WO2019150875A1

WO2019150875A1 - Filler dispersant

Info

Publication number: WO2019150875A1
Application number: PCT/JP2018/048274
Authority: WO
Inventors: 千穂浅井; 将虎城籔; 拓郎木村
Original assignee: 第一工業製薬株式会社
Priority date: 2018-01-31
Filing date: 2018-12-27
Publication date: 2019-08-08
Also published as: TW201938638A; JP2019131690A; JP7013264B2

Abstract

Provided is a filler dispersant which has excellent filler dispersibility, and which can reduce the viscosity of a filler dispersion.　The filler dispersant contains a fatty acid ester (A) of a polyoxyalkylene glycerol ether, wherein the carbon number of the fatty acid constituting the fatty acid ester (A) is 8 to 30. The fatty acid constituting the fatty acid ester (A) can contain an unsaturated fatty acid.

Description

Dispersant for filler

The present invention relates to a dispersant for filler. More specifically, the present invention relates to a dispersant that is useful when a filler is dispersed in a resin.

Various fillers are used for the purpose of improving the physical properties (for example, hardness, impact strength, tensile strength, wear resistance, heat resistance, etc.) of the resin. In order to fully exhibit the performance of the filler, it is necessary to uniformly disperse the filler in the resin. However, for example, a highly hydrophilic filler is easy to aggregate and difficult to disperse uniformly. Even if it can be dispersed, the viscosity tends to increase, and workability improvement is required.

Therefore, a dispersant for uniformly dispersing the filler has been studied. For example, Patent Document 1 discloses a method using a surfactant.

Japanese Patent Publication No. 8-13938

However, it has been found that when the surfactant described in Patent Document 1 is used, the viscosity of the resin increases and the effect of improving physical properties such as impact resistance is small.

An object of the embodiment of the present invention is to provide a filler dispersant which is excellent in filler dispersibility and can lower the viscosity of the filler dispersion.

The filler dispersant according to the embodiment of the present invention is a filler dispersant containing a fatty acid ester (A) of polyoxyalkylene glyceryl ether, and the fatty acid constituting the fatty acid ester (A) has 8 carbon atoms. ~ 30.

The dispersant according to the present embodiment is excellent in filler dispersibility and can reduce the viscosity of the filler dispersion.

Hereinafter, embodiments of the present invention will be described in detail.

The filler dispersant according to the present embodiment contains a fatty acid ester (A) of polyoxyalkylene glyceryl ether (hereinafter sometimes simply referred to as a fatty acid ester (A)). The fatty acid ester (A) has 8 to 30 carbon atoms in the constituent fatty acid.

The production method of the fatty acid ester (A) is not particularly limited, a method of esterifying polyoxyalkylene glyceryl ether and fatty acid, a method of transesterifying polyoxyalkylene glyceryl ether and fatty acid alkyl ester, an ester of glycerin and fatty acid And a method of adding alkylene oxide to the reaction product.

Examples of the polyoxyalkylene glyceryl ether include compounds obtained by addition polymerization of alkylene oxide to glycerin. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Of these, ethylene oxide is preferably included because the dispersibility is better and the viscosity of the dispersion is lower. The content of ethylene oxide in the total alkylene oxide is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more.

The addition form when two or more alkylene oxides are used is not particularly limited, and examples thereof include block addition, random addition, and combined use of block addition and random addition. Of these, block addition is preferred because of better dispersibility and lower viscosity of the dispersion.

