WO2012176881A1 - Wax composition for candle, and candle - Google Patents

Abstract

Provided are: a wax composition for a candle; and a candle which comprises the wax composition and a wick. Even when any wax component is used, the wax composition is less susceptible to cracking and exhibits excellent moldability, duration of combustion, diffusion of an aroma, and surface gloss. When molded into a candle, the wax composition ensures excellent surface appearance and causes little bleeding of oil. Specifically, provided are a wax composition for a candle, and a candle which comprises the wax composition and a wick, said wax composition being a composition which comprises (A) a wax and (B) a side-chain crystalline single-polymer or copolymer prepared using a higher α-olefin having 10 or more carbon atoms and which is characterized in that the content ratio by mass of component (A) : component (B) is 81:19 to 99.99:0.01.

Description

Wax composition for candle and candle

The present invention relates to a wax composition for candles, and a candle having the wax composition and a combustion wick.

The aroma candle is characterized by expressing an effect such as a relaxing effect by aroma while burning. Most waxes contain a fragrance so that the fragrance is diffused together with the wax during combustion (see Patent Documents 1 to 3).
Among the waxes used as the main component of wax, vegetable wax has the characteristics that it has less oil smoke compared to synthetic wax system, can diffuse the original fragrance sufficiently, and has less odor when extinguishing the flame. Recently, it has been favored and used.
Furthermore, the appearance has been improved by adding liquid oil at normal temperature to wax (see Patent Documents 4 to 6).

JP 7-48591 A Japanese Patent Laid-Open No. 9-188893 JP 2000-239694 A U.S. Pat. No. 4,224,204 US Pat. No. 6,776,808 US Patent Application Publication No. 2008/0092434

With conventional candles, the fragrance of the fragrance does not last long, and as soon as it is used (ignited), the fragrance fades away, making it impossible to increase the feeling of use, or the fragrance gradually fades during combustion due to the influence of additives. There was a problem to do. In addition, when vegetable wax is used, there is a problem that cracking is likely to occur and it is difficult to mold alone, and a method of improving by mixing with petroleum wax is known. There exists a problem that the said characteristic of itself reduces.
In addition, the method of improving the appearance by adding liquid oil at normal temperature to wax generates oil bleed, so that it is difficult to apply the method to pillar candles and the like. Although additives may be used to suppress oil bleed, the development of other methods that can achieve both improvement in appearance and suppression of oil bleed is also desired.
Accordingly, an object of the present invention is to provide a wax composition for candles which is less likely to crack even when any wax is used, has high moldability, and has excellent burning sustainability, fragrance diffusibility and surface glossiness, and the wax composition. An object of the present invention is to provide a candle having a good appearance and having a small number of oil bleed.

As a result of intensive studies on the above-mentioned problems, the present inventors have mixed wax with a specific higher α-olefin-based (co) polymer at a specific ratio, so that cracking hardly occurs and moldability is high. The present invention has been completed by finding that it has excellent burning sustainability, perfume diffusibility and surface glossiness, and that there is little oil bleed when it is made into a candle. Furthermore, by using a wax composition for candles in which a dye or pigment is added to a wax and a specific higher α-olefin-based (co) polymer, a stable pattern can be obtained even if the candle production conditions differ. The present inventors have found that the candle has a good appearance and completed the present invention.

That is, the present invention relates to the following [1] to [9].
[1] A candle wax composition containing a homopolymer or a copolymer obtained by using (A) a wax and (B) a higher α-olefin having a side chain crystallinity of 10 or more carbon atoms. The content ratio of the component (A) to the component (B) [component (A): component (B)] is 81:19 to 99.99: 0.01 by mass ratio. Wax composition for candles.
[2] The wax composition for candles according to the above [1], wherein the component (B) has the following characteristics (1) to (3).
(1) The viscosity at 100 ° C. by a B-type viscometer is 10 to 10,000 mPa · s.
(2) The melting point obtained by a differential scanning calorimeter (DSC) is one, the melting point is in the range of 20 to 100 ° C., and the half-value width of the endothermic peak obtained when measuring the melting point is 10 ° C. or less. .
(3) Stereoregularity index value M2 is 75 mol% or less.
[3] The wax composition for candles according to the above [1] or [2], further comprising (C) a fragrance.
[4] The candle wax composition according to any one of [1] to [3], further comprising (D) a dye or a pigment.
[5] The candle according to [4], wherein the content of the component (D) is 0.01 to 20 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B). Wax composition.
[6] The melting point (Tm−A) of the component (A) determined by the differential scanning calorimeter (DSC) and the melting point (Tm−B) of the component (B) determined by the differential scanning calorimeter (DSC). The wax composition for candles according to the above [4] or [5], which satisfies the relationship of the following formula (i).
(Tm−A) ≧ (Tm−B) +10 (i)
[7] The candle wax composition according to any one of [4] to [6], wherein the melting point is in the range of 20 to 55 ° C. in the characteristic (2).
[8] The wax composition for candles according to the above [1] to [7], wherein the component (A) is petroleum wax or vegetable wax.
[9] A candle having the wax composition according to any one of [1] to [8] and a combustion wick.

The wax composition for candles of the present invention is highly resistant to cracking and has high moldability. Moreover, since the wax composition for candles of the present invention is excellent in burning sustainability and perfume diffusibility, it is useful for aroma candles by containing perfume. In particular, when a vegetable wax is contained, the flammability is also excellent.
Furthermore, the candle using the wax composition for candles of the present invention is excellent in the gloss of the candle surface on the side where the flame is lit, and does not impair the mood created by the candle. In addition, since the candle is provided with a pattern such as a floral pattern, snowflakes, snowflakes, stars, etc., the appearance is good, and the effect is that the melting point of the component (B) is 10 ° C. or lower than the component (A). Sometimes even more pronounced. Moreover, since there is little oil bleeding and a fragrance | flavor does not leak out, a fragrance | flavor sustainability is high. And even if candle manufacturing conditions differ, it has the property to show a pattern stably.

It is a photograph which shows the magnitude | size of the flame in evaluation of the combustibility in an Example and a comparative example. It is a photograph which shows the time-dependent change of the flame in evaluation of the combustion sustainability in an Example and a comparative example. It is a photograph which shows the specific spread of the liquid level of the candle surface in evaluation of the fragrance | flavor diffusivity in an Example and a comparative example. It is a photograph which shows the state of the candle surface in evaluation of the surface glossiness in an Example and a comparative example. It is a photograph which shows the state (however, the state put into the 15 ml glass tube) of the candle obtained in Example 7. FIG. It is a photograph which shows the state (however, the state put into the 15 ml glass tube) of the candle obtained in Example 8. FIG. It is a photograph which shows the state of the candle obtained in Example 9. FIG. It is a photograph which shows the state of the candle obtained in Example 10. FIG. It is a photograph which shows the state (however, the state put into a 15 ml glass tube) of the candle obtained in Reference Example 1.

[Wax composition for candle]
The candle wax composition of the present invention comprises:
A wax composition for candles comprising (A) a wax and (B) a homopolymer or copolymer obtained using a higher α-olefin having 10 or more carbon atoms and having side chain crystallinity, A wax composition in which the content ratio of the component A) to the component (B) [component (A): component (B)] is 81:19 to 99.99: 0.01 by mass ratio.
[(A) Wax]
As the wax of the component (A), a known wax used for coating the burning core of the candle can be used, and a solid at 25 ° C. is practical. Examples of the wax include animal waxes, vegetable waxes, mineral waxes, petroleum waxes, and synthetic waxes.
Examples of animal waxes include beeswax, spermaceti, china wax (insect white wax), shellac wax, and lanolin (wool wax).
Examples of the vegetable wax include carnauba palm oil wax, cucumber palm oil wax, jojoba seed oil, candelilla wax, esparto wax, wood wax, soybean oil, white yam, jasmine plant oil, rice wax and rice bran oil.
Examples of the mineral wax include ozokerite, montan, and peat.
Examples of petroleum waxes include paraffin wax and microcrystalline wax.
Synthetic waxes include, for example, polyethylene wax, polypropylene wax, copolymer waxes such as ethylene / propylene / hexene / vinyl acetate, acrylic acid, hydrocarbon waxes such as Fischer-Tropsch wax and polymethylene wax, and synthetic amide waxes. Can be mentioned.
Among these, as the wax, vegetable wax is preferable from the viewpoints of less oily smoke, sufficient diffusion of the original fragrance, less odor when extinguishing the flame, and sustainability of combustion. From the viewpoint of excellent moldability and low cost, petroleum wax is preferable.

