JP2022000503A - Block polymer and antistatic agent comprising the same - Google Patents

Abstract

To provide an acid-modified cycloolefin polymer composition having excellent compatibility with a cycloolefin polymer and a cycloolefin copolymer, a resin modifier including the same, and a method for producing an acid-modified cycloolefin polymer composition.SOLUTION: A block polymer includes a block (a) satisfying the following (1) and a block (b) satisfying the following (2). (1) The block (a) has a (co) polymer that includes a cycloalkene having a norbornene skeleton as a constituent monomer. (2) The block (b) is a repeating unit (B) that is different from the block (a) and has at least one polar atomic group selected from the group consisting of a quaternary ammonio group, an amino group, a carboxyl group, a sulfo group, a phospho group, a hydroxy group, and an oxyethylene group.SELECTED DRAWING: None

Description

The present invention relates to a block polymer and an antistatic agent containing the same.

Cycloolefin polymers and cycloolefin copolymers are used as resins having excellent heat resistance and mechanical strength in molded products such as electrical parts such as connectors and medical parts.
As one of the methods for imparting antistatic properties to such resin-made molded products, a method of kneading a polymer-type antistatic agent such as a polyether / polyolefin block polymer into the resin and molding is known. (Patent Document 1 etc.).

However, the polymer-type antistatic agent described in Patent Document 1 and the like does not have sufficient compatibility even when kneaded into a cycloolefin polymer and a cycloolefin copolymer, so that the appearance of the molded product is poor due to poor dispersion. In addition, there was a problem that the antistatic performance was insufficient.

Japanese Unexamined Patent Publication No. 2001-278985

An object of the present invention is to provide an antistatic agent which is excellent in dispersibility with respect to a cycloolefin polymer and a cycloolefin copolymer and imparts excellent antistatic performance.

The present inventors have arrived at the present invention as a result of studies for achieving the above object.
That is, the present invention is a block polymer containing a block (a) satisfying the following (1) and a block (b) satisfying the following (2).
(1) The block (a) has a (co) polymer containing cycloalkene having a norbornene skeleton as a constituent monomer;
(2) One selected from the group in which the block (b) is other than the block (a) and consists of a quaternary ammonio group, an amino group, a carboxyl group, a sulfo group, a phospho group, a hydroxyl group, and an oxyethylene group. Includes repeating unit (B) with the above polar atomic groups;

The block polymer of the present invention and the antistatic agent containing the same have excellent dispersibility and antistatic property with respect to the cycloolefin polymer and the cycloolefin copolymer.

The block polymer of the present invention is a block polymer containing a block (a) satisfying the following (1) and a block (b) satisfying the following (2).
(1) The block (a) has a (co) polymer containing cycloalkene having a norbornene skeleton as a constituent monomer;
(2) One selected from the group in which the block (b) is other than the block (a) and consists of a quaternary ammonio group, an amino group, a carboxyl group, a sulfo group, a phospho group, a hydroxyl group, and an oxyethylene group. Includes repeating unit (B) with the above polar atomic groups;

<Block (a)>
The block (a) in the present invention has a (co) polymer containing cycloalkene having a norbornene skeleton as a constituent monomer.
In the present invention, the (co) polymer means a polymer and / or a copolymer.

Cycloalkenes having a norbornene skeleton include monocycloalkenes having a norbornene skeleton and having 7 to 25 carbon atoms {norbornene (bicyclo [2.2.1] -2-heptene), tricyclo [4.3.0.1 ^{2, 5} ] -3-decene, tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] -3-dodecene, 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] -3-dodecene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] -3-dodecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, pentacyclo [7.4.0.1 ^{2,5. 19 and 12} . 0 ^8,13] -3-pentadecene, pentacyclo [8.4.0.1 ^{2,5. 19 and 12} . 0 ^8,13] -3-hexadecene, pentacyclo [6.6.1.1 ^3,6. 0 ^2,7 . 0 ^9,14] -4-hexadecene, hexacyclo [6.6.1.1 ^3,6. 1 ^{10, 13} . 0 ^2,7 . 0 ^9,14] -4-heptadecene, heptacyclo [8.7.0.1 ^2,9. 1 ^{4, 7 4} . 1 ^{11, 17} ． 0 ^3,8 . 0 ^12,16 ] -5-eikosen, heptacyclo [8.7.0.1 ^3,6 . 1 ^10,17 . 1 ^{12, 15} ． 0 ^2,7 . 0 ^{11, 16]} -4-eicosene, heptacyclo [8.8.0.1 ^2,9. 1 ^{4, 7 4} . 1 ^{11, 18} . 0 ^3,8 . 0 ^12,17 ] -5-Heneikosen, Octacyclo [8.8.0.1 ^2,9 . 1 ^{4, 7 4} . 1 ^{11, 18} . 1 ^{13, 16} . 0 ^3,8 . 0 ^12,17 ] -5-docosen, and nonacyclo [10.9.1.1 ^4,7 . 1 ^{13, 20} . 1 ^{15, 18} . 0 ^2,10 . 0 ^3,8 . 0 ^{12, 21} . 0 ^14,19] -5-pentacosene and the like.
The cycloalkene may be used alone or in combination of two or more.

Among the above cycloalkenes, tricyclo [4.3.0.1 ^2,5 ] -3-decene and tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] -3-Dodecene.

The block (a) includes a block (a1) having a polymer (PA1) containing only the cycloalkene as a constituent monomer, and a copolymer containing the cycloalkene and an acyclic monoolefin as a constituent monomer (a1). The block (a2) having PA2) can be mentioned.

The block (a1) is a polymer (PA1) obtained by completely hydrogenating (hydrogenating) the double bond in the polymer after ring-opening metathesis polymerization of cycloalkene having a norbornene skeleton by a known method. ) Is preferred.

The block (a2) is preferably obtained from a copolymer (PA2) obtained by addition-copolymerizing a cycloalkene having a norbornene skeleton and an acyclic monoolefin by a known method.

Preferred cycloalkenes constituting the copolymer (PA2) include the same cycloalkenes as those exemplified as cycloalkenes having a norbornene skeleton constituting the polymer (PA1), and preferred cycloalkenes are also the same. Is.

Examples of the acyclic monoolefin constituting the copolymer (PA2) include acyclic monoolefins having 2 to 10 carbon atoms. Of the acyclic monoolefins having 2 to 10 carbon atoms, the acyclic monoolefin having 4 or more carbon atoms is an acyclic monoolefin having a double bond at the end. Examples of these acyclic monoolefins include ethylene, propylene, α-olefins having 4 to 8 carbon atoms (1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and the like).
Of these, ethylene and propylene are preferable.

<Block (b)>
The block (b) in the present invention is one selected from the group consisting of a quaternary ammonio group, an amino group, a carboxyl group, a sulfo group, a phospho group, a hydroxyl group, and an oxyethylene group other than the block (a). The block (b) containing the repeating unit (B) having the above polar atomic group is included.

Examples of the block containing a repeating unit having a quaternary ammonio group include a block made of a cationic polymer having a quaternary ammonio group in the main chain or as a functional group bonded to the main chain.

Examples of the cationic polymer having a quaternary ammonio group in the main chain include polyester containing dialkanol tertiary amine and dicarboxylic acid as essential constituent monomers, polydimethyldiallyl ammonium halide, and dimethyldiallylammonium halide and acrylamide. Examples thereof include polymers obtained by quaternizing a tertiary amine contained in the copolymer of the above, and examples of the cationic polymer having a quaternary ammonio group as a functional group bonded to the main chain include acrylamide having a quaternary ammonium salt unit. Examples thereof include polymers having a quaternary product of dimethylaminopropylacrylamide, etc.) and / or an acrylate having a quaternary ammonium salt unit (quaternary product of dimethylaminoethyl methacrylate, etc.) as a constituent monomer.

Examples of the counter anion of the quaternary ammonio group include superacid anion and other anions.
Examples of the superacid anion include an anion of a superacid (boric acid tetrafluoride, phosphoric acid hexafluoride, etc.) derived from a combination of a protonic acid and a Lewis acid, and an anion of a superacid such as trifluoromethanesulfonic acid. .. Other anions include, for example, halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ^−, etc.), OH ⁻ , PO ₄ ⁻ , CH ₃ OSO ₄ ⁻ , C ₂ H ₅ OSO ₄ ⁻ , ClO ₄ ^−, etc. Can be mentioned. Examples of the protonic acid that induces a super-strong acid include hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide. Examples of Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, and tantalum pentafluoride.

Examples of the block containing a repeating unit having an amino group include a block made of a cationic polymer having an amino group. As the cationic polymer having an amino group, a polymer having an acrylate having an amino group (dimethylaminoethyl methacrylate, etc.) as a constituent monomer, and a dialkanol tertiary amine and a dicarboxylic acid as an essential constituent monomer are used. Examples thereof include polyester, polydimethyldiallyl ammonium halide, and a copolymer of dimethyldiallyl ammonium halide and acrylamide.

