JP2005350644A - Filler dispersing agent for thermoplastic resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dispersing agent excellent in effect for dispersing a filler, particularly hydrophilic filler such as silica into a thermoplastic resin. <P>SOLUTION: The filler-dispersing agent for thermoplastic resins comprises an amine compound (A) represented by general formula (1) (wherein m is an integer of 2-5; R<SP>1</SP>, R<SP>3</SP>and R<SP>4</SP>are each a hydrogen atom or a 1-10C alkyl group and R<SP>2</SP>is a 1-10C alkyl group or R<SP>1</SP>and R<SP>2</SP>together may form a ring having a 2-11 methylene group and the methylene group in the ring may have a 1-14C alkyl group as a substituent group) and/or its salt (B) as an active ingredient. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a filler dispersant. More specifically, the present invention relates to a filler dispersant for thermoplastic resins.

  Examples of a technique for dispersing a filler such as silica in a thermoplastic resin include (i) a method in which a filler surface-treated with a coupling agent is dispersed in a resin (for example, see Patent Document 1), and (ii) a surface activity. A method of dispersing a filler in a resin using an agent (for example, see Patent Document 2) is known.

Japanese Patent Publication No. 7-98657 Japanese Patent Publication No. 8-13938

However, even the above method may not show a sufficient effect. In particular, since the filler is very easily aggregated even when trying to disperse a highly hydrophilic filler such as silica in a hydrophobic resin such as poly α-olefin resin or polystyrene resin, styrene-butadiene rubber, natural rubber, In order to disperse these fillers, there is a problem that the above method (i) or (ii) cannot be sufficiently dispersed.
An object of the present invention is to provide a dispersant having excellent filler dispersibility for thermoplastic resins.

As a result of intensive investigations for the above purpose, the present inventors have found that a specific amine compound has excellent filler dispersibility with respect to a thermoplastic resin, and have reached the present invention.
That is, the present invention relates to a filler dispersant for thermoplastic resins containing the amine compound (A) represented by the general formula (1) and / or a salt thereof (B) as an active ingredient; and the dispersant and the thermoplastic vinyl resin. , A heat comprising one or more thermoplastic resins and / or fillers selected from thermoplastic polyamide resins, thermoplastic polyester resins, thermoplastic polyacetal resins, thermoplastic polycarbonate resins, thermoplastic polyurethane resins and thermoplastic natural resins. Master batch for molding a plastic resin.

In the formula, m is an integer of 2 to 5, R ¹ , R ³ and R ⁴ are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, or R ¹ and R ² may be bonded to form a ring having 2 to 11 methylene groups, and the methylene group in the ring may have an alkyl group having 1 to 14 carbon atoms as a substituent. Good.

The filler dispersant of the present invention has a great effect of dispersing the filler in the thermoplastic resin.
In particular, it is excellent in dispersion of hydrophilic fillers such as silica.
Moreover, since the filler dispersibility is good, the fluidity during the kneading process of the resin is excellent.

The amine compound (A) in the present invention is represented by the general formula (1), and as the alkyl group when R ^{1 to} R ⁴ are alkyl groups having 1 to 10 carbon atoms, a linear or branched alkyl group, for example, Examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, nonyl group and decyl group.
Preferred among R ¹ and R ² are those in which R ¹ and R ² are combined to form a ring having 2 to 11, preferably 3 to 7, more preferably 3 to 5 methylene groups. It is.
In the case where a ring is formed from R ¹ and R ^2, at least one of the methylene groups may have an alkyl group having 1 to 14 carbon atoms, preferably 6 to 12 carbon atoms, as a substituent.
Of R ³ and R ⁴ , a hydrogen atom and a methyl group are preferable. m is preferably 2 to 4, more preferably 3.

Specific examples of (A) include the following cycloamidines described in JP-B-46-37503.
R ¹ and R ² do not form a ring 1-methylimidazoline 1,2-dimethylimidazoline 1-methyl-2-ethylimidazoline 1-methyl-2-octylimidazoline 1,2-diethyl-imidazoline 1-methyl-1, 4,5,6-tetrahydropyrimidine 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine 1-methyl-2-ethyl-1,4,5,6-tetrahydropyrimidine 1,2-diethyl -1,4,5,6-tetrahydropyrimidine 1-methyl-2-propyl-1,4,5,6-tetrahydropyrimidine 1-methyl-2-butyl-1,4,5,6-tetrahydropyrimidine 1-methyl-2-octyl-1,4,5,6-tetrahydropyrimidine 1-ethyl-2-octyl-1,4,5,6-tetrahydro Pyrimidine 1,2,4-trimethyl-1,4,5,6-tetrahydropyrimidine 1,2,5-trimethyl-1,4,5,6-tetrahydropyrimidine 1,2,6-trimethyl-1,4 , 5,6-Tetrahydropyrimidine

R ¹ and R ² combine to form a ring having 2 to 11 methylene groups 5-Diaza-bicyclo (4,2,0) octene-5
1,8-diaza-bicyclo (7,2,0) undecene-8
1,4-diaza-bicyclo (3,3,0) octene-4
3-Methyl-1,4-diaza-bicyclo (3,3,0) octene-4
3,6,7,7-tetramethyl-1,4-diaza-bicyclo (3,3,0) octene-4
7,8,8-trimethyl-1,5-diaza-bicyclo (4,3,0) nonene-5
1,8-diaza-bicyclo (7,3,0) dodecene-8
1,7-diaza-bicyclo (4,3,0) nonene-6
1,5-diaza-bicyclo (4,4,0) decene-5
1,5-diaza-bicyclo (4,3,0) nonene-5 (hereinafter abbreviated as DBN)
1,8-diaza-bicyclo (7,4,0) tridecene-8
1,8-diaza-bicyclo (5,3,0) decene-7
9-Methyl-1,8-diaza-bicyclo (5,3,0) decene-7
1,8-diaza-bicyclo (5,4,0) undecene-7 (hereinafter abbreviated as DBU)
1,6-diaza-bicyclo (5,5,0) dodecene-6
1,7-diaza-bicyclo (6,5,0) tridecene-7
1,8-diaza-bicyclo (7,5,0) tetradecene-8
1,10-diaza-bicyclo (7,3,0) dodecene-9
1,10-diaza-bicyclo (7,4,0) tridecene-9
1,14-diaza-bicyclo (11,3,0) hexadecene-13
1,14-diaza-bicyclo (11,4,0) heptadecene-13

In the case where a ring is formed from R ¹ and R ^2, at least one of the methylene groups has an alkyl group as a substituent, for example, 6-n-alkyl-1,8-diaza-bicyclo ( 5,4,0) undecene-7 (hereinafter abbreviated as 6-n-alkyl DBU) and the like, and examples thereof include 6-ethyl-1,8-diaza-bicyclo (5,4,0) Undecene-7
6-n-propyl-1,8-diaza-bicyclo (5,4,0) undecene-7
6-n-butyl-1,8-diaza-bicyclo (5,4,0) undecene-7 (hereinafter abbreviated as 6-n-butyl DBU)
6-n-pentyl-1,8-diaza-bicyclo (5,4,0) undecene-7
6-n-hexyl-1,8-diaza-bicyclo (5,4,0) undecene-7
6-n-heptyl-1,8-diaza-bicyclo (5,4,0) undecene-7
6-n-octyl-1,8-diaza-bicyclo (5,4,0) undecene-7 (hereinafter abbreviated as 6-n-octyl DBU)
6-n-nonyl-1,8-diaza-bicyclo (5,4,0) undecene-7
6-n-decyl-1,8-diaza-bicyclo (5,4,0) undecene-7
6-Lauryl-1,8-diaza-bicyclo (5,4,0) undecene-7
Most preferred among (A) are DBU, DBN and 6-n-alkyl-DBU, especially DBU, 6-n-butyl DBU and 6-n-octyl DBU.