[(B) Homopolymer or copolymer obtained using a higher α-olefin having 10 or more carbon atoms and having side chain crystallinity]
The component (B) preferably has side chain crystallinity and the following characteristics (1) to (3).
(1) The viscosity at 100 ° C. by a B-type viscometer is 10 to 10,000 mPa · s.
(2) The melting point obtained by a differential scanning calorimeter (DSC) is one, the melting point is in the range of 20 to 100 ° C., and the half-value width of the endothermic peak obtained when measuring the melting point is 10 ° C. or less. .
(3) Stereoregularity index value M2 is 75 mol% or less.
In the present invention, “having crystallinity” means that a melting point as defined above is observed. The term “side chain crystallinity” means that the polymer has crystallinity at a site that becomes a side chain of a polymer other than a carbon-carbon double bond site that becomes a main chain. It has high crystallinity and is hard and has characteristics such as causing a solid-liquid phase change instantly and absorbing heat from the surroundings when it melts, and also has good thermal stability.

In the characteristic (1), the measurement method using a B-type viscometer is as follows.
Measuring instrument: Brookfield, LVDV-I (DV One Plus) for low viscosity Spindle: Dedicated spindle No. 18 (SC4-18)
Measuring method: Set the sample at a predetermined temperature, and after the temperature is stable (within ± 0.2 ° C.), heat for 10 minutes, immerse the spindle for 6 minutes, and measure the viscosity.
With respect to the characteristic (1), the viscosity at 100 ° C. measured by a B-type viscometer is preferably 10 to 1,000 mPa · s, more preferably 10 to 500 mPa · s, and more preferably, from the viewpoint of fluidity and thus moldability. Is 30 to 500 mPa · s, more preferably 30 to 500 mPa · s, still more preferably 30 to 270 mPa · s, and particularly preferably 30 to 230 mPa · s.

In the above characteristic (2), in the present invention, a differential scanning calorimeter (DSC) is used, and 10 mg of a sample is held at 190 ° C. for 5 minutes in a nitrogen atmosphere and then lowered to −10 ° C. at 5 ° C./min. The melting point (Tm-B) is defined as the peak top temperature of the melting endotherm curve obtained by maintaining the temperature at −10 ° C. for 5 minutes and then increasing the temperature to 190 ° C. at 10 ° C./min. The melting point (Tm-B) of the component (B) is preferably 20 to 80 ° C., more preferably 25 to 80 ° C., further preferably 30 to 80 ° C., and particularly preferably 30 to 65 ° C. In particular, when the wax composition for candles of the present invention contains (D) a dye or pigment described later, the melting point (Tm-B) of the component (B) is preferably 20 to 55 ° C. from the viewpoint of the appearance of the candle. More preferably, it is 20 to 50 ° C., more preferably 25 to 50 ° C., further preferably 25 to 45 ° C., and particularly preferably 25 to 40 ° C. Further, in this case, the melting point (Tm−A) obtained by the differential scanning calorimeter (DSC) of the component (A) and the differential scanning calorific value of the component (B) in the same manner as the melting point (Tm−B) described above. It is preferable that the melting point (Tm-B) determined by the total (DSC) satisfies the relationship of the following formula (i).
(Tm−A) ≧ (Tm−B) +10 (i)

In addition, the half-value width of the endothermic peak obtained upon measurement of the melting point of the component (B) is preferably 1 to 9 ° C., more preferably 1 to 7 ° C. from the viewpoint of crystal uniformity of the component (B). The temperature is preferably 2 to 7 ° C. A small half-value width indicates that the endothermic peak is sharp, that is, the melting behavior is rapid. In this case, problems such as storage stability and stickiness are suppressed by the low-temperature melting component. In particular, when the wax composition for candles of the present invention contains a dye or pigment (D) described later, the half width is preferably 10 ° C. or less from the viewpoint of the appearance of the candle. When producing candles by solidifying the wax composition for candles, the half-value width is 10 ° C. or less, so that the overlapping of the solidification temperatures of the component (A) and the component (B) is reduced, resulting in a uniform pattern. It is done.
Here, the full width at half maximum in this specification is an index representing the extent of the chevron shape of the endothermic peak obtained when measuring the melting point of the component (B), and the full width at half maximum (FWHM, Full Width at Half Maximum). ) Means.

(Measurement method of stereoregularity index value M2)
With respect to the characteristic (3), the stereoregularity index value M2 is a ¹³ C-NMR spectrum performed under the following apparatus and conditions, and is a methylene group (—CH ₂ — The stereoregularity index value M2 is obtained by utilizing the fact that the carbon in the structure is split and observed reflecting the difference in stereoregularity.
Apparatus: “EX-400” (manufactured by JEOL Ltd.)
Measurement temperature: 130 ° C
Pulse width: 45 °
Integration frequency: 1,000 times Solvent: Mixed solvent of 1,2,4-trichlorobenzene and heavy benzene [90:10 (volume ratio)] Six large absorption peaks based on the mixed solvent are observed at 127 to 135 ppm. Among these peaks, the fourth peak value from the low magnetic field side is set to 131.1 ppm, which is used as a reference for chemical shift. At this time, an absorption peak based on carbon in the side chain α-position methylene group (—CH ₂ —) is observed in the vicinity of 34 to 37 ppm. Therefore, the stereoregularity index value M2 (mol%) is obtained using the following equation.
M2 = [(integral intensity of 36.2 to 35.3 ppm) / (integral intensity of 36.2 to 34.5 ppm)] × 100
Here, the measurement of the ¹³ C nuclear magnetic resonance spectrum was performed with the following apparatus and conditions.
Apparatus: “JNM-EX400 type ¹³ C-NMR” (manufactured by JEOL Ltd.)
Method: Proton complete decoupling method Concentration: 220 mg / ml
Solvent: Mixed solvent of 1,2,4-trichlorobenzene and heavy benzene [90:10 (volume ratio)] Temperature: 130 ° C.
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times This stereoregularity index value M2 Asakura, M .; Demura, Y .; This is obtained in accordance with the method proposed in “Macromolecules, 24, 2334 (1991)” reported by Nishiyama.

With respect to the characteristic (3), the stereoregularity index value M2 is preferably 5 to 70 mol%, more preferably 10 to 70 mol%, more preferably 20 to 70 mol%, still more preferably 30 to 70 mol%, Particularly preferred is 40 to 70 mol%.

The component (B) preferably satisfies the following property (4) from the viewpoint of influence on combustibility (flame size).
(4) The acid value measured according to the total acid value measuring method described in JIS K2501 (1980) is 5 mgKOH / g or less.
The acid value is more preferably 3 mgKOH / g or less, further preferably 1 mgKOH / g or less, and particularly preferably substantially 0 mgKOH / g.

The “higher α-olefin having 10 or more carbon atoms” is preferably a higher α-olefin having 10 to 40 carbon atoms, more preferably a higher α-olefin having 10 to 30 carbon atoms, and a higher α-olefin having 15 to 30 carbon atoms. -More preferred are olefins, and higher α-olefins having 18 to 25 carbon atoms are particularly preferred. Examples of higher α-olefins having 10 or more carbon atoms include 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, Examples thereof include 1-nonadecene, 1-eicosene, 1-docosene, 1-tetracocene, hexacocene, octacocene and triacontene.
The component (B) used in the present invention is not particularly limited as long as it is obtained using such a higher α-olefin having 10 or more carbon atoms, and one or more higher α-olefins having 10 or more carbon atoms are used. May be obtained by polymerization or copolymerization, or may be obtained by copolymerization of one or more higher α-olefins having 10 or more carbon atoms and one or more other olefins. . The other olefin is, for example, ethylene or an α-olefin having less than 10 carbon atoms. The use ratio of the higher α-olefin having 10 or more carbon atoms and the other olefin is preferably such that the use amount of the higher α-olefin having 10 or more carbon atoms is 80 mol% or more with respect to the total amount thereof. More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more, It is especially preferable that it is substantially 100 mol%.

