JPS63186753A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having excellent heat resistance and moldability and good impact resistance and weathering resistance, by mixing a thermoplastic resin obtained by polymerizing a specified monomer mixture in the presence of a specified graft polymer rubber with a specified carbonate resin. CONSTITUTION:A thermoplastic resin composition comprising 5-95pts.wt. thermoplastic resin (I) obtained by polymerizing 95-50pts.wt. monomer mixture (B) comprising 0-100wt.% aromatic vinyl compound, 0-100wt.% methacrylate and 0-40wt.% vinyl cyanide compound (the sum being 100wt.%) in the presence of 5-50pts.wt. graft polymer rubber (A) obtained by emulsion-polymerizing 95-60pts.wt. polymerizable monomer mixture (a) comprising 0.1-20wt.% polyfunctional monomer, 50-99.9wt.% 1-13 C alkyl acrylate and 0-30wt.% other polymerizable vinyl compounds in the presence of 5-40pts.wt. diene polymer (b) to a conversion of 50-93% and stopping the polymerization and 95-5pts.wt. 4,4'-dihydroxydiarylalkane polycarbonate (II).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a weather-resistant and impact-resistant thermoplastic resin composition with excellent heat resistance and moldability.

(Prior Art) Acrylonitrile-polybutadiene rubber-styrene terpolymer compositions (ABS resins) have been generally known as thermoplastic resins with excellent impact resistance. However, since ABS resin contains many chemically unstable double bonds in its main chain, it is known that it is easily degraded by ultraviolet rays and has poor weather resistance.

In order to improve the weather resistance, which is a drawback of ABS resin, a rubber-like elastic material 9 containing almost no double bonds in the main chain is known, and a typical example is one using acrylic rubber. Many proposals have been made regarding rubber graft copolymers using .

On the other hand, polycarbonate is known as a resin with excellent impact resistance and heat resistance.

(Problems to be solved by the invention) However, from a practical standpoint, rubber graft copolymers (thermoplastic resins) using acrylic rubber have several problems, and there remains room for various improvements. has been done. One of them is heat resistance.

At relatively high temperatures, dimensional stability is significantly impaired due to thermal deformation.

Various attempts have been made to improve this heat resistance. For example, a method involves introducing α-methylstyrene as a constituent component of the resin to improve heat resistance.

However, although the resin produced by this method has improved heat resistance, it has the drawback of significantly poor moldability, and it cannot be said to be a practically effective method. That is.

In injection molding, even if the molding temperature and molding pressure are high, the flow of resin is low, making it difficult to fill the mold.Furthermore, if exposed to extremely high temperatures, thermal decomposition and thermal deterioration will occur, making it difficult to realize the practical molding temperature. There are restrictions. On the other hand, in order to improve the poor moldability of this resin, using a large amount of chain transfer agent to lower the molecular weight, or using a method of polymerization in which the amount of emulsifier used in emulsion polymerization is reduced, satisfactory results were not obtained. cannot be obtained. In other words, the flowability of the resin improves, but
This is because the heat resistance of lii fat itself decreases accordingly. Further, as a method of improving flowability without lowering the molecular weight of the resin, there is a method of adding a lubricant, but in this case as well, a decrease in heat resistance is unavoidable.

Also, when α-methyl-styrene is introduced, the impact strength decreases. In order to improve this decreased impact strength, it is possible to increase the content of the rubber component, but in this case, although the impact strength improves, flowability tends to decrease and heat resistance also tends to decrease. show.

On the other hand, polycarbonate has excellent impact resistance and heat resistance, but has low fluidity and has problems in moldability. In order to improve this shortcoming, conventional methods.

It is known to mix styrene-acrylonitrile copolymer, ABS resin, etc. these are.

It tends to be mixed uniformly with polycarbonate, and has the disadvantage of either improving moldability or reducing heat resistance and impact resistance. In particular, there is a drawback that the molding temperature dependence is large, and the impact strength is significantly reduced when the molding temperature is increased.

The present inventors focused on these points and conducted intensive research on a method of imparting high heat resistance using a rubber graft copolymer and polycarbonate resin, and further improving moldability and impact resistance9. We have arrived at the present invention. In other words, the present invention is as follows.