Examples of the salt (B) in the present invention include the neutralized salt (B1) formed from the above (A) and the acid (a) and the quaternary ammonium salt (B2) derived from (A). Among (B), (B1) is preferred from the viewpoint of filler dispersibility.
The acid (a) forming (B1) includes an organic acid and an inorganic acid.
Examples of the organic acid include carboxylic acids (a1), organic sulfonic acids (a2), organic sulfate esters (a3), organic phosphate esters (a4), and organic phosphonate esters (a5). Examples include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrofluoric acid, HBr, and HI.
Of these, (a) is preferably an organic acid from the viewpoint of filler dispersibility, and (a1) and (a2), particularly (a1), are more preferred.

  Carboxylic acids (a1) include aliphatic monocarboxylic acid (a11), aliphatic polycarboxylic acid (a12), aromatic carboxylic acid (a13), unsaturated carboxylic acid polymer (a14) and amino acid (a15). One or more selected acids, for example, the following acids may be mentioned.

(A11) aliphatic monocarboxylic acid (a111) aliphatic saturated carboxylic acid having 2 to 22 carbon atoms;
Acetic acid, propionic acid, thiopropionic acid, butanoic acid, hexanoic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachin Acid etc.
(A112) an aliphatic unsaturated carboxylic acid having 3 to 22 carbon atoms;
Acrylic acid, methacrylic acid, undecylenic acid, oleic acid, elaidic acid, linoleic acid, linoelaidic acid, eleostearic acid, linolenic acid, parinaric acid, arachidonic acid, setoleic acid, oleoyl sarcosine, etc.
(A113) a mixture of an aliphatic saturated carboxylic acid and an aliphatic unsaturated carboxylic acid;
Linseed oil fatty acid, olive oil fatty acid, cacao fatty acid, sesame oil fatty acid, rice bran oil fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, palm oil fatty acid, castor oil fatty acid, cottonseed oil fatty acid, coconut oil fatty acid, peanut oil fatty acid, beef tallow fatty acid, sheep fatty acid Fatty acids from natural fats such as sardine oil fatty acid, hardened sardine oil fatty acid, Nagas whale oil fatty acid, hardened herring oil fatty acid, sperm whale oil fatty acid.

(A12) Aliphatic polycarboxylic acid (a121) C3-C22 aliphatic polycarboxylic acid (a1211) aliphatic saturated dicarboxylic acid;
Malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid and the like.
(A1212) alkenyl succinic acid;
Octenyl succinic acid, nonenyl succinic acid, decenyl succinic acid, undecenyl succinic acid, dodecenyl succinic acid, tridecenyl succinic acid, tetradecenyl succinic acid, pentadecenyl succinic acid, hexadecenyl succinic acid, heptadecenyl succinic acid Acids, octadecenyl succinic acid, etc.
(A1213) maleated fatty acid;
Maleated oleic acid, maleated castor oil fatty acid, etc.

(A13) aromatic carboxylic acid (a131) C7-22 aromatic carboxylic acid;
Benzoic acid, phenylacetic acid, phenylmethylacetic acid, cinnamic acid, phthalic acid, isophthalic acid, terephthalic acid, helimellitic acid, trimellitic acid, trimesic acid, benzenepolycarboxylic acid, salicylic acid, o-oxycinnamic acid, protocatechuic acid, Vanillic acids, resorcylic acids, etc.

(A14) polymer of unsaturated carboxylic acid (a141) polymer of unsaturated carboxylic acid having 8 to 22 carbon atoms (degree of polymerization 2 or 3);
Dimer acid, trimer acid, maleated dimer acid, etc.

(A15) amino acid (a151) an amino acid having 7 to 22 carbon atoms;
Phenylalanine, tyrosine, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid and the like.

  Of (a1), (a11) and (a12) are preferred, (a111), (a112), (a1212) and (a1213) are more preferred, and stearic acid and oleic acid are particularly preferred. These may be used alone or in combination of two or more.

Examples of the organic sulfonic acids (a2) include aliphatic sulfonic acids (alkane sulfonic acids having 2 to 24 carbon atoms such as ethyl sulfonic acid, octyl sulfonic acid and dodecyl sulfonic acid; carbon numbers 2 such as vinyl sulfonic acid and octenyl sulfonic acid). -24 alkenesulfonic acid; sulfosuccinic acid such as dioctylsulfosuccinic acid) and aromatic ring-containing sulfonic acid (benzenesulfonic acid having 1 to 24 carbon atoms such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid, alkylnaphthalene) Sulfonic acid and phenolsulfonic acid).
Examples of the organic sulfates (a3) include aliphatic sulfates (alkyl sulfates having 1 to 24 carbon atoms such as methyl sulfate ester, ethyl sulfate ester and dodecyl sulfate ester, and carbon numbers such as sulfate ester of dodecyl alcohol ethylene oxide adduct). 1-24 alcohol or unsaturated carboxylic acid alkylene oxide adduct sulfates, sulfated oils, sulfated fatty acid esters and sulfated olefins) and aromatic ring-containing sulfate esters (alkylphenol alkylene oxide adduct sulfates and the like). It is done.
Examples of the organic phosphoric acid esters (a4) and the organic phosphonic acid esters (a5) include those having a structure in which the sulfuric acid ester group in the above (a3) is replaced with a phosphoric acid ester group or a phosphonic acid ester.

  The neutralized salt (B1) can be obtained by sufficiently mixing (A) and (a) at equal equivalent ratios, and if necessary, a method of removing the solvent after mixing using a solvent can also be performed. . As the solvent, for example, methanol, ethanol, isopropanol, toluene, benzene, chloroform and the like can be used.

Examples of the quaternary ammonium salt (B2) include those obtained by reacting (A) with a quaternizing agent, or those obtained by an anion exchange reaction with an organic acid.
Examples of the quaternizing agent include dialkyl carbonate (the alkyl group has 4 to 24 carbon atoms, such as stearyl group and behenyl group), halogenated alkyl or alkenyl halide (alkyl group and alkenyl group having 4 to 24 carbon atoms, Examples of the halogen include chlorine, bromine, iodine, and the like, and dialkyl sulfuric acid (the alkyl group has 4 to 24 carbon atoms). Examples of the organic acid used for anion exchange include the above-described carboxylic acids. Specific examples of (B2) include 5-octadecyl-1,5-diaza-bicyclo (4,3,0) nonenonium bromide and those described in US Pat. No. 3,652,564. It is done.