A homopolymer or copolymer obtained using a higher α-olefin having 10 or more carbon atoms and having side chain crystallinity [hereinafter sometimes referred to as a crystalline higher α-olefin (co) polymer. ] Can be produced using the metallocene catalyst shown below, and among them, it is particularly preferable to use a C ₂ symmetric and C ₁ symmetric transition metal compound capable of synthesizing an isotactic polymer.
That is, (a) a transition metal compound represented by the following general formula (I), and (b) a compound that can react with the transition metal compound of the component (a) or a derivative thereof to form an ionic complex [ (B-1)] and aluminoxane [(b-2)] are polymerized in the presence of a polymerization catalyst containing at least one component selected from one or more higher α-olefins having 10 or more carbon atoms. Alternatively, a copolymerization method, or a method of copolymerizing one or more higher α-olefins having 10 or more carbon atoms with one or more other olefins.

In the general formula (I), M represents a metal element of Groups 3 to 10 or a lanthanoid series of the periodic table. E ¹ and E ² respectively represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group (—N <), a phosphine group (— P <), hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) And a cross-linked structure is formed via A ¹ and A ² , and they may be the same as or different from each other. X represents a σ-bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y. The above “substitution” refers to, for example, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a silicon-containing group, or a heteroatom-containing group. It is substituted with a substituent such as
Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X. A ¹ and A ² are divalent bridging groups for linking two ligands, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, Germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —BR ¹ -or -AlR ¹ -is shown. R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other. q represents an integer of 1 to 5 and represents [(valence of M) −2], and r represents an integer of 0 to 3.

Examples of M include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid metals. Among these, from the viewpoint of polymerization activity and the like, a metal element belonging to Group 4 of the periodic table is preferable, and among these, titanium, zirconium, and hafnium are more preferable.
As the E ¹ and E ^2, substituted cyclopentadienyl group, indenyl group, substituted indenyl group.

Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, carbon Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. Among these, a halogen atom is preferable.
Specific examples of the Lewis base represented by Y include amines, ethers, phosphines, thioethers, and the like.

Next, A ¹ and A ² are divalent bridging groups that bind two ligands. Examples of such bridging groups include those represented by the general formula:

(D is carbon, silicon or tin, R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other, and are bonded to each other to form a ring structure. (E represents an integer of 1 to 4)
The thing represented by is mentioned. Specific examples of the bridging group include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ ═C =), dimethylsilylene. Group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisiylene group, diphenyldisiylene group, and the like. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

Among the transition metal compounds represented by the general formula (I), the general formula (II)

The transition metal compound which makes the ligand the double bridge type biscyclopentadienyl derivative represented by these is preferable.
In the general formula (II), M, A ¹ , A ² , q and r are the same as those in the general formula (I).
X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ include the same ones as exemplified in the description of X in the general formula (I), and preferred ones are also the same.
Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different, may be crosslinked with other Y ¹ or X ^1. Specific examples of Y ¹ are the same as those exemplified in the description of Y in general formula (I).
R ⁴ to R ⁹ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a heteroatom-containing group. , At least one of them must not be a hydrogen atom.
R ⁴ to R ⁹ may be the same or different from each other, and adjacent groups may be bonded to each other to form a ring.
Among these, it is preferable that R ⁶ and R ⁷ form a ring and R ⁸ and R ⁹ form a ring.
R ⁴ and R ⁵ are preferably a group containing a heteroatom such as oxygen, halogen or silicon from the viewpoint of increasing the polymerization activity.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably contains silicon in the bridging group between the ligands.
Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene). (2,1'-methylene) -bis (indenyl) zirconium dichloride, (1,2'-isopropylidene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene)- (5,6-dimethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1,2'-ethylene ) (2,1′-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) Zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) -Bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1'-ethylene) -bis (indenyl) zirconium dichloride, (1,2'-me Len) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-n-butylindenyl) ) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) ) Bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilyl) ) (2,1′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5-benzoindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) Bis (5,6-dimethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4,7-diisopropylindenyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-dimethylsilylene) bis (4-phenylindenyl) zirconium dichloride, ( , 2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride,

(1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-methyl Indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1 ' -Isopropylidene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, 1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethyl) Silylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-phenylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'- Methylene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2 , 1'-methylene) -bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride, ( 1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylme Luindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene ) -Bis (indenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2, 1'-methylene) -bis (3-isopropylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1 , 2'-Diphenylsilylene) (2,1'-methylene) -bis (3-trimethylsilylene) Rumethylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1 '-Dimethylsilylene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methylcyclo Pentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methylcyclopentadienyl) (3'-methylcyclopenta Dienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-methylene) (3- Chill cyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride,

(1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1′-diphenylsilylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1 , 1′-dimethylsilylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1′-diisopropylsilylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1 '-Dimethylsilylene) (2,2'-diisopropylsilylene) bisindenylzirconium dichloride, (1,1'-dimethylsilyleneindenyl) (2,2'-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, ( 1,1'-diphenylsilyleneinde Le) (2,2'-diphenylsilylene-3-trimethylsilyl-indenyl) zirconium dichloride, (1,1'-diphenylsilylene indenyl) (2,2'-dimethylsilylene-3-trimethylsilyl-indenyl) zirconium dichloride,

(1,1′-dimethylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilylene) (2,2′-diphenylsilylene) ( Indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethyl) Silylene) (2,2′-Diphenylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diisopropylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylindene Nyl) zirconium dichloride, (1, 1'-dimethylsilylene) (2,2'-diisopropylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1'-ethylene) (2,2'-tetramethyldisilylene) -bis ( Indenyl) zirconium dichloride, (1,1′-tetramethyldisiylene) (2,2′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-tetramethylethylene) (2,2′-tetramethyl) Disilylene) -bis (indenyl) zirconium dichloride, (1,1′-tetramethyldisylylene) (2,2′-tetramethylethylene) -bis (indenyl) zirconium dichloride, (1,1′-dimethylsilylylene methylene) ) (2,2′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1 Examples include 1'-ethylene) (2,2'-dimethylethylylenemethylene) -bis (3-methylindenyl) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium. It is not limited to these.
Moreover, the analogous compound of the metal element of another group or a lanthanoid series may be sufficient.
In the above compound, (1,1 '-) (2,2'-) may be (1,2'-) (2,1'-) or (1,2 '-) (2 , 1'-) may be (1, 1'-) (2, 2'-).

Next, as the component (b-1) in the component (b), any compound that can react with the transition metal compound of the component (a) to form an ionic complex can be used. Although it can be used, those represented by the following general formulas (III) and (IV) can be preferably used.
([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
(However, L ² is M ² , R ¹¹ R ¹² M ³ , R ¹³ ₃ C or R ¹⁴ M ^3. )
In the above general formulas (III) and (IV), L ¹ is a Lewis base, [Z] ⁻ is a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is a plurality of An anion in which a group is bonded to an element, that is, [M ¹ G ¹ G ² ... G ^f ] ⁻ (where M ¹ is an element of Group 5 to 15 of the periodic table, preferably 13 to 15 of the periodic table. G ¹ to G ^f each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms , An acyloxy group having 1 to 20 carbon atoms, an organic metalloid group, or a heteroatom having 2 to 20 carbon atoms Represents a hydrocarbon group, and two or more of G ¹ to G ^f may form a ring, and f represents an integer of ((valence of central metal M ¹ ) +1). . [Z ² ] ⁻ is a Bronsted acid alone or a conjugate base of a combination of Bronsted acid and Lewis acid having a logarithm (pKa) of the reciprocal of the acid dissociation constant of −10 or less, or an acid generally defined as a super strong acid The conjugate base of In addition, a Lewis base may be coordinated. R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹¹ and R ¹² are each independently a cyclopenta A dienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group; R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an integer of 1 to 3 in terms of ionic valences of [L ¹ -R ¹⁰ ] and [L ² ], a is an integer of 1 or more, and b is (k × a). M ² includes elements in groups 1 to 3, 11 to 13, and 17 of the periodic table, and M ³ represents elements in groups 7 to 12 of the periodic table.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, amines such as p-bromo-N, N-dimethylaniline and p-nitro-N, N-dimethylaniline; nitrogen-containing heterocyclic compounds such as pyridine; phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine; Examples include thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, trityl group and the like. Specific examples of R ¹¹ and R ¹² include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.
Specific examples of R ¹³ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹⁴ include tetraphenylporphyrin, phthalocyanine, allyl, methallyl and the like.
Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, I _{3 and the} like. Specific examples of M ³ include Mn, Fe, Co, Ni, Zn and the like.