As the fatty acid, those having 8 to 30 carbon atoms are used. For example, n-octylic acid, 2-ethylhexylic acid, isooctylic acid, n-nonylic acid, isononylic acid, n-decylic acid, isodecylic acid, n- Undecyl acid, isoundecyl acid, n-dodecyl acid, isododecyl acid, n-tridecyl acid, isotridecyl acid, n-tetradecyl acid, isotetradecyl acid, n-pentadecyl acid, isopentadecyl acid, n-hexadecyl acid, isohexadecyl acid Acid, 2-hexyldecyl acid, n-heptadecyl acid, isoheptadecyl acid, n-octadecyl acid, isooctadecyl acid, 2-octyl decyl acid, 2-hexyl decyl acid, n-nonadecyl acid, isononadecylic acid, n-eicosyl acid, Isoeicosylic acid, n-heneicosyl acid, isoheneicosyl acid, n- Cosylic acid, isodocosylic acid, n-tricosylic acid, isotricosic acid, n-tetracosyl acid, isotetracosyl acid, n-pentacosyl acid, isopentacosyl acid, n-hexacosyl acid, isohexacosyl acid, n-heptacosyl acid, isoheptacosyl acid, n-octacosyl acid Saturated fatty acids such as isooctacosic acid, n-nonacosyl acid, isononacosyl acid, n-triacontylic acid, isotriacontylic acid, octenyl acid, nonenylic acid, decenyl acid, undecenyl acid, dodecenyl acid, tridecenyl acid, tetradecenyl acid, 2- Ethyl decenyl acid, pentadecenyl acid, hexadecenyl acid, heptadecenyl acid, octadecenyl acid, nonadecenyl acid, eicosenyl acid, heneicosenyl acid, dococenyl acid, tricosenyl acid, tetracosenyl acid, pentacosenilic acid Acid, Hekisakoseniru acid, Heputakoseniru acid, Okutakoseniru acid, Nonakoseniru acid, unsaturated fatty acids such as thoria Conte sulfonyl acid. Any 1 type may be used for the said fatty acid, and 2 or more types may be used for it.

Among these, it is preferable to use an unsaturated fatty acid because the dispersibility is more excellent and the viscosity of the dispersion becomes lower. That is, in one embodiment, the fatty acid ester (A) is preferably an unsaturated fatty acid ester whose constituent fatty acid contains an unsaturated fatty acid. In the fatty acid ester (A), the content of the unsaturated fatty acid in the constituent fatty acid is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more. preferable. In addition, since the dispersibility is more excellent and the viscosity of the dispersion becomes lower, the number of carbon atoms of the fatty acid constituting the fatty acid ester (A) is preferably 8 to 24, more preferably 8 to 20, and even more preferably 8 to 18. preferable.

When fatty acid alkyl ester is used, methyl ester or ethyl ester of the above fatty acid can be used. When using a fatty acid alkyl ester, it is preferable to carry out the reaction while removing by-produced alcohol (methanol, ethanol, etc.) under reduced pressure if necessary.

The fatty acid ester (A) preferably has 1 to 30 oxyalkylene groups in the molecule, and preferably 1.5 to 25, because the dispersibility is better and the dispersion has a lower viscosity. Is more preferable, and 2 to 20 is more preferable.

The fatty acid ester (A) is preferably a compound represented by the following general formula (1).

In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an aliphatic acyl group having 8 to 30 carbon atoms, and at least one is an aliphatic acyl group. A ¹ O, A ² O and A ³ O are each independently an oxyalkylene group having 1 to 4 carbon atoms, a, b and c represent the average number of added moles of alkylene oxide, and a + b + c is 1 ~ 30.

Examples of the aliphatic acyl group having 8 to 30 carbon atoms include the acyl groups derived from fatty acids exemplified above. Among these, an unsaturated aliphatic acyl group having 8 to 30 carbon atoms is preferable because the dispersibility is superior and the viscosity of the dispersion becomes lower. In one embodiment, the ratio of the unsaturated aliphatic acyl group in the total aliphatic acyl group is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more. Further, since the dispersibility is more excellent and the viscosity of the dispersion becomes lower, the number of carbon atoms is preferably 8 to 24, more preferably 8 to 20, and still more preferably 8 to 18.

Examples of the oxyalkylene group having 1 to 4 carbon atoms include an oxyethylene group, an oxypropylene group, and an oxybutylene group as described above for the alkylene oxide, and preferably includes an oxyethylene group. When an oxyethylene group is included, the content in all oxyalkylene groups is not particularly limited, and may be, for example, 50 mol% or more, 70 mol% or more, or 80 mol% or more. Moreover, the addition form in the case of containing 2 or more types of oxyalkylene groups is not specifically limited, Block addition, random addition, combined use of block addition and random addition, etc. are mentioned, Block addition is preferable. Further, a + b + c is more preferably 1.5 to 25, and further preferably 2 to 20.