The dispersant of the present invention may be either (A) alone, (B) alone, or one containing (A) and (B).
In the case of including (A) and (B), the ratio (B) / (A) of (B) based on the weight of (A) is usually used in an arbitrary mixing ratio, but from the viewpoint of filler dispersibility. Preferably it is 0.01-100, More preferably, it is 0.1-10.

  The dispersant of the present invention can provide good filler dispersibility only by (A) and / or (B), but may contain a polyether chain-containing compound (E) if necessary. By adding (E), it is excellent in preventing re-aggregation without impairing dispersibility, further improving kneading processability, and improving mold releasability during molding.

Examples of (E) include polyether (E1) and its derivative (E2), and (E1) is represented by the following general formula (2).
R ⁵ -{(OA) n-OH} q (2)
In the formula, R ⁵ is a residue obtained by removing at least one hydroxyl group from a compound having 1 to 6 carbon atoms having 1 to 24 carbon atoms, A is an alkylene group having 2 to 24 carbon atoms, and q is 1 to 6 carbon atoms. An integer, n is an integer of 1 to 600.

R ⁵ is a residue obtained by removing at least one, preferably all hydroxyl groups, from a compound having 1 to 6 hydroxyl groups having 1 to 24 carbon atoms, and is a linear, branched or alicyclic aliphatic 1 to 6 Residue of monovalent alcohol, residue of 1-6 valent phenols, and residue of 1-6 valent araliphatic alcohols. These alcohols and phenols include the following (e1) to ( e6).

(E1) aliphatic monohydric alcohol linear or branched aliphatic saturated monool having 1 to 24 carbon atoms:
Methanol, ethanol, propanol (n-propanol, isopropanol), butanol, pentanol, hexanol, heptanol, octanol (n-octanol, 2-ethylhexyl alcohol), nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol (N-tridecyl alcohol, isotridecyl alcohol), tetradecyl alcohol, pentadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, eicosyl alcohol, heneicosyl alcohol, docosyl alcohol, tricosyl alcohol and tetra Cosyl alcohol, etc .;

Linear or branched aliphatic unsaturated monool having 3 to 24 carbon atoms (cis- or trans-):
Alkenyl alcohols (1-, 2- and iso-propenyl alcohol, butenyl alcohol, pentenyl alcohol, hexenyl alcohol, heptenyl alcohol, nonenyl alcohol, decenyl alcohol, undecenyl alcohol, dodecenyl alcohol, tridecene Nyl alcohol, tetradecenyl alcohol, pentadecenyl alcohol, hexadecenyl alcohol, heptadecenyl alcohol, octadecenyl alcohol, nonadecenyl alcohol, eicosenyl alcohol, henecocenyl alcohol, Dococenyl alcohol, tricocenyl alcohol and tetracocenyl alcohol); and alkynyl alcohol (pentynyl alcohol etc.).

C4-C24 alicyclic monool:
Cyclopentanol and cyclohexanol.

(e2) Aliphatic dihydric alcohol C2-C24 aliphatic diol:
Alkylene glycol (ethylene glycol, propylene glycol, 1,3-, 1,4- and 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2- and 1,8-octanediol, isobutylene Glycol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1 , 3-propanediol and 2,5-dimethylhexane-2,5-diol);
C4-C18 alicyclic diol:
Cycloalkylene glycols (such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol) and hydrogenated bisphenols (such as hydrogenated bisphenol A and hydrogenated bisphenol F);
And heterocyclic diols:
1,4,3,6-sorbide and the like.

(e3) Aliphatic 3- to 6-valent alcohol Trivalent alkanetriol having 3 to 24 carbon atoms (glycerin, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3 -Propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4- Propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylol Ethane and trimethylolpropane); 4- to 6-valent alkane polyols having 5 to 24 carbon atoms and their intramolecular or intermolecular dehydrates (pentaerythridine). Lithol, dipentaerythritol, sorbitol, mannitol, 1,5-, 3,6- and 1,4-sorbitan and diglycerin); and saccharides and derivatives thereof (such as sucrose, glucose, mannose, fructose and methylglucoside) .

(e4) Monohydric phenols Monohydric phenols having 6 to 24 carbon atoms [phenol, alkylphenol (o, m or p-methylphenol, m, p-dimethylphenol, 2,6-dimethylphenol, o, m or p -Ethylphenol, pn-butylphenol, p-octylphenol, p-nonylphenol, etc.), monostyrylphenol, monobenzylphenol, etc.].
(e5) 2-6 valent phenols 2-6 valent phenols having 6 to 24 carbon atoms [monocyclic polyphenols {divalent phenols (catechol, resorcin, hydroquinone, etc.), monocyclic 3-6 valent phenols (tri Oxybenzene, tetraoxybenzene, hexaoxybenzene, etc.)} and bisphenols (bisphenol A, bisphenol F, etc.).

(e6) 1 to 6 valent araliphatic alcohols Aralkyl alcohols having 7 to 24 carbon atoms (such as benzyl alcohol and phenethyl alcohol); Substituted aralkyl alcohols having 8 to 24 carbon atoms (o, m or p-methylbenzyl alcohol and p- n-butylphenethyl alcohol, etc.).

  Of these, preferred are (e1) to (e3), more preferred are those having 1 to 20 carbon atoms, particularly preferred are aliphatic 1 to 3 alcohols, and particularly preferred is hydrophobic. This is a linear or branched aliphatic saturated or unsaturated monohydric alcohol having 3 to 18 carbon atoms in that the compatibility with the thermoplastic resin is good. When the number of carbon atoms is 24 or less, the flow characteristics are good and the kneadability is excellent.

  A in the general formula (2) is an alkylene group having 2 to 24 carbon atoms, for example, ethylene group, 1,2- and 1,3-propylene group, 1,2-, 2,3- and 1,4- Examples include butylene group and isobutylene group. A mixture of two or more of these may be used, and the polymerization type may be random or block, but it is preferable to have a random polymerization portion in terms of excellent flow characteristics. Among these, an alkylene group having 2 to 16 carbon atoms is preferable, an ethylene group, a 1,2-propylene group, and a 1,4-butylene group are more preferable, and a viewpoint of kneadability is particularly preferable. To 1,2-propylene group and 1,4-butylene group.

  N in General formula (2) is 1-600, Preferably it is 2-300, More preferably, it is 3-100. q is preferably 1 to 3, particularly 1 from the viewpoint of good compatibility with a hydrophobic thermoplastic resin. When q is 6 or less, the flow characteristics are excellent.