In [Z ¹ ] ⁻ , that is, [M ¹ G ¹ G ² ... G ^f ], specific examples of M ¹ include B, Al, Si, P, As, Sb, etc. B and Al.
Specific examples of G ¹ and G ² to G ^f include a dialkylamino group substituted with an alkyl group having 1 to 5 carbon atoms such as a dimethylamino group and a diethylamino group; a methoxy group, an ethoxy group, an n-butoxy group, An alkoxy group having 1 to 6 carbon atoms such as a phenoxy group or an aryloxy group having 6 to 10 carbon atoms; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group, an alkyl group having 1 to 20 carbon atoms such as n-eicosyl group; an aryl group having 6 to 20 carbon atoms such as phenyl group, p-tolyl group, 4-t-butylphenyl group and 3,5-dimethylphenyl group; benzyl Group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, , 4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, hetero atom-containing hydrocarbon group such as bis (trimethylsilyl) methyl group; pentamethylantimony group, trimethylsilyl group And organic metalloid groups such as trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, and diphenylboron.

Specific examples of non-coordinating anions, that is, Bronsted acids having a pKa of −10 or less or a conjugate base [Z ² ] ⁻ of a combination of Bronsted acids and Lewis acids include trifluoromethanesulfonic acid anions (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ⁻ , trifluoroacetate anion (CF ₃ CO ₂ ) ⁻ , hexafluoroantimony anion (SbF ₆ ) ⁻ , fluorosulfonate anion (FSO ₃ ) ⁻ , chlorosulfonate anion (ClSO ₃ ) ⁻ , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅₎ ) ^-, fluorosulfonic acid anion / 5 Fluoride arsenic ^{_{(FSO 3 / AsF 5) -}} , trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - , and the like.

Specific examples of the ionic compound that reacts with the transition metal compound of the component (a) to form an ionic complex, ie, the component compound (b-1) include triethylammonium tetraphenylborate, tetraphenylboric acid. Tri-n-butylammonium, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenyl tetraphenylborate Ammonium, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylboron Methyl (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) boric acid Tetra-n-butylammonium, tetrakis (pentafluorophenyl) tetraethylammonium borate, tetrakis (pentafluorophenyl) benzyl benzyl (tri-n-butyl) borate, tetrakis (pentafluorophenyl) methyldiphenylammonium borate, tetrakis (pentafluorophenyl) ) Triphenyl (methyl) ammonium borate, methylanilinium tetrakis (pentafluorophenyl) borate, Tet Dimethylanilinium kiss (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [ Bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, tetraphenylboron Acid silver, triphenyl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) Decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid Tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, triflu Examples include silver olomethanesulfonate.
(B-1) may be used alone or in combination of two or more.

On the other hand, as the aluminoxane of the component (b-2), the following general formula (V)

(Wherein R ¹⁵ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization. Usually, it is an integer of 2 to 50, preferably 2 to 40. Note that each R ¹⁵ may be the same or different.
A chain aluminoxane represented by the following general formula (VI)

(In the formula, R ¹⁵ and w are the same as those in the general formula (V).)
The cyclic aluminoxane shown by these is mentioned.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method.
For example, (i) a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, (ii) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (iii) a metal There is a method of reacting water adsorbed on salt or the like with water adsorbed on inorganic or organic materials with an organoaluminum compound, and (iv) a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and further reacting with water. .
The aluminoxane may be insoluble in toluene.
These aluminoxanes may be used alone or in combination of two or more.

The use ratio of the component (a) to the component (b) is preferably 10: 1 to 1: 100, more preferably 2 when the compound (b-1) is used as the component (b). The range of: 1 to 1:10 is desirable, and if it is within the above range, the catalyst cost per unit mass polymer does not become so high and is practical.
When the compound (b-2) is used, the molar ratio is preferably in the range of 1: 1 to 1: 1,000,000, more preferably 1:10 to 1: 10,000.
If it exists in this range, the catalyst cost per unit mass polymer will not become so high, and it is practical.
In addition, as the component (b), one type of compound (b-1) and compound (b-2) may be used alone, or two or more types may be used in combination.

In addition to the above components (a) and (b), the polymerization catalyst for producing the crystalline higher α-olefin (co) polymer can use an organoaluminum compound as the component (c). .
Here, as the organoaluminum compound of component (c), the general formula (VII)
R ¹⁶ _v AlJ _3-v (VII)
(Wherein R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, and J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom. v is an integer of 1 to 3.)
The compound shown by these is used.
Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹⁶ include those having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. An alkyl group is preferred. Examples of the alkoxy group having 1 to 20 carbon atoms represented by J include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group, and an alkoxy group having 1 to 10 carbon atoms is preferable. An alkoxy group of 1 to 5 is more preferable. Examples of the aryl group having 6 to 20 carbon atoms represented by J include a phenyl group, a naphthyl group, and an anthryl group, and an aryl group having 6 to 10 carbon atoms is preferable. Examples of the halogen atom represented by J include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. v is preferably 3.
Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like. Among these, triisobutylaluminum is preferable.
These organoaluminum compounds may be used individually by 1 type, and may use 2 or more types together.

The use ratio of the component (a) to the component (c) is preferably 1: 1 to 1: 10,000, more preferably 1: 5 to 1: 2,000, and still more preferably 1:10 in molar ratio. A range of ˜1: 1,000 is desirable.
By using the component (c), the polymerization activity per transition metal can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.
In the production of the crystalline higher α-olefin (co) polymer, at least one catalyst component can be supported on a suitable carrier and used.
The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferable.

In the crystalline higher α-olefin (co) polymer, the polymerization method is not particularly limited, and any of slurry polymerization method, gas phase polymerization method, bulk polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, etc. Although a method may be used, a solution polymerization method and a bulk polymerization method are particularly preferable.
Regarding the polymerization conditions, the polymerization temperature is usually −100 to 250 ° C., preferably −50 to 200 ° C., more preferably 0 to 150 ° C.
The polymerization time is usually preferably 5 minutes to 10 hours, and the reaction pressure is usually preferably normal pressure to 20 MPa (gauge), more preferably normal pressure to 10 MPa (gauge).

In the method for producing a crystalline higher α-olefin (co) polymer, it is preferable to add hydrogen because polymerization activity is improved. When hydrogen is used, the pressure is usually from normal pressure to 5 MPa (gauge), preferably from normal pressure to 3 MPa (gauge), more preferably from normal pressure to 2 MPa (gauge).
When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. A monomer such as α-olefin may be used as a solvent. Depending on the polymerization method, it can be carried out without solvent.

In the polymerization, prepolymerization can be performed using the polymerization catalyst. The prepolymerization can be performed, for example, by bringing a small amount of α-olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used.
The α-olefin used in the prepolymerization is not particularly limited, and examples thereof include those similar to those exemplified above, for example, ethylene, α-olefin having 3 to 20 carbon atoms, or a mixture thereof. It is advantageous to use the same α-olefin as the higher α-olefin or other α-olefin used in the reaction.

The prepolymerization temperature is usually −20 to 200 ° C., preferably −10 to 130 ° C., more preferably 0 to 80 ° C.
In the prepolymerization, an aliphatic hydrocarbon, aromatic hydrocarbon, monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferred.
Moreover, you may perform prepolymerization without a solvent.
In the prepolymerization, the intrinsic viscosity [η] (measured in 135 ° C. decalin) of the prepolymerized product is 0.1 deciliter / g or more, and the amount of the prepolymerized product per 1 mmol of the transition metal component in the catalyst is 1 It is desirable to adjust the conditions so that it becomes ˜10,000 g, particularly 10 to 1,000 g.
In addition, the method for adjusting the molecular weight of the polymer includes selection of the type of each catalyst component, the amount used, the polymerization temperature, and polymerization in the presence of hydrogen. An inert gas such as nitrogen may be present.
The homopolymer or copolymer thus obtained has a comb structure rather than a hyperbranch structure, and therefore has side chain crystallinity.

The content ratio of the component (A) and the component (B) in the candle wax composition of the present invention is from 81:19 to 99.99: 0.01 in terms of mass ratio from the viewpoint of combustion sustainability and moldability. There must be. From this viewpoint, the content ratio of the component (A) and the component (B) in the candle wax composition of the present invention is preferably a mass ratio of 85:15 to 99.9: 0.1, more preferably 87: 13-99.9: 0.1. From the viewpoint of combustibility, it is particularly preferably 90:10 to 99.9: 0.1, and most preferably 95: 5 to 99.9: 0.1.