Examples of the block containing a repeating unit having a carboxyl group include a block made of an anionic polymer having a carboxyl group, and examples of the anionic polymer having a carboxyl group include α, β-unsaturated carboxylic acid {(meth) acrylic. Examples thereof include an addition-polymerized polymer containing an acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, etc.} as an essential constituent monomer.

Examples of the block containing a repeating unit having a sulfo group include a block made of an anionic polymer having a sulfo group, and the anionic polymer having a sulfo group is indispensable to contain a dicarboxylic acid having a sulfonyl group and a diol. Examples thereof include polyester as a component, a polymer having styrene sulfonic acid as a constituent unit, and an addition-polymerized polymer containing an acrylate having a sulfo group (2-sulfoethyl methacrylate or the like) as an essential constituent monomer.

In the present invention, the sulfo group contained in the block (b) is a metal ion (preferably an alkali metal or an alkaline earth metal), ammonia, a mono having at least one hydroxyalkyl (2 to 4 carbon atoms) group, or a di. Alternatively, a salt may be formed with triamine, a quaternary ammonium compound of the amine, or the like. When referred to as a sulfo group in the present specification, it means a sulfo group or a salt thereof.

Examples of the block containing a repeating unit having a phospho group include a block made of an anionic polymer having a phospho group, and examples of the anionic polymer having a phospho group include a polymer having vinylphosphonic acid as a constituent monomer. And an addition polymerization type polymer containing an acrylate having a phospho group (phosphoethyl acrylate, phosphopropyl acrylate, etc.) as an essential constituent monomer and the like can be mentioned.

Examples of the block containing a repeating unit having a hydroxyl group include a block made of a polymer having a hydroxyl group, and examples of the polymer having a hydroxyl group include polyvinyl alcohol and an acrylate having a hydroxyl group (2-hydroxyethyl acrylate and 4-hydroxybutyl). Examples thereof include an addition-polymerized polymer containing acrylate or the like as an essential constituent monomer.

Examples of the block containing a repeating unit having an oxyethylene group include a block made of a polymer having a (poly) oxyethylene chain, and the polymer having a (poly) oxyethylene chain contains an essential constituent monomer of ethylene oxide. A (poly) alkylene oxide compound as a body, a polyol containing a (poly) alkylene oxide compound containing ethylene oxide as an essential constituent monomer, a polyurethane of a polyisocyanate compound, and an ethylene oxide as an essential constituent monomer (poly). Examples thereof include polyols containing alkylene oxide compounds and polyesters of polycarboxylic acids.

In addition, (poly) oxyethylene means polyoxyethylene and / or oxyethylene. Further, polyoxyethylene is preferable.

In the block polymer, the block (a) and the block (b) are bonded via an atomic group selected from the group consisting of an ester bond, an amide bond, a urethane bond, a urea bond and an imide bond and containing one kind of bond. It is preferable that the block polymer contains two or more kinds of atomic groups constituting the above bond.

Examples of the block polymer in which the block (a) and the block (b) are bonded via an atomic group containing an ester bond include the following.

(Block polymer 1 bonded via an atomic group containing an ester bond)
An acid-modified polycycloolefin (co) polymer having a (co) polymer containing cycloalkene as a constituent monomer and having a carboxyl group at the terminal thereof, and a quaternary ammonio group, an amino group, a carboxyl group, and a sulfo group. , A block polymer (p11) obtained by esterifying a terminal hydroxyl group polymer (b1) containing a repeating unit having one or more polar atomic groups selected from the group consisting of a phospho group, a hydroxyl group and an oxyethylene group by a known method.

(Block polymer 2 bonded via an atomic group containing an ester bond)
A hydroxyl group-modified polycycloolefin (co) polymer having a (co) polymer containing cycloalkene as a constituent monomer and having a hydroxyl group at the terminal thereof, and a quaternary ammonio group, an amino group, a carboxyl group, a sulfo group, A block polymer (p12) obtained by esterifying a terminal carboxylic acid polymer (b2) containing a repeating unit having one or more polar atomic groups selected from the group consisting of a phospho group, a hydroxyl group and an oxyethylene group by a known method.

In addition, in this specification, a polycycloolefin (co) polymer means a polycycloolefin polymer [polymer (PA1)] or a polycycloolefin copolymer [polymer (PA2)].

The acid-modified polycycloolefin (co) polymer constituting the block (a) in the block polymer (p11) can be obtained by the following method or the like.
(Method 1) A thermally reduced product of a (co) polymer containing cycloalkene having a norbornene skeleton as a constituent monomer is reacted with an unsaturated carboxylic acid and / or its anhydride in the absence of a radical polymerization initiator. Method.
(Method 2) A method of oxidizing a polymer (co) containing a cycloalkene having a norbornene skeleton as a constituent monomer (method 3) containing a cycloalkene having a norbornene skeleton as a constituent monomer (co). A method in which a heat-reduced product of a polymer is hydroformylated to introduce a formyl group, and further oxidized by the method described in US Pat. No. 3,692,877.
Further, the secondary acid-modified cycloolefin (co) polymer obtained by further modifying the carboxyl group of the acid-modified polycycloolefin (co) polymer and introducing the carboxyl group can be used as the block (a).

As the polymer (PA1) to be a heat-reduced product, a polymer obtained by ring-opening metathesis polymerization of the cycloalkene having a norbornene skeleton under known polymerization conditions and subsequently hydrogenating can be used. , Commercial products (for example, Zeonex series and Zeonoa series manufactured by Nippon Zeon Co., Ltd.) can be used.

The thermal attenuation of the polymer (PA1) is preferably 300 under an atmosphere of a gas (hereinafter referred to as an inert gas) in which the polycycloolefin polymer is not reactive with the polycycloolefin polymer. It can be carried out by heating at ~ 450 ° C., more preferably for 0.5 to 10 hours.

Examples of the inert gas used in the heat reduction include argon, nitrogen, carbon dioxide gas, steam and the like, and nitrogen is preferable. The inert gas is preferably aerated in the reaction vessel at a flow rate of 0.1 to 100 L / min during heating.
The heating temperature is preferably 300 to 450 ° C, more preferably 320 to 430 ° C. When the reaction temperature is in this range, the obtained modified cycloolefin polymer is less colored, and no unpleasant odor is generated, which is preferable. In the present specification, a state in which the color tone and the odor are good means that there is little coloring and no unpleasant odor is generated.
The reaction time is preferably 0.5 to 10 hours, more preferably 1 to 7 hours. When the reaction time is in this range, the color tone and odor of the obtained modified cycloolefin polymer are good, and the heat is uniformly reduced, which is preferable.

The pressure at the time of heat reduction is preferably normal pressure (atmospheric pressure) to 200 kg / cm ^{2, and} more preferably normal pressure to 150 kg / cm ² . Within this range, the color tone and odor of the polymer (a1) and the polymer (a2) are good.

As the method of heat reduction, either a batch method or a continuous method may be used.
When the batch method is used, the inert gas is aerated in a reaction vessel made of stainless steel or the like equipped with a stirrer, the cycloolefin polymer as a raw material is put in, and the mixture is heated at a predetermined temperature for a predetermined time under stirring. Thermal reduction can be carried out.
When the continuous method is used, the inert gas is aerated in a continuous reaction vessel such as a tubular reactor and an extruder, the cycloolefin polymer as a raw material is put in, and the mixture stays in the reaction vessel at a predetermined temperature for a predetermined time. Thermal reduction can be carried out by heating and melting while adjusting the input amount of the raw material.
Among them, the continuous method is preferable, and the tubular reactor used in the continuous method is preferably a reaction vessel in which two or more tubes having different inner diameters are connected in series and a static mixer as a part of the tubular reactor. Examples include those used.

When heating for heat reduction, a phenol-based antioxidant may be added, and as the phenol-based antioxidant, 2,6-di-tert-butyl-4-methylphenol, 2 Hindered phenols such as -tert-butyl-4-methylphenol, 6-tert-butyl-2,4-methylphenol, 2,6-di-tert-butylphenol, and 2-tert-butyl-4-ethylphenol. Examples include compounds.

In thermal reduction, a catalyst can also be used for the purpose of promoting the decomposition reaction. The catalyst to be added includes radical generation catalysts [peroxides such as benzoyl peroxide, di-tert-butyl peroxide, and dicumyl peroxide; 2,2'-azobis (isobutyronitrile), 2,2'. -Azobisos (2,4-dimethylvaleronitrile) and azonitriles such as 4,4'-azobis (4-cyanovalerian acid)] and cracking catalysts (silica-alumina, silica-magnesia, activated clay, etc.) and the like. ..

