JP2003048990A - Block polymer having branched skeleton and antistatic agent made of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a block polymer capable of giving a molded product which has excellent permanent antistatic properties, even when a small amount thereof is added to the product, and is excellent in mechanical strength, to provide an antistatic agent containing the block polymer, and to provide an antistatic resin composition composed of the block polymer and a thermoplastic resin. SOLUTION: This block polymer has such a structure that blocks of a polyolefin and blocks of a hydrophilic polymer are repeatedly and alternately coupled with each other, wherein the block of the hydrophilic polymer has polyoxyalkylene groups of a branched structure so that the hydrophilic polymer has a volume specific resistivity of 10<4> to 10<11> Ω.cm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a block polymer having a branched hydrophilic polymer and an antistatic agent comprising the same. More specifically, it relates to a block polymer for an antistatic agent, which is suitable for a molded article to be painted or printed, and an antistatic agent comprising the block polymer.

[0002]

2. Description of the Related Art A block polymer having a structure in which a block of a polyolefin and a block of a branched hydrophilic polymer are repeatedly and alternately bonded is not known. on the other hand,
A known method for imparting permanent antistatic properties to thermoplastic resins such as polyolefins is to knead an antistatic agent composed of a block polymer having a structure in which blocks of polyolefin and blocks of hydrophilic polymer are alternately and repeatedly bonded. (For example, International Publication WO00 /
47652 pamphlet). However, in order to obtain the target volume resistivity value of the thermoplastic resin, a relatively large amount of this conventional block polymer must be added to the resin, and the addition amount also depends on the molding method. However, there is a problem that the mechanical strength of the resin is lowered and the cost is inevitably increased.

[0003]

Therefore, regardless of the molding method, there is a strong demand for an antistatic agent which gives a thermoplastic resin composition excellent in permanent antistatic property and mechanical strength with a smaller amount added. It was

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that a block polymer having a structure in which a block of polyolefin and a block of a branched hydrophilic polymer are repeatedly and alternately bonded. However, they have found that a smaller addition amount gives a thermoplastic resin composition excellent in permanent antistatic property and mechanical strength, and arrived at the present invention. That is, the present invention relates to the polyolefin (a)
And the block of hydrophilic polymer (b),
In a block polymer having a structure in which it is alternately and repeatedly bonded, (b) has a polyoxyalkylene group having a branched structure and has a volume specific resistance value of 10 ⁴ to 10 ¹¹ Ω · cm ( A); the (A)
An antistatic agent containing: an antistatic resin composition comprising the (A) and a thermoplastic resin (B); a molded product obtained by molding the resin composition; and coating or printing on the molded product. It is a molded article obtained by applying.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The block polymer (A) of the present invention
Is a block of the polyolefin (a) and a block of the hydrophilic polymer (b) are ester bond, amide bond,
It has a structure in which it is repeatedly and alternately bonded through at least one bond selected from an ether bond, a urethane bond and an imide bond. As the block of the polyolefin (a) constituting the block polymer (A), a polyolefin (a1) having carbonyl groups at both ends of the polymer,
Polyolefin having hydroxyl groups at both ends of the polymer (a
2) and the polyolefin (a3) having amino groups at both ends of the polymer. Further, a polyolefin having a carbonyl group at one end of the polymer (a4) and a polyolefin having a hydroxyl group at one end of the polymer (a
5) and polyolefin (a6) having an amino group at one end of the polymer. Of these, the polyolefins (a1) and (a4) having a carbonyl group are preferable because they are easily modified.

As (a1), a polyolefin whose both ends can be modified is a main component (content of 50% or more, preferably 7%).
5% or more) in which a carbonyl group is introduced at both ends of the polyolefin (a0), (a2)
0) with hydroxyl groups introduced at both ends, and (a3)
Examples of (a0) include amino groups introduced at both ends. (A0) has 2 to 2 carbon atoms
Polyolefin obtained by polymerization of one or a mixture of two or more olefins of 30 (preferably olefin having 2 to 12 carbon atoms, particularly preferably propylene and / or ethylene), and a high molecular weight (Mn 12,000 to 10).
50,000, preferably 17,000 to 70,000)
Polyolefin (having 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, particularly preferably ethylene and / or
Alternatively, a low molecular weight polyolefin obtained by a thermal degradation method of a polyolefin obtained by the polymerization of propylene) can be mentioned.

Number average molecular weight by gel permeation chromatography (a0) (hereinafter abbreviated as Mn)
Is preferably 800 to 20,000, from the viewpoint of easiness of modification and heat resistance of the block polymer (A).
It is more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000. The measurement conditions of Mn are as follows. (Hereinafter, Mn is measured under the same conditions.) Device: High temperature gel permeation chromatography solvent: Orthodichlorobenzene reference substance: Polystyrene sample concentration: 3 mg / ml Column temperature: 135 ° C (a0) is 1 Preferably 1 to 40 per 1,000 carbons
More preferably 1 to 30, particularly preferably 4 to
The main component is one having 20 double bonds. Among the above-mentioned (a0), low molecular weight polyolefin by thermal degradation method is preferable in terms of easiness of modification,
Particularly preferable is polyethylene and / or polypropylene having Mn of 1,200 to 6,000. Regarding the average amount of terminal double bonds per molecule, in the case of the low molecular weight polyolefin obtained by the thermal degradation method, Mn is in the range of 800 to 6,000, and usually 1.5 to 2 can be obtained [Murata Katsuhide, Makino Tadahiko, Journal of the Chemical Society of Japan, p192 (1975)]. Low molecular weight polyolefins obtained by the thermal degradation method are disclosed, for example, in Japanese Patent Laid-Open No.
It can be obtained by the method described in JP-A-62804.

As (a4), a polyolefin whose one end can be modified is a main component (content of 50% or more, preferably 7%).
(5% or more) with a carbonyl group introduced at one end of the polyolefin (a00), (a5)
(00) with a hydroxyl group introduced at one end, and (a
Examples of 6) include those obtained by introducing an amino group into one end of (a00). (A00) is (a0)
The Mn of (a00) is preferably 2,000 to 50,000, more preferably 2,500 to 5,000, from the viewpoint of easy modification and heat resistance of the block polymer (A). 30,000, especially 3,000-2
10,000 is preferable. (A00) preferably has 0.3 to 20 double carbons per 1,000 carbons, more preferably 0.5 to 15 double carbons, and particularly preferably 0.7 to 10 double bonds as the main component. To do. From the viewpoint of easiness of modification, a low molecular weight polyolefin by a thermal degradation method, particularly Mn of 2,000 to 20,000 is preferable.
0 and polyethylene and / or polypropylene. 1
The average terminal double bond amount per molecule is such that Mn is 5,000 to 30,
In the range of 000, 1 to 1.5 are usually obtained.
Although (a0) and (a00) are usually obtained as a mixture thereof, these mixtures may be used as they are, or may be purified and separated before use. From the viewpoint of production cost and the like, it is preferable to use it as a mixture.

As (a1), a carbonyl group obtained by modifying the terminal of (a0) with an unsaturated carboxylic acid (anhydride) [an unsaturated carboxylic acid and / or its anhydride, and the same expressions are used below] Having a polyolefin (a1-
1), a polyolefin having a carbonyl group obtained by secondary modification of (a1-1) with a lactam or an aminocarboxylic acid (a
1-2), a polyolefin having a carbonyl group obtained by modifying (a0) by oxidation or hydroformylation (a1-
3), Polyolefin (a1-3) having a carbonyl group obtained by secondary modification with lactam or aminocarboxylic acid (a)
1-4), and mixtures of two or more thereof.

The unsaturated carboxylic acid (anhydride) used for the modification to obtain (a1-1) is a monocarboxylic acid [(meth) acrylic acid or the like] or a dicarboxylic acid (anhydride).
[Maleic acid (anhydride), fumaric acid, itaconic acid (anhydride), citraconic acid (anhydride), etc.] and the like. Of these, dicarboxylic acids (anhydrides) are preferable, maleic acid (anhydride) and fumaric acid are more preferable, and maleic acid (anhydride) is particularly preferable from the viewpoint of easiness of modification. The amount of unsaturated carboxylic acid (anhydride) used for modification is usually 0.5 to 40%, preferably 1 to 30% based on the weight of the polyolefin (a0) (in the above and below,% is the weight). Represents%). Modification with an unsaturated carboxylic acid (anhydride) is carried out by thermally adding an unsaturated carboxylic acid (anhydride) to the terminal double bond in (a0) by either a solution method or a melting method. Reaction). The temperature at which the unsaturated carboxylic acid (anhydride) is reacted with (a0) is usually 1
The temperature is 70 to 230 ° C, preferably 180 to 220 ° C.

(A1-2) can be obtained by secondarily modifying (a1-1) with a lactam or an aminocarboxylic acid. Examples of the lactam used for the secondary modification include lactams having 6 to 12 carbon atoms, such as caprolactam, enantolactam, laurolactam and undecanolactam. As the aminocarboxylic acid, an aminocarboxylic acid having 2 to 12 carbon atoms, for example, amino acids such as glycine, alanine, valine, leucine, isoleucine and phenylalanine, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocapryl. Acids, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Among these, caprolactam and 12-aminododecanoic acid are preferable from the viewpoint of reactivity with the hydrophilic polymer (b) described later. The amount of lactam or aminocarboxylic acid used in the secondary modification is preferably 0.1 to 50, more preferably 0.3 to 20, and particularly preferably 0.1 to 50 per residue of the unsaturated carboxylic acid (anhydride). 0.5-10
And most preferably 1.

(A1-3) can be obtained by oxidizing (a0) with oxygen and / or ozone or hydroformylating by the oxo method. Introduction of carbonyl groups by oxidation is described, for example, in US Pat. No. 3,692,877.
The method described in the specification can be used.

(A1-4) can be obtained by secondarily modifying (a1-3) with a lactam or an aminocarboxylic acid. Lactams and aminocarboxylic acids are represented by (a1
The same as those mentioned in -2) can be mentioned.

The Mn of the polyolefin (a1) having carbonyl groups at both ends of the polymer is 800 to 25,000.
0 is preferable, 1,000 to 20,000 is more preferable, and 2,500 to 10,000 is particularly preferable. Mn is 800 ~
The range of 25,000 is preferable in terms of heat resistance and reactivity with the hydrophilic polymer (b) described later. The acid value of the (a1) is preferably 4 to 280 (mg
KOH / g, only numerical values will be described below), more preferably 4 to 100, particularly preferably 5 to 50. When the acid value is within this range, the hydrophilic polymer (b) described later
It is preferable in terms of reactivity with.

As the polyolefin (a2) having hydroxyl groups at both ends of the polymer, the polyolefins (a2-1) and (a1-3) having hydroxyl groups obtained by modifying (a1-1) with hydroxylamine are modified with hydroxylamine. Having a hydroxyl group (a
2-2) and mixtures of two or more thereof.
As the hydroxylamine that can be used for modification, hydroxylamine having 2 to 10 carbon atoms, for example, 2-aminoethanol, 3-aminopropanol, 1-amino-2-
Propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol and the like can be mentioned. Among these, 2-aminoethanol is preferable. Modification with hydroxylamine is (a
It can be carried out by directly reacting 1) with hydroxylamine. The reaction temperature is preferably 120-
230 ° C, more preferably 150 to 210 ° C.
The amount of hydroxylamine used for modification is preferably 0.1 to 2 per residue of unsaturated carboxylic acid (anhydride).
The number is more preferably 0.3 to 1.5, particularly preferably 0.5 to 1.2, and most preferably 1.

