminum hydrate, magnesia, calcium hydroxide, silicic acid, metal powder, etc. A blending amount of about 100 parts by weight is selected.

The present ester may be blended with the cyclic polyolefin resin in combination with various ester compounds conventionally known as plasticizers. Examples of such a plasticizer include benzoic acid esters such as ethylene glycol dibenzoate and propylene glycol dibenzoate, dibutyl phthalate, dihexyl phthalate, and di (2-phthalate).
Ethylhexyl), di (n-octyl) phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, diadol 7
9, phthalate esters such as 911, LINEBALL 79, phthalate esters, dibutoxyethyl phthalate and butylbenzyl phthalate of 911;

Di (2-ethylhexyl) adipate, di-n-octyl adipate, diisononyl adipate, diisodecyl adipate, adipate of Alfol 610, adipate of Diadol 79,
Adipates of Lineball 79, dibutoxyethyl adipate, dibutoxyethoxyethyl adipate,
Aliphatic esters such as dioctyl azelate and di (2-ethylhexyl) sebacate;

Tri (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisononyl trimellitate, triisodecyl trimellitate, trimellitate ester of Diadol 79, trimellitate ester of Lineball 79, trimellitate Trimellitic esters such as tributoxyethyl acid,

Phosphates such as tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, and tribubutoxyethyl phosphate;

Polyester plasticizers such as propylene glycol / adipic acid, propylene glycol / phthalic acid, butylene glycol / adipic acid, and propylene glycol / sebacic acid;

Epoxidized soybean oil, epoxidized linseed oil,
Octyl epoxy stearate, dioctyl 4,5-epoxyhexahydrophthalate, bis (9,10-epoxystearyl) 4,5-epoxyhexahydrophthalate
And the like, and epoxy plasticizers, chlorinated paraffins and the like.

The amount of the plasticizer used in combination as desired is not particularly limited as long as a predetermined effect is obtained, but is usually about 1 to 30 parts by weight based on 100 parts by weight of the cyclic polyolefin resin. It is.

The cyclic polyolefin resin composition according to the present invention may contain a stabilizer, a stabilizing aid, a processability improving resin, an ultraviolet absorber, a filler, a coloring agent, a foaming agent, a lubricant,
Various additives such as a resin reinforcing agent, a cross-linking agent, an antibacterial agent, a fungicide, a flame retardant, a release agent, an insect repellent, a repellent, a plate-out inhibitor, and an antistatic agent can be compounded.

The processing method of the cyclic polyolefin resin composition according to the present invention is not particularly limited. For example,
A method for obtaining a product by passing a cyclic polyolefin resin composition obtained by pre-kneading a cyclic polyolefin-based resin, the present ester and additives blended as necessary through various molding machines, and a method for directly molding the resin composition into a molding machine. It is possible to use a method of feeding and forming the material.

The pre-kneading of the cyclic polyolefin resin composition is prepared by kneading a predetermined amount of various components using a conventionally known kneading machine such as a Banbury mixer, a Henschel mixer, a ribbon blender, etc., in the order of addition. It doesn't matter.

The cyclic polyolefin resin composition thus obtained is molded by a method conventionally used in various fields such as calender molding, extrusion molding, injection molding, paste processing, etc., and is used for leather, film, stretch film, agricultural use. Film, sheet, foam, flooring agent, wallpaper, footwear, hose, tube, electric wire, paste sol molded product,
Automotive and vehicle parts such as packaging, roofing materials, pipes, joints, plates, corrugated sheets, flooring materials, containers, toys, roofing materials, tents, bumpers, trims, fuel tubes, instrument panels, headrest skins, grips, etc. It is useful as a soft, semi-hard, hard, sol and gel composition applied to refrigerator parts, battery cases, concrete flexibility imparting agents, porous films, adhesive compositions and the like.

Among them, the thermoplastic elastomer is useful as a material for automobiles and vehicles, electric wires and home appliances, civil engineering and construction, building materials, hoses and tubes, which are applications.

