JP7389688B2 - block polymer - Google Patents

Description

The present invention relates to block polymers.

Polyolefins are commonly used as general purpose materials. Furthermore, modified polyolefins have been developed for use in a wide range of applications. (For example, Patent Document 1).

Japanese Patent Application Publication No. 2016-156007

However, even the technique disclosed in Patent Document 1 has insufficient solvent solubility and cannot be applied to coating agents. An object of the present invention is to provide a block polymer with excellent solvent solubility.

The present inventors conducted studies to achieve the above object, and as a result, they arrived at the present invention. That is, the present invention provides a block polymer having a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as constitutional units, wherein (a) is a polyolefin containing propylene as a constituent monomer. (a2) is a block polymer in which the isotacticity of the propylene moiety of (a2) is 1 to 50%, the weight ratio of the ethylene units and propylene units of (a2) [ethylene units/propylene units ] is 5/95 to 40/60 .

The block polymer (A) of the present invention has the following effects.
(1) Excellent solvent solubility.
(2) Excellent adhesion to substrates.
(3) Excellent antistatic properties.

<Polyolefin (a2)>
The polyolefin (a2) in the present invention is a hydrophobic polymer (a), and is a polyolefin containing propylene as a constituent monomer. Note that the hydrophobic polymer (a) means a polymer having a volume resistivity value exceeding 1×10 ¹¹ Ω·cm.
Note that the volume resistivity value in the present invention is a value obtained by measurement in an atmosphere of 23° C. and 50% RH in accordance with ASTM D257 (1984).
In addition, in the present invention, the polyolefin (a2) may be described as a hydrophobic polymer (a) for convenience, and may be described as (a1) in the examples described below.

The isotacticity of the propylene moiety of polyolefin (a2) is 1 to 50%, preferably 4 to 45%, and more preferably 10 to 40%.
If the isotacticity is less than 1%, the adhesion to the substrate will be poor, and if the isotacticity is more than 50%, the solvent solubility will be poor.

By selecting a polyolefin whose propylene moiety has an isotacticity within the above range and bonding it with the hydrophilic polymer block (b), the isotacticity of the propylene moiety of the polyolefin (a2) is within the above range. A block polymer (A) can be obtained.

It is known that the degree of stereoregularity of the propylene moiety depends on the selection of the polymerization catalyst used when polymerizing propylene, the polymerization conditions of the polyolefin, and the like. The isotacticity of the polyolefin used as a raw material and the isotacticity of the polyolefin (a2) can be confirmed using ¹³ C-NMR (nuclear magnetic resonance spectroscopy). In general, the side chain methyl group is present on both sides (triad, triad), on both sides of the triad (pentad, pentad), and even on both sides of the quintad (septad, heptad). It is known that peaks are observed at different chemical shifts due to the influence of the configuration (meso or racemo) with the methyl group, and stereoregularity is generally evaluated for pentads. The isotacticity in can also be calculated based on the pentad evaluation.
That is, regarding the carbon peak derived from the side chain methyl group in propylene obtained by ¹³ C-NMR, each pentad peak (H), the peak derived from the methyl group in isotactic propylene in which the pentad is formed only in a meso structure (H _a ), isotacticity is calculated using the following formula.
Isotacticity (%) = [(H _a )/Σ(H)]×100 (1)
However, in the formula, H _a is the peak height of an isotactic signal (pentads are formed only with a meso structure), and H is the height of each peak of the pentad.

From an industrial standpoint, the polyolefin (a2) preferably contains ethylene and propylene as constituent monomers.
In that case, the weight ratio of the ethylene units and propylene units [ethylene units/propylene units] is preferably 2/98 to 50/50, more preferably 5/95 from the viewpoint of substrate adhesion and solvent solubility. ~40/60, particularly preferably 10/90 ~ 30/70.
The weight ratio [ethylene units/propylene units] can be calculated, for example, by ¹ H-MNR.

In addition to ethylene and propylene, other monomers may be used as constituent monomers in (a2). In that case, the weight of other monomers is preferably 10% by weight or less, more preferably 5% by weight or less, particularly preferably 1% by weight or less, based on the weight of all monomers constituting (a2). It is.
Examples of the other monomers mentioned above include 1- and 2-butene, isobutene, α-olefins having 5 to 30 carbon atoms (sometimes abbreviated as C) (1-hexene, 1-decene, 1-dodecene, etc.), C4-30 unsaturated monomers (eg, vinyl acetate).

Examples of the polyolefin (a2) include polyolefin (a2-1) having carboxyl groups at both ends of the polymer, polyolefin (a2-2) having hydroxyl groups at both ends of the polymer, and polyolefin (a2) having amino groups at both ends of the polymer. -3) and a polyolefin having isocyanate groups at both ends of the polymer (a2-4), a polyolefin having a carboxyl group at one end of the polymer (a2-5), a polyolefin having a hydroxyl group at one end of the polymer (a2-6) , a polyolefin (a2-7) having an amino group at one end of the polymer, and a polyolefin (a2-8) having an isocyanate group at one end of the polymer. Among these, preferred are (a2-1) and (a2-5) having a carboxyl group at the end.
Note that the terminus in the present invention refers to a terminal portion where the repeating structure of monomer units constituting the polymer is interrupted. Further, "both ends" means both ends of the main chain of the polymer, and "one end" means either end of the main chain of the polymer.