(E1) has a weight average molecular weight (Mw) of preferably 200 to 30,000, more preferably 500 to 10,000, and particularly preferably 1,000 to 6,000.
If Mw is 200 or more, the filler dispersibility is excellent, and if it is 30,000 or less, the viscosity tends to be low, which is convenient in terms of handling. Mw is measured by gel permeation chromatography (GPC) (column: TSKgel G2000, G3000, G4000HXL, solvent: tetrahydrofuran).

As a production method of (E1), a compound having 1 to 6 hydroxyl groups having 1 to 24 carbon atoms represented by R ⁵ (OH) q is preferably used at a temperature of 30 to 120 ° C. in the presence of a catalyst. Includes a method in which one or more alkylene oxides having 2 to 24 carbon atoms (hereinafter abbreviated as AO) are added alone or randomly or in blocks at a pressure of 0 to 0.6 MPa. The method obtained by removing a catalyst as needed is mentioned.

A known catalyst can be used as the catalyst, but among AO, AO having a 4-membered ring (oxetane) or 5-membered ring (tetrahydrofuran) is homo-added or copolymerized with a 3-membered ring (ethylene oxide, propylene oxide, etc.). The range of a preferable catalyst differs in the case of carrying out addition reaction and the single addition reaction of AOs having a three-membered ring.
As a catalyst in the case of a single addition reaction of AO having a 4- or 5-membered ring, or a copolymerization addition reaction of AO having a 4- or 5-membered ring and AO having a 3-membered ring, for example, BF ₃ , BCl ₃ , AlCl _3, FeCl ₃ and SnCl ₃ or the like Lewis acids and their complexes [e.g. BF ₃ ether complex, BF ₃ tetrahydrofuran complex _{(BF 3 · THF)];} H 2 SO 4, protonic acid HClO _4, etc.; KClO _4, NaClO Alkali metal perchlorates such as ₄ ; alkaline earth metal perchlorates such as Ca (ClO ₄ ) ₂ and Mg (ClO ₄ ) ₂ ; and other metals such as Al (ClO ₄ ) ₃ A chlorate etc. are mentioned.
Among these, BF ₃ ether complex and BF ₃ tetrahydrofuran complex (BF ₃ · THF) are preferable.
As a catalyst in the case of an addition reaction between AOs having a three-membered ring, in addition to the above-mentioned catalyst, an alkali catalyst, for example, an alkali metal or alkaline earth metal such as hydroxide [KOH, NaOH, CsOH, Ca (OH) _2, etc. Hydroxides; oxides (oxides of alkali metals or alkaline earth metals such as K ₂ O, CaO, BaO); alkali metals (Na, K, etc.) and hydrides thereof (NaH, KH, etc.); triethylamine And amines such as trimethylamine.
Among these, KOH, NaOH, CsOH, BF ₃ ether complex and BF 3 tetrahydrofuran complex (BF ₃ · THF) are preferable.

  Among AOs, ethylene oxide, propylene oxide, and 1,4-butylene oxide are preferable, and propylene oxide and 1,4-butylene oxide are more preferable.

  As the derivative (E2) of (E1) in the present invention, the alkyl etherified product (E21) or esterified product (E22) of (E1), or the reaction product (E23) or (E1) of (E1) and a polyisocyanate is used. ) And a polyhalide reaction product (E24).

(E21) is preferably an alkyl etherified product having 1 to 8 carbon atoms, for example, an etherified product having a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, or an n-octyl group. Preferred are methyl etherified compounds.
(E21) can be produced by reacting (E1) with an alkyl halide (C1-8) in the presence of an alkali (such as a hydroxide of an alkali metal such as KOH, NaOH and CsOH). The amount of the alkyl halide is preferably an alkyl halide / hydroxyl group = 1/1 to 5/1, particularly preferably 1.2 / 1 to 4/1, in an equivalent ratio with respect to the hydroxyl group of (E1). Further, the addition amount of the alkali is preferably alkali / hydroxyl group = 1/1 to 10/1, particularly preferably 1.2 / 1 to 5/1, in terms of an equivalent ratio with respect to the hydroxyl group of (E1). If necessary, a solvent such as toluene or benzene can be used for the reaction. The etherification reaction can be carried out at normal pressure or under pressure. The progress of the etherification reaction can be judged by the alkali number of the reaction system, the viscosity, the number average molecular weight of the reaction system, and the like.

(E22) is derived from (E1), a carboxylic acid having 2 to 22 carbon atoms, a carboxylic acid anhydride, a carboxylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, and a carboxylic acid halide having 2 to 22 carbon atoms. An esterified product with at least one esterifying agent (b) selected from the group consisting of:
Examples of the esterifying agent (b) include the following.
(B1) an aliphatic monocarboxylic acid having 2 to 22 carbon atoms;
Acetic acid, propionic acid, thiopropionic acid, butanoic acid, hexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid and the like.
(B2) an aliphatic dicarboxylic acid having 2 to 22 carbon atoms;
Oxalic acid, malonic acid, succinic acid, propanedicarboxylic acid, thiodipropionic acid, tetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, highmic acid, tetrabromophthalic acid, tetrachlorophthalic acid and the like.
(B3) a C3-C22 aliphatic tri- or tetravalent or higher carboxylic acid;
Propanetricarboxylic acid, methylcyclohexanetricarboxylic acid, cyclohexentricarboxylic acid, methylcyclohexentricarboxylic acid, cyclohexanetetracarboxylic acid and the like.
(B4) an aromatic monocarboxylic acid;
Benzoic acid, phenylacetic acid, naphthalenecarboxylic acid.
(B5) Aromatic dicarboxylic acid Phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, xylylene dicarboxylic acid and the like.
(B6) Aromatic tri- to tetra-valent or higher carboxylic acid.
Benzenetricarboxylic acid, benzenetetracarboxylic acid, naphthalenetetracarboxylic acid and the like.
(B7) The acid anhydride of the above (b2), (b3), (b5) or (b6);
(B8) Lower alkyl (having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, butyl) esters of the above (b1) to (b6):
(B9) Acid halides (chlorine, bromine, etc.) of the above (b1) to (b6).
(B) may contain 1 to 3, preferably 1 heteroatom (sulfur, phosphorus, etc.).

Of these, (b), (b2), (b5) and (b7) are preferred, and more preferred are oxalic acid (anhydride), malonic acid (anhydride), succinic acid (anhydride), and propanedicarboxylic acid. Acid (anhydride), thiodipropionic acid, tetrahydrophthalic acid (anhydride), methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride (anhydride), hymic acid (anhydride), norbornene dicarboxylic acid (anhydride), phthalate Acid (anhydride), isophthalic acid and terephthalic acid, particularly preferred are oxalic acid (anhydride), malonic acid (anhydride), succinic acid (anhydride), propanedicarboxylic acid (anhydride) and thiodipropion It is an acid.
(E2) using these has a low viscosity and is easy to handle.