The average degree of esterification of the fatty acid ester (A) is not particularly limited, but is preferably 0.5 to 2.5, more preferably 1.0 to 2.3. Here, the average degree of esterification is an arithmetic average of the number (esterification degree) in which hydrogen atoms of three hydroxyl groups of polyoxyalkylene glyceryl ether are substituted with aliphatic acyl groups, that is, polyoxyalkylene glyceryl ether. It is the ratio of the number of moles of fatty acid esterified to 1 mole. The average degree of esterification is calculated from the weighted average of the areas of the monoester, diester and triester of the fatty acid ester (A) by GPC analysis (gel permeation chromatography). The measurement conditions for GPC are as follows.

[GPC measurement conditions]
For the measurement of GPC, THF (tetrahydrofuran) as an eluent is flowed at a flow rate of 0.8 mL per minute and the column is stabilized in a constant temperature bath at 30 ° C. using the following measuring apparatus. Measurement is performed by injecting 100 μL of a sample solution having a concentration of 5 mg / mL dissolved in THF.
・ Measuring device: Shimadzu GPC system (manufactured by Shimadzu Corporation)
・ Pump: LC-10A (manufactured by Shimadzu Corporation)
・ Detector: RID-10A (manufactured by Shimadzu Corporation)
・ Analytical column: Shodex KF-G, Shodex KF-801, Shodex KF-802, Shodex KF-802.5 and Shodex KF-803 are connected in series (all manufactured by Showa Denko KK)
Data analysis: LabSolution GPC (manufactured by Shimadzu Corporation).

The filler dispersant according to the present embodiment contains the fatty acid ester (A) and may be composed only of the fatty acid ester (A), or alternatively, the fatty acid ester (A) as a main component. As long as the effect is not impaired, various additives may be included as optional components. Examples of such additives include impact resistance modifiers, weather resistance modifiers, antioxidants, ultraviolet absorbers, heat stabilizers, mold release agents, dyes, pigments, flame retardants, antistatic agents, Antifogging agent, lubricant, anti-blocking agent, fluidity modifier, plasticizer, antibacterial agent, wax, anti-aging agent, vulcanizing agent, vulcanization accelerator, scorch preventing agent, softening agent, stearic acid, etc. It is done.

The filler dispersant of this embodiment is used for dispersing various fillers. Specific examples of the filler include metal oxides, metal hydroxides, metal carbonates, metal sulfates, metal silicates, metal nitrides, carbons, and other fillers.

Examples of the metal oxide include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, and antimony oxide.

Examples of the metal hydroxide include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and basic magnesium carbonate.

Examples of the metal carbonate include calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite and hydrotalcite.

Examples of the metal sulfate include calcium sulfate, barium sulfate, and gypsum fiber.

Examples of the metal silicate include calcium silicate, talc, kaolin, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, serisalite, glass fiber, glass beads, and silica-based balloon.

Examples of the metal nitride include aluminum nitride, boron nitride, and silicon nitride.

Examples of carbons include carbon black, graphite, carbon fiber, carbon balloon, charcoal powder and fullerene.

Other fillers include, for example, other various metal powders (gold, silver, copper, tin, etc.), potassium titanate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless fiber, zinc borate, slag Examples thereof include fiber, fluororesin powder, wood powder, cellulose fiber, rubber powder, and aramid fiber.

These fillers may be used alone or in combination of two or more. Among these, metal oxides, metal hydroxides, metal carbonates, metal silicates, and carbon black are preferable, and more preferably at least one selected from the group consisting of silica, montmorillonite, and carbon black. .

The amount of the filler dispersant used is not particularly limited, and for example, 1 to 100 parts by mass or 1 to 30 parts by mass may be used with respect to 100 parts by mass of filler.

The filler dispersant according to the present embodiment is used for dispersing the filler in the resin in the resin composition containing the filler. The resin is a general term for natural resins and synthetic resins, and includes rubber. Specific examples of the resin include styrene butadiene rubber, acrylonitrile butadiene rubber, butyl rubber, isoprene rubber, butadiene rubber, chloroprene rubber, acrylic rubber, silicone rubber, fluorine rubber, natural rubber, acrylic resin, polyester resin, polyamide resin, polyolefin resin, Examples include polystyrene resin, polyacetal resin, alkyd resin, urethane resin, silicone resin, fluororesin, polycarbonate resin, and polyvinyl chloride resin. One of these may be applied to a resin used, or two or more resins may be applied in combination.