[(C) Fragrance]
In addition to the component (A) and the component (B), the candle composition for candles of the present invention may further contain a fragrance as the component (C), whereby a wax composition useful as an aroma candle can be obtained. .
Citrus, green, fruity, floral, musky, spicy, woody, sweet, and other fragrances of fragrances, and citrus green, green herbal, and green It can also be floral.
The perfume ingredient is not particularly limited, but for example, limonene, lemon oil, orange oil, bitter orange oil, sweet orange oil, grapefruit oil, bergamot oil, mandarin oil, lime oil, citral, n-octanal (Aldehyde C-8), n-nonenal (aldehyde C-9), decanal (aldehyde C-10), undecanal (aldehyde C-11), α-damascon, β-damascon, γ-damascon, δ-damascon, Citrus flavors such as α-terpineol; cis-3-hexenol, galvanum oil, star anise oil, sage oil, violet leaf oil, rosemary oil, basil oil, lavandin oil, lavender oil, laurel oil, cassis base 345, Styraryl acetate, cis-3-hexenyl acetate, sali Green perfumes such as cis-3-hexenyl thiolate, 5-methyl-3-heptanone oxime, rose oxide, etc .; γ-undecalactone, α-damascon, β-damascon, γ-damascon, δ-damascon, γ- Fruity perfumes such as decalactone, γ-dodecalactone, raspberry ketone; rose oil, jasmine absolute, linalool, ethyl linalool, geranyl acetate, benzyl acetate, cyclamenaldehyde, ylang ylang oil, chamomile oil, geranium oil, tageto oil, neroli oil, Benzyl acetate, Isoesuper, Coumarin, Heliotropin, Oris oil, Patchouli oil, α-amylcinnamic aldehyde, Citronellol, Geraniol, Methyl dihydrojasmonate (= Hedione), Hydroxycitronellal, 4 (3)-(4 -Hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde (= Lilal), β-phenylethyl alcohol, p-tert-butyl-α-methylhydrocinnamic aldehyde (= Lilial), α-hexylcin Examples thereof include floral fragrances such as namic aldehyde, methyl isoeugenol, methyl ionone, α-ionone and β-ionone. These may be used individually by 1 type and may use 2 or more types together.
When the component (C) is contained in the candle wax composition, the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). The amount is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and particularly preferably 3 to 10 parts by mass.

[(D) Dye or Pigment]
In addition to the component (A) and the component (B), the wax composition for candles of the present invention further contains a dye or pigment as the component (D). can do.
A dye or pigment can be used to color the candle, and examples of the dye include oil-based dyes, aqueous dyes, and oil dyes. The pigment may be an inorganic pigment or an organic pigment, and crayon is preferably used. When the wax composition for candles contains a dye or pigment, the content thereof is preferably 0.01 to 20 parts by mass, more preferably 100 parts by mass of the total amount of component (A) and component (B). Is 0.05 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 10 parts by mass.
As described above, in the case where the candle wax composition of the present invention contains a dye or pigment, in the characteristic (2), the melting point (Tm-B) of the component (B) is 20 to 55 ° C. (more preferably 20 to 50 ° C., more preferably 25 to 50 ° C., further preferably 25 to 45 ° C., particularly preferably 25 to 40 ° C.), the candle has a pattern of flowers, snowflakes, snowflakes, stars, etc. Since it is imparted, the appearance is further improved. The effect becomes more prominent when the melting point of the component (B) is 10 ° C. or higher (preferably 13 ° C. or higher, more preferably 15 ° C. or higher, more preferably 20 ° C. or higher) lower than the component (A). The reason is presumed as follows. The melting point (Tm-B) of the component (B) is significantly lower than the melting point of the component (A), so that when the candle is produced, the component (A) is solidified and the component (B) is in a liquid state Via. Since the component (B) condenses when solidified, a void is formed between the component (A) and the component (B), and the void looks like the pattern, so that the appearance is improved.
In general, oil is added to the composition for the purpose of improving the appearance, but in this case, an oil bleeding problem may occur. However, according to the present invention, the addition of the oil is not denied, but the appearance can be improved without adding the oil, so that the problem of oil bleeding can be avoided. In addition, oil is a liquid at normal temperature, and there is no restriction | limiting in particular as oil used for the wax composition for candles, For example, the oil-based component etc. which are mentioned later are mentioned.

[Other ingredients]
The wax composition for candles of the present invention comprises, in addition to the above-mentioned components (A) and (B), furthermore, in addition to the components (C) and (D), known components used for constituting candle wax. You may contain. Examples of such components include surfactants, oily components, powders, antioxidants, cosmetic components, preservatives, water-soluble polymers, ultraviolet absorbers, aqueous components, gelling agents, oil-soluble resins, chelating agents, Examples include medicinal ingredients, but are not limited thereto. By adding such components, it can be expected that effects such as an improvement in appearance (hue, pattern, shape), a relaxation effect, environmental compatibility, and the like are exhibited.
~ Surfactant ~
Examples of the surfactant include nonionic surfactants, anionic surfactants, and amphoteric surfactants.
Nonionic surfactants include, for example, glycerin fatty acid esters and alkylene glycol adducts thereof, polyglycerin fatty acid ester alkylene glycol adducts, propylene glycol fatty acid esters and alkylene glycol adducts, sorbitan fatty acid esters and alkylene glycol adducts thereof. , Fatty acid ester of sorbitol and its alkylene glycol adduct, polyalkylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyalkylene alkyl ether, glycerin alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene hydrogenated castor oil, alkylene glycol of lanolin Adduct, polyoxyalkylene-modified silicone, polyoxyalkylene alkyl co-modified silico Emissions, and the like.
Examples of the anionic surfactant include fatty acids such as stearic acid and lauric acid and their inorganic and organic salts, alkylbenzene sulfates, alkyl sulfonates, α-olefin sulfonates, dialkyl sulfosuccinates, α- Sulfonated fatty acid salt, acylmethyl taurate, N-methyl-N-alkyl taurate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, poly Examples thereof include oxyethylene alkylphenyl ether phosphates, N-acyl amino acid salts, N-acyl-N-alkyl amino acid salts, o-alkyl substituted malates, and alkyl sulfosuccinates.
Examples of amphoteric surfactants include amino acid type and betaine type carboxylic acid types, sulfate ester types, sulfonic acid types, and phosphate ester types, and those that are safe for the human body can be used. For example, soybean phospholipid, N, N-dimethyl-N-alkyl-N-carboxylmethyl ammonium betaine, N, N-dialkylaminoalkylene carboxylic acid, N, N, N-trialkyl-N-sulfoalkylene ammonium betaine, N, N-dialkyl-N, N-bis (polyoxyethylene sulfate) ammonium betaine, 2-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine and the like can be mentioned.

~ Oil component ~
Examples of the oil component include liquid saturated hydrocarbons such as liquid paraffin, fats and oils such as owl, olive oil, castor oil, mink oil and macadamian nut oil, waxes such as beeswax, carnauba wax, candelilla and gay wax, stearic acid , Fatty acids such as lauric acid, myristic acid, behenic acid, isostearic acid, oleic acid, higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol, dimethylpolysiloxane, methylphenylpoly Siloxane, Decamethylcyclopentasiloxane, Octamethylcyclotetrasiloxane, Polyether-modified Organopolysiloxane, Polyoxyalkylene, Alkylmethyl Polysiloxane, Methyl Polysiro Sun copolymers, silicones such as alkoxy-modified polysiloxanes and fluorine-modified organopolysiloxanes, fluorine-based oils such as perfluorodecane, perfluorooctane and perfluoropolyether, lanolin derivatives such as lanolin fatty acid isopropyl and lanolin alcohol Etc.