Thermal decompression means an operation of cutting a part of the main chain by a thermal decomposition reaction of the polymer to reduce the molecular weight, and the thermal reduction described above causes partial cleavage of the main chain in the cycloolefin polymer. Occurs, resulting in an unsaturated double bond at the end of the resulting chain. An acid-modified cycloolefin polymer can be obtained by adding an unsaturated carboxylic acid and an acid anhydride thereof, which will be described later, to the unsaturated double bond generated here.
Depending on the location where the main chain is cleaved due to heat reduction, unsaturated double bonds at the ends may occur only at one end of the heat reduction product or at both ends, and the heat reduction product may occur at one end. It is considered to be a mixture of one having an unsaturated double bond at the end and one having a saturated double bond at both ends.

The reaction of the heat-reduced product of the polymer (PA1) with the unsaturated carboxylic acid and / or its anhydride is incompatible with the heat-reduced product of the cycloolefin polymer in the reaction vessel in the absence of the radical polymerization initiator. This can be done by heating a saturated carboxylic acid and / or its anhydride under mixing.

An acid-modified cycloolefin polymer can be obtained by adding an unsaturated carboxylic acid and an acid anhydride thereof, which will be described later, to the unsaturated double bond of the heat-reduced product.
Since the heat-reduced product is considered to be a mixture of a product having an unsaturated double bond at one end and a product having a saturated double bond at both ends, it is not compatible with the heat-reduced product of the cycloolefin polymer. The acid-modified cycloolefin polymer obtained by heating with a saturated carboxylic acid and / or an anhydride thereof is also considered to be a mixture of one having a carboxyl group at one end and one having a carboxyl group at both ends.

Examples of the unsaturated carboxylic acid and its acid anhydride used for producing the acid-modified cycloolefin polymer include unsaturated carboxylic acid having 3 to 9 carbon atoms and its acid anhydride, and include (meth) acrylic acid, maleic acid, and the like. Examples thereof include fumaric acid, itaconic acid, maleic anhydride, itaconic acid anhydride, citraconic acid anhydride, allyl succinic acid anhydride and nagic acid anhydride. Of these, maleic acid and maleic anhydride are preferred.

The weight ratio of the unsaturated carboxylic acid and its anhydride in the step of reacting the heat-reduced product of the polymer (PA1) with the unsaturated carboxylic acid and / or its anhydride is the weight of the cycloolefin polymer (100 weight). Parts) are preferably 0.1 to 20 parts by weight, more preferably 1 to 15 parts by weight. Within this range, the hue is good, which is preferable.

The heating temperature in the step of reacting the heat-reduced product of the polymer (PA1) with the unsaturated carboxylic acid and / or its anhydride is preferably 100 to 270 ° C. (more preferably 130 to 240 ° C.), and is heated. The time is preferably 0.5 to 30 hours (more preferably 1 to 20 hours).
The reaction between the heat-decomposed product of the cycloolefin polymer and the unsaturated carboxylic acid and / or its anhydride can be carried out by using a known reactor equipped with a known mixing device and a heating device, and the heat is described above. It can be carried out by using the same continuous reaction vessel such as a stainless steel reactor, a tubular reactor and an extruder illustrated in the reduction.

As the polymer (PA2), a copolymer obtained by addition-copolymerizing the cycloalkene having a norbornene skeleton and the acyclic monoolefin under known polymerization conditions can be used, and a commercially available product (a commercially available product (PA2) can be used. For example, an Apel series manufactured by Mitsui Chemicals Co., Ltd., a TOPAS series manufactured by Polyplastics Co., Ltd., etc.) can be used.

The heat reduction of the polymer (PA2) and the reaction of the heat reduction product with the unsaturated carboxylic acid and / or its anhydride can be carried out in the same manner as in the above-mentioned acid-modified cycloolefin polymer.

The secondary acid-modified cycloolefin (co) polymer used in Method 3 is a method of reacting the acid-modified cycloolefin (co) polymer with lactam, and the acid-modified cycloolefin (co) polymer and amino. It can be obtained by reacting with a carboxylic acid.
When the acid group introduced by modification in the acid-modified cycloolefin (co) polymer is a monocarboxylic acid, the amide bond is 1 and the acid group introduced by modification in the acid-modified cycloolefin (co) polymer is 1. , 2-Dicarboxylic acid (anhydrous) group, amide bond and / or imide bond to obtain a secondary acid-modified cycloolefin (co) polymer.
The amide bond and the imide bond generated by the reaction can be confirmed by measuring the infrared absorption spectrum.

Examples of the lactam include lactam having 6 to 12 carbon atoms, caprolactam, enantractam, laurolactam, undecanolactam and the like.

Examples of the aminocarboxylic acid include amino carboxylic acids having 2 to 12 carbon atoms (amino acids such as glycine, alanine, valine, leucine, isoleucine and phenylalanine, ω-aminocaproic acid, ω-aminoenant acid, ω-aminocapric acid, etc. Ω-Aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc.) and the like. Lactam, which is an intramolecular condensate of aminocarboxylic acid, can also be used.
Preferred amino carboxylic acids are caprolactam and 12-aminododecanoic acid. The amount of aminocarboxylic acid used in the production of the secondary acid-modified cycloolefin (co) polymer is per residue of the unsaturated carboxylic acid (anhydride) contained in the acid-modified cycloolefin (co) polymer. The number is preferably 0.1 to 50, more preferably 0.3 to 20, particularly preferably 0.5 to 10, and most preferably 1.

The acid-modified polycycloolefin (co) polymer preferably has a number average molecular weight of 800 to 50,000, more preferably 1,000 to 18,000.

The number average molecular weight of the acid-modified cycloolefin (co) polymer can be obtained by measuring using gel permeation chromatography (GPC) under the following conditions.
Equipment: "HLC-8120" [manufactured by Tosoh Corporation]
Column: "TSKgelGMHXL" [manufactured by Tosoh Corporation] (2 bottles) and "TSKgel Multipore HXL-M" [manufactured by Tosoh Co., Ltd.] (1 bottle) are linked. Sample solution: 0.3 wt% orthodichlorobenzene solution Injection volume: 100 μL
Flow rate: 1 mL / min Measurement temperature: 135 ° C
Detection device: Refractive index detector Reference material: Standard polystyrene (TSKstandardPOLYSTYRENE)
12 points (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2 , 890,000) [manufactured by Tosoh Corporation]

The acid value of the acid-modified cycloolefin (co) polymer is preferably 0.1 to 60, more preferably 1 to 50.
The acid value of the acid-modified cycloolefin (co) polymer is measured by the neutralization titration method described in JIS K 0070-1992 using a KOH / methanol solution containing phenolphthalein as an indicator.
When the acid group introduced by the modification in the acid-modified cycloolefin (co) polymer is a carboxylic acid anhydride group, it is measured as the half-esterified acid value after being half-esterified with methanol.
The acid value of the acid-modified cycloolefin (co) polymer is the weight ratio of the unsaturated carboxylic acid and its acid anhydride used in the conditions for producing the acid-modified cycloolefin (co) polymer. ) The above range can be obtained by setting the weight ratio based on the weight of the polymer.

One or more polar atomic groups selected from the group consisting of a quaternary ammonio group, an amino group, a carboxyl group, a sulfo group, a phospho group, a hydroxyl group and an oxyethylene group constituting the block (b) in the block polymer (p11). Preferred as the terminal hydroxyl group polymer (b1) containing a repeating unit having a polyoxyethylene chain is a polyether diol (b11) having a polyoxyethylene chain, a polyether diol having a polyoxyethylene chain, and a polyester containing a dicarboxylic acid as essential constituents. Contains a diol (b12), a polyester diol (b13) containing a tertiary amino group-containing diol and a dicarboxylic acid as essential constituents, and a quaternary ammonium group obtained by quaternizing the tertiary amino group of the polyester diol (b13). Examples thereof include a polyester diol (b14), and a polyester diol (b15) containing a dicarboxylic acid having a sulfo group and a diol as essential constituents.

The polyether diol (b11) having a polyoxyethylene chain can be obtained by adding ethylene oxide to an active hydrogen-containing compound having two active hydrogen atoms by a known method.

Active hydrogen-containing compounds having two active hydrogen atoms include dihydric alcohols (eg, aliphatic alcohols with 2 to 12 carbon atoms, alicyclic or aromatic dihydric alcohols), dihydric phenols with 6 to 18 carbon atoms, and trihydric alcohols. Examples thereof include grade amino group-containing diols.

Examples of the aliphatic dihydric alcohol include alkylene glycol (ethylene glycol, propylene glycol), 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,12-dodecanediol. Examples of the alicyclic dihydric alcohol include cyclohexanedimethanol and the like, and examples of the aromatic dihydric alcohol include xylylenediol and the like. Examples of the dihydric phenol include monocyclic dihydric phenol (hydroquinone, catechol, resorcin, ursiol, etc.), bisphenol (bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-2,2-butane, etc. Dihydroxybiphenyl, etc.) and condensed polycyclic dihydric phenol (dihydroxynaphthalene, binaphthol, etc.) can be mentioned.