It has high heat resistance that could not be obtained with conventional technology, has excellent moldability, has excellent impact resistance, and
The present invention provides a thermoplastic resin composition with good weather resistance.

(Means and effects for solving the problems) The present invention has the following features:
Polyfunctional monomer (I) 0.1 to 20% by weight, carbon number 1 to
Acrylic acid ester (II) having 13 alkyl groups
50 to 99.9% by weight and 0 to 30% by weight of another vinyl compound (III) copolymerizable with (II) to a total of 10% by weight.
Polymerizable monomer obtained by using it so that it becomes 0% by weight (
a) 95 to 60 parts by weight of diene polymer (b) 5 to 40 parts by weight
Graft polymer rubber [A] obtained by emulsion polymerization to a polymerization rate of 50 to 93 Ti in the presence of 5 to 93 Ti in the presence of 1 part of 5 to 50 Ti, aromatic monomer CB] I vinyl compound (IV) O-100 heavy!忤、
Methacrylic acid ester (V) 0 to 100% by weight and vinyl cyanide compound (■) 0 to 40% by weight in a total of 1
5 to 95 parts by weight of thermoplastic resin (α) and 95 to 5 parts by weight of 4,4'-dioxydiarylalkane polycarbonate (β) obtained by polymerizing 95 to 50 parts by weight at a ratio of 0,000% by weight. The present invention relates to a thermoplastic resin composition containing the following.

9 Important points in the present invention are that the graft polymer rubber [
A] is obtained by graft polymerizing a diene polymer (Ill) as a core and blending an acrylic acid ester and a polyfunctional monomer as essential components as a nine-polymerizable monomer (a), and this graft In the synthesis of polymer rubber, graft polymerization is not completed to a polymerization rate of 100%, but polymerization is stopped at a polymerization rate of 50 to 93 cm.

That is, in an impact-resistant graft resin obtained by graft polymerizing styrene, acrylonitrile, etc. to a crosslinked acrylic rubber obtained by copolymerizing an acrylic acid ester with a polyfunctional monomer, when the degree of crosslinking of the acrylic rubber is increased, Although the appearance of the molded product improves, the impact resistance decreases, and conversely, when the degree of crosslinking is lowered, dichroism in the weld part of the molded product becomes noticeable. The first point of the present invention is to balance these two contradictory factors by using a diene copolymer rubber latex with excellent rubber properties as a core, adding an acrylic ester and a polyfunctional resin as a crosslinking agent to this core. The purpose of this method is to use a graft polymer rubber obtained by emulsion graft polymerization of a polypropylene monomer, thereby making it possible to significantly improve the appearance of the molded product. However, this alone is insufficient to obtain a product with sufficiently high impact resistance, and in order to improve the impact resistance, the graft polymer rubber [A] must be obtained by completing the polymerization to a polymerization rate of 100%. It is necessary that the polymerization is obtained by stopping the polymerization at a polymerization rate of 50 to 93 degrees. It is necessary to use a graft polymer rubber obtained by stopping such polymerization midway.

This further eliminates the dependence of impact strength on molding temperature.
Molding width can be expanded.

Furthermore, since the weight average molecular weight (Mw) of the acetone-soluble portion of the thermoplastic resin (α) is 200,000 to 500,000, the above characteristics are remarkable.

In addition, 1 weight average molecular weight here is thermoplastic resin (α)
After stirring in a large excess of acetone at 25°C for 12 hours, the acetone-insoluble matter was separated.

The acetone soluble content was analyzed by gel permeation chromatography and measured using a standard polystyrene calibration curve. For example, 3 g of the former and 2009 g of the latter are used for the thermoplastic resin (α) and acetone.

When obtaining the graft polymer rubber [A] of the present invention.

As the diene polymer (b), polybutadiene, butadiene-styrene copolymer, etc. can be used, and monopolymerizable monomer (
a) includes the polyfunctional monomer (1), an acrylic ester having an alkyl group having 1 to 13 carbon atoms (I[), and if necessary, another vinyl compound copolymerizable with (II) (Iff ) can be used. As the polyfunctional monomer (I), ethylene glycol dimethacrylate and diethylene glycol dimethacrylate are used.