~ Powder ~
The powder is not particularly limited by a spherical shape, a plate shape, a needle-like shape, a foggy shape, a fine particle, a particle size such as a pigment grade, a particle structure such as a porous or non-porous material, and the like. Examples include glitter powders, organic powders, pigment powders, metal powders, and composite powders.
Specifically, white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide and barium sulfate, colored inorganic pigments such as iron oxide, carbon black, chromium oxide, chromium hydroxide, bitumen and ultramarine, talc, muscovite, gold Mica, red mica, biotite, synthetic mica, sericite (sericite), synthetic sericite, kaolin, silicon carbide, bentonite, smectite, aluminum oxide, magnesium oxide, zirconium oxide, antimony oxide, diatomaceous earth, aluminum silicate , Magnesium Metasilicate, Calcium Silicate, Barium Silicate, Magnesium Silicate, Calcium Carbonate, Magnesium Carbonate, Hydroxyapatite, Boron Nitride Powder, Titanium Dioxide Coated Mica, Titanium Dioxide Coated Bismuth Oxychloride, Iron Oxide Mica titanium, bitumen treated mica titanium, mosquito Bright powder such as min-treated mica titanium, bismuth oxychloride, fish scale foil, polyamide resin, polyethylene resin, polyacrylic resin, polyester resin, fluorine resin, cellulose resin, polystyrene resin, styrene-acrylic Copolymers such as copolymers, organic polymer resin powders such as polypropylene resins, silicone resins and urethane resins, organic low molecular weight powders such as zinc stearate and N-acyl lysine, starch, silk powder, cellulose powder, etc. Natural organic powder, red 201, red 202, red 205, red 226, red 228, orange 203, orange 204, blue 404, yellow 401, etc., organic pigment powder, red 3 , Red 104, red 106, orange 205, yellow 4, yellow 5, green 3, blue 1, etc. , Organic pigment powder such as barium or aluminum lake or metal powder such as aluminum powder, gold powder, silver powder, fine titanium oxide coated mica titanium, fine zinc oxide coated mica titanium, barium sulfate coated mica titanium, titanium dioxide containing silicon dioxide And composite powders such as zinc oxide-containing silicon dioxide, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polyolefin laminated film powder, and lamellar agent of polyethylene terephthalate / polymethyl methacrylate laminated film powder.

-Antioxidant-
Examples of the antioxidant include α-tocopherol and ascorbic acid.
~ Beauty ingredients ~
Examples of the beauty component include vitamins, amino acids, anti-inflammatory agents and the like.
~ Preservative ~
Examples of the preservative include p-oxybenzoic acid ester and phenoxyethanol.
-Water-soluble polymer-
Examples of water-soluble polymers include natural products such as guar gum, sodium chondroitin sulfate, hyaluronic acid, gum arabic, and carrageenan, semi-synthetic products such as methylcellulose, hydroxyethylcellulose, and carboxymethylcellulose, and synthetic systems such as carboxyvinyl polymer. Can be mentioned.

(Candles manufacturing method)
There is no restriction | limiting in particular in the manufacturing method of the candle using the wax composition for candles of this invention, The manufacturing method of a well-known candle can be utilized. For example, the wax composition for candles of the present invention is melted at 50 to 100 ° C. and stirred and mixed, and then by a molding method, dipping method, rolling method, pressing method, etc., preferably at 40 ° C. or less, using a combustion core. More preferably, the candle can be produced by cooling to 0 to 40 ° C., more preferably 10 to 40 ° C. The present invention also provides a candle having the candle wax composition thus obtained and a combustion wick.
The candle of the present invention preferably has a penetration (unit: 10 ⁻¹ mm) of 1 to 9 measured according to the following method from the viewpoint of suppressing cracking and increasing moldability, and preferably 1 to 4. More preferably, it is more preferably 1 to 3, more preferably 1 to 2.5, and particularly preferably 1.5 to 2.5.
(Measurement method of penetration)
In accordance with JIS K2235, the length (mm) that the needle has entered when the needle is inserted for 5 seconds at a load of 100 g at 25 ° C. is measured, and the value 10 times that value is defined as the “needle penetration”.

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

Synthesis Example 1 Synthesis of 2-chlorodimethylsilylindene Under a nitrogen stream, 50 ml of THF (tetrahydrofuran) and 2.5 g (41 mmol) of magnesium were added to a 1 L three-necked flask. 1 ml was added and stirred for 30 minutes to activate the magnesium.
After stirring, the solvent was extracted and 50 ml of THF was newly added.
A solution of 5.0 g (25.6 mmol) of 2-bromoindene in THF (200 ml) was added dropwise thereto over 2 hours.
After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, cooled to −78 ° C., a solution of 3.1 ml (25.6 mmol) of dichlorodimethylsilane in THF (100 ml) was added dropwise over 1 hour, and the mixture was stirred for 15 hours. The solvent was distilled off.
The residue was extracted with 200 ml of hexane, and then the solvent was distilled off to obtain 6.6 g (24.2 mmol, 94% yield) of 2-chlorodimethylsilylindene.

<Synthesis Example 2> Synthesis of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indene) 400 ml of THF obtained in Synthesis Example 1 in a 1 L three-necked flask under nitrogen flow -8 g of chlorodimethylsilylindene was added and cooled to -78 ° C. To this solution, 38.5 ml (38.5 mmol) of a THF solution (1.0 mol / L) of LiN (SiMe ₃ ) ₂ was added dropwise.
After stirring at room temperature for 15 hours, the solvent was distilled off and extracted with 300 ml of hexane. The solvent was distilled off to obtain 2.0 g (6.4 mmol, yield 33.4%) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene).

<Synthesis Example 3> Synthesis of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride In Synthesis Example 2, in a 200 ml Schlenk bottle under a nitrogen stream 2.5 g (7.2 mmol) of the obtained (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) and 100 ml of ether were added.
After cooling to −78 ° C. and adding 9.0 ml (14.8 mmol) of a hexane solution (1.6M) of n-butyllithium (n-BuLi), the mixture was stirred at room temperature for 12 hours.
The solvent was distilled off, and the resulting solid was washed with 20 ml of hexane and dried under reduced pressure to quantitatively obtain a lithium salt as a white solid.
In a Schlenk bottle, lithium salt (6.97 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) was dissolved in 50 ml of THF, and 2.1 ml of iodomethyltrimethylsilane at room temperature ( 14.2 mmol) was slowly added dropwise and stirred for 12 hours.
The solvent was distilled off, and 50 ml of ether was added, followed by washing with a saturated ammonium chloride solution.
After liquid separation, the organic phase was dried and the solvent was removed to remove 3.04 g (5.9 mmol, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) Yield 84%) was obtained.
Next, in a Schlenk bottle under a nitrogen stream, 3.04 g (5.9 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) obtained above was obtained. And 50 ml of ether were added.
After cooling to −78 ° C., 7.4 ml (11.8 mmol) of a hexane solution (1.6M) of n-butyllithium (n-BuLi) was added, and the mixture was stirred at room temperature for 12 hours.
The solvent was distilled off, and the resulting solid was washed with 40 ml of hexane to obtain 3.06 g of the lithium salt as an ether adduct.
Under a nitrogen stream, 3.06 g of the lithium salt obtained above was suspended in 50 ml of toluene. The mixture was cooled to −78 ° C., and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride previously cooled to −78 ° C. in toluene (20 ml) was added dropwise. After dropping, the mixture was stirred at room temperature for 6 hours.
After distilling off the solvent of the reaction solution, the obtained residue was recrystallized from dichloromethane to obtain (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilyl) having the following structure. 0.9 g (1.33 mmol, yield 26%) of yellow crystallites of methylindenyl) zirconium dichloride was obtained.

(In the formula, TMS represents a trimethylsilyl group.)

Synthesis Example 4 Synthesis of (1,1′-SiMe ₂ SiMe ₂ ) (2,2′-SiMe ₂ ) bis (indenyl) zirconium dichloride 2.5 g of magnesium and tetrahydrofuran in a 300 ml three-necked flask under a nitrogen stream 100 ml of (THF) was added, and a piece of iodine (about 5 mg) was added. To this, 5.0 g (25.6 mmol) of 2-bromoindene dissolved in 40 ml of THF was dropped from a dropping funnel. After completion of dropping, the mixture was further stirred at room temperature for 2 hours, and then 1.5 ml (12.4 mmol) of dichlorodimethylsilane was dropped. After completion of the dropwise addition, the mixture was stirred overnight at room temperature, then THF was distilled off, and the residue was extracted with 50 ml of hexane to obtain 2.68 g (yield 73%) of bis (indenyl) dimethylsilane as a pale yellow oil.
This was dissolved in 30 ml of ether, and 12.2 ml of an n-hexane solution (1.52 mol / L) of n-butyllithium (n-BuLi) was added at −78 ° C. After stirring at room temperature overnight, the supernatant was filtered off, and the resulting white solid was washed with hexane and then dried under reduced pressure to obtain a dilithium salt. This salt was dissolved in 30 ml of THF, and 1.1 ml of 1,2-dichlorotetramethyldisilane was added dropwise. After stirring at room temperature for 3 hours, the solvent was removed and the residue was extracted with 30 ml of hexane. After filtration, the solvent was distilled off to obtain 2.42 g of (1,1′-SiMe ₂ SiMe ₂ ) (2,2′-SiMe ₂ ) bis (indene).
This was dissolved in 30 ml of ether, and 7.9 ml of n-BuLi in n-hexane (1.52 mol / L) was added dropwise at −78 ° C. After stirring at room temperature overnight, the supernatant was filtered off and the resulting white precipitate was dried under reduced pressure to obtain 2.01 g of a dilithium salt. This salt was suspended in 10 ml of toluene, and 0.96 g (4.1 mmol) of zirconium tetrachloride suspended in 10 ml of toluene at −78 ° C. was added.
After stirring overnight at room temperature, the supernatant is filtered off, concentrated to 1/3, cooled to −20 ° C., and stored (1,1′-SiMe ₂ SiMe ₂ ) (2 , 2′-SiMe ₂ ) bis (indene) yellow powder was precipitated (23% yield).