Examples of the tertiary amino group-containing diol include aliphatic or alicyclic primary monoamines having 1 to 12 carbon atoms (methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, amylamine, isoamylamine, hexylamine). , 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-aminoheptane, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, dodecylamine, etc.) A bishydroxyalkylated product, a bishydroxyalkylated product of an aromatic primary monoamine (aniline, benzylamine, etc.) having 6 to 12 carbon atoms, the primary monoamine [preferably N-alkyl (1 to 8 carbon atoms) dialkanolamine, particularly preferable. Is an alkylene oxide adduct of N-methyldiethanolamine, N-ethyldiethanolamine or N-methyldiisopropanolamine], and tertiary amino group-containing heterocyclic diols [2-phenyl-4,5-bis (hydroxymethyl) imidazole, etc. Imidazole derivative] and the like.

Of these, aliphatic dihydric alcohols and bisphenols are preferable, and ethylene glycol and bisphenol A are particularly preferable.

The polyether diol (b11) may have an alkylene oxide other than ethylene oxide added thereto, and the preferred alkylene oxide that can be used in combination with ethylene oxide is an alkylene oxide having 3 or 4 carbon atoms {more preferably, propylene oxide. , 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination of two or more thereof. }.
Further, other alkylene oxides such as α-olefins having 5 to 12 carbon atoms, styrene oxides, epichlorohydrin (epichlorohydrin and the like) or substituted alkylene oxides (hereinafter, these are also collectively referred to as alkylene oxides) are used as antistatic agents. It can also be used in combination within a range that can be used (preferably 30% or less based on the weight of the total alkylene oxide). When two or more kinds of alkylene oxides are used in combination, the binding form may be either random and / or block.
The addition number of ethylene oxide in the polyether diol (b11) is preferably 1 to 300 mol, more preferably 2 to 250 mol, per 1 mol of the active hydrogen atom of the above-mentioned active hydrogen-containing compound having two active hydrogen atoms. It is mol, particularly preferably 10 to 100 mol.

The content of the oxyethylene group in the polyether diol (b11) is preferably 30 to 80%, more preferably 40 to 70%, based on the weight of the polyether diol (b11), from the viewpoint of antistatic property and moldability.

The number average molecular weight of the polyether diol (b11) is preferably 150 to 20,000, more preferably 300 to 20,000, and particularly preferably 1,000 from the viewpoint of heat resistance and reactivity with the block (a). It is ~ 15,000, most preferably 1,200 to 8,000.

The number average molecular weight of the polyether diol (b11) is obtained by measuring using gel permeation chromatography (GPC) under the following conditions.
-Device: "HLC-8120" [manufactured by Tosoh Corporation]
-Columns: TSKgel SuperH4000, TSKgel SuperH3000 and TSKgel SuperH2000 [manufactured by Tosoh Corporation]
-Column temperature: 40 ° C
-Detector: Differential refractometer (RI)
・ Solvent: Tetrahydrofuran ・ Flow rate: 0.6 mL / min ・ Sample concentration: 0.25%
・ Injection amount: 10 μL
-Standard substance: TSK STANDARD POLYETHYLENE OXIDE [manufactured by Tosoh Corporation]

The polyester diol (b12) containing a polyether diol having a polyoxyethylene chain and a dicarboxylic acid as essential components is the above-mentioned polyether diol (b11) and a dicarboxylic acid, and the number of moles of the polyether diol (b11) is dicarboxylic. It can be obtained by esterification by a known method under the condition of being excessive with respect to the number of moles of the acid.

As the dicarboxylic acid, a dicarboxylic acid having 4 to 20 carbon atoms is preferable, and an aliphatic dicarboxylic acid having 4 to 20 carbon atoms (succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandic acid). And dodecandic acid, etc.), and aromatic dicarboxylic acids with 4 to 20 carbon atoms (terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6- or -2,7-dicarboxylic acid, diphenyl-4,4'dicarboxylic acid. , Diphenoxyetanedicarboxylic acid, sulfonic acid of 3-sulfoisophthalic acid and its alkali metal salt (sodium salt, potassium salt, etc.), etc.), and alicyclic dicarboxylic acid (1,4-cyclohexane) having 4 to 20 carbon atoms. Dicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, etc.).
Further, these ester-forming derivatives {lower alkyl (1 to 6 carbon atoms) ester, anhydride, etc.} can also be used.

The polyester diol (b12) may contain a diol other than the polyether diol (b11), a lactone and an oxycarboxylic acid as constituent monomers.
Examples of the diol other than the polyether diol (b11) include a dihydric alcohol, a dihydric phenol having 6 to 18 carbon atoms, and a tertiary amino group-containing diol exemplified as the active hydrogen-containing compound constituting the polyether diol (b11). And the preferred ones are the same.

As the lactone, a lactone having 6 to 12 carbon atoms (caprolactone, enant lactone, laurolactone, undecanolactone, etc.) is preferable.
As the oxycarboxylic acid, an oxycarboxylic acid having 6 to 12 carbon atoms (ω-oxycaproic acid, ω-oxyenant acid, ω-oxycaprylic acid, ω-oxypelargonic acid, ω-oxycapric acid, 11-oxyundecanoic acid) Acids, 12-oxide decanoic acid, etc.) are preferred.

Specific examples of the polyester diol (b12) include, for example, Japanese Patent Publication No. 58-19696, Japanese Patent Publication No. 46-11480, Japanese Patent Application Laid-Open No. 56-92919, Japanese Patent Application Laid-Open No. 49-33948, and Japanese Patent Publication No. 38-11298. The polyester diol described in the above can be mentioned.

The content of the segment derived from the polyether diol (b11) contained in the polyester diol (b12) is preferably 30 to 80%, preferably 40 to 70%, based on the weight of the polyester diol (b12) from the viewpoint of moldability. More preferred. The content of the oxyethylene group in the polyester diol (b12) is preferably 30 to 80%, more preferably 40 to 70%, based on the weight of the polyester diol (b12), from the viewpoint of antistatic property and moldability.

The number average molecular weight of the polyester diol (b12) is preferably 150 to 20,000, more preferably 300 to 20,000, and particularly preferably 1,000 to 1,000 from the viewpoint of heat resistance and reactivity with the block (a). It is 15,000, most preferably 1,200 to 8,000.

The number average molecular weight of the polyester diol (b12) is obtained by measuring using gel permeation chromatography (GPC) under the following conditions.
-Device: "HLC-8120" [manufactured by Tosoh Corporation]
-Columns: TSKgel SuperH4000, TSKgel SuperH3000 and TSKgel SuperH2000 [manufactured by Tosoh Corporation]
-Column temperature: 40 ° C
-Detector: Differential refractometer (RI)
・ Solvent: Tetrahydrofuran ・ Flow rate: 0.6 mL / min ・ Sample concentration: 0.25%
・ Injection amount: 10 μL
-Standard substance: Standard polystyrene (TSKstandardPOLYSTYRENE)
12 points (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2 , 890,000) [manufactured by Tosoh Corporation]

The polyester diol (b13) containing a tertiary amino group-containing diol and a dicarboxylic acid as essential constituents is the tertiary amino group-containing diol exemplified as an active hydrogen-containing compound in the polyether diol (b11) and the polyester diol. It can be obtained by esterifying the tertiary amino group-containing diol by a known method using the dicarboxylic acid exemplified in (b12) under the condition that the number of moles of the tertiary amino group-containing diol is excessive with respect to the number of moles of the dicarboxylic acid.

As the polyester diol (b14) containing a quaternary ammonium group, a polyester diol obtained by quaternizing the tertiary amino group of the polyester diol (b13) by a known method can be preferably used. Known quaternizing agents such as methyl chloride, dimethyl sulfate, benzyl chloride and dimethyl carbonate can be used for quaternization.

The polyester diol (b15) containing a dicarboxylic acid having a sulfonyl group and a diol as essential components uses the dicarboxylic acid having a sulfo group and the diol in excess of the number of moles of the diol with respect to the number of moles of the dicarboxylic acid. It can be obtained by esterification by a known method under the above conditions.
Examples of the sulfo group-containing dicarboxylic acid include aromatic dicarboxylic acids having a sulfonyl group {5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid and these. Ester-forming derivatives [lower alkyl (1 to 4 carbon atoms) esters (methyl esters, ethyl esters, etc.), acid anhydrides, etc.]}, and aliphatic dicarboxylic acids having a sulfo group {sulfosuccinic acid and its ester-forming derivatives [ Lower alkyl (1 to 4 carbon atoms) esters (methyl esters, ethyl esters, etc.), acid anhydrides, etc.]} and the like can be mentioned.
Examples of the diol which is a constituent monomer of the polyester diol (b15) include a dihydric alcohol and a polyether diol (b11) exemplified as an active hydrogen-containing compound in the above-mentioned method for producing a polyether diol (b11). ..

The concentration of sulfo groups contained in the polyester diol (b15) is preferably 2 to 80 on average in one molecule of the polyester diol (b15) from the viewpoint of antistatic properties of the block polymer and the like. It is more preferable to have 60 pieces.