The Mn of (a2) is 800 to 25,000.
Is more preferable, and 1,000 to 20,000 is more preferable, and 2,500 to 10,000 is particularly preferable. Mn is 800 ~
The range of 25,000 is preferable in terms of heat resistance and reactivity with the hydrophilic polymer (b) described later. The hydroxyl value of (a2) is 4 to 280 (mgKOH /
g, only numerical values below are preferred), and further 4 to
100, especially 5 to 50 are preferred. A hydroxyl value within this range is preferable from the viewpoint of reactivity with the hydrophilic polymer (b) described later.

As the polyolefin (a3) having amino groups at both ends of the polymer, a polyolefin (a3-1) having an amino group obtained by modifying (a1) with a diamine,
And mixtures of two or more thereof. As the diamine used for this modification, a diamine having 2 to 12 carbon atoms (preferably 2 to 10), for example, aliphatic diamine (ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, etc.), fat Cyclic diamines (1,4-cyclohexanediamine etc.), aromatic diamines (o-, m- and p
-Phenylenediamine and the like). Of these, aliphatic diamines are preferable, and ethylenediamine is more preferable. Modification with a diamine is (a
It can be carried out by directly reacting 1) with a diamine. The reaction temperature is preferably 120 to 230 ° C,
More preferably, it is 150 to 210 ° C. The amount of diamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, and particularly preferably 0.5 to 1 per residue of unsaturated carboxylic acid (anhydride). 1.2 pieces,
Most preferably, it is one.

The Mn of (a3) is 800 to 25,000.
Is more preferable, and 1,000 to 20,000 is more preferable, and 2,500 to 10,000 is particularly preferable. Mn is 800 ~
The range of 25,000 is preferable in terms of heat resistance and reactivity with the hydrophilic polymer (b) described later. The amine value of (a3) is 4 to 280 (mgKOH /
g, only numerical values below are preferred), and further 4 to
100, especially 5 to 50 are preferred. When the amine value is within this range, it is preferable in terms of reactivity with the hydrophilic polymer (b) described later.

As the polyolefin (a4) having a carbonyl group at one end of the polymer, a polyolefin (a4-1) having a carbonyl group obtained by modifying the end of (a00) with an unsaturated carboxylic acid (anhydride), (a4-) (1) is a polyolefin (a4-2) having a carbonyl group secondary modified with a lactam or aminocarboxylic acid, and (a00) is a polyolefin having a carbonyl group modified by oxidation with oxygen and / or ozone or hydroformylation by an oxo method ( The polyolefin (a4-4) having a carbonyl group obtained by secondary modification of a4-3) and (a4-3) with a lactam or an aminocarboxylic acid, and a mixture of two or more thereof can be used. (A4) can be obtained in the same manner as (a1). Mn of (a4) is 800 to 5
10,000 is preferable, and 1,000 to 30,000 is more preferable.
0, especially 2,000 to 20,000 is preferable. When Mn is in the range of 800 to 50,000, it is preferable in terms of heat resistance and reactivity with the hydrophilic polymer (b) described later. The acid value of (a4) is preferably 1 to 70, particularly preferably 2 to 50. When the acid value is within this range, it is preferable in terms of reactivity with the hydrophilic polymer (b) described later.

As the polyolefin (a5) having a hydroxyl group at one end of the polymer, a polyolefin (a5-1) obtained by modifying (a4) with hydroxylamine, and a mixture of two or more thereof can be used. (A5) is (a5
It can be obtained in the same manner as in 2). Mn of (a5)
Is preferably 800 to 50,000, more preferably 1.00
0 to 30,000 is preferable, and 2,000 to 20,000 is particularly preferable. When Mn is in the range of 800 to 50,000,
It is preferable in terms of heat resistance and reactivity with the hydrophilic polymer (b) described later. The hydroxyl value of (a5) is preferably 1 to 70, particularly preferably 2 to 50. A hydroxyl value within this range is preferable from the viewpoint of reactivity with the hydrophilic polymer (b) described later.

As the polyolefin (a6) having an amino group at one end of the polymer, (a4) is the above (a3).
The diamine-modified polyolefin described in 1 above, and a mixture of two or more thereof can be used. (A6)
Can be obtained in the same manner as in (a3). (A6)
The Mn is preferably 800 to 50,000, more preferably 1,000 to 30,000, and particularly 2,000 to 20,000.
00 is preferable. When Mn is in the range of 800 to 50,000, the heat resistance and the hydrophilic polymer (b) described later
It is preferable in terms of reactivity with. The amine value of (a6) is preferably 1 to 70, particularly preferably 2 to 50. When the amine value is within this range, it is preferable in terms of reactivity with the hydrophilic polymer (b) described later. Note that (a1)
And (a4) are usually obtained as a mixture thereof,
These mixtures may be used as they are, or may be purified and separated before use. From the viewpoint of manufacturing cost, etc.
Preference is given to using it as a mixture. Similarly, (a2) and (a5) and (a3) and (a6) may be used as they are, and it is preferable to use them as a mixture from the viewpoint of production cost and the like.

In the alkylene group of the polyoxyalkylene group of the block of the hydrophilic polymer (b) which constitutes the block polymer (A), at least a part of its repeating unit is a substituent represented by the following general formula (1). It may be an alkylene group and the rest may be an alkylene group having 2 to 4 carbon atoms. As the alkylene group having 2 to 4 carbon atoms, ethylene,
Propylene, 1,2-, 1,4-, 2,3- and 1,3
A butylene group and two or more of these. Among these, an ethylene group is preferable from the viewpoint of antistatic property.
When the repeating unit is composed of an oxy-substituted alkylene group and one or more oxyalkylene groups, the bond form is:
It may be either block or random or a combination thereof. In the repeating unit, the proportion of the oxy-substituted alkylene group is preferably 0.1 with respect to the total number of moles of the oxy-substituted alkylene group and the (unsubstituted) oxyalkylene group.
˜100 mol%, particularly preferably 30 to 80 mol%. -CHR-CHR'- (1) In the general formula (1), R, is one of R ', the general formula -CH ₂
The group represented by O (A ¹ O) _S R ″ (2), the other is H, and in the general formula (2), s is 1 to 10 (preferably 2 to 10).
It is an integer of 4). R "is H and has 1 to 10 carbon atoms
, Alkyl group (methyl group, ethyl group, isopropyl group, n-butyl group, 2-ethylhexyl group, etc.), aryl group (phenyl group, etc.), alkylaryl group (ethylphenyl group, etc.), arylalkyl group (benzyl group) Etc.) and acyl groups (acetyl group, benzoyl group, etc.) and the like. Of these, preferred is an alkyl group having 1 to 3 carbon atoms. A ¹ is an alkylene group having 2 to 4 carbon atoms, and ethylene, propylene, 1,2-, 1,4-, 2,
3- and 1,3-butylene groups and two or more of these groups can be mentioned. Among these, an ethylene group is preferable from the viewpoint of antistatic property. When A ¹ is composed of two or more alkylene groups, the bonding form of the oxyalkylene group may be block, random or a combination thereof.

As the hydrophilic polymer (b), polyether (b1) and polyether-containing hydrophilic polymer (b
2) and an anionic polymer (b3), all of which are alkylene groups of the polyoxyalkylene group, at least a part of which is a substituted alkylene group represented by the general formula (1), and the rest are carbon. It is a group which may be an alkylene group of the number 2 to 4. Examples of the polyether (b1) include polyether diol (b1-1), polyether diamine (b1-2), and modified products thereof (b1).
-3). As the polyether-containing hydrophilic polymer (b2), a polyether ester amide (b2-1) having a segment of a polyether diol (b1-1) as a polyether segment forming component, and a segment of the same (b1-1) are also included. The polyether amide imide (b2-2), the polyether ester (b2-3) also having the segment of (b1-1), the polyether amide (b2-4) also having the segment of (b1-2) and the same ( b1-1) or (b1-2)
Polyether urethane having a segment of (b2-
5) are mentioned. The anionic polymer (b3) has a dicarboxylic acid having a sulfonyl group and a polyether (b1) as essential constituent units, and preferably has 2 to 80, more preferably 3 to 60, sulfonyl groups in the molecule. And an anionic polymer (b3-1) having

The volume resistivity value of the hydrophilic polymer (b) (value measured by the method described below in an atmosphere of 23 ° C. and 50% RH) is usually 10 ⁴ to 10 ¹¹ Ω · cm, preferably It is 10 ⁶ to 10 ⁹ Ω · cm. Volume resistivity value is 10
^If it is less than ⁴ Ω · cm, the water resistance is deteriorated, and if it exceeds 10 ¹¹ Ω · cm, the antistatic property is deteriorated.

Among the hydrophilic polymers (b), the polyether (b1) will be described first. Of (b1),
Polyether diol (b1-1) has the general _{^{formula: H- (OA 2) m -O}} -E 1 -O- (A 2 O) m ' those represented by -H and the like. In the formula, E ¹ is a residue obtained by removing a hydroxyl group from the divalent hydroxyl group-containing compound (b0), A ² is at least a part of the substituted alkylene group represented by the general formula (1), and the rest is the number of carbon atoms. It is a group which may be an alkylene group of 2 to 4. m and m ′ are integers of 1 to 300 or more. m (OA ² ) and m '(A ²
It may be the same as or different from O). m and m'are
1 to 300 are preferable, further 2 to 250, and especially 10
100 is preferred. Further, m and m ′ may be the same or different.

Examples of the divalent hydroxyl group-containing compound (b0) include dihydric alcohols having 2 to 12 carbon atoms (aliphatic, alicyclic and araliphatic dihydric alcohols, etc.) and 6 to 18 carbon atoms.
And dihydric phenols and diols containing a tertiary amino group having 3 to 18 carbon atoms. As dihydric alcohol,
Aliphatic alcohol [Alkylene glycol (C2-C2
12, for example ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,12-dodecanediol)]; alicyclic alcohol [C4-12, eg 1 , 2- and 1,3-cyclopentanediol,
1,2-, 1,3- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol]; aromatic aliphatic alcohols [C8-12, for example, xylylenediol] and the like. Examples of the dihydric phenol include monocyclic phenols (hydroquinone, catechol,
Resorcin, urushiol, etc.), bisphenols (bisphenol A, bisphenol F, bisphenol S,
4,4'-dihydroxydiphenyl-2,2-butane,
Dihydroxybiphenyl, etc.) and condensed polycyclic phenols (dihydroxynaphthalene, binaphthol, etc.).

Examples of the tertiary amino group-containing diol include a bishydroxyalkyl compound (having 1 to 12 carbon atoms of one alkyl group) of a primary monoamine. As the primary monoamine, aliphatic monoamine (having 1 to 12 carbon atoms, such as methylamine, ethylamine, 1-propylamine,
2-propylamine, amylamine, isoamylamine, hexylamine, 1,3-dimethylbutylamine,
3,3-dimethylbutylamine, 2-aminoheptane,
3-aminoheptane, hexylamine, heptylamine, nonylamine, decylamine, undecylamine,
Dodecylamine), alicyclic monoamine (carbon number 3 to 1)
2, eg cyclopropylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine),
Aromatic (aliphatic) monoamines (having 6 to 12 carbon atoms, such as aniline and benzylamine) can be mentioned. Among the above divalent hydroxyl group-containing compounds (b0), dihydric alcohols and dihydric phenols are preferable, aliphatic dihydric alcohols and bisphenols are more preferable, and ethylene glycol and bisphenol A are particularly preferable.