The method of using the filler dispersant is not particularly limited. For example, the filler dispersant may be added to the resin together with the filler and mixed. Various additives usually blended in the resin may be added and mixed together with the filler and filler dispersant.

[Production Example 1 (Synthesis of Dispersant 1)]
The autoclave was charged with 92 g (1 mol) of glycerin and 0.3 g of potassium hydroxide, and the inside of the reactor was purged with nitrogen. Ethylene oxide (440 g, 10 mol) was introduced under the conditions of a pressure of 2.0 kg / cm ² and a temperature of 130 ° C., and further reacted for 3 hours, and then neutralized with acetic acid to obtain polyoxyethylene glyceryl ether. The polyoxyethylene glyceryl ether was transferred to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a reflux tube, and a test tube, and 245 g (1.7 mol) of 2-ethylhexanoic acid and 0.5 g of tetrabutyl titanate were added. And then removing water using a test tube in a nitrogen atmosphere at 220 ° C. for 6 hours, followed by dehydration condensation, whereby dispersant 1 represented by the above formula (1) (a + b + c = 10, aliphatic acyl) Group: C ₇ H ₁₅ CO—, average degree of esterification: 1.7).

[Production Example 2 (Synthesis of Dispersant 2)]
The same procedure as in Production Example 1 was carried out except that 287 g (1.7 mol) of isononanoic acid was used in place of 2-ethylhexanoic acid. Dispersant 2 represented by formula (1) (a + b + c = 10, fat Group acyl group: C ₈ H ₁₇ CO—, average degree of esterification: 1.7).

[Production Example 3 (Synthesis of Dispersant 3)]
The same procedure as in Production Example 1 was carried out except that 340 g (1.7 mol) of lauric acid was used in place of 2-ethylhexanoic acid, and dispersant 3 (a + b + c = 10, fat represented by formula (1) Group acyl group: C ₁₁ H ₂₃ CO—, average degree of esterification: 1.7).

[Production Example 4 (Synthesis of Dispersant 4)]
The same procedure as in Production Example 1 was carried out except that 483 g (1.7 mol) of stearic acid was used in place of 2-ethylhexanoic acid. Dispersant 4 represented by formula (1) (a + b + c = 10, fat Group acyl group: C ₁₇ H ₃₅ CO—, average degree of esterification: 1.7).

[Production Example 5 (Synthesis of Dispersant 5)]
The same procedure as in Production Example 1 was carried out except that oleic acid 480 g (1.7 mol) was used instead of 2-ethylhexanoic acid, and dispersant 5 (a + b + c = 10, fat represented by formula (1) Group acyl group: C ₁₇ H ₃₃ CO—, average degree of esterification: 1.7).

[Production Example 6 (Synthesis of Dispersant 6)]
The same procedure as in Production Example 1 was carried out except that behenic acid 580 g (1.7 mol) was used instead of 2-ethylhexanoic acid, and dispersant 6 (a + b + c = 10, fat represented by formula (1) Group acyl group: C ₂₁ H ₄₃ CO—, average degree of esterification: 1.7).

[Production Example 7 (Synthesis of Dispersant 7)]
The same procedure as in Production Example 1 was conducted except that 433 g (1.7 mol) of palmitoleic acid was used instead of 2-ethylhexanoic acid, and dispersant 7 (a + b + c = 10, fat represented by formula (1) was obtained. Group acyl group: C ₁₅ H ₂₉ CO—, average degree of esterification: 1.7).

[Production Example 8 (Synthesis of Dispersant 8)]
The same operation as in Production Example 5 was carried out except that the amount of oleic acid used was changed to 339 g (1.2 mol). Dispersant 8 represented by formula (1) (a + b + c = 10, aliphatic acyl group: C ₁₇ H ₃₃ CO—, average degree of esterification: 1.2) was obtained.