The number average molecular weight of the polyester diols (b13) to (b15) is preferably 150 to 20,000, more preferably 300 to 20,000, and particularly preferably 300 to 20,000 from the viewpoint of heat resistance and reactivity with the block (a). It is 1,000 to 15,000, most preferably 1,200 to 8,000.

The number average molecular weights of the polyester diols (b13) to (b15) are obtained by measuring using gel permeation chromatography (GPC) under the following conditions.
-Device: "HLC-8120" [manufactured by Tosoh Corporation]
-Columns: TSKgel SuperH4000, TSKgel SuperH3000 and TSKgel SuperH2000 [manufactured by Tosoh Corporation]
-Column temperature: 40 ° C
-Detector: Differential refractometer (RI)
・ Solvent: Tetrahydrofuran ・ Flow rate: 0.6 mL / min ・ Sample concentration: 0.25%
・ Injection amount: 10 μL
-Standard substance: Standard polystyrene (TSKstandardPOLYSTYRENE)
12 points (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2 , 890,000) [manufactured by Tosoh Corporation]

The hydroxyl group-modified polycycloolefin (co) polymer constituting the block (a) in the block polymer (p12) is the acid-modified cycloolefin (co) polymer and the alkanolamine compound (alkanolamine compound) exemplified in the block polymer (p11). Amidation and / or imidization is carried out by a known method under the condition of using an excess monoalkanolamine compound with respect to the carboxyl group of the acid-modified cycloolefin (co) polymer, preferably using a monoalkanolamine compound). , The residual monoalkanolamine compound can be obtained by distilling off the residual monoalkanolamine compound by a known method.

Examples of the monoalkanolamine compound include aliphatic monoalkanolamines (2-amino-ethanol (sometimes referred to as ethanolamine), 3-aminopropanol, 1-amino-2-propanol, etc.), and alicyclics. Formula monoalkanolamines (3-aminomethyl-3,5,5-trimethylcyclohexanol, etc.) and the like can be mentioned.

When the acid-modified cycloolefin (co) polymer is reacted with the alkanolamine compound, an amidation reaction and / or an imidation reaction also occurs in parallel with the esterification, so that the amine-modified polycycloolefin (co) polymer is used. , A hydroxyl-modified cycloolefin (co) polymer, an amine / hydroxyl group mixed cycloolefin (co) polymer, or a mixture thereof may be obtained. Therefore, when the terminal carboxylic acid polymer (b2) is reacted, the block (a) and the block (b) are bonded by an atomic group containing an ester bond, and the block (a) and the block (b) are amides. A block polymer containing a moiety bonded with an atomic group containing a bond may be obtained.

One or more polar atomic groups selected from the group consisting of a quaternary ammonio group, an amino group, a carboxyl group, a sulfo group, a phospho group, a hydroxyl group and an oxyethylene group constituting the block (b) in the block polymer (p12). As the terminal carboxylic acid polymer (b2) containing the repeating unit, the same raw material as the polyester diol (b12) is used, and the number of moles of the dicarboxylic acid is excessive with respect to the number of moles of the polyether diol (b11). A polyester that can be obtained by esterification in the same manner as the polyester diol (b12) can be preferably used, and more preferably, the polyether diol (b11) having a polyoxyethylene chain and a dicarboxylic acid are essential. Examples thereof include a dicarboxylic acid polymer (b21) as a constituent component.

Examples of the block polymer in which the block (a) and the block (b) are bonded via an atomic group containing an amide bond include the following.

(Block polymer 1 bonded via an atomic group containing an amide bond)
Known are an amine-modified polycycloolefin (co) polymer having a (co) polymer containing a cycloalkene as a constituent monomer and an amino group at the terminal thereof, and the terminal carboxylic acid polymer (b2). Block polymer amidated by the method (p21)

(Block polymer 2 bonded via an atomic group containing an amide bond)
One or more polar atomic groups selected from the group consisting of the acid-modified polycycloolefin (co) polymer and a quaternary ammonio group, an amino group, a carboxyl group, a sulfo group, a phospho group, a hydroxyl group and an oxyethylene group. A block polymer (p22) amidated with a terminal amino group-containing polymer (b3) containing a known method.

The amine-modified polycycloolefin (co) polymer constituting the block (a) in the block polymer (p21) is a diamine compound and the above-mentioned acid-modified cycloolefin (co) polymer exemplified in the block polymer (p11). The amidation reaction and / or imidization is carried out by a known method under the condition that an excess diamine compound is used for the carboxyl group of the acid-modified cycloolefin (co) polymer, and the residual diamine compound is obtained by a known method. It can be obtained by distilling off.
When the acid group introduced by modification in the acid-modified cycloolefin (co) polymer is a 1,2-dicarboxylic acid (anhydrous) group, it becomes amidation and / or imidization, and the acid introduced by modification. When the group is a monocarboxylic acid group, it is amidated.
The amide bond and the imide bond generated by the reaction can be confirmed by measuring the infrared absorption spectrum.

Examples of the diamine compound include aliphatic diamines having 2 to 20 carbon atoms (ethylene diamine, propylene diamine, hexamethylene diamine, 1,12-dodecanediamine, bis (2-aminoethyl) ether, etc.) and 6 to 15 carbon atoms. Alicyclic diamines (1,4-cyclohexylenediamine, isophoronediamine, 4,4'-diaminocyclohexylmethane, etc.), aromatic aliphatic diamines with 8 to 15 carbon atoms (xylylene diamine, etc.), 6 to 15 carbon atoms. Aromatic diamines [p-phenylenediamine, 2,4- or 2,6-toluenediamine, 2,2-bis (4,4'-diaminophenyl) propane, etc.] and the like can be mentioned.

The preferred terminal amino group-containing polymer (b3) to be amidated with the acid-modified polycycloolefin (co) polymer is a diamine-containing polymer (b31) in which the hydroxyl group of the polyether diol (b11) is converted into an amino group. ).
The diamine-containing polymer (b31) can be produced by a known method such as a method in which the hydroxyl group of the polyether diol (b11) is cyanoalkylated to further reduce the terminal obtained by hydrogenation or the like to convert it into an amino group. ..

The block polymer in which the block (a) and the block (b) are bonded via an atomic group containing a urethane bond includes the above-mentioned hydroxyl group-modified polycycloolefin (co) polymer and the above-mentioned terminal hydroxyl group polymer (b1). , A block polymer (p3) obtained by urethaneizing diisocyanate by a known method can be mentioned.

In the block polymer (p3), as the terminal hydroxyl group polymer (b1) constituting the block (b), a polyether diol (b11) is preferable.

Examples of the diisocyanate include aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the isocyanato group, the same applies hereinafter), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, and 8 carbon atoms. ~ 15 aromatic aliphatic diisocyanates, modified versions of these diisocyanates and mixtures of two or more thereof can be used.

Examples of the aromatic diisocyanate having 6 to 20 carbon atoms include 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'-or 4 , 4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-di Examples thereof include isocyanatodiphenyl methane and 1,5-naphthylene diisocyanate.

Examples of the aliphatic diisocyanate having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisosia. Examples thereof include natomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Examples of the alicyclic diisocyanate having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (isocyanate). 2-Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornan diisocyanate and the like can be mentioned.

Examples of the aromatic aliphatic diisocyanate having 8 to 15 carbon atoms include m- or p-xylylene diisocyanate (XDI), α, α, α', α'-tetramethylxylylene diisocyanate (TMXDI) and the like.

Examples of the modified diisocyanate include urethane modified products, urea modified products, carbodiimide modified products, and uretdione modified products.

Of these diisocyanates, TDI, MDI and HDI are preferable, and HDI is particularly preferable.

The block polymer (p4) in which the block (a) and the block (b) are bonded via an atomic group containing a urea bond includes the amine-modified polycycloolefin (co) polymer and the amino group-containing polymer. (B3), a block polymer (p41) obtained by ureaizing diisocyanate by a known method, the amine-modified polycycloolefin (co) polymer, the terminal hydroxyl group polymer (b1), and diisocyanate are known. A block polymer (p41) that has been urethane-ureaized by the method can be mentioned.

The block polymer (p5) in which the block (a) and the block (b) are bonded via an atomic group containing an imide bond is a 1,2-dicarboxylic acid among the above-mentioned acid-modified polycycloolefin (co) polymers. Examples thereof include a block polymer (p51) in which an acid-modified polycycloolefin (co) polymer obtained by using (anhydrous) and the terminal amino group-containing polymer (b3) are imidized by a known method. ..