Polyvalent vinyl compounds such as ethylene glycol diacrylate, divinylbenzene, diallyl phthalate, dicyclopentadiene acrylate, dicyclopentadiene methacrylate, polyvalent allyl compounds such as triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, etc. Among these, triallyl isocyanurate, triallyl cyanurate, dicyclopentadiene acrylate, and dicyclopentadiene methacrylate are particularly preferred. As the polyfunctional monomer to be copolymerized, in the polymerizable monomer (a), 0.1 to 20% by weight, preferably 1
It is used within the range of 0.5 to 10% by weight. 0.
If it is less than 1% by weight, the degree of crosslinking will be insufficient, resulting in poor impact resistance and poor appearance of the molded product, and if it exceeds 20% by weight, the degree of crosslinking will be excessive, resulting in a decrease in impact resistance. Examples of the acrylic ester (I) having an alkyl group having 1 to 13 carbon atoms include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and among these, butyl acrylate is particularly preferred. This acrylic ester fn) is present in the monomer (a) in an amount of 50 to 99.9% by weight, preferably 6% by weight.
5-99.5% by weight is used. If the weight range is less than 50%, the properties of the acrylic rubber deteriorate. Acrylic acid ester (n
) Other vinyl compounds (III) that can be copolymerized with the polymerizable monomer (III) include acrylonitrile, styrene, etc.
a) Medium, O~3013 quantity section.

It is preferably used within the range of 0 to 25% by weight.

If it exceeds 30% by weight, sufficient properties as an acrylic rubber cannot be obtained when the polymerizable monomer (a'j) is polymerized.

The polymerizable monomer (a) and the diene polymer (b) have a weight ratio of (b)/(a) of 5/95 to 40/60.
used at a rate of If it exceeds 5/95, impact resistance,
The effect of improving the appearance of the molded product is insufficient.

If it is less than 40/60, the weather resistance will be poor, which is not preferable.

Further, it is preferable to use the diene polymer (b) in the form of a latex which has been previously dispersed in an aqueous medium in order to facilitate dispersion during emulsion polymerization.

The emulsion polymerization for obtaining the above-mentioned graft polymer rubber [A] can be carried out by a method generally known to those skilled in the art. In this emulsion polymerization, the polymerization rate is 50 to 93%, without performing the polymerization until the polymerization rate reaches 100%.

Preferably, stopping at 60 to 90% is a high durability (i'
This is an essential condition for obtaining i-attack resistance. When the polymerization rate is less than 50%, the proportion of copolymerization with monomer CBI during polymerization of monomer [B] increases, and the heat distortion temperature decreases. If the polymerization rate exceeds 93, the impact resistance cannot be sufficiently improved.

A small amount of sodium oleate is used as an emulsifier during emulsion polymerization to obtain graft polymerization/coalescing rubber.

Anionic emulsifiers such as potassium oleate, sodium lauryl sulfate, and sodium dodecylbenzenesulfonate, and nonionic emulsifiers such as polyoxyethylene cetyl ether may also be used.

As the polymerization initiator, for example, a redox type initiator which is used in ordinary emulsion polymerization and is composed of persulfate or cumene hydroperoxide-sodium formaldehyde sulfoxylate is used.

Next, in the presence of the graft polymer rubber [A].

Aromatic vinyl compound (IV) 0-1 as monomer [B]
00 weight range, methacrylic acid ester (V) 0-100
The vinyl cyanide compound (■) is used in a weight range of 0 to 40% by weight so that the total amount is 100% by weight for polymerization. If the amount of the vinyl cyanide compound (■) as the monomer [B] is too large, the moldability will decrease, so 40
Must be used within a range not exceeding % by weight. Furthermore, when 30% by weight or more of the aromatic vinyl compound (IV) is used, the moldability of the resin finally obtained in the present invention is good, and when 10% by weight or more of the vinyl cyanide compound is used, the resin is resistant to chemicals. Sexuality, etc. improves. Therefore, monomer [B]
As for C■) above, 30-1000-100 weight 0-
90 weight width), fv) from 0 to 70 weight width (especially from 0 to 40
(wt%) and (Vl) from 0 to 30 wt%, especially from 10 to
30% by weight).