  The reaction conditions of (E1) and (b) can be carried out under general esterification reaction conditions. For example, in the case of a one-step synthesis method, an esterification catalyst, preferably an acid catalyst (for example, paratoluenesulfonic acid, sulfuric acid, etc.) is used, preferably 50 to 150 ° C., more preferably 70 to 130 ° C. for 8 to 20 hours. Can be synthesized. The equivalent ratio (E1) / (b) of the functional groups of (E1) and (b) is preferably 0.5 to 2.0, more preferably 0.9 to 1.5. If it is 0.5 or more, a large amount of unreacted (b) does not remain and treatment such as washing is unnecessary, and if it is 2.0 or less, the lubricity of (E2) is good. Moreover, solvents, such as toluene and benzene, can be used for reaction as needed. The esterification reaction can be carried out at normal pressure, reduced pressure, or increased pressure, but the reduced pressure is preferable because the reaction time becomes shorter. The degree of reduced pressure is preferably 30 mmHg or less, particularly preferably 10 mmHg or less, at the final stage of the reaction. The progress of the esterification reaction can be judged by the amount of water distilled from the reaction system, the amount of lower alcohol, the acid value of the reaction system, the viscosity, the number average molecular weight of the reaction system, and the like.

As the polyisocyanate (c) used in (E23), a polyisocyanate having a valence of 2 to 6 or more is used, and those conventionally used for polyurethane production are exemplified. Specifically, the following (c1) To (c4).
(C1) Aromatic polyisocyanate 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′- Diisocyanatodiphenylmethane, etc .;
(C2) aliphatic polyisocyanate ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, Bis (2-isocyanatoethyl) fumarate and the like;

(C3) Cycloaliphatic polyisocyanate Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) and the like;
(C4) araliphatic polyisocyanate m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like;
Among these, (b-1) and (b-2) are preferable, and 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6- are more preferable. Tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI) ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI).

  The reaction conditions of (E1) and (c) can be performed under the conditions of a general urethanization reaction. For example, a urethanization catalyst, preferably a transition metal catalyst (for example, dibutyltin dilaurate) is used, and it can be synthesized at 50 to 150 ° C., more preferably at 70 to 130 ° C. for 8 to 20 hours. The functional equivalent ratio (E1) / (c) of (E1) and (c) is preferably 0.5 to 2.0, more preferably 0.9 to 1.5. When it is 0.5 or more and 2.0 or less, the lubricity of (E2) becomes good. Further, if necessary, a solvent such as toluene, xylene, dimethylformamide, butyl acetate or the like can be used for the reaction. The urethanization reaction can be carried out at normal pressure or under pressure. The progress of the urethanization reaction can be judged by the isocyanate group content of the reaction system, the viscosity, the number average molecular weight of the reaction system, and the like.

Examples of the polyhalide (d) that can be used in (E24) include divalent to tetravalent or higher C1-5 chlorides or bromides. Specifically, the following (d1) and (d2) Is mentioned.
(D1) a polyhalide having 1 to 2 carbon atoms;
Dichloromethane, dichloroethane, dibromomethane, dibromoethane, trichloroethylene and the like.
(D2) a polyhalide having 3 or more carbon atoms;
1,3-dichloropropane, 1,3-trichloropropane, 1,2 dibromobutane and the like.
Of these, (d1) is preferred among (d). Particularly, (E2) using dichloromethane or dichloroethane has a low viscosity and is easy to handle.

  The reaction conditions of (E1) and (d) can be synthesized under the general etherification reaction conditions. For example, an alkali, preferably an inorganic alkali (for example, sodium hydroxide, potassium hydroxide) is added in an amount of 0.9 to 1.5 equivalents to the halogen, preferably 50 to 150 ° C, more preferably 70 to 130 ° C. It can be synthesized in 6 to 24 hours. The equivalent ratio (E1) / (d) of the functional groups of (E1) and (d) is preferably 0.5 to 2.0, more preferably 0.9 to 1.5. When it is 0.5 or more and 2.0 or less, the lubricity of (E2) becomes good. Also. If necessary, a solvent such as toluene or benzene can be used for the reaction. The etherification reaction can be carried out at normal pressure or under pressure. The progress of the etherification reaction can be judged by the alkali number of the reaction system, the viscosity, the number average molecular weight of the reaction system, and the like.

  The preferable content of (E) in the dispersant of the present invention is 10 to 95% by weight, more preferably 15 to 85% by weight, based on the weight of the dispersant.

In the present invention, examples of the method for adding these dispersants to the thermoplastic resin include the following methods.
(I): When only (A) is an essential component, (A) is added to and mixed with the thermoplastic resin.
(Ii): When only (B) is an essential component, (B) produced in advance is added, or (A) equivalent to (A) is added to and mixed with the thermoplastic resin, Form (B) in it.
(Iii): When (A) and (B) are essential components, (A) is added separately from (B) produced in advance, or an excess equivalent of (A) than (a) is added. It is added to and mixed with a thermoplastic resin, and a part of (A) is converted to (B) in the resin.
In these methods, (A) and / or (B) can be dissolved or dispersed in (E) if necessary.

The dispersant of the present invention can be used for known fillers used as fillers for synthetic or natural resins. Examples of fillers include metal oxides, metal hydroxides, metal carbonates, metal sulfates, and 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, sericite, 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 balun, 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, Teflon powder, wood powder, pulp, rubber powder, aramid fiber, and starch.
These may be used alone or in combination of two or more.
Of these fillers, metal oxides are preferable from the viewpoint of affinity with amines, and silica is more preferable. Among the silicas, wet process silica is preferable, and precipitated silica is particularly preferable.

The shape of the filler is not particularly limited, and examples thereof include a fiber shape, a needle shape, a plate shape, a spherical shape, a granular shape (indefinite shape, hereinafter the same meaning), a tetrapot shape, and a balloon shape. Moreover, the filler may be surface-treated with a treating agent as necessary.
As the surface treatment agent, known surface treatment agents can be used, for example, silane coupling agents, titanate coupling agents, aluminate coupling agents, fats and oils, polyethylene glycol type nonionic surfactants, polyhydric alcohol type nonionics. Surfactants, waxes, fatty acids, carboxylic acid coupling agents, phosphoric acid coupling agents and the like can be mentioned.

  Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-methyldimethoxysilylpropyl) tetrasulfide, and bis (3-triethoxy Silylethyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) trisulfide, 3-mercaptopropyltrimethoxysilane, 3- Mercaptopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimeth Sisilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylcarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetra Sulfide, 3-trimethoxysilylpropylmethacryloyl monosulfide, γ-chloropropyltrimethoxysilane, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane and the like, and one or more of these can be used.

Examples of titanate coupling agents include isopropyl triisostearoyl titanium.
Examples of the aluminate coupling agent include acetoalkoxyaluminum diisopropylate.

  The addition amount in the case of using a filler coupling agent such as a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Preferably it is 2-10 weight part.