As the block (a) constituting the block polymer of the present invention, the isocyanate group-modified polycycloolefin (co) weight that can be obtained by reacting the amine-modified polycycloolefin (co) polymer with phosgen or the like can be obtained. Epoxy resins (preferably epoxy equivalents) such as the above-mentioned acid-modified polycycloolefin (co) polymer or amine-modified polycycloolefin (co) polymer and diepoxyd (diglycidyl ether, diglycidyl ester, alicyclic diepoxyd). By reacting the epoxy-modified polycycloolefin (co) polymer obtained by reacting with 85-600)) and the above-mentioned acid-modified polycycloolefin (co) polymer with epihalohydrin (epicchlorohydrin, etc.). The obtained epoxy-modified polycycloolefin (co) polymer or the like may be used.
When these modified polycycloolefin (co) polymers are used as the block (a), the block (a) and the block (b) are bonded according to the type of functional group of the polymer or the like constituting the block (b). The atomic group to be used can be selected as appropriate.

The block (b) constituting the block polymer included in the block polymer of the present invention, the volume resistivity described in JP 2001-278985 by using the hydrophilic polymer of ¹⁰ 5 ^{~10 11 Ω} · cm Is also good.
When the hydrophilic polymer described in JP-A-2001-278985 is used as the block (b), the block (b) depends on the type of functional group of the modified polycycloolefin (co) polymer constituting the block (a). The atomic group that bonds a) and the block (b) can be appropriately selected.

The block polymers (p1) to (p5) are block polymers in which blocks (a) and blocks (b) are alternately and repeatedly bonded.
The number of iterations in the binding of the block polymer may have a distribution.
Further, the acid-modified, hydroxyl-modified, secondary acid-modified or amine-modified cycloolefin (co) polymer used as the block (a) has a carboxyl group, a hydroxyl group or an amino group at one end and one having both ends. It may be a mixture, and the block polymer (p1) may contain a block polymer having the block (a) on both or one of the ends.
That is, the block polymer of the present invention may be a mixture containing a block polymer in which blocks (a) and blocks (b) are alternately and repeatedly bonded, and containing a block polymer having a different number of repetitions and a different terminal structure. good.
Regarding the number of repetitions of the block (a) and the block (b) in the block polymer of the present invention, the acid-modified, hydroxyl-modified, secondary acid-modified or amine-modified cycloolefin (co) polymer constituting the block (a) is used. , The molar ratio of the terminal hydroxyl group polymer (b1), the terminal carboxylic acid polymer (b2), the terminal amino group-containing polymer (b3) constituting the block (b) and the isocyanate used as necessary can be adjusted. 2 It is preferably ~ 50, and more preferably an integer of 3 to 30.

In the block polymer of the present invention, the number average molecular weight of the block polymer is preferably 2,000 to 60,000, more preferably 5,000 to 40,000, and particularly preferably 8,000 to 8,000 to 60,000 from the viewpoint of antistatic performance and the like. It is 30,000.
The number average molecular weight can be measured by the same method as the number average molecular weight of the acid-modified cycloolefin (co) polymer.
The number average molecular weight of the block polymer is the acid-modified, hydroxyl-modified, secondary acid-modified or amine-modified cycloolefin (co) polymer constituting the block (a), and the terminal hydroxyl group polymer constituting the block (b). It can be adjusted by the molar ratio of b1), the terminal carboxylic acid polymer (b2), the terminal amino group-containing polymer (b3), and the isocyanate used if necessary.

In the block polymer of the present invention, the weight ratio of the block (a) constituting the block polymer to the block (b) is preferably 10/90 to 90/10, more preferably 20/80 to 75/25. be. Within this range, antistatic properties and water resistance are preferable. The weight ratio of the block (a) and the block (b) constituting the block polymer is the weight of the acid-modified, hydroxyl-modified, secondary acid-modified or amine-modified cycloolefin (co) polymer constituting the block (a). , The weight ratio of the terminal hydroxyl group polymer (b1), the terminal carboxylic acid polymer (b2), the terminal amino group-containing polymer (b3) constituting the block (b) and the isocyanate used if necessary can be adjusted.

<Antistatic agent>
The antistatic agent of the present invention contains the above-mentioned block polymer as an essential component, and is used as an antistatic resin composition by mixing with a thermoplastic resin described later.

In addition to the block polymer, the antistatic agent of the present invention comprises the acid-modified, hydroxyl-modified, secondary acid-modified or amine-modified cycloolefin (co) polymer used as a raw material for the block polymer, and the terminal hydroxyl group polymer ( b1), a terminal carboxylic acid polymer (b2), a terminal amino group-containing polymer (b3), or the like may be contained.
In the antistatic agent of the present invention, the content of the block polymer is preferably 70 to 100% by weight based on the total weight of the antistatic agent from the viewpoint of antistatic property and mechanical strength of the molded product. ..

<Antistatic resin composition>
The antistatic resin composition of the present invention contains the antistatic agent and the thermoplastic resin as essential components.

Examples of the thermoplastic resin contained in the antistatic resin composition of the present invention include a polymer (PA1), a polymer (PA2), and the thermoplastic resin [polyphenylene ether resin (B1)] described in JP-A-2015-166446. , Polyolefin resin (B2), Poly (meth) acrylic resin (B3), Polystyrene resin (B4), Polyester resin (B5) Polyamide resin (B6), Polycarbonate resin (B7), Polyacetal resin (B8), and 2 of these. A mixture of more than seeds] and the like.
Among them, the thermoplastic resin contained in the antistatic resin composition of the present invention includes a polymer (PA1) and a polymer (PA2) [a resin which is a (co) polymer containing cycloalkene as a constituent monomer]. Is preferable.

In the antistatic resin composition of the present invention, the content of the antistatic agent is preferably 1 to 1 from the viewpoint of antistatic property and mechanical properties of the molded product based on the total weight of the antistatic agent and the thermoplastic resin. It is 40% by weight, more preferably 5 to 20% by weight.

The antistatic resin composition of the present invention contains, if necessary, an antistatic agent (metal or quaternary ammonium salt, surfactant) described in JP-A-2015-166446, as long as the effect of the present invention is not impaired. Activators and ionic liquids, etc.), compatibilizers and other resin additives (pigments, dyes, nucleating agents, lubricants, plasticizers, mold release agents, antioxidants, UV absorbers, antibacterial agents, etc.), etc. It may be contained.

In the antistatic resin composition of the present invention, the above-mentioned antistatic agent, thermoplastic resin, antistatic agent used as necessary, compatibilizer, other resin additives and the like are melt-mixed by a known method. Obtained by
As a method of melt-mixing, a method of mixing pellet-like or powder-like components with an appropriate mixer (Henschel mixer or the like) and then melt-mixing with an extruder to form pellets can be applied.
The method of adding each component at the time of melt mixing is not particularly limited, and the components can be added by the method described in (Method 1) or (Method 2) below, and (Method 2) is preferable.

(Method 1) A method of collectively melting and mixing an antistatic agent, a thermoplastic resin, an antistatic agent used as necessary, and the like.
(Method 2) A part of the thermoplastic resin and the antistatic agent are melt-mixed in advance to prepare a high-concentration resin composition (masterbatch resin composition) of the antistatic agent, and then the remaining thermoplastic resin and necessary A method of melting and mixing an antistatic agent or the like.
In the above (method 2), the concentration of the antistatic agent in the masterbatch resin composition is preferably 40 to 80% by weight, more preferably 50 to 70% by weight, based on the total weight of the masterbatch.

The antistatic resin molded product of the present invention is a molded product obtained by molding the antistatic resin composition. Molding methods for the antistatic resin composition include injection molding, compression molding, calender molding, slush molding, rotary molding, extrusion molding, blow molding, foam molding, film molding (cast method, tenter method, inflation method, etc.), etc. Can be molded by any method depending on the purpose. Of the above-mentioned molded products, it is preferably suitable as an injection-molded product.
The antistatic resin composition of the present invention can be molded in a wide range of temperatures, and it is preferable to mold in a temperature range of 150 to 300 ° C. Within this range, excellent formability is exhibited.

The antistatic resin molded product of the present invention can be used for parts of electric / electronic devices, packaging materials, transport materials, living materials, building materials and the like.

The antistatic resin molded product of the present invention has excellent permanent antistatic properties and mechanical properties, as well as good paintability and printability.
Examples of the method of applying the paint to the molded product include, but are not limited to, an air spray method, an airless spray method, an electrostatic spray method, a dipping method, a roller method, and a brush coating method. Examples of the paint include various paints such as polyester melamine, epoxy melamine, acrylic melamine and acrylic urethane resin paint.
The coating film thickness (film thickness after drying) can be appropriately selected depending on the intended purpose, but is preferably 10 to 50 μm, more preferably 15 to 40 μm from the viewpoint of the physical characteristics of the coating film.
Further, as a method of printing on the molded product, various printing methods such as gravure printing, flexographic printing, screen printing and offset printing can be mentioned. Examples of the printing ink include those usually used for printing plastics.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto. In an embodiment, parts mean parts by weight.