Examples of the aromatic vinyl compound (Pi') include α-substituted styrenes such as α-methylstyrene and α-ethylstyrene, chlorostyrene, vinyltoluene, nuclear-substituted styrenes such as t-butylsmethine, styrene, and vinyl cyanide compounds. As (V), acrylonitrile, methacrylonitrile, etc. can be used, and as the methacrylic acid ester, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. can be used.

In the present invention, the above-mentioned graft polymer rubber [A] and the above-mentioned monomer [B] are [based on 35 to 50 parts by weight of A].

(B) It is preferable to use 95 to 50 parts by weight.

(A]/CB''] 2>At content ratio of less than 5/95, the impact resistance of the final resin will decrease, and 50150
If it exceeds this value, mechanical strength and heat deformation resistance will decrease.

In order to polymerize the monomer CB) in the presence of the grafted rubber [A], an emulsion polymerization method is used.

Polymerization methods such as suspension polymerization and solution polymerization can be employed.

During polymerization, an emulsifier, a polymerization initiator, a chain transfer agent, and the like are added as appropriate. As the polymerization initiator, a redox initiator such as persulfate or cumene hydroperoxide-sodium formaldehyde sulfoxylate is used in an amount of about 0.1 to 2 by weight based on the monomer [B]. As the chain transfer agent, tert-dodecyl mercaptan or the like is used in an amount of about 1 weight percent or less based on the monomer (B). What is the polymerization temperature?

The temperature is preferably 20 to 100°C, particularly 50 to 90°C. Note that similar conditions may be employed when producing the graft polymer rubber.

The monomers to be polymerized in the presence of the graft polymer rubber [A) can be polymerized in one go, divided into several times, or polymerized while dropping all the monomers. After polymerizing using either polymerization method, the second
It is preferable that the remaining amount of monomer [B] is added and polymerized in the step. By employing such a two-step polymerization method, it is possible to obtain a resin that has high fluidity, high heat distortion temperature, and high impact resistance, and is therefore a desirable method. The first polymer to be polymerized is 5 to 3 of monomer CB]
0 weight range is preferable, and if it is less than 5% by weight, the total amount is 1
There is no difference from polymerization in stages.

If the amount exceeds 30% by weight, the effect of improving impact resistance and heat generated by adding monosulfur [B] in portions and polymerizing tends to decrease.

Even when the monomer [B] is divided and used in this way, the total amount is blended so that the proportions for potatoes shown above are (IV), (V) and (Vl). .

Monomers used separately in the first and second stages [
”B] respectively.

Aromatic vinyl compound C■) O~100fr amount Thimethacrylic acid ester (V) 0~100ilii'fi and cyanide vinyl compound (■) O~40 weight range, and proportion such that the whole becomes 100 weight range Preferably used in In the first stage and the second stage, the above-mentioned blending ratios may be the same or different.

The thermoplastic resin (α) obtained by polymerizing the monomer CB in the presence of the graft polymer rubber [A') is obtained by heating the latex after the polymerization with potassium alum when the polymerization is emulsion polymerization. It is coagulated and separated using a method such as salting out by mixing with water, dehydrated and dried, and then, if necessary, pelletized using an extruder or the like for use.

The 4,4'-dioxydiarylalkane polycarbonate (β) is 2,2'-(4,4'-dihydroxy-diphenyl)-furopane carbonate, etc., and the manufacturing method thereof is 4,4'-dihydroxydiaryl. The phosgene method is produced by blowing phosgene into the presence of an aqueous caustic alkali solution and a solvent using an alkane, and the transesterification method is produced by transesterifying 4,4'-dihydroxydiarylalkane and carbonic acid diester in the presence of a catalyst. be.

In the present invention, thermoplastic resin (α) and 4,4′-
The dioxyarylalkane polycarbonate (β) is used in an amount of 5 to 95 parts by weight and 95 to 5 parts by weight. Here, if the thermoplastic resin (α) is too small, the impact strength will decrease.

If it is too large, heat resistance will decrease. Polycarbonate (β)
If it is too small, the impact strength and thermal properties will be reduced, and if it is too large, the flowability will be reduced.

The thermoplastic resin composition according to the present invention includes:

? lJ, tba, styrene-acrylonitrile copolymer.

Styrene/-α-methylstyrene-acrylonitrile copolymer, styrene-acrylonitrile-methyl methacrylate copolymer, etc. may be mixed and used as appropriate. These can be summarized into those manufactured in the following 9-order manner. Namely.