[Production Example 9 (Synthesis of Dispersant 9)]
Except that the amount of oleic acid used was changed to 621 g (2.2 mol), the same operation as in Production Example 5 was performed, and dispersant 9 represented by formula (1) (a + b + c = 10, aliphatic acyl group: C ₁₇ H ₃₃ CO—, average degree of esterification: 2.2).

[Production Example 10 (Synthesis of Dispersant 10)]
The same operation as in Production Example 5 was performed except that the amount of ethylene oxide used was 88 g (2 mol), and dispersant 10 represented by formula (1) (a + b + c = 2, aliphatic acyl group: C ₁₇ H ₃₃ CO -, Average degree of esterification: 1.7).

[Production Example 11 (Synthesis of Dispersant 11)]
Except that the amount of ethylene oxide used was 880 g (20 mol), the same operation as in Production Example 5 was performed, and dispersant 11 represented by formula (1) (a + b + c = 20, aliphatic acyl group: C ₁₇ H ₃₃ CO -, Average degree of esterification: 1.7).

[Production Example 12 (Synthesis of Dispersant 12)]
Except for using 580 g (10 mol) of propylene oxide in place of ethylene oxide, the same operation as in Production Example 5 was performed, and dispersant 12 represented by formula (1) (a + b + c = 10, aliphatic acyl group: C ₁₇ H ₃₃ CO-, average degree of esterification: 1.7) was obtained.

[Production Example 13 (Synthesis of Dispersant 13)]
Instead of 440 g (10 mol) of ethylene oxide, the same operation as in Production Example 5 was carried out except that 220 g (5 mol) of ethylene oxide and 290 g (5 mol) of propylene oxide were simultaneously reacted, and the dispersion represented by the formula (1) Agent 14 (a + b + c = 10, aliphatic acyl group: C ₁₇ H ₃₃ CO—, average degree of esterification: 1.7) was obtained.

[Production Example 14 (Synthesis of Dispersant 14)]
In place of 440 g (10 mol) of ethylene oxide, 290 g (5 mol) of propylene oxide and then 220 g (5 mol) of ethylene oxide were reacted, and the same operation as in Production Example 5 was carried out and represented by formula (1) Dispersant 14 (a + b + c = 10, aliphatic acyl group: C ₁₇ H ₃₃ CO—, average degree of esterification: 1.7) was obtained.

[Production Example 15 (Synthesis of Dispersant 15)]
In place of 440 g (10 mol) of ethylene oxide, 360 g (5 mol) of 1,2-butylene oxide and subsequently 220 g (5 mol) of ethylene oxide were reacted, and the same procedure as in Production Example 5 was carried out to obtain a compound of formula (1) Dispersant 15 (a + b + c = 10, aliphatic acyl group: C ₁₇ H ₃₃ CO—, average degree of esterification: 1.7)

[Production Example 16 (Synthesis of Dispersant 16)]
The autoclave was charged with 92 g (1 mol) of glycerin and 0.3 g of potassium hydroxide, and the inside of the reactor was purged with nitrogen. Ethylene oxide (440 g, 10 mol) was introduced under the conditions of a pressure of 2.0 kg / cm ² and a temperature of 130 ° C., and further reacted for 3 hours, and then neutralized with acetic acid to obtain polyoxyethylene glyceryl ether. This polyoxyethylene glyceryl ether was transferred to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a reflux tube, and a test tube, and charged with 504 g (1.7 mol) of methyl oleate and 0.5 g of tetrabutyl titanate, Dispersant 16 represented by formula (1) (a + b + c = 10, aliphatic acyl group: by performing transesterification while removing methanol using a test tube in a nitrogen atmosphere at 200 ° C. for 6 hours: C ₁₇ H ₃₃ CO—, average degree of esterification: 1.7) was obtained.

[Production Example 17 (Synthesis of Dispersant 17)]
A reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux tube and a water sampling tube was charged with 92 g (1 mol) of glycerin, 480 g (1.7 mol) of oleic acid and 0.5 g of tetrabutyl titanate at 220 ° C. Water was removed using a test tube under a nitrogen atmosphere for 6 hours, and dehydration condensation was performed to obtain glycerin monooleate. This glycerin monooleate was transferred to an autoclave, charged with 0.3 g of potassium hydroxide, and the inside of the reactor was purged with nitrogen. Dispersion represented by the formula (1) by introducing 440 g (10 mol) of ethylene oxide under the conditions of a pressure of 2.0 kg / cm ² and a temperature of 130 ° C., further reacting for 3 hours, and neutralizing with acetic acid. Agent 17 (a + b + c = 10, aliphatic acyl group: C ₁₇ H ₃₃ CO—, average degree of esterification: 1.7) was obtained.