<Production Example 1: Production of Acid-Modified Cycloolefin Polymer>
^{Cycloolefin polymer ["ZEONOR1020R" manufactured by Nippon Zeon Co., Ltd., tricyclo [4.3.0.1 2,5} ]) in a 3L 4-necked flask equipped with a nitrogen introduction tube, a thermometer, an exhaust gas distilling tube and a stirring rod. A hydrogenated product of -3-decene polymer, number average molecular weight: 33,000] was charged under a nitrogen atmosphere. After that, nitrogen continued to be aerated in the flask at a flow rate of 80 mL / min until the end of heat reduction.
Next, heat was reduced by heating with a mantle heater, raising the temperature, and stirring the mixture at 410 ± 1 ° C. under nitrogen aeration for 16 minutes. The heat-reduced product was then cooled to 200 ° C. and then removed from the flask. The obtained heat-reduced product (a1-1) has a number average molecular weight of 3,400, the number of terminal double bonds per 1000 carbons is 7.4, and the amount of double bonds per molecule. The number was 1.8, and 90% by weight of a cycloolefin polymer having a double bond at both ends was contained.
90 parts of the heat-reduced product (a1-1), 10 parts of maleic anhydride and 30 parts of xylene are charged in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introduction tube and a decompression device. After uniformly mixing, the mixture was replaced with nitrogen, and the temperature was raised to 200 ° C. with stirring under sealing to melt the mixture, and the mixture was reacted for 10 hours. After the reaction, the temperature inside the system was reduced to 1.3 kPa or less while the temperature was maintained at 200 ° C., and a degassing step was performed for 3 hours to remove volatile components (unreacted maleic anhydride and xylene) at 160 ° C. After cooling to, the reaction product, an acid-modified cycloolefin polymer (a1-1-1α), was taken out. The acid value of the acid-modified cycloolefin polymer (a1-1-1α) was 28.0, and the number average molecular weight (Mn) was 3,600.

<Production Example 2: Production of secondary acid-modified cycloolefin polymer>
88 parts of the acid-modified polycycloolefin polymer (a1-1-1α) obtained in Production Example 1 and 12 parts of 12-aminododecanoic acid were charged into a stainless steel autoclave, and 200 parts were stirred in a nitrogen gas atmosphere. The mixture was heated and melted at ° C., and the amidation reaction was carried out under reduced pressure (1.3 kPa or less) for 3 hours while maintaining the temperature to obtain 96 parts of a secondary acid-modified cycloolefin polymer (a1-1-2). .. The acid value of the secondary acid-modified cycloolefin polymer (a1-1-2) was 25.2, and the Mn was 4,000.

<Production Example 3: Production of Hydroxyl Modified Cycloolefin Copolymer>
Cycloolefin copolymer [“APL6015T” manufactured by Mitsui Chemicals, Inc., tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] -3-dodecene-ethylene copolymer, ethylene content 73 mol%, number average molecular weight: 120,000] were charged under a nitrogen atmosphere. After that, nitrogen continued to be aerated in Kolben at a flow rate of 80 mL / min until the end of heat reduction. Next, heat was reduced by heating with a mantle heater, raising the temperature, and stirring the mixture at 410 ± 0.1 ° C. under nitrogen aeration for 16 minutes. The heat-reduced product was then cooled to 200 ° C. and then removed from the flask. The obtained heat-reduced product (a1-2) has a number average molecular weight of 10000, the number of terminal double bonds per 1000 carbons is 2.5, and the amount of double bonds per molecule is 1. It was 0.8 and contained 90% of cycloolefin copolymers having double bonds at both ends.
94 parts of the heat-reduced product (a1-2), 6 parts of maleic anhydride and 30 parts of xylene are charged in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introduction tube and a depressurizing device. After uniformly mixing, the mixture was replaced with nitrogen, heated to 200 ° C. with stirring under sealing, melted, and reacted at 200 ° C. for 10 hours. After the reaction, the inside of the system was depressurized while the temperature was maintained at 200 ° C., and then the inside of the system was depressurized to 1.3 kPa or less and degassed for 3 hours to carry out volatile components (unreacted maleic anhydride and xylene). ) Was removed, and after cooling to 160 ° C., the acid-modified cycloolefin copolymer (a1-2-1α) as a reactant was taken out. The acid value of the acid-modified cycloolefin copolymer (a1-2-1α) was 9.8, and the number average molecular weight was 10200.
Next, 97 parts of (a1-2-1α) and 5 parts of ethanolamine were put into the same pressure-resistant reaction vessel as in Production Example 1, and the temperature was raised to 180 ° C. with stirring under a nitrogen gas atmosphere, and 2 at the same temperature. Reacted for time. Excess ethanolamine was distilled off under reduced pressure (0.013 MPa or less) at 180 ° C. for 2 hours to obtain a hydroxyl group-modified cycloolefin copolymer (a2-1) having a hydroxyl group at the end. The hydroxyl value of the hydroxyl group-modified cycloolefin copolymer (a2-1) was 9.8, the amine value was 0.01, and Mn was 10,200.

<Production Example 4: Production of Amine-Modified Cycloolefin Polymer>
A heat-reduced product (a1-1β) was obtained in the same manner except that the heat-reducing time was changed from 16 minutes to 20 minutes in Production Example 1. The obtained heat-reduced product (a1-1β) has a number average molecular weight of 1,500, the number of terminal double bonds per 1000 carbons is 17.8, and the amount of double bonds per molecule. Was 1.9 and contained 95% by weight of a cycloolefin polymer having double bonds at both ends. 80 parts of the heat-reduced product (a1-1β), 20 parts of maleic anhydride and 30 parts of xylene are charged in a stainless steel pressure resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introduction tube and a depressurizing device. After uniformly mixing, the mixture was replaced with nitrogen, heated to 200 ° C. with stirring under sealing, melted, and reacted at 200 ° C. for 10 hours. After the reaction, the inside of the system was depressurized while the temperature was maintained at 200 ° C., and then the inside of the system was depressurized to 1.3 kPa or less and degassed for 3 hours to carry out volatile components (unreacted maleic anhydride and xylene). ) Was removed, and after cooling to 160 ° C., the acid-modified cycloolefin polymer (a1-1-1β) as a reaction product was taken out. The acid value of the acid-modified cycloolefin polymer (a1-1-1β) was 62.9, and Mn was 1,700.
Next, 90 parts of (a1-1-1β) and 10 parts of bis (2-aminoethyl) ether were put into the same pressure-resistant reaction vessel as in Production Example 1, and the temperature was raised to 200 ° C. with stirring under a nitrogen gas atmosphere. Then, the reaction was carried out at the same temperature for 2 hours. Excess bis (2-aminoethyl) ether was distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 2 hours to obtain an amine-modified cycloolefin polymer (a3-1). The amine-modified cycloolefin polymer (a3-1) had an amine value of 62.9 and Mn of 1,700.

<Production Example 5: Production of a terminal hydroxyl group polymer having a quaternary ammonium group as a repeating unit>
41 parts of N-methyldiethanolamine, 49 parts of adipic acid and 0.3 part of zirconyl acetate were put into the same pressure-resistant reaction vessel as in Production Example 1, and after nitrogen substitution, the temperature was raised to 220 ° C. over 2 hours and 1 hour. The pressure was reduced to 0.013 MPa and the polyesterification reaction was carried out. After completion of the reaction, the mixture was cooled to 50 ° C. and 100 parts of methanol was added to dissolve the reaction. The temperature in the reaction vessel was maintained at 120 ° C. with stirring, 31 parts of dimethyl carbonate was added dropwise over 3 hours, and the reaction was continued at the same temperature for 6 hours. After cooling to room temperature, 100 parts of a 60 wt% hexafluorophosphoric acid aqueous solution was added, and the mixture was stirred at room temperature for 1 hour. Next, methanol was distilled off under reduced pressure, and a terminal hydroxyl group polymer (b1-1) having a quaternary ammonium group having an average of 10 quaternary ammonium groups (hydroxyl value: 30.1, acid value: 0.5, volume resistivity) was used. Value: 1 × 10 ⁵ Ω · cm) was obtained.
The average number of quaternary ammonium groups contained in the terminal hydroxyl group polymer (b1-1) is calculated using the average molecular weight of the polymer calculated from the hydroxyl value and the acid value and the molecular weight of the monomers constituting the polymer. The number of repeating units contained in one polymer chain.

<Production Example 6: Production of a terminal hydroxyl group polymer having a sulfo group as a repeating unit>
114 parts of diethylene glycol, 268 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 parts of dibutyltin oxide were put into the same pressure resistant reaction vessel as in Production Example 1, and the temperature was raised to 190 ° C. under a reduced pressure of 0.067 MPa. After warming and transesterifying at the same temperature for 6 hours while distilling off methanol, a terminal hydroxyl group polymer (b1-2) having a sulfo group having an average of 6 sodium sulfonate bases in one molecule (hydroxyl value is 49, acid value 0.6, volume resistivity was obtained ^{3 × 10 8 Ω · cm)} .
The average number of sodium sulfonate bases contained in the terminal hydroxyl group polymer (b1-2) is calculated using the average molecular weight of the polymer calculated from the hydroxyl value and the acid value and the molecular weight of the monomers constituting the polymer. The number of repeating units contained in one polymer chain.