The method for producing the polyether diol (b1-1) is not particularly limited, but the following method may be mentioned, for example. (1) Polymerization of a glycidyl ether (j) represented by the following general formula (13) using a divalent hydroxyl group-containing compound (b0) as a starting material or (j) and an alkylene oxide (having 2 to 4 carbon atoms). Copolymerization [preferably 99/1 weight ratio
~ 50/50]

[0029]

[Chemical 4]

In the general formula (13), A ¹ , R "and s
Is the same as in the general formula (2). (J) is manufactured, for example, by the following method or. When R ″ is other than H, epichlorohydrin, polyalkylene (alkylene carbon number 2-4) glycol and R ″ X (X is Cl, Br or I) in the presence of alkali (sodium hydroxide, potassium hydroxide, etc.) React with. When R ″ is H, the monocarbyl group in (j) obtained above is decarbylated (eg, ethanethiol is added and reacted at room temperature in the presence of an aluminum chloride catalyst). At this time, epichlorohydrin and polyalkylene (alkylene having 2 to 4 carbon atoms) glycol monocarbyl [alkyl having 1 to 10 carbon atoms, aryl,
Alkylaryl, arylalkyl, acyl, etc.] ether is reacted in the presence of an alkali. When R ″ is H, the monocarbyl group in the obtained (j) is decarbylated in the same manner as above. (2) Using the divalent hydroxyl group-containing compound (b0) as a starting material, the side chain is chloro. Starting from the method (b0) via a polyether having a methyl group, epichlorohydrin is subjected to addition polymerization, or epichlorohydrin and an alkylene oxide are subjected to addition copolymerization to obtain a polyether having a chloromethyl group in a side chain, The polyether and the polyalkylene (alkylene having 2 to 4 carbon atoms) glycol and R "X are reacted in the presence of an alkali, or the polyether and the polyalkylene (alkylene having 2 to 4 carbon atoms) glycol monocarbyl (the above-mentioned The same) is reacted with an ether in the presence of an alkali.

The addition reaction of the above alkylene oxide, glycidyl ether and epichlorohydrin with the starting material (b0) can be carried out by a known method, for example, in the presence of a catalyst at a temperature of 100 to 200 ° C. Examples of the catalyst used include basic catalysts such as sodium methylate, sodium hydroxide, potassium hydroxide and lithium carbonate, acidic catalysts such as boron trifluoride, amine-based catalysts such as trimethylamine and triethylamine.

Examples of the alkylene oxide having 2 to 4 carbon atoms used for producing the polyether diol (b1-1) (in each of the main chain and the side chain) include ethylene oxide, propylene oxide, 1,2-, 1,4
-, 2,3- and 1,3-butylene oxide and a combination system of two or more kinds of them are mentioned, but if necessary, other alkylene oxides or substituted alkylene oxides (hereinafter, these are collectively referred to as alkylene oxides). ), For example, α-olefin oxide having 5 to 12 carbon atoms, styrene oxide and the like can be used in combination.
In any case, the bonding form when two or more kinds of alkylene oxides are used in combination may be random and / or block.

Examples of the polyether diamine (b1-2), the general ^{_{formula: H 2 N-A 4 -}} (OA 2) ^{_{m -O-E 1 -O- (A}} 2 O) m '-A 4
—NH ₂ (the symbols E ¹ , A ² , m and m ′ in the formula are the same as described above, and A ⁴ is an alkylene group having 2 to ⁴ carbon atoms). (B1-2) is a known method for the hydroxyl group of the polyether diol (b1-1) [(b1
-1) can be obtained by converting the hydroxyl group of -1) to an amino group by reducing the terminal obtained by cyanoalkylation, etc., for example, by reacting (b1-1) with acrylonitrile and hydrogenating the obtained cyanoethylated product. And the like.

As the modified product (b1-3), for example,
Examples thereof include aminocarboxylic acid-modified products (terminal amino groups) of (b1-1) or (b1-2), isocyanate-modified products (terminal isocyanate groups) and epoxy-modified products (terminal epoxy groups) thereof. The aminocarboxylic acid modified product is (b)
It can be obtained by reacting 1-1) or (b1-2) with an aminocarboxylic acid or lactam. Isocyanate modified products are (b1-1) or (b1-2)
Can be obtained by reacting with an organic diisocyanate as described below or by reacting (b1-2) with phosgene. The epoxy modified product is obtained by reacting (b1-1) or (b1-2) with a diepoxide (epoxy resin such as diglycidyl ether, diglycidyl ester, alicyclic diepoxide: epoxy equivalent 85 to 600), or It can be obtained by reacting b1-1) with epihalohydrin (epichlorohydrin etc.). Among the above-mentioned polyether (b1) [polyether diol (b1-1), polyether diamine (b1-2) and modified products thereof (b1-3)], from the viewpoint of antistatic property, the polyether diol (b1) -1) is preferable.

From the viewpoint of heat resistance, Mn of (b1) is 3
00 or more, particularly 1,000 or more, and from the viewpoint of reactivity, 20,000 or less, particularly 15,000 or less.

The content of oxyalkylene units having 2 to 4 carbon atoms in (b1) (in the main chain and side chains) and the content of oxyethylene units in the polyoxyalkylene chain are
The volume resistivity of (b) is determined within a range of 10 ⁴ to 10 ¹¹ Ω · cm. Exemplifying the range of the preferable content, the carbon number is 2 to 4 with respect to the weight of (b1).
The content of oxyalkylene units is preferably 50 to 99.8% by weight, more preferably 60 to 99.6% by weight, especially 70% by weight.
˜99 wt% is preferred. The content of oxyethylene units in the polyoxyalkylene chain is 50 to 100% by weight.
Is preferred, and further 70 to 100% by weight, especially 80 to 1
00 wt% is preferred.

Next, the polyether-containing hydrophilic polymer (b2) will be described. The polyether ester amide (b2-1) is a polyamide (Q1) having a carboxyl group at the terminal and the above polyether diol (b1-).
1) and. Polyether amide imide (b
2-2) is composed of a polyamide-imide (Q2) having at least one imide ring and the above-mentioned polyether diol (b1-1). The polyether ester (b2-3) is composed of the polyester (Q3) and the above-mentioned polyether diol (b1-1). The polyether amide (b2-4) is composed of the polyamide (Q1) and the above-mentioned polyether diamine (b1-2). The polyether urethane (b2-5) includes the organic diisocyanate (Q4) and the above-mentioned (b1-1) or (b).
1-2) and optionally a chain extender (Q5).

The above (b2) [(b2-1), (b2-)
2), (b2-3), (b2-4) and (b2-
5)] [in the main chain and side chain of (b1-1) or (b1-2)], the content of the oxyalkylene unit having 2 to 4 carbon atoms and the content of the oxyethylene unit in the polyoxyalkylene chain are The volume resistivity of (b) is 10 ⁴ to 10
It is determined within the range of ¹¹ Ω · cm. Exemplifying a preferable range of the content, the content of the oxyalkylene unit having 2 to 4 carbon atoms is 50 to 50 with respect to the weight of (b2).
It is preferably 99% by weight, more preferably 60 to 99% by weight, particularly preferably 70 to 98% by weight. The content of oxyethylene units in the polyoxyalkylene chain is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, and particularly 80.
-100% by weight is preferred. Specific examples of the above-mentioned production method (b2) and (b2) and (Q1 to 3) include a production method and a specific example of "polyether-containing hydrophilic polymer" described in International Publication WO00 / 47652 pamphlet. However, the part having an alkylene structure of the polyoxyalkylene in this document may be at least a part of a substituted alkylene group represented by the general formula (1), and the rest may be an alkylene group having 2 to 4 carbon atoms. It shall be replaced with the base. ] Is mentioned.

As the organic diisocyanate (Q4),
Carbon number (excluding carbon in NCO group, the same applies hereinafter) 6 to 20
Aromatic diisocyanate, C 2-18 aliphatic diisocyanate, C 4-15 alicyclic diisocyanate, C 8-15 aromatic-aliphatic diisocyanate,
Modifications of these diisocyanates and mixtures of two or more thereof are included. Specific examples of the aromatic diisocyanate include 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate (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,
Examples include 1,5-naphthylene diisocyanate. Specific examples of the aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethyl carboxy. Proate,
Bis (2-isocyanatoethyl) fumarate, bis (2
-Isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and the like.

Specific examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI),
Bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and 2,6-
Examples thereof include norbornane diisocyanate. Specific examples of the araliphatic diisocyanate include m- and p-xylylene diisocyanate (XDI), α,
Examples include α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI). Examples of the modified diisocyanate include urethane modified products, urea modified products, carbodiimide modified products, isocyanurate modified products, and uretdione modified products. Of these, preferred are aromatic diisocyanates and aliphatic diisocyanates, and more preferred are TDI and M.
DI and HDI, especially preferred is HDI.

Examples of the method for producing the polyether urethane (b2-5) include the methods described in JP-A-62-236854 and JP-B-3-296565. If necessary, a catalyst usually used may be used to accelerate the polyurethane-forming reaction. Examples of such a catalyst include a metal catalyst, an amine catalyst, and a combination of two or more of these. Examples of the metal catalyst include tin catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannas octoate, dibutyltin maleate, etc.); lead catalysts (lead oleate, Lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.); other metal catalysts (metal naphthenate salts such as cobalt naphthenate, phenylmercuric propionate, etc.). As an amine catalyst,
For example, triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diazabicycloalkene {1,8-diazabicyclo [5,4,0]
Undecene-7 [DBU, registered trademark of San-Apro Ltd.]}, dialkylaminoalkylamine (dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropylaminopropylamine) Etc.) and heterocyclic aminoalkylamines {2- (1-aziridinyl) ethylamine,
4- (1-piperidinyl) -2-hexylamine, etc.}, N-methylmorpholine, N-ethylmorpholine,
Examples thereof include triethylamine, diethylethanolamine, dimethylethanolamine, and carbonates and organic acid salts (formate salts, etc.) of these amines.

The amounts of these catalysts used are such that the total weight of the reaction products {organic diisocyanate (Q4) and (b
1-1), (b1-2) or the total weight of the chain extender (Q5) optionally used}, and is usually 0.000.
It is 1 to 3%, preferably 0.001 to 2%.

As the chain extender (Q5), a diol [a dihydric alcohol exemplified as the above (b0), for example, ethylene glycol, 1,4-butanediol, 1,2-,
1,3- and 1,4-cyclohexanediol, xylylenediol], diamine [aliphatic diamine (eg ethylenediamine etc.), alicyclic diamine (eg 1,4
-Cyclohexanediamine etc.), aromatic diamine (eg methylenedianiline etc.)] etc.

Polyether-containing hydrophilic polymer (b2)
Of Mn is 800 or more, especially 1.00 from the viewpoint of heat resistance.
0 or more is preferable, and polyolefins (a4) to (a6)
50,000 or less, especially 30,0 from the viewpoint of reactivity with
00 or less is preferable. Among the above (b2), from the viewpoint of antistatic property and heat resistance, polyether ester amide (b
2-1) is preferable.