<Production Example 1> Production of higher α-olefin homopolymer 1 having side chain crystallinity 1 ml of 1-octadecene (C ₁₈ ), 1 mmol of triisobutylaluminum [component (c)], synthesized in 1 L autoclave heated and dried (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride [component (a)] obtained in Example 3 1 μmol, dimethylanilinium tetrakispentafluorophenylborate [Component (b-1)] 4 μmol was added, 0.1 MPa of hydrogen was further introduced, and polymerization was carried out at a polymerization temperature of 112 ° C. for 60 minutes.
After completion of the polymerization reaction, the mixture is heated and dried under reduced pressure to give a higher α-olefin homopolymer having side chain crystallinity [hereinafter referred to as crystalline higher α-olefin homopolymer 1]. 221g was obtained.

<Production Example 2> Production of higher α-olefin copolymer 2 having side chain crystallinity An α-olefin mixture having a carbon number of 20, 22, and 24 [42:37:21 (molar ratio) was added to a heat-dried 1 L autoclave. ] 400 ml, triisobutylaluminum [component (c)] 1 mmol, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride obtained in Synthesis Example 3 [Component (a)] 1 μmol and dimethylanilinium tetrakispentafluorophenylborate [component (b-1)] 4 μmol were added, and 0.1 MPa of hydrogen was further introduced, followed by polymerization at a polymerization temperature of 100 ° C. for 60 minutes.
After completion of the polymerization reaction, the mixture is heated and dried under reduced pressure, whereby a higher α-olefin copolymer having side chain crystallinity [hereinafter referred to as crystalline higher α-olefin copolymer 2]. ] 205g was obtained.

<Production Example 3> Production of higher α-olefin copolymer 3 having side chain crystallinity In a 1 L autoclave that has been dried by heating, 280 ml of 1-hexadecene (C16), 120 ml of 1-octadecene (C18), triisobutylaluminum [( c) component] 1 mmol, 1 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride [component (a)] obtained in Synthesis Example 3; 4 μmol of dimethylanilinium tetrakispentafluorophenylborate [component (b-1)] was added, 0.1 MPa of hydrogen was further introduced, and polymerization was carried out at a polymerization temperature of 105 ° C. for 60 minutes.
After completion of the polymerization reaction, the mixture is heated and dried under reduced pressure to give a higher α-olefin copolymer having side chain crystallinity (hereinafter referred to as crystalline higher α-olefin copolymer 3). 196 g was obtained.

<Production Example 4> Production of higher α-olefin homopolymer 4 having side chain crystallinity In a heat-dried 1 L autoclave, 1-octadecene (C18) 400 ml, triisobutylaluminum [component (c)] 1 mmol, synthesis example (1,1′-SiMe ₂ SiMe ₂ ) (2,2′-SiMe ₂ ) bis (indenyl) zirconium dichloride 1 μmol obtained in 4 and dimethylanilinium tetrakispentafluorophenylborate [component (b-1)] 4 μmol In addition, 0.05 MPa of hydrogen was further introduced, and polymerization was performed at a polymerization temperature of 90 ° C. for 60 minutes.
After completion of the polymerization reaction, the mixture is heated and dried under reduced pressure to give a higher α-olefin homopolymer having side chain crystallinity (hereinafter referred to as crystalline higher α-olefin homopolymer 4). ] Was obtained 212g.

Crystalline higher α-olefin homopolymer 1, crystalline higher α-olefin copolymer 2, crystalline higher α-olefin copolymer 3 and crystalline higher α-olefin homopolymer 4 used in the examples, and comparison Table 1 below summarizes the characteristics of “Viver 103” (manufactured by Baker Petrolite), “Viber 260” (manufactured by Baker Petrolite) and “Viver 343” (manufactured by Baker Petrolite) used in the examples.
The viver 103, the viver 260, and the viver 343 all have a hyper-branch structure.

<Examples 1 to 10, Comparative Examples 1 to 17, Reference Example 1>
In the mixing ratios shown in Tables 2 to 4 (unit: parts by mass), the components other than the pigment were melted at 85 ° C. and mixed with stirring. Mixed. The mixture thus obtained was poured into a 20 ml glass cup in which a combustion core was previously placed, and then solidified at room temperature (20 ° C.) to produce a candle.
According to the following method, each candle was evaluated for moldability, combustibility (flame size), combustion sustainability, perfume diffusibility, surface glossiness and appearance. The results are shown in Tables 2-4.
1 to 4 show photographs showing the state of combustion in the evaluation of combustibility, combustion sustainability, perfume diffusibility, and surface gloss. In addition, when evaluating the appearance, photographs showing the state of the candle obtained in each example are shown in FIGS.

(Formability evaluation method)
Based on JIS K2235, the length (mm) that the needle entered when the needle was inserted for 5 seconds at a load of 100 g at 25 ° C. was measured, and a value 10 times that was obtained as “needle penetration”. The moldability was evaluated according to the following evaluation criteria based on the penetration.
○: The penetration is 9 or less, and it is hard and difficult to crack.
(Triangle | delta): The penetration degree exceeds 9 and is 15 or less, and when it touches with a hand, it will feel a little brittle.
X: The penetration is over 15 and is brittle.
(Flammability evaluation method)
The combustibility was evaluated according to the following evaluation criteria using the size of the flame produced by the candle produced in Comparative Example 11 as a reference. Moreover, the magnitude | size of the flame in each evaluation is shown in FIG.
○: A large flame similar to that in Comparative Example 11.
Δ: A flame slightly smaller than that of Comparative Example 11 (70 to 50%).
X: The flame is significantly smaller than that in Comparative Example 11.
(Combustion sustainability evaluation method)
The change over time of the flame after igniting the candle was investigated, and the combustion sustainability was evaluated according to the following evaluation criteria. Moreover, the time-dependent change of the flame in each evaluation is shown in FIG.
○: After 10 minutes, the size of the flame is almost the same as the initial level of ignition, and even after 30 minutes, it is not likely to disappear at all.
Δ: After 10 minutes, the size of the flame is similar to that at the beginning of ignition, and after 30 minutes, the flame is small, but the state of the flame is stable.
X: The flame has already become small after 15 minutes, and it is in a state where it is likely to disappear.

(Perfume diffusivity evaluation method)
The spread of the liquid level on the candle surface (on the flame side, the upper surface) 20 minutes after ignition was investigated and used as an indicator of fragrance diffusibility. The perfume diffusivity was performed according to the following evaluation criteria. In addition, if the spread of a liquid level (melting site | part) is favorable, it means that the diffusibility of a fragrance | flavor is also favorable. Moreover, the extent of the liquid level spread on the candle surface in each evaluation is shown in FIG.
○: The liquid level spreads over the entire surface.
(Triangle | delta): Although the liquid level does not spread sideways, melting has progressed downward.
X: The liquid level does not spread much.
(Surface gloss evaluation method 1)
The state of the candle surface after molding to immediately after ignition (the side where the combustion core is visible and the upper surface) was investigated and used as an index of surface gloss. The surface gloss was evaluated according to the following evaluation criteria. Moreover, the state of the candle surface in each evaluation is shown in FIG. 4 (photograph of the candle immediately after ignition).
○: The candle surface is smooth.
X: The candle surface has irregularities.
(Surface gloss evaluation method 2; Ra, Rz)
The surface roughness of the candle after molding [Rait Arithmetic Mean Deviation of the Profile (Rz) and Maximum Height of the Profile (Rz)] (unit: μm) is measured with the laser scanning microscope “ It measured with the scanning confocal microscope H1200 "(made by Lasertec Corporation). The smaller the value, the smaller the roughness and the surface gloss.
(Appearance evaluation method)
The candle was visually observed and evaluated according to the following evaluation criteria. The state of the candle obtained in each example is shown in FIGS.
○: The candle has a pattern (mottled pattern).
X: The candle has no pattern.