<Production Example 7: Production of a terminal hydroxyl group polymer having an oxyethylene group as a repeating unit>
43.7 parts of ethylene glycol, 28.6 parts of terephthalic acid, 28.6 parts of isophthalic acid, and 0.3 part of triethanolamine titanate are put into the same pressure-resistant reaction vessel as in Production Example 1, and the temperature is 220 ° C. with stirring. The temperature was raised to 17.9 and polymerized at the same temperature under reduced pressure (0.040 MPa or less) to obtain a terminal hydroxyl group polymer (b1-3) (hydroxyl value: 17.9, Mn: 3,300).

<Example 1>
66.7 parts of the acid-modified polycycloolefin polymer (a1-1-1α) obtained in Production Example 1 and a polyether diamine [α, ω-diaminoPEG (Mn: 2,000, volume specific) are placed in a stainless steel autoclave. Resistance value: 1 × 10 ⁷ Ω · cm)] 33.3 parts, 0.3 parts of the antioxidant “Irganox 1010” and 0.5 parts of zirconyl acetate were added, and the temperature was raised to 220 ° C. with stirring. Polymerization was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 3 hours to obtain a viscous block polymer (X-1). The Mn of the block polymer (X-1) was 50,000.

<Example 2>
66.7 parts of the acid-modified polycycloolefin polymer (a1-1-1α) and 33.3 parts of the polyether diamine were added to the secondary acid-modified cycloolefin polymer (a1-1-2) obtained in Production Example 2. ) 59.7 parts and 40.3 parts of polyether diol [PEG (Mn: 3,000, volume specific resistance value: 1 × 10 ⁷ Ω · cm)] in the same manner as in Example 1. A block polymer (X-2) was obtained. The Mn of (X-2) was 30,000.

<Example 3>
66.7 parts of the acid-modified polycycloolefin polymer (a1-1-1α) and 33.3 parts of the polyether diamine were added to the secondary acid-modified cycloolefin polymer (a1-1-2) obtained in Production Example 2. ) 52.6 parts and EO adduct of bisphenol A (Mn: 4,000, volume specific resistance value: 2 × 10 ⁷ Ω) 48.5 parts in the same manner as in Example 1 except that the block polymer (Mn: 4,000, volume specific resistance value: 2 × 10 7 Ω) X-3) was obtained. The Mn of (X-3) was 24,000.

<Example 4>
A terminal hydroxyl group polymer (b1-1) having 48.5 parts of the hydroxyl group-modified cycloolefin copolymer (a2-1) obtained in Production Example 3 and a quaternary ammonio group obtained in Production Example 5 in a stainless steel autoclave. 48.5 parts and 3 parts of hexamethylene diisocyanate (HDI) were added, the temperature was raised to 200 ° C. with stirring, and the mixture was polymerized for 3 hours to obtain a viscous block polymer (X-4). The Mn of (X-4) was 100,000.

<Example 5>
45.0 parts of the amine-modified cycloolefin polymer (a1-3) obtained in Production Example 4 and a terminal hydroxyl group polymer (b1-2) 45.0 having a sulfo group obtained in Production Example 6 in a stainless steel autoclave. Add 9 parts of dodecane diic acid, 0.3 part of antioxidant "Irganox 1010" and 0.5 part of zirconyl acetate, raise the temperature to 220 ° C with stirring, and reduce the pressure (0.013 MPa or less). Polymerization at temperature for 3 hours gave a viscous block polymer (X-5). The Mn of (X-5) was 100,000.

<Example 6>
In a stainless steel autoclave, 41.2 parts of the acid-modified polycycloolefin polymer (a1-1-1α) obtained in Production Example 1, 58.8 parts of polyester obtained in Production Example 7, and the antioxidant "Irganox". 1010 ”0.3 parts was added, the temperature was raised to 220 ° C. with stirring, and the mixture was polymerized at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours to obtain a viscous block polymer (X-6). .. The Mn of the block polymer (X-6) was 30,000.

<Comparative manufacturing example 1>
In Production Example 1, the cycloolefin polymer was made of low molecular weight polypropylene [Mn 3,400, double bond content of 7.4 per 1,000 carbon atoms, average number of double bonds per molecule of 1.8, both-ended modification. An acid-modified polypropylene (ratio a1-1-α) was obtained in the same manner as in Production Example 1 except that the content was changed to 90% of possible propylene. The acid value of (ratio a1-1-1α) was 28.0, and Mn was 3,600.

<Comparative Example 1>
Same as Example 1 except that 66.7 parts of the acid-modified polycycloolefin polymer (a1-1-1α) was changed to 66.7 parts of the acid-modified polypropylene (ratio a1-1-1α). A comparative block polymer (ratio X-1) was obtained. The Mn of (ratio X-1) was 50,000.

<Examples 7 to 15, Comparative Examples 2 to 3>
Each of the obtained block polymers (X) is used as an antistatic agent as it is, and the composition (unit: parts by weight) shown in Table 1 is blended with a Henschel mixer for 3 minutes, and then 100 rpm with a twin-screw extruder with a vent. Each antistatic resin composition was obtained by melt-kneading at 200 ° C. and a residence time of 5 minutes.

<Manufacturing of antistatic resin molded products>
Each of the obtained antistatic resin compositions is an antistatic resin molded product using an injection molding machine [“PS40E5ASE”, manufactured by Nissei Resin Industry Co., Ltd.] at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. Specimens were prepared, evaluated by the following performance tests, and the results are shown in Table 1.

The contents of the symbols in Table 1 are as follows.
(C-1): Polycycloolefin polymer ["Zeonoa 1020R", manufactured by Nippon Zeon Corporation]
(C-2): Copolymer ["Apel APL6013T", manufactured by Mitsui Chemicals, Inc.]
(D1-1): 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (D1-2): sodium dodecylbenzene sulfonic acid salt (D4-1): antioxidant {"Irganox 1010", Ciba Specialty Chemicals Co., Ltd., Tetrakiss [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane}

<Performance test>
(1) Surface specific resistance value (unit: Ω)
According to ASTM D257, the test piece (100 mm × 100 mm × 2 mm) was measured using a super insulation meter “DSM-8103” [manufactured by Toa Denpa Co., Ltd.] in an atmosphere of 23 ° C. and 50% humidity RH.

(2) Izod impact strength (unit: J / m)
Measured according to ASTM D256 Methods A (notched, 3.2 mm thick).

(3) Appearance (3-1) Surface appearance The appearance of the surface of the test piece (100 mm × 100 mm × 2 mm) was visually observed and evaluated according to the following criteria.
[Evaluation criteria]
A: Good without any abnormalities (equivalent to thermoplastic resin containing no antistatic agent)
C: Rough surface, blisters, etc. are observed.

(3-2) Cross-sectional appearance The test piece was cut with a cutter perpendicular to the surface so as to pass through the center of the surface of the test piece (100 mm × 100 mm × 2 mm), and the cross section was visually observed and evaluated according to the following criteria. ..
[Evaluation criteria]
A: The cross section is uniform and good (equivalent to a thermoplastic resin that does not contain an antistatic agent).
C: The cross section is layered and non-uniform.

(4) Heat resistance (4-1) Pyrolysis temperature (° C)
A 10 mg test piece was cut out and subjected to thermogravimetric analysis at a heating rate of 10 ° C./min and in an air atmosphere, and the temperature at which the sample weight was reduced by 5% was defined as the thermal decomposition start temperature (° C.). As the thermogravimetric analyzer, TGA-50 (manufactured by Shimadzu Corporation) was used.

(4-2) Deflection temperature under load (° C)
The deflection temperature under load (° C.) was measured according to JIS K7191-2.

From Table 1, the antistatic agent of the present invention can obtain a molded product having excellent antistatic properties as compared with the comparative one, and the obtained molded product is excellent in appearance, mechanical strength and heat resistance. I understand. This is considered to be due to the good dispersibility.

The block polymer of the present invention can be used as a polymer type antistatic agent.

Claims (5)

A block polymer containing a block (a) satisfying the following (1) and a block (b) satisfying the following (2).
(1) The block (a) has a (co) polymer containing cycloalkene having a norbornene skeleton as a constituent monomer;
(2) One selected from the group in which the block (b) is other than the block (a) and consists of a quaternary ammonio group, an amino group, a carboxyl group, a sulfo group, a phospho group, a hydroxyl group, and an oxyethylene group. Includes repeating unit (B) with the above polar atomic groups; The block polymer according to claim 1, wherein the weight ratio of the block (a) to the block (b) is 10/90 to 90/10. An antistatic agent comprising the block polymer according to claim 1 or 2. An antistatic resin composition containing the antistatic agent according to claim 3 and a thermoplastic resin. An antistatic resin molded product obtained by molding the antistatic resin composition according to claim 4.