[Production Example 18 (Synthesis of Dispersant 18)]
The same operation as in Production Example 1 was carried out except that 102 g (1.7 mol) of acetic acid was used instead of 2-ethylhexanoic acid, and dispersant 18 (in formula (1), a + b + c = 10, acyl group: CH ₃ CO-, average degree of esterification: 1.7) was obtained.

[Production Example 19 (Synthesis of Dispersant 19)]
The autoclave was charged with 92 g (1 mol) of glycerin and 0.3 g of potassium hydroxide, and the inside of the reactor was purged with nitrogen. Introducing 440 g (10 mol) of ethylene oxide under the conditions of a pressure of 2.0 kg / cm ² and a temperature of 130 ° C., further reacting for 3 hours, and then neutralizing with acetic acid to disperse 19 ( a + b + c = 10, R ¹ , R ² , R ³ = H).

[Examples 1 to 17, Comparative Examples 1 and 2]
67 parts by mass of polylactic acid (trade name: Terramac TP-4000, manufactured by Unitika), 30 parts by mass of montmorillonite (Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.), and 3 parts by mass of the dispersant shown in Table 1 were uniformly mixed using a tumbler mixer. Then, the mixture was melt-mixed at a kneading temperature of 200 ° C. using a twin screw extruder (KRC kneader, manufactured by Kurimoto Iron Works Co., Ltd.) to obtain a pellet-shaped thermoplastic resin composition.

[Comparative Example 3]
A pellet-shaped thermoplastic resin composition was obtained in the same manner as in Example 1 except that 69 parts by mass of polylactic acid and 31 parts by mass of montmorillonite were used and no dispersant was used.

[Example 18, comparative example 4]
67 parts by mass of polyamide 6 (A1030BRL, manufactured by Unitika) instead of polylactic acid, 30 parts by mass of glass fiber (T-187, manufactured by Nippon Electric Glass) instead of montmorillonite, and 3 parts by mass of the dispersant described in Table 1 A pellet-shaped thermoplastic resin composition was obtained in the same manner as in Example 1 except that the kneading temperature was 300 ° C.

[Comparative Example 5]
A pellet-shaped thermoplastic resin composition was obtained in the same manner as in Example 18 except that 69 parts by mass of polyamide 6 and 31 parts by mass of glass fiber were used and no dispersant was used.

[Example 19, comparative example 6]
In the same manner as in Example 18, except that 30 parts by mass of talc (Microace SG-95, manufactured by Nippon Talc Co., Ltd.) and 3 parts by mass of the dispersant shown in Table 1 were used instead of glass fiber, pellets were obtained. A thermoplastic resin composition was obtained.

[Comparative Example 7]
A pellet-shaped thermoplastic resin composition was obtained in the same manner as in Example 19 except that polyamide 6 was 69 parts by mass, talc was 31 parts by mass, and no dispersant was used.

The melt viscosity and impact resistance of the obtained resin composition were evaluated by the following methods. The results are shown in Table 1.

(Melt viscosity)
The melt viscosity was measured at a predetermined temperature using a dynamic viscoelasticity measuring apparatus (“Rheosol-G3000” manufactured by UBM Co., Ltd.). The measurement temperatures are 200 ° C. in Examples 1 to 18 and Comparative Examples 1 to 3, and 300 ° C. in Examples 19 to 20 and Comparative Examples 4 to 7.

(Impact resistance)
Using an injection molding machine (SG75Mk-II, manufactured by Sumitomo Heavy Industries, Ltd.), injection molding was performed under the conditions of a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. to prepare a test piece having a thickness of 3 mm. Using this, the notched Charpy impact strength (kJ / m ² ) at a temperature of 23 ° C. was measured according to ISO179.