Specific examples of the anionic polymer (b3) and a method for producing the anionic polymer (b3) include a specific example of an "anionic polymer" described in International Publication WO00 / 47652 and a method for producing the same [however, the polyoxyalkylene of this document is used. At least a part of the alkylene structure-having moiety is a substituted alkylene group represented by the general formula (1), and the rest is replaced with a group which may be an alkylene group having 2 to 4 carbon atoms. ] Is mentioned.

The Mn of (b3) is preferably 500 to 20,000, more preferably 1,0 from the viewpoints of antistatic property and reactivity with the polyolefins (a1) to (a3).
00 to 15,000, particularly preferably 1,200 to 8,
It is 000. From the viewpoint of antistatic properties and reactivity with the polyolefins (a1) to (a3), the (b3) preferably has 2 to 80 sulfonyl groups in the molecule, and has 3 to 60 sulfonyl groups. More preferred are:

Mn of the block polymer (A) of the present invention
Is 2,000 to 60,000 from the viewpoint of antistatic property.
Is preferable, and more preferably 5,000 to 40,000.
0, particularly preferably 8,000 to 30,000.

As an embodiment of the present invention, a block polymer (A1) having a structure in which blocks of a polyolefin (a) and blocks of a hydrophilic polymer (b) are repeatedly and alternately bonded will be described. (A1) includes a polymer having a repeating unit represented by the following general formula (3).

[0049]

[Chemical 5]

[0050]

[Chemical 6]

[0051]

[Chemical 7]

[In the general formula (3), ^one of R ¹ and R ² is H, the other is H or an alkyl group having 1 to 10 carbon atoms; E ¹ is a divalent hydroxyl group-containing compound (b0) from which a hydroxyl group is excluded. A residue; X and X ′ are groups selected from the groups represented by the above general formulas (4) to (10) and the corresponding general formulas (4 ′) to (1
0 ') is a group selected from the groups represented by the formula (4'), that is, when X is a group represented by the formula (4)
And the same relations with respect to the general formulas (5) to (10) and the general formulas (5 ′) to (10 ′);
A ² is a substituted alkylene group at least a part of which is represented by the general formula (1), and the rest may be an alkylene group having 2 to 4 carbon atoms; y is 15 to 800, m and m ′ are 1
To 300 and n are integers of 2 to 50 respectively; in the general formulas (4) to (10) and (4 ′) to (10 ′), R ³ ,
R ³ 'is a C 2 to C ³ trivalent hydrocarbon group, R ⁴ is a C 1 to C 11 divalent hydrocarbon group, and R ⁵ is H or C 1 to C 1.
10 alkyl groups, R ⁶ is a divalent hydrocarbon group having 2 to 22 carbon atoms; E ² is an organic diisocyanate residue; A ³ is an alkylene group having 2 to 4 carbon atoms; r is 1 to 10, u, v Is 0 or 1 respectively; Q, Q ′, T and T ′ are each of the general formula (1
1), (11 ′), (12) and (12 ′), and in each formula, R ⁷ is H or a methyl group. ]

Polyether segment {(OA ² ) _m --O-- in {} in the repeating unit represented by the general formula (3).
E ¹ —O— (A ² O) _{m ′} } is the polyether (b1)
Of the polyether moiety of E ¹ , A ² ,
m and m ′ are the same as above.

In the general formula (3), X is the general formula (4).
The block polymer (A1) in which X'is a group represented by the general formula (4 ') comprises the above-mentioned carbonyl group-containing polyolefin (a1-1) and polyether diol (b1-1). It can be obtained by direct reaction. Formula (4) and (4 ') R ³ and R ^3' in the formula R ³ formed from unsaturated dicarboxylic ^{acids: -CHR 9 -CH <R 3 '} :> CH-CHR 9 - (R ⁹ is H or a methyl group.) For example, when maleic acid or fumaric acid is used for carbonyl modification of polyolefin, R ³ is —CH ₂ —CH.
<And R ³ 'is> CH-CH _2- .

The method for producing the block polymer (A1) is not particularly limited, but (a1-1) and (b1-
It can be produced by a method of adding 1) and conducting a polymerization (polycondensation) reaction at 200 to 250 ° C. under reduced pressure. In addition, a known catalyst can be usually used in the above polymerization reaction. As the catalyst, a protic acid such as phosphoric acid;
Alkali metal, alkaline earth metal, Group IVA metal, VA
Group metals and transition metals (IIB group, IVB group, VB group, etc.)
Organic acid (having 1 to 15 carbon atoms) salts, carbonates, sulfates, phosphates, oxides, chlorides, hydroxides and alkoxides; and a combination of two or more of these, among which preferred Are organic acid salts, carbonates, sulfates of Group IVA metals, Group VA metals and transition metals (Groups IIB, IVB),
Phosphates, oxides, chlorides, hydroxides and alkoxides; and combinations of two or more of these, more preferably tin catalysts (monobutyltin oxide etc.), antimony catalysts (antimony trioxide etc.), titanium catalysts [ Titanic acid ester (tetrabutyl titanate, etc.), zirconium catalyst [zirconium hydroxide (zirconic acid), zirconate ester (tetrabutyl zirconate, etc.) and zirconium organic acid salt (zirconyl acetate, etc.)], IIB
Group metal organic acid salt catalyst [metal acetate metal salt (zinc acetate, etc.)] and a combination of two or more thereof, more preferably a zirconium catalyst and a IIB metal acetate catalyst, and particularly preferably a zirconium organic acid salt and Metal acetate, most preferably zirconyl acetate. The amount of catalyst used is
It is usually 0.001 to 5%, preferably 0.01 to 3%, and more preferably 0.1 to 1% with respect to the total weight of (a1-1) and (b1-1).

In the general formula (3), X is the general formula (5).
And a block polymer (A1) having a group represented by the formula (5 ′) in which X ′ is represented by the general formula (5 ′) includes (a1-1) and (b1)
It can be obtained by directly reacting with -2).

In the general formula (3), X is the general formula (6).
The block polymer (A1) in which X'is a group represented by the general formula (6 ') can be obtained by directly reacting (a1-2) with (b1-1). . The polymerization reaction of (a1-2) and (b1-1) is
It can be carried out by the same method as the polymerization reaction of (a1-1) and (b1-1).

In the general formula (3), X is the general formula (7).
The block polymer (A1) in which X'is a group represented by the general formula (7 ') can be obtained by directly reacting (a1-2) with (b1-2). . In addition, after (b1-2) is secondarily modified with the lactam or aminocarboxylic acid, this and (a1-
It may be produced by reacting with 1). These polymerization reactions can be performed by the same method as the polymerization reaction of (a1-1) and (b1-1).

In the general formula (3), X is the general formula (8).
And the block polymer (A1) in which X ′ is a group represented by the general formula (8 ′) has (a1-3) (r
= 1) or (a1-4) (when r ≧ 2),
It can be obtained by reacting with (b1-1) (when u = 0) or polyether diamine (b1-2) (when u = 1). (A1-3) or (a1-4)
And the polymerization reaction of (b1-1) or (b1-2),
It can be carried out by the same method as the polymerization reaction of (a1-1) and (b1-1).

In the general formula (3), X is the general formula (9).
And a block polymer (A1) in which X ′ is a group represented by the general formula (9 ′),
(B1-1) (when u = 0) or (b1-2) (u =
And (in the case of 1) are bound via an organic diisocyanate, and they can be obtained by reacting them simultaneously or sequentially. As a method of sequentially reacting, for example, after reacting (a2-1) with an organic diisocyanate to obtain an isocyanate-modified polyolefin,
It can be obtained by reacting this with (b1-1) or (b1-2).

In the general formula (3), X is the general formula (1
0) and a block polymer (A1) in which X ′ is a group represented by the general formula (10 ′),
3) (when v = 0) or (a2-2) (when v = 1) and (b1-1) or (b1-2) are bound via an organic diisocyanate, These can be obtained by reacting them simultaneously or sequentially. As a method of sequentially reacting, for example, (a1-3) or (a2-2) is reacted with an organic diisocyanate to obtain an isocyanate-modified polyolefin, and then this is reacted with (b1-1) or (b1-2). Can be obtained. Reaction of (a2-1) or (a2-2) with an organic diisocyanate, (b1-1) or (b1)
-2) with an organic diisocyanate, and with an isocyanate-modified polyolefin (b1-1) or (b1-)
The reaction with 2) can be carried out in the same manner as in the usual urethanization or urea formation reaction.

When forming the isocyanate-modified polyolefin, the equivalent ratio (NCO / OH ratio) of the organic diisocyanate and (a2-1) or (a2-2), and the isocyanate-modified polyolefin and (b1-1) or (b).
The equivalent ratio to 1-2) (NCO group / OH group ratio or NCO group / amino group) is usually 1.8 / 1 to 3/1, preferably 2/1. Examples of the organic diisocyanate include those similar to the above-mentioned (Q4), and the reaction conditions can be the same as those in the above-mentioned production method (b2-5).

Among the block polymers (A1) having the repeating unit represented by the general formula (3), those in which X is represented by the general formulas (4) and (6) are preferable, and the preferable one is the general formula ( 6). The amount of the polyether (b1) constituting the block polymer (A1) is usually 20 to 90%, preferably 25 to 90%, particularly preferably 30 to, based on the total weight of (a1) and (b1). 70%. The amount of (b1) within this range is more preferable from the viewpoint of antistatic property. The Mn of (A1) is usually 2,000 to 60,000, preferably 5,000 to 40,000, and particularly preferably 8,000.
~ 30,000. Those having Mn in this range are particularly excellent in antistatic performance.

In the structure of the block polymer (A1), the average repeating number (Nn) of repeating units of the block of the polyolefin (a) and the block of the hydrophilic polymer (b) is usually 2 to 50, preferably 2. 3-30,
More preferably 2.7 to 20, particularly preferably 3-1.
It is 0. Nn in this range is preferable from the viewpoint of antistatic property. Nn is Mn of (A1) and 1H-NM
It can be determined by R analysis. For example, (a1-
The case of (A1) having a structure in which the block of 1) and the block of (b1-1) are alternately and repeatedly bonded will be described. In 1 H-NMR analysis, 4.0 to 4.1.
ppm ester bond {-C (C = O) -OCH2-}
Signal attributed to the protons of, and 3.2-3.7
A signal attributed to ppm of polyethylene glycol protons can be observed. By calculating the ratio of these proton integral values, Nn can be calculated from this ratio and Mn. Nn can be obtained in the same manner even when the other blocks (a) and (b) are used.

Both ends of (A1) are polyether (b
1) any one selected from a hydroxyl group, an amino group, an isocyanate group and an epoxy group, a carbonyl group derived from a polyolefin (a1), an amino group, a hydroxyl group, an isocyanate group, an alkyl group, an alkenyl group and an isocyanate group derived from an organic diisocyanate. It has a terminal group.

Next, the block polymer (A2) will be described as the second embodiment of the present invention. (A
In 2), the block of polyolefin (a) and the block of hydrophilic polymer (b) are (a)-(b) type or (a).
It is a block polymer formed by bonding in a-(b)-(a) type. (A2) is the same as (b2) and the following general formula (14).
It can be obtained by a reaction with a polyolefin (a4) having a carbonyl group represented by any one of to (16) at one end of the polymer.