Examples of the fats and oils include coconut oil, rice dregs oil, soybean oil, linseed oil, dehydrated castor oil, safflower oil, and tung oil.
Examples of the polyethylene glycol type nonionic surfactant include higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts.
Examples of the polyhydric alcohol type nonionic surfactant include polyethylene oxide, fatty acid ester of glycerol, fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, and aliphatic amide of alkanolamine. Is mentioned.

Examples of the wax include maleated polypropylene and maleated polyethylene.
Fatty acids are used as a lubricant during kneading or as a crosslinking accelerator when crosslinking after molding, and examples thereof include stearic acid, oleic acid, linoleic acid, linolenic acid, and eleostearic acid. However, in the present invention, when a dispersant containing (B) and not containing (A) is used, the fatty acid is used as the above-mentioned lubricant or crosslinking accelerator, while the dispersion containing (A) is used. When an agent is used, fatty acids equal to or less than the equivalent ratio of (A) are consumed to form (B) acting as a neutralizing agent (a), and excess when using an excess equivalent of (a) Minor fatty acid acts as a lubricant or a crosslinking accelerator.
Examples of the carboxylic acid coupling agent include carboxylated polybutadiene and carboxylated polyisoprene.
Examples of the phosphoric acid coupling agent include phosphoric acid monooctyl ester, phosphoric acid mono (2,6-dimethyl-7-octenyl) ester, phosphoric acid mono (6-mercaptohexyl) ester and phosphoric acid mono (2-methacrylate). And phosphoric acid coupling agents such as (roxypropyl) ester.
In addition, in the carboxylic acid coupling agent and the phosphoric acid coupling agent, as in the case of the above fatty acid, when a dispersant containing (B) and not containing (A) is used, these coupling agents are coupled. On the other hand, when a dispersing agent containing (A) is used, these coupling agents having an equivalent ratio or less of (A) act as a neutralizing agent (a) and (B). When an excess equivalent of (a) is used, the excess acts as a coupling agent.

  The thermoplastic resin (C) to which the dispersant of the present invention can be applied is not particularly limited. For example, thermoplastic vinyl resin (C1), thermoplastic polyamide (C2), thermoplastic polyester (C3), thermoplasticity Examples include polyacetal (C4), thermoplastic polycarbonate (C5), thermoplastic polyurethane (C6), thermoplastic natural resin (C7), and mixtures of two or more thereof. (C) may be oil-extended with a highly aromatic oil and / or a naphthenic oil.

(C1) includes resins obtained by (co) polymerizing the following vinyl monomers (m1) to (m7) by known polymerization methods (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.). It is done.

(M1) an aliphatic hydrocarbon vinyl monomer;
Alkenes (ethylene, propylene, 1-octene, etc.) having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10) and 4 to 30 carbon atoms (preferably 4 to 12, more preferably 4 to 5). ) Of alkadienes (butadiene, isoprene) and the like.
(M2) an aromatic vinyl monomer;
Styrene and its homologues, for example, styrene, o-, m- or p-alkyl (C1-10) styrene (e.g., vinyltoluene), α-alkyl (C1-10) styrene (e.g., α -Methylstyrene etc.) and halogenated styrene (eg chlorostyrene etc.).

(M3) (meth) acrylic monomers;
Alkyl (C1-C20) (meth) acrylate {eg, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.}, mono- or di-alkyl (C1-C4) aminoalkyl (C2-C4) (meth) acrylate {for example, aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.}, (meth) acrylonitrile, (meth) acrylamide, etc.].

(M4) other unsaturated mono- or di-carboxylic acids;
C2-C30 (preferably 3-20, more preferably 4-15) unsaturated mono- or di-carboxylic acid etc. [crotonic acid, maleic acid, fumaric acid, itaconic acid etc.] and their derivatives [mono- Or di-alkyl (C1-C20) ester, an acid anhydride (for example, maleic anhydride etc.), an imide (for example, maleic acid imide), etc.].
(M5) carboxylic acid ester of unsaturated alcohol;
Carboxylic acid (carbon number 2 to 4) esters (vinyl acetate and the like) such as vinyl alcohol and (meth) allyl alcohol.
(M6) alkyl ethers of unsaturated alcohols;
Alkyl (C1-C20) ethers such as vinyl alcohol and (meth) allyl alcohol.
(M7) halogen-containing vinyl monomer;
Vinyl chloride, vinylidene chloride, chloroprene, etc.

Examples of (C1) include polyolefin resin (C11), polystyrene resin (C12), acrylic resin (C13), and fluorine resin (C14).

As (C11), one or more (co) polymers of alkenes and one or more of alkenes and one or more of (m2) to (m7) (weight ratio; usually 5/95 to 95/5, preferably Copolymer (C111) with 50/50 to 90/10); and one or more (co) polymers of alkadienes and copolymers of alkadienes with one or more of (m2) to (m7) (C112) ).

Examples of (C111) include polypropylene, polyethylene, ethylene / propylene copolymer, propylene and / or copolymer of ethylene and one or more of other alkenes (random or block), ethylene / vinyl acetate copolymer. (EVA) and ethylene / ethyl acrylate copolymer (EEA).
Among (C111), polypropylene, polyethylene, and an ethylene / propylene copolymer are preferable.
Examples of (C112) include polybutadiene rubber (BR), styrene / butadiene rubber (SBR), polyisoprene rubber (IR), acrylonitrile / butadiene rubber (NBR), butyl rubber (IIR), and the like, preferably SBR. It is.

  As (C12), one or more (co) polymers of (m2) and one or more of (m2) and one or more of (m3) to (m7) (weight ratio; usually 5/95 to 95 / 5, preferably 50/50 to 90/10).

  Examples of (C12) include polystyrene, polyvinyltoluene and the like; a copolymer of (m2) and one or more monomers selected from the group consisting of methyl methacrylate, acrylonitrile and butadiene [for example, styrene / acrylonitrile copolymer ( AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), styrene / methyl methacrylate / acrylonitrile copolymer, methyl methacrylate / butadiene / styrene copolymer (MBS resin)] and the like.

  (C13) includes one or more (co) polymers of (m3) (for example, polymethyl methacrylate, polybutyl acrylate, etc.) and one or more of (m3) and one of (m4) to (m7). A copolymer with the above (weight ratio is usually 5/95 to 95/5, preferably 50/50 to 90/10).

  Examples of the fluororesin (C14) include a binary or ternary copolymer of vinylidene fluoride and hexafluoropropylene, and further tetrafluoroethylene, and an alternating copolymer of (m1) and tetrafluoroethylene.

As thermoplastic polyamide (C2),
For example, nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 66 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 610 by polycondensation of hexamethylenediamine and sebacic acid, nylon 11 by polycondensation of 11-aminoundecanoic acid , Nylon 12 by ring-opening polymerization of ω-laurolactam or polycondensation of 12-aminododecanoic acid, and copolymerized nylon containing two or more components of the nylon.