Acrylonitrile 5-30 weight range.

Aromatic vinyl compounds such as styrene and α-methyl-styrene 95-50% by weight and methacrylic esters such as methyl methacrylate 0-4
This is a copolymer obtained by polymerizing 5% by weight. Here, the polymerization is
It can be carried out in the same manner as the polymerization method of monomer [B) described above. These copolymers are used in an amount of 0 to 60% based on the total amount of these and the above-mentioned thermoplastic resin (α) and polycarbonate (β) to adjust flowability, impact strength, etc. be able to. If the amount of these copolymers is too large, impact strength tends to decrease. The above monomer combination is thermoplastic resin (α) and polycarbonate (β)
preferred from the viewpoint of compatibility with

The thermoplastic resin composition according to the present invention further includes:

If necessary, other known polymers, lubricants, various stabilizers, pigments, various organic or inorganic fibers, etc. may be included.

The thermoplastic resin composition according to the present invention can be appropriately kneaded using an extruder or the like, and can be made into pellets before use.

In the present invention, the ratio is determined from the sampled polymerization reaction solution (latex in the case of emulsion polymerization), which is completely dried using an infrared moisture meter, and then the weight of non-volatile components is measured, and from this value and the charging ratio. be done.

The unit of polymerization rate is tsu, which means parts by weight.

(Examples) Next, nine examples of the present invention will be shown. "Part" and "Chi" below
indicates "parts by weight" and "% by weight".

Production Example 1 1-1 Production of graft polymer rubber latex [Blend composition] Component I Polybutadiene latex 300 parts (solid content) Ingredients ■ Butyl acrylate 700 parts and triallylisocyanurate 14 parts Ingredients ■ Potassium persulfate 0. 4 parts sodium sulfite 0.04 parts fatty acid soap) and 1420 parts deionized water [Polymerization operation] Charge the ingredients and the uniformly dissolved component (■) into a reaction vessel, mix and stir, then add the uniformly dissolved component (■) death,
After purging with nitrogen, the temperature was raised and polymerization was carried out at 60 to 65° C. for about 4 hours, and then cooled to stop the polymerization. The polymerization rate at this time was 67.

1-2 Emulsion polymerization in the presence of graft polymer rubber latex [Blend composition] Ingredients ■ Deionized water 1425 parts and Rongalit 28 parts Ingredients ■ Styrene 432 parts Acrylonitrile 168 parts Cumene hydroperoxide 21 parts Side (CHP) and [Polymerization procedure ] Charge the uniformly dissolved components (1) and (V) into a reaction vessel, stir and mix uniformly, and then add 400 parts of the graft polymer rubber latex obtained in 1-1 above [solid content, graft polymer rubber (including unreacted monomers)] ).

40% of the total amount of styrene and acrylonitrile was added, and the mixture was further stirred and mixed for 30 minutes while purging with nitrogen. Thereafter, polymerization was carried out at 65°C for about 6 hours.

After confirming that the polymerization rate was 90°, polymerization was further carried out at 90° C. for 2 hours to obtain a resin latex. This resin latex was salted out in hot water in which potassium alum was dissolved, and then dehydrated and dried to obtain a resin powder.

Production Examples 2 to 5 In Production Example 1, the graft polymer rubber latex was polymerized at a yield of 55% (Production Example 2).

Resin powder was obtained according to Production Example 1, except that it was stopped at 60 inches (Production Example 3), 83 inches (Production Example 4), and 90 inches (Production Example 5).

Production Examples 6 to 7 In Production Example 1, the polymerization rate of 9 was stopped at 45% (Production Example 6) and 95% (Production Example 7) during the polymerization of the graft copolymer rubber latex, and during emulsion polymerization,
A resin powder was obtained according to Production Example 1 except that 3.5 parts of TDM was used.

Production Example 8 In Production Example 1, the polymerization rate of 9 was increased to 90 during polymerization of the graft copolymer rubber latex.

At this point, the temperature was raised to 90°C and the polymerization was further carried out for 2 hours to reach a polymerization rate of 98cm.
A resin powder was obtained in the same manner as in Production Example 1, except that 3.5 parts of .