[0046]

The present invention will be described in detail below with reference to examples. The properties of the resin composition in each example were measured and evaluated by the following methods.

Preparation of test piece: A cyclic polyolefin-based resin and a predetermined ester were prepared by using a laboplast mill for 20 minutes.
The mixture is mixed at 0 to 230 ° C. to obtain a cyclic polyolefin resin composition.

Next, using a 30-ton press heated to 200 ° C., a sheet having a thickness of about 1 mm is prepared under the conditions of preheating (3 minutes) and pressurization (2 minutes, 100 kg / cm ² ). The obtained sheet is cut into a predetermined size and subjected to each test.

Bleed resistance: Pressed sheet at room temperature
After standing for a week, the presence or absence of bleed was visually observed, and evaluated according to the following three grades. When there is no bleed ◎ When there is a little bleed ○ When there is a noticeable bleed ×

Transparency: After the press sheet was allowed to stand at room temperature for one week, the degree was evaluated by measuring the haze value (the ratio of light that diffuses transmitted light).

Tensile test: According to JIS K 6723,
A tensile test was performed at 25 ° C., and the plasticizing efficiency was evaluated by measuring the elongation at break.

Cold resistance: The softness temperature of Crashberg was measured according to JIS K 6745.

Example 1 Ethylene / cyclic olefin copolymer [trade name "APEL"
−LTMA ”, MFR (2.16 kg load, 230 ° C.) =
39.0 g / 10 min, manufactured by Mitsui Petrochemical Co.] 100 parts by weight of tridecyl stearate (hereinafter referred to as "ST / TD").
A ". ) 25 parts by weight were blended to prepare a press sheet, and the physical properties of the sheet were measured. Table 1 shows the obtained results.

Example 2 The sheet properties were measured in the same manner as in Example 1 except that the amount of ST / TDA was changed to 40 phr. The obtained result is
It is shown in the table.

Example 3 Example 1 was repeated except that the amount of ST / TDA was changed to 3 phr.
The sheet properties were measured according to the above. Table 1 shows the obtained results.

Example 4 The sheet properties were measured in the same manner as in Example 1 except that 2-hexyldecyl isostearate (hereinafter abbreviated as “IST / 160”) was used as the present ester. Table 1 shows the obtained results.

Example 5 The sheet properties were measured in the same manner as in Example 1 except that 2-hexyldecyl oleate (hereinafter abbreviated as "D100 / 160") was used as the present ester. Table 1 shows the obtained results.

Example 6 As the present ester, oleyl oleate (hereinafter referred to as “OL
O ". ) Was used, and the sheet properties were measured in the same manner as in Example 1. Table 1 shows the obtained results.

Example 7 Sheet properties were measured in the same manner as in Example 1 except that 2-hexyldecyl benzoate (hereinafter abbreviated as "BA / 160") was used as the present ester. Table 1 shows the obtained results.

Example 8 The sheet properties were measured in the same manner as in Example 1 except that di (2-ethylhexyl) tetrahydrophthalate (hereinafter abbreviated as "DOTP") was used as the present ester. Table 1 shows the obtained results.

Example 9 Sheet properties were measured according to Example 1, except that diundecyl tetrahydrophthalate (hereinafter abbreviated as "DUTP") was used as the present ester. Table 1 shows the obtained results.

Example 10 The sheet properties were measured in the same manner as in Example 1 except that di (2-hexyldecyl) tetrahydrophthalate (hereinafter abbreviated as "TH / 160") was used as the present ester.
Table 1 shows the obtained results.

Example 11 The sheet properties were measured in the same manner as in Example 9 except that the amount of TH / 160 was changed to 40 phr. The obtained result is
It is shown in the table.

Example 12 The physical properties of the sheet were the same as in Example 1 except that di (2-hexyldecyl) 4-methyltetrahydrophthalate (hereinafter abbreviated as "MT / 160") was used as the present ester. It was measured. Table 1 shows the obtained results.