[0067]

[Chemical 8]

In the formula, R ¹⁰ is a polyolefin residue, Q ′ is a group represented by the formula —CH (R ¹² ) —CH═C (R ¹² ) —CH ₂ —, and R ¹¹ is a group having 2 to 3 carbon atoms. Valent hydrocarbon radical, R ¹²
Is H or an alkyl group having 1 to 10 carbon atoms, and R ¹³ is H or a methyl group. As (A2), one or both of the terminals of (b2) are replaced with a group represented by the following general formulas (17) to (19) {when the terminal of (b2) is a hydroxyl group or an epoxy group}. Structures (bonded via an ester bond); Structures in which the groups represented by the general formulas (20) to (22) {when the terminal of (b2) is an amino group or an isocyanate group} are replaced (amide bond) And a group represented by the general formula (23) {when the terminal of (b2) is an amino group} (bonded via an imide bond).

[0069]

[Chemical 9]

The symbols in the formula are the same as in formulas (14) to (16).

The block polymer (A2) can be produced by reacting (a4) to (a6) with (b2), or in the process of producing (b2), for example, in the presence of (a4) (b2). Of the block polymer (A) together with the formation of the block of the polymer (b2) by reacting the precursor (reaction raw material) of
2) and the like. When (b2) is a polyether ester amide (b2-1), the following production methods are specifically exemplified, but are not particularly limited. Further, the block polymer (A2) in which (b2) is a polymer segment other than the polyether ester amide (b2-1) can also be produced by the same method. Production method 1: A method of carrying out a polymerization reaction of (a4-1) and polyether ester amide (b2-1) at 200 to 250 ° C. under reduced pressure. Production method 2: A method in which (a4-1), (Q1), and (b2-1) are subjected to a polymerization reaction under reduced pressure at 200 to 250 ° C. Production method 3: 180 to 250 ° C. in the presence or absence of water
(A4-1) in (Q)
1) is formed, (b2-1) is added thereto, and the polymerization reaction is carried out at 200 to 250 ° C. under reduced pressure. Production Method 4: (a4-1), (Q1), and (b2-1)
A method of performing pressure reaction at 180 to 250 ° C. in the presence or absence of water, and then performing a polymerization reaction at 200 to 250 ° C. under reduced pressure.

In addition, a known catalyst can be usually used in the above polymerization reaction. As the catalyst, the same catalysts as those exemplified as the polymerization catalyst in the method for producing the block polymer (A1) can be used. The amount of the catalyst used is the reaction product to be reacted (for example, in the case of the production method 1, (a4
-1) and (b2-1)} based on the total weight, usually 0.001 to 5% by weight, preferably 0.01 to 3% by weight, more preferably 0.1 to 1% by weight.

Constituting the block polymer (A2) (b
The amount of 2) is usually 20 to 8 based on the weight of (A2).
It is 0% by weight, preferably 30 to 70% by weight from the viewpoint of antistatic properties and compatibility with the thermoplastic resin described later. The Mn of (A2) is usually 2,000 to 60,000.
It is 0, preferably 5,000 to 40,000. In the structure of the block polymer (A2), the average repeating number (Nn) of repeating units of the block of the polyolefin (a) and the block of the hydrophilic polymer (b) is usually 0.4 to 2.1, preferably 0. .5 to 2.0, more preferably 0.6 to 1.9, and particularly preferably 0.7 to 1.
8 Nn in this range is preferable from the viewpoint of antistatic property. This Nn can be determined by Mn and (1H-NMR) analysis of (A2) in the same manner as in (A1).

Next, a block polymer (A3) will be described as a third embodiment of the present invention. (A3)
Is, as (b), a dicarboxylic acid (e1) having a sulfonyl group and a polyether (b1) as essential constituent units, and preferably 2 to 80, more preferably 3 to 60 sulfonyl in the molecule. It has a block of an anionic polymer (b3) having a group, and has a structure in which (a) and (b3) are repeatedly and alternately bonded. (A
3) can be obtained by a polymerization reaction of (b3) and (a1) to (a3), and can be produced by the same method as the above-mentioned polymerization reaction of (a1) and (b1-1). . In addition, if necessary, the (b3) and the (b1-1) may be used together in an arbitrary ratio (for example, a weight ratio of 1: 9 to 9: 1). Mn of (A3) is usually 2,000 to 60,000.
It is 0, preferably 5,000 to 40,000, and particularly preferably 8,000 to 30,000. Within this range, the antistatic property is excellent. The content of the sulfonyl group in (A3) is preferably 2 to 5 per (A3) molecule.
The number is 00, more preferably 10 to 300, and particularly preferably 15 to 250. Within this range, the antistatic property is preferable. The Mn of (A3) per one sulfonyl group is preferably 120 to 30,000, more preferably 200 to 6,000, and particularly preferably 300 to.
It is 4,000.

In the structure of the block polymer (A3), the average repeating number (Nn) of repeating units of the block of the polyolefin (a) and the block of the hydrophilic polymer (b) is usually 2 to 50, preferably 2. 3-30,
More preferably 2.7 to 20, particularly preferably 3-1.
It is 0. Nn in this range is preferable from the viewpoint of antistatic property. This Nn can be determined by Mn of (A3) and 1H-NMR analysis in the same manner as in (A1).

In the antistatic agent containing the block polymer (A) of the present invention, the above (A1), (A2) and (A3) can be used alone, respectively.
You may use it combining each in arbitrary compositions.
The antistatic agent of the present invention containing (A) can impart antistatic properties to the thermoplastic resin (B) by blending it with the resin. As the thermoplastic resin (B),
For example, polyolefin resin (B1), polystyrene resin (B2), acrylic resin (B3), vinyl resin such as rubber-like (co) polymer (B4), polyamide resin (B
5), polyester resin (B6), polyacetal resin (B7), polycarbonate resin (B8), thermoplastic polyurethane resin (B9), fluororesin (B10), and a mixture of two or more thereof. Examples of the vinyl resin include resins obtained by (co) polymerizing the following vinyl monomers by known polymerization methods (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.).

Examples of vinyl monomers include aliphatic hydrocarbon vinyl monomers, aromatic vinyl monomers, acrylic monomers, other unsaturated mono- and dicarboxylic acids and their derivatives, carboxylic acid esters of unsaturated alcohols, alkyl ethers of unsaturated alcohols. , Halogen-containing vinyl monomers and combinations of two or more of these (random and / or block). As the aliphatic hydrocarbon vinyl monomer, for example, ethylene, propylene, an α-olefin having 4 to 30 carbon atoms (1-butene,
Olefins such as 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, etc., and dienes having 4 to 30 carbon atoms (alkadienes such as butadiene and isoprene, cycloalkenes such as cyclopentadiene). Diene). Examples of the aromatic vinyl monomer include styrene and its homologues such as o- and m-.
And p-alkyl (having 1 to 10 carbon atoms) styrene (such as vinyltoluene), α-alkyl (having 1 to 10 carbon atoms)
Examples thereof include styrene (for example, α-methylstyrene) and halogenated styrene (for example, chlorostyrene) (hereinafter abbreviated as styrenes).

Examples of the acrylic monomer include (meth) acrylic acid and its derivatives. (Meta)
As the derivative of acrylic acid, for example, alkyl (C 1-20) (meth) acrylate {for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.}, mono- and di-alkyl (carbon Number 1 to 4) aminoalkyl (carbon number 2 to 4)
(Meth) acrylate (for example, aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.), (meth) acrylonitrile, (meth) acrylamide and the like can be mentioned. Other unsaturated mono- and dicarboxylic acids include, for example, crotonic acid, maleic acid, fumaric acid, itaconic acid, and the like, and derivatives thereof include, for example, mono- and di-alkyl (having 1 carbon atom).
To 20) esters, acid anhydrides (such as maleic anhydride) and imides (such as maleic acid imide). As the unsaturated alcohol ester, vinyl alcohol,
Carboxylic acid such as (meth) allyl alcohol (having 2 to 2 carbon atoms)
4) Esters (vinyl acetate, etc.) are mentioned, and as ethers of unsaturated alcohols, alkyl (C 1-20) such as vinyl alcohol, (meth) allyl alcohol, etc.
An example is ether. Examples of the halogen-containing vinyl monomer include vinyl chloride, vinylidene chloride, chloroprene and the like.

The polyolefin resin (B1) contains the above-mentioned olefin monomers (ethylene, propylene, carbon number 4 to 4).
One or more (co) polymers of 30 α-olefins) and one or more vinyl monomers copolymerizable with one or more of the above olefin monomers (weight ratio; usually 5 / 95-9).
5/5, preferably 50/50 to 90/10). As the copolymerizable vinyl monomer, the above-mentioned monomers other than olefin, for example, vinyl ester, acrylic monomer [alkyl (C1-20)
(Meth) acrylate, acrylonitrile and the like], and aromatic vinyl monomers (styrene and the like). (B
Specific examples of 1) include polypropylene, polyethylene, a copolymer of propylene and ethylene, a copolymer of propylene and / or ethylene and at least one other α-olefin (random and / or block), ethylene / Examples thereof include vinyl acetate copolymer resin (EVA) and ethylene / ethyl acrylate copolymer resin (EEA). (B
Preferred specific examples of 1) are (co) polymers of propylene and / or ethylene, copolymers of propylene and / or ethylene with at least one α-olefin having 4 to 12 carbon atoms (random and / or random). Block, weight ratio 9: 1 ~
1: 9).

Melt flow rate (MFR) of (B1)
Is usually 0.5 to 150, preferably 1 to 100. The melt flow rate is JISK6758 (for polypropylene resin; temperature 230 ° C, load 2.16 kg)
f, polyethylene resin; temperature 190 ° C., load 2.
It can be measured according to 16 kgf). (B1)
Has a crystallinity of usually 25% to 90%, preferably 30%
~ 70%. The crystallinity can be measured by methods such as X-ray diffraction and infrared absorption spectrum [Hatsugoro Minamishino, "Solid Structure of Polymers-Polymer Experimental Course 2", p4
2. Kyoritsu Publishing (1958)].

As the polystyrene resin (B2), one or more (co) polymers of the above-mentioned aromatic vinyl monomers (such as the above-mentioned styrenes) and one of vinyl monomers copolymerizable with one or more of these monomers are used. Seed or more (weight ratio; usually 5
/ 95 to 95/5, preferably 50/50 to 90/1
0) and a copolymer thereof. Examples of the copolymerizable vinyl monomer include the above-mentioned monomers other than the aromatic vinyl monomer, for example, vinyl ester, acrylic monomer [alkyl (C1-20) (meth) acrylate, acrylonitrile, etc.], diene, halogen-containing vinyl monomer and the like. Can be mentioned. Specific examples of (B2) include polystyrene, polyvinyltoluene and the like; copolymers of styrenes and one or more monomers selected from the group consisting of methyl methacrylate, acrylonitrile and butadiene, for example, styrene / acrylonitrile copolymer. Polymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS
Resin), styrene / methyl methacrylate / acrylonitrile copolymer, methyl methacrylate / butadiene / styrene copolymer (MBS resin), styrene / butadiene copolymer and the like.