As thermoplastic polyester (C3),
For example, aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate and polycyclohexanedimethylene terephthalate by polycondensation of diols such as ethylene glycol, butylene glycol and cyclohexanedimethanol and dicarboxylic acids such as terephthalic acid and adipic acid, and polybutylene Examples include aliphatic polyesters such as adipate and polyethylene adipate, and aliphatic polyesters such as poly-ε-caprolactone by ring-opening polymerization such as ε-caprolactone.

  Thermoplastic polyacetals (C4) include formaldehyde or trioxane homopolymers, such as polyoxymethylene homopolymers, and coforms of formaldehyde or trioxane with cyclic ethers (eg, alkylene oxides such as ethylene oxide, propylene oxide, dioxolane, etc.). Examples of the polymer include polyoxymethylene / polyoxyethylene copolymer (polyoxymethylene / polyoxyethylene weight ratio 90 to 99/1 to 10 block copolymer).

  Examples of the thermoplastic polycarbonate (C5) include a polycarbonate having a bisphenol skeleton, such as a condensate of bisphenol A and phosgene and a condensate of bisphenol A and carbonic acid diester.

Examples of the thermoplastic polyurethane (C6) include the above-mentioned organic diisocyanate, a polymer diol and a chain extender, and a polyurethane obtained by a one-shot method or a prepolymer method, if necessary, with a reaction terminator.
As the polymer diol, a diol having a Mn of 500 to 5,000, for example, a polyether diol, a polyester diol, or the like is used.

  Examples of polyester diols include polyester diols obtained by reacting diols and / or polyether diols with dicarboxylic acids having 4 to 20 carbon atoms (preferably 4 to 18, more preferably 6 to 12) or the lactone. Can be mentioned.

Examples of the thermoplastic natural resin (C7) include gutta percha, balata and natural rubber (NR).
Among (C7), natural rubber is preferable.

  Among (C), from the viewpoint that the dispersant of the present invention easily exerts a filler dispersion effect, (C1), (C2), (C3), (C4), (C7) and a mixture thereof are preferable. More preferred are (C1) and (C7), particularly preferred are (C11) and (C12) of (C1), especially natural rubber of (C112) and (C7) and (C112). ) And natural rubber.

  The Mn of (C) is preferably 10,000 to 1,000,000, more preferably 15,000 to 800,000, and particularly preferably 20,000 to 700,000.

(C) The weight ratio of the filler to 100 parts by weight is preferably 1 to 180 parts by weight, and more preferably 2 to 120 parts by weight.
Moreover, the weight ratio of the dispersing agent to (C) 100 parts by weight is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight.

  Further, the weight ratio of the dispersant of the present invention based on the weight of the filler can be variously changed according to the performance required for the resin composition, but from the viewpoint of the cost, mechanical strength or flow characteristics of the resin composition, The dispersant is preferably 1 to 80 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the filler.

The master batch for molding a thermoplastic resin of the present invention contains the above-mentioned dispersant and a thermoplastic resin and / or filler, and a master batch made of a thermoplastic resin and a dispersant is preferred.
The dispersibility of the filler is further improved by once producing the master batch and blending the master batch into the thermoplastic resin.
The mixing ratio of the dispersant based on the weight of the master batch is preferably 1 to 80% by weight, more preferably 1 to 50% by weight.

As a method of mixing and kneading in the production of a masterbatch or a thermoplastic resin composition (a composition comprising a dispersant, a filler and a thermoplastic resin, or a composition comprising a masterbatch and a thermoplastic resin) In general, the pellet or powdery components can be mixed using an appropriate mixer such as a kneader, an internal mixer, a Banbury mixer, or a roll.
The masterbatch and the resin composition may further include a crosslinking accelerator (aldehyde / ammonia-amine system, thiourea system, guanidine system, thiazole system, sulfenamide system thiuram system, dithiocarbamate system, xanthate system as required. , Dithiophosphates, etc.), crosslinking agents (sulfur, etc.), scorch inhibitors (organic acids, N-nitroso compounds, etc.), colorants, UV absorbers, general-purpose plasticizers (phthalic acid, trimellitic acid, Phosphoric acid type, epoxy type, etc.), softening agent, anti-aging agent, organic peroxide, etc. can be added as appropriate.
The order of adding each component during kneading is not particularly limited, and the dispersant may be mixed with the filler in advance and blended with the resin, or the dispersant, the filler, and the resin may be mixed simultaneously.
The obtained master batch or resin composition may be molded, and may be further pelletized or powdered by a pelletizer or the like.

  A resin molded product obtained using the dispersant or master batch of the present invention is obtained by molding the thermoplastic resin composition. Examples of molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), vulcanization press molding, etc. Depending on the method, it can be molded by any method.

<Example>
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In addition, a part shows a weight part below.

Examples 1-12, Comparative Examples 1-4
Based on the blending ratios (parts) shown in Table 1 and Table 3, the respective components were blended and then thoroughly mixed to obtain filler dispersants of A1 to A12 and B1 to B4.
In addition, the used component is as follows.

DBU; "DBU" made by Sun Apro
Stearic acid: Reagent "Stearic acid" manufactured by Nacalai Tesque

6-n-octyl DBU;
Synthesized in Synthesis Example 1 below.
Synthesis Example 1: J.M. Heterocycl. Chem. (1986), 23 (3), 885-7, a crude 6-n-octyl DBU was synthesized in a yield of about 75%. Further, the product was distilled at 130 ° C./1 mmHg to improve the purity to 99.3%.

DMOA: Reagent “N, N-dimethyl-n-octadecylamine” manufactured by Tokyo Chemical Industry Co., Ltd.

PP-2000: Polypropylene glycol “New Paul PP-2000” manufactured by Sanyo Chemical Industries

PEG-4000S: Polyethylene glycol “PEG-4000S” manufactured by Sanyo Chemical Industries

Polyether E1:
Synthesis Example-2 of 1,4-butanediol synthesized in the following Synthesis Example-2, 14.3 mol of THF / 20.4 mol of EO, random adduct:
A glass autoclave was charged with 90 parts (1.0 mol) of 1,4-butanediol, 1032 parts (14.3 mol) of THF, and 12.8 parts of BF ₃ · THF, and EO 896 parts (20 .4 mol) was added dropwise at 35 to 50 ° C. over 10 hours. Then, it reacted at 50 degreeC for 5 hours, and cooled. Further, after adding 7.4 parts of 48% NaOH aqueous solution, unreacted substances were distilled off at 30 mmHg or less. Thereafter, an adsorption treatment agent [Kyoward 600 and Kyoward 1000 manufactured by Kyowa Chemical Industry Co., Ltd. The same shall apply hereinafter. ], Filtered, dehydrated under reduced pressure (130 ° C., 30 mmHg or less, 1 hour, the same shall apply hereinafter), 1,4 butanediol in THF 14.3 mol / EO 20.4 mol random adduct ( Polyether E1) 2,000 parts were obtained.