As shown in Table 1, when blending montmorillonite with polylactic acid, Examples 1 to 17 using the dispersants 1 to 17 according to this embodiment were used in Comparative Example 3 where no dispersant was used. On the other hand, the melt viscosity was remarkably reduced and the impact resistance was greatly improved by the excellent dispersibility. On the other hand, the dispersants 18 and 19 according to the comparative examples were inferior to the examples in both the effect of reducing the melt viscosity and the effect of improving the impact resistance as in the comparative examples 1 and 2. Similarly, when polyamide is used as the resin and glass fiber or talc is blended therein, the melt viscosity of Examples 18 and 19 using the dispersant according to this embodiment is higher than that of Comparative Examples 4 to 7. It was greatly reduced and the impact resistance was greatly improved.

[Examples 21 to 38, Comparative Examples 8 to 10]
40 parts by mass of natural rubber (TSR20), 60 parts by mass of styrene butadiene rubber (trade name: Nipol NS116R, manufactured by ZS Elastomer), 35 parts by mass of carbon black (trade name: Asahi Thermal, manufactured by Asahi Carbon Co., Ltd.), silica (trade name) : Nip seal AQ, manufactured by Tosoh Silica Co., Ltd.) 70 parts by mass, silane coupling agent (trade name: Si69, manufactured by Evonik Degussa) 7 parts by mass, zinc white 3 parts by mass, stearic acid 2 parts by mass, paraffin wax 1 part by mass Parts, anti-aging agent (N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine) 3 parts by mass, sulfur 1 part by mass, vulcanization accelerator (N-oxydiethylene-2-benzothia 1 part by mass of zolylsulfenamide) and 3 parts by mass of the dispersant listed in Table 2 (however, Comparative Example 8 does not use a dispersant). By kneading by Barry mixer to obtain a rubber composition.

The Mooney viscosity was measured by the following method using the obtained rubber composition. Further, the rubber composition was put into a mold and vulcanized at 180 ° C. for 1 hour to obtain a test piece. Filler dispersibility was evaluated by the following method using the obtained test piece. The results are shown in Table 2.

(Mooney viscosity)
In accordance with JIS K6300-1, Mooney viscosity was measured using an L-shaped rotor at a preheating of 1 minute, a rotor rotation time of 4 minutes, and a temperature of 100 ° C. The result was an index when the Mooney viscosity of Comparative Example 8 was taken as 100. The lower this number, the lower the Mooney viscosity and the better the processability.

(Filler dispersibility)
The rubber composition was put into a mold and vulcanized at 180 ° C. for 1 hour to obtain a test piece. Using the obtained test piece, the test piece was cut out in accordance with the ISO11345B method, the cross section was observed, and the dispersion state was quantified by image processing to evaluate filler dispersibility. The results are shown as an index when Comparative Example 8 is taken as 100. Larger numbers indicate fewer filler dispersions and better filler dispersion.

As shown in Table 2, when carbon black and silica are dispersed in rubber, Examples 20 to 36 using the dispersants 1 to 17 according to this embodiment are comparative examples using no dispersant. 8 and Comparative Examples 9 and 10 using the dispersants 18 and 19 according to the Comparative Examples were able to reduce the viscosity of the unvulcanized rubber and were excellent in filler dispersibility.

Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. These embodiments and their omissions, replacements, changes, and the like are included in the inventions described in the claims and their equivalents as well as included in the scope and gist of the invention.

Claims

A filler dispersant containing a fatty acid ester (A) of polyoxyalkylene glyceryl ether,
A dispersant for filler, wherein the fatty acid constituting the fatty acid ester (A) has 8 to 30 carbon atoms.
The filler dispersant according to claim 1, wherein the fatty acid constituting the fatty acid ester (A) of the polyoxyalkylene glyceryl ether contains an unsaturated fatty acid.
The filler dispersant according to claim 1 or 2, wherein the polyoxyalkylene glyceryl ether fatty acid ester (A) has an average of 1 to 30 oxyalkylene groups in the molecule.
Use in dispersion of at least one filler selected from the group consisting of metal oxide, metal hydroxide, metal carbonate, metal silicate, and carbon black. Dispersant for filler.
The filler dispersant according to any one of claims 1 to 4, which is used for dispersing the filler in a resin.