The acrylic resin (B3) includes at least one (co) of the above-mentioned acrylic monomers [alkyl (C1-20) (meth) acrylate, acrylonitrile, etc.].
Polymers (eg polymethylmethacrylate, polybutyl acrylate, etc.) and one or more vinyl monomers copolymerizable with one or more of these monomers (weight ratio usually 5/95
˜95 / 5, preferably 50/50 to 90/10). Examples of the copolymerizable vinyl monomer include the above-mentioned monomers other than the acrylic monomer, such as vinyl ester, diene, and halogen-containing vinyl monomer. Examples of the rubbery (co) polymer (B4) include diene (co) polymers such as polybutadiene, polyisoprene, polychloroprene, ethylene / propylene / butadiene copolymers, acrylonitrile / butadiene copolymers and the like.

As the polyamide resin (B5), nylon 66, nylon 69, nylon 610, nylon 61
2, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12 and the like. Examples of the polyester resin (B6) include aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, and aliphatic polyesters such as polybutylene adipate, polyethylene adipate, and poly-ε-caprolactone. As the polyacetal resin (B7), a homopolymer of formaldehyde or trioxane, for example, a polyoxymethylene homopolymer, and formaldehyde or trioxane and a cyclic ether (the above-mentioned alkylene oxides such as ethylene oxide, propylene oxide, dioxolane, etc.)
And a polyoxymethylene / polyoxyethylene copolymer (polyoxymethylene / polyoxyethylene weight ratio 90 to 99/1 to 10 block copolymer). Examples of the polycarbonate resin (B8) include a polycarbonate having a bisphenol skeleton, for example, a condensate of bisphenol A and phosgene and a condensate of bisphenol A and a carbonic acid diester.

Examples of the thermoplastic polyurethane resin (B9) include the organic diisocyanate, a polymer diol [a diol having a molecular weight of 500 to 5,000, such as the polyether diol (b1-1), a polyester diol (the diol and / or Polyether diol (b1
-1) and a dicarboxylic acid (anhydride) [as described in (a1-1) above] or a polyester diol obtained by reacting with said lactone), vinyl monomers (eg acrylonitrile and / or styrene) in these diols. A polymer polyol or the like obtained by polymerizing the above), a chain extender [for example, the divalent hydroxyl group-containing compound (b0) and / or the diamine described in (a3) above and optionally a reaction terminator (monohydric alcohol, 1 Polyurethanes obtained by reacting primary or secondary monoamines, mono- or dialkanolamines, etc.) by the one-shot method or the prepolymer method. As the fluororesin (B10), a fluorine-containing monomer, for example, a fluorinated olefin containing 2 to 10 carbon atoms and 1 to 20 fluorine atoms (tetrafluoroethylene, hexafluoropropylene, perfluorohexylethylene, etc.), fluorinated Alkyl (C1-C1
0) One or more (co) polymers of (meth) acrylate [perfluorohexylethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, etc.].

Of these, preferred are (B1),
(B2) and (B1) in combination with at least one resin selected from (B5), (B6) and (B7). In a preferred embodiment of the present invention, the amount of the resin (BB) used in combination with (B1) is (from the viewpoint of more effectively exhibiting the antistatic property of the block polymer (A) and the moldability of the resin ( B1) 1
It is preferable to use (BB) in combination at a ratio of 1 to 20 parts, especially 3 to 15 parts per 00 parts. Among (BB) used in combination with (B1), preferred are nylon 6, polybutylene terephthalate, polyethylene terephthalate and polyacetal.

The melting peak temperature (melting point) of (BB) by DSC (differential scanning calorimetry) is the point of antistatic property [block polymer (A) is easily oriented to the surface of the resin molded product] and the kneading of the resin. From the point of easiness of, usually 140-270
C, preferably 150 to 260 C, particularly preferably 16
It is 0-240 degreeC. Also, the intrinsic viscosity [η] of (BB)
(In the case of polyacetal resin, in parachlorophenol 0.5% solution, 60 ° C, in the case of polyester resin, orthochlorophenol 0.5% solution, 25 ° C, in the case of polyamide resin, orthochlorophenol 0.5% solution There is no particular limitation on the temperature of the medium (25 ° C.), but it is usually 0.1 to 4.

Mn of the thermoplastic resin (B) is usually 20,
It is 000 to 500,000. The amount of (A) to be blended with (B) can be variously changed according to the required performance, but from the viewpoint of imparting sufficient antistatic property and mechanical strength, the amount of (A) and (B) Based on total weight
0.5-40%, especially 1-30% is preferable. The amount of (B) in the resin composition is preferably 60 to 99.5%, particularly preferably 70 to 99%, based on the total weight of (A) and (B).
At the time of compounding, a resin composition (masterbatch) containing (A) in a high concentration [for example, 10 to 80% based on the total weight of (A) and (B)] may be formed.

In the resin composition of the present invention, particularly (A)
And a thermoplastic resin (B) other than the polyolefin resin (B1) for the purpose of improving compatibility with the compatibilizing agent (E)
May be included. Note that (E) may be contained in the antistatic agent containing (A). As (E), a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group, specifically, For example, JP-A-3-258
The polymers described in JP-A-850 can be mentioned. Further, for example, a modified vinyl polymer having a sulfonyl group and a block polymer having a polyolefin portion and an aromatic vinyl polymer portion described in JP-A-6-345927 can be used. When (E) is used, the amount of (E) used is usually 0.1 to 15%, preferably 1 to 10% based on the total weight of (A) and (B) from the viewpoint of resin physical properties. is there.

The resin composition of the present invention may contain a salt (C) of an alkali metal and / or an alkaline earth metal for the purpose of further improving the antistatic property. Note that (C) may be contained in the antistatic agent containing (A). As (C), alkali metals (lithium, sodium, potassium, etc.) and / or alkaline earth metals (magnesium, calcium, etc.)
Organic acids (mono- and dicarboxylic acids having 1 to 12 carbon atoms,
For example, formic acid, acetic acid, propionic acid, oxalic acid, succinic acid and the like; sulfonic acid having 1 to 20 carbon atoms, such as methanesulfonic acid, fluorosulfonic acid, fluoroalkane (methane, ethane, butane, pentane, hexane, etc.) sulfonic acid, Examples thereof include salts of p-toluenesulfonic acid and the like; thiocyanic acid and the like, and salts of inorganic acids (hydrohalic acid, such as hydrochloric acid, hydrobromic acid; perchloric acid; sulfuric acid; phosphoric acid; thiocyanic acid and the like).

Specific examples of (C) include organic acid salts (lithium acetate, sodium acetate, potassium acetate, lithium oxalate, sodium oxalate, potassium oxalate, etc.);
Halide (lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, odor Magnesium iodide, calcium bromide, lithium iodide, sodium iodide, potassium iodide, magnesium iodide, calcium iodide, etc .; perchlorates (lithium perchlorate, sodium perchlorate, potassium perchlorate, periolate) Magnesium chlorate, calcium perchlorate, etc .; Fluorosulfonates (lithium fluorosulfonate, sodium fluorosulfonate, potassium fluorosulfonate, magnesium fluorosulfonate,
Calcium fluorosulfonate, etc.); Methanesulfonate (lithium methanesulfonate, sodium methanesulfonate, potassium methanesulfonate, magnesium methanesulfonate, calcium methanesulfonate, etc.); Fluoroalkanesulfonate (lithium trifluoromethanesulfonate) , Sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, lithium pentafluoroethanesulfonate, sodium pentafluoroethanesulfonate, potassium pentafluoroethanesulfonate, pentafluoroethanesulfone Magnesium acid, Calcium pentafluoroethanesulfonate, Lithium nonafluorobutanesulfonate , Sodium nonafluorobutane sulfonate, potassium nonafluorobutane sulfonate, magnesium nonafluorobutane sulfonate, calcium nonafluorobutane sulfonate, lithium undecafluoropentane sulfonate, sodium undecafluoropentane sulfonate, undecafluoropentane sulfonate Potassium acid, magnesium undecafluoropentanesulfonate, calcium undecafluoropentanesulfonate, lithium tridecafluorohexanesulfonate, sodium tridecafluorohexanesulfonate,
Potassium tridecafluorohexanesulfonate, magnesium tridecafluorohexanesulfonate, calcium tridecafluorohexanesulfonate, etc.); Sulfate (potassium sulfate, sodium sulfate, etc.); Phosphate (potassium phosphate, sodium phosphate, etc.) ; Thiocyanates (potassium thiocyanate, sodium thiocyanate, etc.)
Etc. Of these, preferred are alkali metal salts, more preferred are alkali metal halides (especially lithium chloride, sodium chloride, potassium chloride), acetates (especially potassium acetate), perchlorates (especially perchloric acid). Lithium, sodium perchlorate, potassium perchlorate) and fluoroalkane sulfonates (particularly lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate).

When (C) is used in combination, the amount of (C) used is usually 0.001 to 3% based on the weight of (A) from the viewpoint of giving a resin having a good appearance without depositing on the resin surface. , Preferably 0.01 to 2%. The method of adding (C) is not particularly limited, but it is preferable to disperse it in the block polymer (A) in advance, because it is easy to effectively disperse it in the composition. Also, into (A) into (C)
In the case of dispersing (C), it is particularly preferable that (C) is added and dispersed in advance during the production (polymerization) of (A).

Further, the antistatic resin composition of the present invention may contain a nonionic, anionic, cationic or amphoteric surfactant (D) to further improve the antistatic property. Note that (D) may be contained in the antistatic agent containing (A).

Examples of the nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts and the like; Polyethylene oxide, fatty acid ester of glycerin, fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, polyhydric alcohol type nonionic surfactant such as aliphatic amide of alkanolamine, and the like. .

As the anionic surfactant, compounds other than (C) can be used. For example, carboxylic acid salts such as alkali metal salts of higher fatty acids; sulfuric acid such as higher alcohol sulfuric acid ester salts and higher alkyl ether sulfuric acid ester salts. Sulfonates such as ester salts, alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates;
Examples thereof include phosphate ester salts such as higher alcohol phosphate ester salts.

Examples of the cationic surfactant include quaternary ammonium salts such as alkyl trimethyl ammonium salts. Examples of the amphoteric surfactant include amino acid type amphoteric surfactants such as higher alkylaminopropionate, and betaine type amphoteric surfactants such as higher alkyldimethyl betaine and higher alkyldihydroxyethyl betaine. These may be used alone or in combination of two or more. Of these, preferred are anionic surfactants, and particularly preferred are sulfonates such as alkylbenzene sulfonate, alkyl sulfonate, and paraffin sulfonate.

When (D) is used, the amount of (D) used is usually 0.00 based on the total weight of (A) and (B).
It is 1 to 5%, preferably 0.01 to 3%. The method of adding (D) is not particularly limited, but it is preferable to disperse it in (A) in advance in order to effectively disperse it in the resin composition. When (D) is dispersed in (A), it is particularly preferable to add (D) and disperse it in advance during the production (polymerization) of (A).

Further, the resin composition of the present invention may optionally contain a known polymer type antistatic agent such as polyetheresteramide. The known polymer antistatic agent may be contained in the antistatic agent containing (A) of the present invention. As the polymer type antistatic agent, polyether ester amide, for example, JP-A-7-
Examples thereof include polyether ester amides composed of polyoxyalkylene adducts of bisphenol A described in JP-A-10989. The amount of polymeric antistatic agent used is
Usually 0 to 40% with respect to the total weight of (A) and (B),
It is preferably 1 to 30%, particularly preferably 5 to 20%.

Further, to the resin composition of the present invention, other additives for resins can be optionally added within a range not impairing the characteristics of the composition according to various uses. The other resin additives may be contained in the antistatic agent containing (A) of the present invention.