Example 13 As the present ester, di (2-ethylhexyl) 3,6-endomethylenetetrahydrophthalate (hereinafter referred to as “NA / 1
60 ". ) Was used, and the sheet properties were measured in the same manner as in Example 1. Table 1 shows the obtained results.

Example 14 The sheet properties were measured in the same manner as in Example 1 except that di (n-octyl) hexahydrophthalate (hereinafter abbreviated as "HH / nOct") was used as the present ester. Table 1 shows the obtained results.

Example 15 Except that diisononyl hexahydrophthalate (hereinafter abbreviated as "HH / INA") was used as the present ester,
The sheet properties were measured according to Example 1. Table 1 shows the obtained results.

Example 16 Sheet properties were measured in the same manner as in Example 1 except that di (n-decyl) hexahydrophthalate (hereinafter abbreviated as "HH / C10") was used as the present ester. Table 1 shows the obtained results.

Example 17 The sheet properties were measured in the same manner as in Example 15 except that the amount of HH / C10 was changed to 40 phr. Table 1 shows the obtained results.

Example 18 Sheet physical properties were measured in the same manner as in Example 1 except that di (2-hexyldecyl) hexahydrophthalate (hereinafter abbreviated as “HH / 160”) was used as the present ester. .
Table 1 shows the obtained results.

Example 19 The sheet properties were the same as in Example 1, except that di (2-hexyldecyl) 4-methylhexahydrophthalate (hereinafter abbreviated as "MH / 160") was used as the present ester. Was measured. Table 1 shows the obtained results.

Comparative Example 1 Sheet properties of a resin composition prepared according to Example 1 except that di (2-ethylhexyl) phthalate (hereinafter abbreviated as "DOP") was used instead of the present ester. Was measured. Table 1 shows the obtained results.

Comparative Example 2 The sheet properties of the resin composition were measured in the same manner as in Example 1 except that the amount of DOP was changed to 40 phr. Table 1 shows the obtained results.

Comparative Example 3 An APEL-LTMA press sheet containing no ester compound was prepared, and its physical properties were measured in accordance with Example 1. Table 1 shows the obtained results.

[0075]

EFFECT OF THE INVENTION By blending the ester compound according to the present invention, it is excellent in compatibility, plasticization efficiency, cold resistance, impact resistance, fluidity and gasoline resistance, and is thermoplastic and easily formed by various molding methods. Molding can be performed, and a cyclic polyolefin resin composition useful as a molding material can be obtained.

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 23/00-49/00 C08L 65/00 C08K 3/00-13/08

Claims (1)

(57) [Claims] 1. A cyclic polyolefin resin is blended with at least one ester compound represented by the general formula (1), (2), (3) or (4). A cyclic polyolefin-based resin composition characterized by comprising an ester-based compound
Was added to 100 parts by weight of the cyclic polyolefin-based resin.
2 to 100 parts by weight [however, S represented by the general formula (1)
6 to 100 parts by weight in the case of a ter-based compound]
Liolefin resin composition. R ¹ COOR ² (1) [wherein, R ¹ represents a linear or branched alkyl or alkenyl group having 5 to 35 carbon atoms. R ² represents a linear or branched alkyl or alkenyl group having 6 to 28 carbon atoms. ] [In the formula, R3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched alkenyl group having 2 to 10 carbon atoms. R4 represents a linear or branched alkyl or alkenyl group having 6 to 28 carbon atoms. ] [Wherein, R ⁵ , R ⁶ , and R ⁷ are the same or different and each represent a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched chain having 2 to 5 carbon atoms. Alkenyl group or endomethylene group. R ⁸ and R ⁹ are the same or different and represent a linear or branched alkyl or alkenyl group having 6 to 28 carbon atoms. ] [Wherein R ¹⁰ , R ¹¹ , and R ¹² are the same or different,
It represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkenyl group having 2 to 5 carbon atoms or an endmethylene group. R ¹³ , R
¹⁴ is the same or different and represents a linear or branched alkyl or alkenyl group having 6 to 28 carbon atoms. ]