Explanation of notes in Tables 2-4.
* 1: Crystalline higher α-olefin homopolymer 1 obtained in Production Example 1
* 2: Crystalline higher α-olefin copolymer 2 obtained in Production Example 2
* 3: Crystalline higher α-olefin copolymer 3 obtained in Production Example 3
* 4: Crystalline higher α-olefin homopolymer 4 obtained in Production Example 4
* 5: Baker Petrolite * 6: “Paraffin 155”, paraffin wax, Nippon Seiwa Co., Ltd., melting point 68 ° C.
* 7: "Soy wax", melting point 55 ° C
* 8: Measurement was impossible because the candle was broken.
* 9: “Paraffin 145”, paraffin wax, manufactured by Nippon Seiwa Co., Ltd., melting point 62 ° C.
* 10: Crayon * 11: Liquid paraffin (special grade), manufactured by Junsei Chemical Co., Ltd.

From Tables 2 to 4, it can be seen that the candles obtained by the present invention are less prone to cracking, have high moldability, are excellent in burning sustainability and perfume diffusibility, and are excellent in surface gloss. In addition, when vegetable wax was utilized as (A) component, it was excellent also in combustibility. Furthermore, the candles obtained in Examples 7 to 10 to which a pigment has been added have an excellent appearance. Moreover, it turns out that the external appearance of a candle can be made favorable, without adding liquid oil at normal temperature.
On the other hand, none of the comparative examples satisfies all of moldability, burning sustainability, perfume diffusivity, surface glossiness and appearance, and there remains a problem in using as a candle. In particular, Comparative Examples 7 and 8 have a high penetration, because (1) the viver 103 and the viver 206 also contain low molecular weight components because of the wide molecular weight distribution, and ( 2) Since the viver 103 and the viver 206 have a hyperbranch structure and a high acid value, it is considered that the compatibility with the paraffin wax is insufficient, and thus there is a poor dispersion and a soft part exists. I guess that.

<Examples 11 to 14 and Comparative Examples 18 to 20> Candles containing fragrances At a blending ratio (unit: parts by mass) described in Table 5, the mixture was melted at 85 ° C. with stirring and mixed, and a combustion core was arranged in advance. After pouring into a 60 ml glass cup, the candle containing a fragrance | flavor was manufactured by making it solidify at room temperature (20 degreeC).
According to the following method, the fragrance diffusibility, oil bleed amount, appearance and pattern stability of each candle were evaluated. The results are shown in Table 5.

(Fragrance diffusibility)
The candle was placed in a 500 ml collection bottle and held for 1 minute. Thereafter, the lid was opened, and the odor intensity was evaluated according to the following evaluation criteria.
Based on a 3% fragrance product, the evaluation was made as strong “5”, slightly strong “4”, equivalent strength “3”, slightly weak “2”, and weak “1”. It shows that a fragrance | flavor diffusibility is so large that an evaluation value is large.
In addition, evaluation was implemented by 10 persons of 5 men and women who were evaluated for soundness, and the average value was shown.
(Oil bleed amount, surface appearance after standing at 35 ° C)
A cylindrical molded article having a diameter of 2.5 cm and a height of 1 cm was produced from the candle. A degreased paper was laid on an aluminum pan (aluminum frying pan), and a cylindrical molded product was placed thereon and kept at 35 ° C. for 24 hours. The oil bleed amount (unit: g) was measured by subtracting the weight of the cylindrical molded product before heating from the weight of the subsequent degreased paper. The smaller the value, the less oil bleed, that is, the better the property of keeping the fragrance inside the candle.
Furthermore, the state of the surface of the candle left at 35 ° C. for 2 days was visually observed and evaluated according to the following evaluation criteria.
○: No change on the surface.
X: Oil droplets are observed on the surface.
(appearance)
The candle was visually observed and evaluated according to the following evaluation criteria. The state of the candle obtained in each example is shown in FIGS.
○: The candle has a pattern (mottled pattern).
X: The candle has no pattern.
(Pattern stability)
When the temperature for solidification is changed to 35 ° C. and a candle is produced, “○” is used when a pattern is formed in the same manner as when it is cooled to 20 ° C. and solidified, and “X” is displayed when no pattern is formed. " When it is ○, the pattern expression does not depend on the production conditions, and it can be said that the pattern expression is highly stable.

Explanation of annotations in Table 5.
* 1: Crystalline higher α-olefin homopolymer 1 obtained in Production Example 1
* 4: Crystalline higher α-olefin homopolymer 4 obtained in Production Example 4
* 5: Baker Petrolite * 12: "HP310", paraffin wax, Exxon Mobil, melting point 52 ° C
* 13: Paraffin wax 135, Nippon Seiwa Co., Ltd., melting point 57 ° C
* 14: “Fruity blend N90048”, manufactured by Airabella * 15: Oil-based dye

From Table 5, it can be said that the candle obtained by the present invention is excellent in fragrance diffusibility, has a small amount of oil bleed, has a high fragrance sustainability, and does not impair the appearance, and further exhibits a pattern, particularly manufactured. It can be seen that the pattern can be presented stably without depending on the conditions.
Comparing Example 11 with Comparative Example 18 and Example 12 with Comparative Example 19, it can be seen that Comparative Examples 18 and 19 are inferior in fragrance diffusibility and at the same time have a large amount of oil bleed. Further, when Example 13 and Comparative Example 20 are compared, the amount of oil bleed in Comparative Example 20 is slightly inferior, but oil droplets are observed on the surface of the candle left at 35 ° C. for 2 days. It turns out that the appearance of is damaged.

The wax composition of the present invention is highly resistant to cracking and has high moldability. Furthermore, since it is excellent in burning sustainability, perfume diffusibility, and surface glossiness, has an excellent appearance when made into a candle, and has a small amount of oil bleed, it is useful for candles. Furthermore, the wax composition of the present invention is useful for an aroma candle by containing a fragrance, and further a dye or a pigment.

Claims (9)

1. A wax composition for candles comprising (A) a wax and (B) a homopolymer or copolymer obtained using a higher α-olefin having 10 or more carbon atoms and having side chain crystallinity, A wax for candles, wherein the content ratio of the component A) to the component (B) [component (A): component (B)] is from 81:19 to 99.99: 0.01 by mass ratio. Composition.
2. The candle wax composition according to claim 1, wherein the component (B) has the following characteristics (1) to (3).
   (1) The viscosity at 100 ° C. by a B-type viscometer is 10 to 10,000 mPa · s.
   (2) The melting point obtained by a differential scanning calorimeter (DSC) is one, the melting point is in the range of 20 to 100 ° C., and the half-value width of the endothermic peak obtained when measuring the melting point is 10 ° C. or less. .
   (3) Stereoregularity index value M2 is 75 mol% or less.
3. Furthermore, the wax composition for candles according to claim 1 or 2, further comprising (C) a fragrance.
4. The wax composition for candles according to any one of claims 1 to 3, further comprising (D) a dye or a pigment.
5. The wax composition for candles according to claim 4, wherein the content of the component (D) is 0.01 to 20 parts by mass with respect to 100 parts by mass in total of the components (A) and (B).
6. The melting point (Tm-A) determined by the differential scanning calorimeter (DSC) of the component (A) and the melting point (Tm-B) determined by the differential scanning calorimeter (DSC) of the component (B) The wax composition for candles according to claim 4 or 5, which satisfies the relationship i).
   (Tm−A) ≧ (Tm−B) +10 (i)
7. The wax composition for candles according to any one of claims 4 to 6, wherein in the characteristic (2), the melting point is in the range of 20 to 55 ° C.
8. The wax composition for candles according to any one of claims 1 to 7, wherein the component (A) is petroleum wax or vegetable wax.
9. A candle comprising the wax composition according to any one of claims 1 to 8 and a combustion wick.

Images