Other resin additives include pigments, dyes,
Examples include fillers, nucleating agents, lubricants, plasticizers, release agents, antioxidants, flame retardants, ultraviolet absorbers and antibacterial agents.

Examples of the pigment include inorganic pigments [white pigments (titanium oxide, lithopone, lead white, zinc white, etc.), cobalt compounds (aureoline, cobalt green, cerulean blue, cobalt blue, cobalt violet, etc.), iron compounds (iron oxide. , Dark blue, etc.), chromium compounds (chromium oxide, lead chromate, barium chromate, etc.), sulfides (cadmium sulfide, cadmium yellow, ultramarine, etc.)], organic pigments [azo pigments (azo lake, monoazo, disazo) Type, chelate azo type, etc.), polycyclic pigments (benzimidazolone type, phthalocyanine type, quinacridone type, dioxane type, isoindolinone type, thioindigo type, perylene type, quinophthalone type, anthraquinone type, etc.)]; as a dye Is azo, anthraquinone, indigo Dedo, sulfide, triphenylmethane, pyrazolone, stilbene, diphenylmethane, xanthene, alizarin, acridine, quinoneimine, thiazole, methine, nitro, nitroso, aniline, etc. .

As the filler, talc, mica, calcium carbonate, clay, silicic acid (salt), asbestos, glass fiber, glass balloon, carbon fiber, metal fiber, ceramic whisker, titanium whisker, carbon nanotube, etc .; as a nucleating agent Is sorbitol, dibenzylidene sorbitol, benzoic acid metal salt (alkali metal salt such as sodium benzoate); lubricants are hydrocarbon-based [liquid paraffin, natural paraffin, paraffin wax, microwax, polyolefin wax (polyethylene wax, etc.) Etc.], fatty acid-based [higher fatty acids (C12 to C20, for example, stearic acid, oleic acid),
Oxy fatty acids and their salts (calcium stearate, barium stearate, lead stearate, etc.), etc.],
Fatty acid amide type (stearic acid amide, oleic acid amide, palmitic acid amide, methylenebisstearylamide, etc.), ester type [fatty acid lower alcohol ester (butyl stearate, etc.), fatty acid polyhydric alcohol ester (hardened castor oil, etc.), fatty acid Glycol ester (ethylene glycol monostearate, etc.)].

As the plasticizer, phthalic acid ester, phosphoric acid ester, toluenesulfonamide, adipic acid ester, sebacic acid ester, glycolic acid ester, etc .; as the releasing agent, straight silicone oil (dimethylpolysiloxane, methylphenylpolyester) is used. Siloxane) and organic modified silicone oil (silicone oil having polyoxyalkylene group, hydroxyl group, amino group, epoxy group, carboxyl group, mercapto group, etc.),
Paraffin wax, polyolefin wax, etc .; as antioxidants, hindered phenol-based [2,6-di-t-butyl-p-cresol (BHT), 2,2'-
Methylenebis (4-methyl-6-t-butylphenol), tetrakis [methylene- (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane [trade name Irganox 1010: Ciba Geigy Corporation]
]], Sulfur-based [dilauryl 3,3′-thiodipropionate (DLTDP), distearyl 3,3′-thiodipropionate (DSTDP), etc.], phosphorus-based [triphenylphosphite (TPP), Triisodecyl phosphite (TDP) etc.], amine-based [octyldiphenylamine, Nn-butyl-p-aminophenol, N,
N-diisopropyl-p-phenylenediamine and the like] and the like.

As flame retardants, halogen flame retardants (decabromobiphenyl ether, tetrabromobisphenol A, het acid, etc.), phosphate ester flame retardants [tricresyl phosphate, tris (2,3-dibromopropyl) phosphate] Etc.], antimony flame retardants (antimony trioxide etc.), metal hydroxide flame retardants (magnesium hydroxide, aluminum hydroxide etc.), borate flame retardants (zinc borate, barium metaborate etc.), red Phosphorus, ammonium polyphosphate, etc .; UV absorbers include benzophenone-based (2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, etc.), salicylate-based (phenyl salicylate, 2,4-di-t-butylphenyl-)
3,5-di-t-butyl-4-hydroxybenzoate, etc.), benzotriazole-based [(2′-hydroxyphenyl) benzotriazole, (2′-hydroxy-
5'-methylphenyl) benzotriazole, etc.], acrylic [ethyl-2-cyano-3,3'-diphenylacrylate, methyl-2-carbomethoxy-3- (paramethoxybenzyl) acrylate, etc.], hindered amines, etc. Can be mentioned.

As antibacterial agents, isothiazolone compounds, halogenated aliphatic nitro compounds (2-bromo-2-
Nitro-1,3-propanediol, 2,2-dibromo-2-nitroethanol, etc.) and their esters,
Dibromonitrile propionamide, alkylenebisthiocyanate (methylenebisthiocyanate, etc.), 1,
4-bisbromoacetoxy-2-butene, hexabromodimethyl sulfone, isophthalonitrile compound (5-chloro-2,4,6-trifluoroisophthalonitrile,
Tetrachloroisophthalonitrile etc.), dimethyldithiocarbamate, 4,5-dichloro-1,2-diol-
3-one, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, triiodoallyl alcohol, bromonitrostyrene, aldehyde compounds (glutaraldehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, etc.), dichloro Glyoximes, benzaldoxime compounds (α-chlorobenzaldoxime, α-chlorobenzaldoxime acetate, etc.), halogenated hydantoin compounds (1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5) , 5-dimethylhydantoin, etc.) and the like.

The amount of the other resin additives used is (A)
Based on the total weight of (B) and (B), the filler is usually 50% or less, preferably 5 to 30%; the pigment, the dye, the flame retardant, and the plasticizer are usually 30% or less, preferably 5 to 25%;
The antibacterial agent is usually 10% or less, preferably 0.5 to 5%; the nucleating agent, the lubricant, the release agent, the antioxidant and the ultraviolet absorber are each usually 5% or less, preferably 0.01 to 1%; is there.

The resin composition of the present invention comprises (A) or (A)
It is obtained by melt-mixing the antistatic agent containing (B) with. As a method for melt mixing, a usual method is used, and generally, pellet-like or powder-like polymers are mixed with an appropriate mixer such as a Henschel mixer, and then melt-mixed with an extruder. A pelletizing method can be applied. The order of addition of each component at the time of kneading is not particularly limited. For example, Method A: a method of blending (A) or an antistatic agent containing (A) and (B) and kneading, Method B A method of blending and kneading a small amount of (B) and (A) or an antistatic agent containing (A) or (C) and (D), and then blending and kneading the remaining (B), And method C: (A) or an antistatic agent containing (A),
Examples include a method of blending and kneading (C) and (D), and then blending and kneading (B). Out of these
The methods of B and C are methods called a masterbatch method or a master pellet method.

As a method for obtaining the resin composition of the present invention via a masterbatch, for example, a mixture of (A) or an antistatic agent containing (A) and (C) and (D) [ Preferably, (A) 100 parts (weight part, the same applies hereinafter)
(C) is 0 or 0.01 to 3 parts, particularly preferably 0 or 0.03 to 2 parts, and (D) is 0 or 0.1 to 20.
Parts, particularly preferably 0 or 0.2 to 10 parts are contained]
(B) is usually 0 or 0.1 to 50 parts per 100 parts.
Parts, preferably 0 or 5 to 20 parts are blended and kneaded to form a masterbatch, and this masterbatch and the remaining amount of (B) are blended and kneaded. This method is particularly suitable for a small amount of (A) in a large amount of (B),
There is an advantage that (C) and (D) can be dispersed uniformly.

The method for molding the resin composition of the present invention is as follows:
Injection molding, compression molding, calendar molding, slush molding,
Examples include rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), and any method can be used according to the purpose. A molded article obtained by molding the resin composition of the present invention has excellent mechanical strength and permanent antistatic property, and also has good coatability and printability, and a molded article coated or printed. Is widely used for various purposes described below. Examples of the method for coating the molded body include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, dip coating, roller coating, and brush coating. Examples of the paint include polyester melamine resin paints, epoxy melamine resin paints, acrylic melamine resin paints, acrylic urethane resin paints, and other paints generally used for painting plastics. The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm. As a method of printing on the molded body, any printing method generally used for printing plastics can be used.
For example, gravure printing, flexo printing, screen printing,
Offset printing etc. are mentioned. As the printing ink, those commonly used for printing plastics can be used.

Further, the antistatic agent (A) or the antistatic agent containing (A) of the present invention may be used as an antistatic coating material by adding it to a known coating material or solvent (eg xylene, toluene). You can

The antistatic agent containing (A) or (A) of the present invention is injection molding, compression molding, calendar molding, slush molding, rotation molding, extrusion molding, blow molding, film molding (casting method, Various products such as housing products for home electric appliances / OA equipment, game machines, office equipment, IC trays, etc. obtained by various molding methods such as the tenter method and the inflation method) and further subjected to the above-mentioned painting and printing as necessary. It can be used as a polymer for an antistatic agent for various molding materials such as plastic containers, films for various packaging materials, sheets for flooring materials, artificial turf, mats and automobile parts that require antistatic properties.

[0111]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following, “part” means “part by weight”.

Production Example 1 80 parts of a low molecular weight polypropylene obtained by the thermal degradation method having Mn of 2,500 and a density of 0.89 was melted at 160 ° C. to obtain 7 parts of maleic anhydride and 12-aminododecanoic acid. 1
4 parts was added, and the reaction was carried out for 1 hour under aeration of nitrogen. Then, it reacted at 200 degreeC for 20 hours, and obtained the acid modified polypropylene (a1-1). The acid value of (a1-1) is 3
2.1 and Mn were 2,800.

Production Example 2 45 parts of epichlorohydrin and 55 parts of diethylene glycol monomethyl ether were reacted in the presence of 5 parts of sodium hydroxide to synthesize methyldiethylene glycol glycidyl ether. 20 parts of ethylene oxide and 80 parts of methyldiethylene glycol glycidyl ether were reacted at 100 ° C. in the presence of 0.05 part of potassium hydroxide to obtain a polyether diol (b1-1). (B1-1
) Had a hydroxyl value of 57.0, Mn of 2,000, and a volume resistivity of 1 × 10 ⁷ Ω · cm.

Production Example 3 64 parts of the acid-modified polypropylene (a1-1) obtained in Production Example 1 and 36 parts of the polyether diol (b1-1) obtained in Production Example 2 were placed in a stainless steel autoclave.
Antioxidant (“Irganox 1010”, manufactured by Ciba-Gaiki, 0.3 part) and zirconyl acetate 0.
5 parts was added, and the mixture was polymerized for 4 hours under reduced pressure of 230 ° C. and 1 mmHg or less to obtain a viscous polymer. The block polymer (A1) of the present invention was obtained by taking out this polymer in a strand form on a belt and pelletizing it. The Mn of (A1) was 22,000.

Comparative Production Example 1 In a stainless steel autoclave, 64 parts of the acid-modified polypropylene (a1-1) obtained in Production Example 1 and Mn of 2, were used.
Of polyethylene glycol (36 parts), antioxidant (0.3 parts) and zirconyl acetate (0.5 parts),
Polymerization was carried out for 4 hours under reduced pressure of 1 ° C. or less and 1 mmHg to obtain a viscous polymer. Thereafter, the same operation as in Production Example 3 was performed to obtain a block polymer (A1 ′). (A1 ')
Had a Mn of 25,000.