Production Example 9 Production method of acrylonitrile-styrene copolymer Ingredients ■ Styrene 760 parts Acconitrile 240 parts Lauroyl peroxide 5 parts Bis-t-butylperoxycyclo 0.55N hexane tertiary dodecyl mercaptan 3.2 parts Dodecylbe/zensulfone Acid 0.000072m Sodium Tricalcium Phosphate 24 parts [Polymerization procedure] The uniformly dissolved and mixed component (1) was charged into a reaction vessel, stirred and mixed uniformly, and then suspended polymerized at 65°C for about 12 hours and at 105°C for 2 hours. The mixture was dehydrated and dried to obtain an acrylonitrile-styrene copolymer.

A thermoplastic resin composition was obtained by pelletizing with a machine. This was used as a sample for physical property evaluation and tested. The results are shown in Table 2.

Table 1 below shows the termination polymerization rate during the production of graft copolymer latex in Production Examples 1 to 8 and the weight average molecular weight (Mw) of the acetone soluble portion of the resin powder obtained in each Production Example. .

The polycarbonate in Table 1 is Panrai) L-1250.
Z (trade name of Ondai Kasei) was used.

Further, the liquid gel permeation chromatography conditions for measuring the acetone-soluble W of the resin powder were as follows.

Column: 1 bottle of Gelco GL-AI 00M' (Hitachi Chemical ■Product name) LFI liquid: Tetrahydrofuran Temperature: 25℃ Pressure Crab 20 kg/cm' Flow rate: 1ml! /min Injection volume: 0.5 ml Sample concentration = 0.2% Apparatus: Hitachi 635A (manufactured by Hitachi, Ltd.) fi2,
Heat i-type temperature 1iHJIS K 7207 (1/2:18
, 6 kg/cm (without annealing), melt flow index 1 dJIs K 6758 and Izot impact strength were tested according to JIS K 6871 (23°C, notched).

The impact strength test piece was tested at cylinder temperature, 240°250°.
．． The moldings injection molded at 260°C and 270°C were measured, respectively, and the dependence of impact strength on molding temperature was investigated.

From now on, '1 (Effect of the invention) The thermoplastic resin composition according to the present invention has heat resistance.

Excellent moldability (flowability) and impact strength.

Claims (1)

[Scope of Claims] 1. 0.1 to 20% by weight of polyfunctional monomer (I), acrylic ester having an alkyl group having 1 to 13 carbon atoms (
II) 50 to 99.9% by weight and 0 to 30% by weight of another vinyl compound (III) copolymerizable with (II) to a total of 10% by weight.
Polymerizable monomer obtained by using it so that it becomes 0% by weight (
a) 95 to 60 parts by weight of diene polymer (b) 5 to 40 parts by weight
In the presence of 5 to 50 parts by weight of graft polymer rubber [A] obtained by emulsion polymerization to a polymerization rate of 50 to 93% in the presence of 50 to 93% by weight and then stopping the polymerization, as monomer [B] Aromatic vinyl compound (IV) 0 to 100% by weight, methacrylic acid ester (V) 0 to 100% by weight, and vinyl cyanide compound (IV) 0 to 40% by weight, totaling 100% by weight.
5 to 95 parts by weight of thermoplastic resin (α) obtained by polymerizing 95 to 50 parts by weight and 4.4'
-Dioxy-diarylalkane polycarbonate (
β) 95 to 5 parts by weight of a thermoplastic resin composition. 2. The thermoplastic resin composition according to claim 1, wherein the weight average molecular weight (@M@w) of the acetone-soluble portion of the thermoplastic resin (α) is from 200,000 to 500,000. 3. Thermoplastic resin (α) is graft polymer rubber [A]
When polymerizing monomer [B] in the presence of monomer [
5 to 30% by weight of monomer [B] is polymerized until the polymerization rate reaches 50% by weight or more, and then the remainder of monomer [B] is added and polymerized, and the separated monomer [B] Each one. Aromatic vinyl compound (IV) 0 to 100% by weight methacrylic acid ester (V) 0 to 100% by weight and vinyl cyanide compound (VI) 0 to 40% by weight in a total of 1%
5. The thermoplastic resin composition according to claim 1, 2, 3, or 4, which is obtained by blending the components in an amount of 0.00% by weight.