Polyether E2:
Ester obtained from butanol PO 25 mol adduct synthesized in Synthesis Example 3 below and succinic acid Synthesis Example -3:
Butanol PO 25 mol adduct (“New Paul LB-385” manufactured by Sanyo Chemical Industries, Ltd.) 1,524 parts (1.0 mol), succinic acid 59 parts (0.5 mol), paratoluenesulfonic acid monohydrate 4 .8 parts and 3.2 parts of hypophosphorous acid were charged at 100 to 120 ° C. and reacted (esterified) for 12 hours while removing nitrogen in the liquid and removing the reaction product water, and an adsorption treatment agent [manufactured by Kyowa Chemical Industry Co., Ltd. Treated with Kyoward 1000 and Kyoword 600] and filtered to remove paratoluenesulfonic acid monohydrate and hypophosphorous acid, and after dehydration under reduced pressure, it is liquid at room temperature and has an acid value (JIS K 1557). 1) 400 parts of a polyether compound (polyether E2) of 3.0 was obtained.

Production of a thermoplastic resin composition;
2.2 parts of any one of dispersants (A1) to (A12) and (B1) to (B4), 28 parts of “Nip seal AQ” (manufactured by Nippon Silica Kogyo Co., Ltd.) as filler, and the following thermoplastic resin 35 parts of any one of the above were kneaded using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.), taken out, and then cooled to room temperature to obtain a block-shaped resin composition. The kneading conditions were changed as follows depending on the type of thermoplastic resin.
Thermoplastic resin (I): "PM771M" (manufactured by Sun Allomer, polypropylene resin)
Thermoplastic resin (II): “SBR1712” (manufactured by JSR, SBR)

Kneading conditions when using thermoplastic resin (I);
Temperature: 200 ° C
Rotation speed: 10rpm
Resin preparation: 1 minute Resin mastication: 1 minute Filler and dispersant mixing: 10 minutes Kneading: 10 minutes

Kneading conditions when using thermoplastic resin (II);
Temperature: 140 ° C
Rotation speed: 30rpm
Resin preparation: 1 minute Resin mastication: 1 minute Filler and dispersant mixing: 10 minutes Kneading: 10 minutes

  The dispersion state of the filler of the obtained resin composition was evaluated visually (the following evaluation criteria) and SEM observation (the following evaluation conditions). The evaluation results are shown in Table 1, Table 2, and Table 3.

Visual evaluation criteria;
The following four-step evaluation was performed.
(Double-circle): A silica particle cannot be visually recognized but there exists a feeling of transparency.
○: Silica particles are not visible, but are opaque.
(Triangle | delta): It can visually recognize that the silica particle is scattered in resin, and is opaque.
X: It is visible that the silica particles are scattered in the resin, is opaque, and cracks are seen on the surface of the resin composition.

Evaluation by SEM [scanning electron microscope (S-800, manufactured by Hitachi, Ltd.)]
The surface of the resin composition (about 1 g) was smoothed using a cryomicrotome, and the smooth surface was observed by SEM. Dispersibility was evaluated by counting aggregated particles having a particle size of 50 nm or more per unit area. The fewer the particles of 50 nm or more, the better the dispersibility.

Production of Resin Molded Product Additives of the following parts by weight were added to 100 parts by weight of the resin composition using the thermoplastic resin (II) and kneaded under the following conditions to obtain an additive-containing resin composition. Then, after crosslinking and molding into a sheet with a pressure press machine at 500 kgf / cm ² and 165 ° C. for 20 minutes, dispersibility evaluation by SEM observation and autograph (Shimadzu AGS-500B) were used as described above. A tensile test (JIS K6301, room temperature 25 ° C., using No. 3 dumbbell) was performed.
(1) Additives Stearic acid: 1
Zinc oxide: 1.5
Sulfur: 0.7
Cross-linking accelerator: 0.5
(Nt-butyl-2-benzothiazoylsulfenamide)
(2) Kneading condition temperature: 60-80 ° C
Rotation speed: 10rpm
Resin charge: 2 minutes Resin mastication: 1 minute Additive mixing: 1 minute Kneading: 20 minutes

The dispersion state [SEM observation (evaluation conditions)] and tensile test results (tensile strength and elongation) of the filler of the obtained resin composition are shown as Evaluation Examples 1 to 7 and Comparative Evaluation Examples 1 to 4, respectively. As shown in FIG. From Tables 4 and 5, it can be seen that Evaluation Examples 1 to 7 using the dispersant of the present invention are excellent in silica dispersibility even when the thermoplastic resin is cross-linked, and the tensile strength is increased by finely dispersing the filler. .

  The filler dispersant of the present invention can be used to disperse fillers in various thermoplastic resins, and the obtained thermoplastic resin molded products include housing products for home appliances / OA equipment, game equipment and office equipment, and various rubbers. It can be used for products, various plastic containers such as IC trays, various packaging films, flooring sheets, artificial turf, mats, and automobile parts.

Claims (7)

A filler dispersant for a thermoplastic resin comprising as an active ingredient an amine compound (A) represented by the general formula (1) and / or a salt thereof (B).
[Wherein, m is an integer of 2 to 5, R ¹ , R ³ and R ⁴ are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, Alternatively, R ¹ and R ² may combine to form a ring having 2 to 11 methylene groups, and the methylene group in the ring has a C 1-14 alkyl group as a substituent. Also good. ] The filler dispersant according to claim 1, wherein R ¹ and R ² in the general formula (1) are bonded to form a ring having 2 to 11 methylene groups.   (B) is an aliphatic monocarboxylic acid having 2 to 22 carbon atoms, an aliphatic polycarboxylic acid having 6 to 22 carbon atoms, an aromatic carboxylic acid having 7 to 22 carbon atoms, or an unsaturated carboxylic acid (8 to 22 carbon atoms). The filler dispersant according to claim 1 or 2, which is a neutralized salt of (A) with at least one acid selected from a polymer (degree of polymerization 2 or 3) and an amino acid having 7 to 22 carbon atoms.   Furthermore, the filler dispersing agent in any one of Claims 1-3 which contains a polyether chain containing compound (E) 10 to 95weight% based on the weight of a dispersing agent. The filler dispersant according to claim 4, wherein the polyether chain-containing compound (E) is a polyether (E1) represented by the following general formula (2) and / or a derivative (E2) thereof.
R ⁵ -{(OA) n -OH} q (2)
[Wherein R ⁵ is a residue obtained by removing at least one hydroxyl group from a compound having 1 to 6 hydroxyl groups having 1 to 24 carbon atoms, A is an alkylene group having 2 to 24 carbon atoms, and q is 1 to 6 N is an integer of 1 to 600. ]   The filler dispersant according to any one of claims 1 to 5, wherein the filler is silica.   The dispersant according to any one of claims 1 to 6, and a thermoplastic vinyl resin, a thermoplastic polyamide resin, a thermoplastic polyester resin, a thermoplastic polyacetal resin, a thermoplastic polycarbonate resin, a thermoplastic polyurethane resin, and a thermoplastic natural resin. A master batch for molding a thermoplastic resin, comprising at least one thermoplastic resin and / or filler.