Examples 1 to 5 and Comparative Examples 1 to 4 According to the formulations (parts) shown in Table 1, the block polymer (A
1, A1 ') and the thermoplastic resin (B1, B2), optionally with an alkali metal salt and a surfactant, in a Henschel mixer for 3 minutes, and then in a vented twin-screw extruder at 240 ° C, 100 rpm. , Residence time 5
The resin composition of the present invention (Examples 1 to 5) and the comparative resin composition (Comparative Examples 1 to 4) were obtained by melt-kneading under the condition of minutes.

[0117]

[Table 1]

(Note 1) B1: polypropylene {trade name: Ubepolypro J60
9, manufactured by Ube Industries Ltd. B2: ABS resin {trade name: ABS10, manufactured by Techno Polymer Co., Ltd.} C1: lithium chloride C1: sodium trifluoromethanesulfonate D1: sodium dodecylbenzenesulfonate C1, C1, D1 It was added during the production of the block polymer {simultaneously with the hydrophilic polymer (b)}.

Performance Test The resin composition of the present invention and the comparative resin composition were subjected to an injection molding machine at a cylinder temperature of 240.
℃, mold temperature 50 ℃, to prepare a test piece, impact strength, flexural modulus, compatibility, surface resistivity value, volume resistivity value, surface resistivity after washing, primary adhesion, water resistance and coating It was used to evaluate the wearing efficiency. Also, using a compression molding machine, the temperature of 20
A test piece was prepared at 0 ° C., a pressure of 20 kg / cm ² , and a time of 30 seconds, and used to evaluate the surface specific resistance value. These test pieces were tested for resin mechanical strength (impact strength, impact strength,
Flexural modulus, compatibility), antistatic property (surface resistivity value,
The volume resistivity, the surface resistivity after washing with water) and the coating properties (primary adhesion, water resistance, coating efficiency) were evaluated. The results are shown in Table 2.

[0120] (1) Impact strength: ASTM D256 (1984)                       (Notched, 3.2 mm thick)                   Measured by Method A, test piece (injection molding) (2) Flexural modulus: ASTM D790 (1984)                   Test piece (10 x 4 x 100 mm), distance between fulcrums 60 mm (3) Compatibility: Bending a test piece (injection molding: 100 × 100 × 2 mm)                 , And evaluated by observing the fracture surface.                   Evaluation criteria ○: Uniform and no delamination                            X: The compatibility between A and B is poor and delamination occurs. (4) Surface specific resistance value: test piece (injection molding: 100 × 100 × 2 mm, compression molding                 Shape: 100mm diameter disk shape, thickness 2mm), super insulation               Measured by Toa Denpa's DSM-8103, 23 ° C, humidity             It was measured in an atmosphere of 50% RH.                   Based on ASTM D257 (1984). (5) Volume resistivity value: using a test piece (injection molding: 100 × 100 × 2 mm)                 , 23 with a super insulation meter (DSA-8103 manufactured by Toa Denpa Co., Ltd.)               The measurement was performed in an atmosphere of ℃ and humidity of 50% RH.                   Based on ASTM D257 (1984). (6) Surface resistivity after washing with water: test piece (injection molding: 100 × 100 × 2 mm                 ) Was washed with water and dried in a normal air dryer at 80 ° C. for 3 hours. this               The operation was repeated 10 times, and a super insulation meter (DSA manufactured by Toa Denpa Co., Ltd.             8103), measured in an atmosphere of 23 ° C and 50% RH.           Decided                   Based on ASTM D257 (1984).

(7) Coating test: Test piece (injection molding: 1
(00 × 100 × 2 mm) is grounded, and electrostatic coating is performed using an electrostatic atomizing electrostatic coating machine combined with air flow [Turbo near G minibell type automatic electrostatic coating machine manufactured by Nippon Lansburgh Co., Ltd.] (applied voltage = -90 KV, discharge rate = 100 cc / min, rotation speed = 24,000 rpm, atomizing head diameter = 70 mm, two-component urethane paint: Nippon Oil & Fat Co., Ltd. Hi-Urethane # 50
00 is used). After the coated plate was baked at 80 ° C. for 2 hours, the following test was conducted. (8) Primary adhesion: coating surface of coated plate JIS K
A 5400 (1990) cross-cut test was conducted. That is,
After making 100 squares of 1 mm width on the coating surface, 2
An adhesive tape of 4 mm width was completely adhered to the cross-cut, and one end of the tape was immediately kept at right angles to the effective surface to be momentarily separated, and the number of masses where the coating film remained was measured. (9) Water resistance: The coated plate was immersed in warm water of 50 ° C. for 240 hours, and then a cross-cut test of JIS K5400 (1990) was performed. (10) Coating efficiency: It was calculated according to the following formula. Coating efficiency = (weight of test piece after coating−weight of test piece before coating) × 100 ÷ (absolute dry weight of discharged coating material) (Note 1) An example in which a thermoplastic resin (B1) was used for the test piece. In the comparative example, a coating test was conducted after the corona discharge treatment. [Corona discharge treatment: High frequency power supply HFS-203 manufactured by Kasuga Denki KK was used as a high frequency power supply, and an applied voltage of 30
The surface of the molded body was treated under the conditions of KV and 20 seconds. ] (Note 2) In the formula of (10), the absolutely dry condition is 80 ° C.
× 2 hours

[0122]

[Table 2]

As is clear from Table 2, the physical properties of the resin to which the block polymer of the present invention is added are compared with those of Comparative Examples 1, 2 and 4 to which the same amount of the comparative block polymer is added.
It has excellent resin mechanical strength, surface specific resistance value (2 × 10 ¹¹ Ω or less) that exhibits preferable antistatic property, and coating property.
Furthermore, the resin to which the block polymer of the present invention is added,
It exhibits a surface specific resistance value (2 × 10 ¹¹ Ω or less) that exhibits a preferable antistatic property even if the molding method is different, and the antistatic property does not deteriorate even when washed with water, and lasts semipermanently. Further, by adding a metal salt or a surfactant, more excellent performance (surface resistivity value, volume resistivity value and coating efficiency) is exhibited.

[0124]

INDUSTRIAL APPLICABILITY The block polymer of the present invention and the antistatic agent containing the same can impart excellent permanent antistatic properties to the resin, which cannot be achieved by the conventional techniques. Further, it exerts an effect that it is possible to impart extremely good paintability and is also excellent in mechanical properties.
From the above effect, the block polymer of the present invention is molded by various molding methods such as injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, and film molding, and if necessary, the above-mentioned. Home appliances / OA equipment, game equipment, office equipment housing products, various plastic containers such as IC trays, various packaging films, floor sheets, artificial turf, mats, etc. It is extremely useful as a polymer for antistatic agents of various molding materials that require antistatic properties for automobile parts and the like.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 53/00 C08L 53/00 101/00 101/00 C09K 3/16 102 C09K 3/16 102L 106 106A 106F F term ( Reference) 4F071 AA14 AA22 AA33 AA43 AA50 AA51 AA53 AA54 AA75 AC09 AE16 AF38 AH03 AH04 AH07 AH12 BA01 BB03 BB04 BC07 4J002 BB001 BC021 BD121 GH01 GD05 001A00A0A01 A0A4 A0A4 AO4 AF30

Claims (12)

[Claims] 1. A block of polyolefin (a) and a parent
Blocks of water-based polymer (b) are repeatedly and alternately bonded.
In a block polymer having a combined structure, (b)
Has a branched polyoxyalkylene group and is volume specific
Resistance value is 10 ^Four-10¹¹Characterized by being Ω · cm
Block polymer (A). 2. In the alkylene group of the polyoxyalkylene group of (b), at least a part of the repeating unit is a substituted alkylene group represented by the general formula (1),
The block polymer (A) according to claim 1, wherein the rest may be an alkylene group having 2 to 4 carbon atoms. -CHR-CHR'- (1) [In formula, R,
One of R ′ is a group represented by the general formula: —CH ₂ O (A ¹ O) _S R ″ (2), and the other is H. In the general formula (2), s is an integer of 1 to 10. , R ″ is H or an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group or an acyl group having ¹ to 10 carbon atoms, and A ¹ is an alkylene group having 2 to 4 carbon atoms. ] 3. The number average molecular weight of (A) as determined by gel permeation chromatography is 2,000 to 60,0.
The block polymer (A) according to claim 1 or 2, which is 00. 4. The block polymer (A) according to claim 1, wherein (a) is a polyolefin having a carbonyl group. 5. The block polymer (A) according to claim 1, wherein (A) comprises a block polymer (A1) having a repeating unit represented by the following general formula (3). [Chemical 1] [Chemical 2] [Chemical 3] [In the general formula (3), ^one of R ¹ and R ² is H, the other is H or an alkyl group having 1 to 10 carbon atoms; E ¹ is a residue obtained by removing a hydroxyl group from the divalent hydroxyl group-containing compound (b0). ; X and X '
Is a group selected from the groups represented by the general formulas (4) to (10) and the corresponding group represented by the general formulas (4 ′) to (10 ′), that is, X is a general formula (4). ) Is a group represented by the general formula (4 ′), and X ′ is a group represented by the general formula (5) to (10) and the general formula (5 ′) to
The same applies to (10 '); at least a part of A ² is a substituted alkylene group represented by the general formula (1), and the rest is an alkylene group having 2 to 4 carbon atoms. ; Y is 15 to 800, m and m ′ are 1 to 300, n
Are each an integer of 2 to 50; general formulas (4) to (1
0) and (4 ′) to (10 ′), R ³ and R ³ ′ are trivalent hydrocarbon groups having 2 to 3 carbon atoms, and R ⁴ is 2 having 1 to 11 carbon atoms.
A divalent hydrocarbon group, R ⁵ is H or an alkyl group having 1 to 10 carbon atoms, R ⁶ is a divalent hydrocarbon group having 2 to 22 carbon atoms; E ² is an organic diisocyanate residue; A ³ is a carbon number 2 ~ 4 alkylene group; r is 1 to 10, u and v are 0 or 1, respectively;
Q, Q ′, T and T ′ are represented by general formulas (11) and (1
1 '), (12) and (12'), and R in each formula
⁷ is H or a methyl group. ] 6. E ¹ in the general formula (3) is an aliphatic 2
The block polymer (A) according to claim 5, which is a residue obtained by removing a hydroxyl group from a dihydric alcohol, a dihydric phenol or a diol containing a tertiary amino group. 7. An antistatic agent comprising (A) according to any one of claims 1 to 6. 8. An antistatic resin composition comprising (A) according to any one of claims 1 to 6 and a thermoplastic resin (B). 9. A vinyl resin, a polyamide resin, a polyester resin, a polycarbonate resin, a thermoplastic polyurethane resin or a polyacetal resin, wherein (B) is selected from the group consisting of polyolefin resins, polystyrene resins, acrylic resins and rubber (like) copolymers. The resin composition according to claim 8, which is at least one thermoplastic resin selected from the group consisting of: and a fluororesin. 10. The resin composition according to claim 8 or 9, further comprising a salt (C) of an alkali metal and / or an alkaline earth metal. 11. A molded product obtained by molding the resin composition according to claim 8. 12. A molded article obtained by applying coating or printing to the molded article according to claim 11.