As (a2-1), the polyolefin (a2 -01) with carboxyl groups introduced at both ends; (a2-2) is (a2-01) with hydroxyl groups introduced at both ends; (a2-3) is (a2-01) As (a2-4), (a2-01) with isocyanate groups introduced at both ends can be used.

(a2-5) to (a2-8), instead of polyolefin (a2-01), a polyolefin that can be modified at one end is used as a main component (preferably content of 50% by weight or more, more preferably 75% by weight) Polyolefin (a2-02) having a carboxyl group, a hydroxyl group, an amino group, or an isocyanate group introduced at one end can be used.

The polyolefin (a2-01) whose main component is a polyolefin that can be modified at both ends includes one or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10). (Co)polymerization of the mixture [(Co)polymerization means polymerization or copolymerization. Same below. ] Polyolefins obtained by (polymerization method) and degraded polyolefins {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 50,000 to 150,000] polyolefins are mechanically, thermally or chemically (degradation method)} is included.
Among these, preferred are degraded polyolefins from the viewpoint of ease of modification and availability when introducing carboxyl groups, hydroxyl groups, amino groups, or isocyanate groups, and more preferred are degraded polyolefins. It is a degraded polyolefin. According to the thermal degradation, a low molecular weight polyolefin having an average terminal double bond number of 1.5 to 2 per molecule can be easily obtained as described later, and the low molecular weight polyolefin has carboxyl groups, hydroxyl groups, and amino groups. Alternatively, it is easy to modify by introducing an isocyanate group or the like.

Mn (number average molecular weight) and Mw (weight average molecular weight) in the present invention can be measured using gel permeation chromatography (GPC) under the following conditions.
Device (one example): "HLC-8120" [manufactured by Tosoh Corporation]
Column (one example): "TSKgelGMHXL" (2 columns)
"TSKgelMultiporeHXL-M" (1 piece)
Sample solution: 0.3% by weight orthodichlorobenzene solution Solution injection amount: 100μl
Flow rate: 1ml/min Measurement temperature: 135℃
Detection device: Refractive index detector Reference material: 12 points of standard polystyrene (TSK standard POLYSTYRENE) (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 heat-degraded polyolefin is not particularly limited, but it is one obtained by heating a high molecular weight polyolefin in an inert gas (at 300 to 450°C for 0.5 to 10 hours, for example, JP-A No. 3-62804). (obtained by the method described in the publication), and those thermally degraded by heating in air.

The high molecular weight polyolefin used in the thermal degradation method is a (co)polymer of one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10). [Mn is preferably 12,000 to 100,000, more preferably 15,000 to 70,000. The melt flow rate (hereinafter abbreviated as MFR, unit: g/10min) is preferably 0.5 to 150, more preferably 1 to 100. ] etc.
Here, MFR is a numerical value representing the melt viscosity of the resin, and the larger the numerical value, the lower the melt viscosity. For the measurement of MFR, an extrusion type plastometer defined in JIS K6760 is used, and the measurement method is based on the method defined in JIS K7210 (1976). For example, in the case of polypropylene, it is measured at 230° C. and a load of 2.16 kgf.
Examples of the olefin having 2 to 30 carbon atoms include α-olefins having 2 to 30 carbon atoms and dienes having 4 to 30 carbon atoms.
Examples of α-olefins having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-icosene, and 1- Examples include tetracosene.
Examples of the diene having 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene, and 1,11-dodecadiene.
Among olefins having 2 to 30 carbon atoms, preferred from the viewpoint of molecular weight control are ethylene, propylene, α-olefins having 4 to 12 carbon atoms, butadiene, isoprene, and mixtures thereof, and more preferred are ethylene, Propylene, α-olefins having 4 to 10 carbon atoms, butadiene and mixtures thereof, particularly preferred are ethylene, propylene, butadiene and mixtures thereof.

From the viewpoint of solvent solubility and substrate adhesion, Mn of the polyolefin (a2-01) is preferably 800 to 20,000, more preferably 1,000 to 10,000, particularly preferably 1,200 to 6,000.
The number of terminal double bonds in (a2-01) is preferably 1 to 40 per 1,000 carbon atoms, more preferably 2 to 30, from the viewpoint of solvent solubility and substrate adhesion. Particularly preferably 4 to 20 pieces.

(a2-01) The average number of terminal double bonds per molecule is preferably 1.1 to 5 from the viewpoint of ease of forming a repeating structure in the molecule, solvent solubility, and substrate adhesion. , more preferably 1.3 to 3, particularly preferably 1.5 to 2.5, most preferably 1.8 to 2.2.

By using the method of obtaining low molecular weight polyolefins by thermal degradation, it is easy to obtain (a2-01) with Mn in the range of 800 to 6,000 and an average number of terminal double bonds per molecule of 1.5 to 2. [Katsuhide Murata, Tadahiko Makino, Journal of the Chemical Society of Japan, p. 192 (1975)].

Polyolefin (a2-02) whose main component is a polyolefin that can be modified at one end can be obtained in the same manner as (a2-01), and Mn in (a2-02) is determined by solvent solubility and substrate adhesion. From the viewpoint of performance, it is preferably 2,000 to 50,000, more preferably 2,500 to 30,000, particularly preferably 3,000 to 20,000.
The number of double bonds per 1,000 carbon atoms in (a2-02) is preferably 0.3 to 20, more preferably 0.5 to 20, from the viewpoint of controlling the molecular weight of the block polymer (A). The number is 15, particularly preferably 0.7 to 10.

(a2-02) The average number of double bonds per molecule is preferably 0.5 to 1.4 from the viewpoint of ease of forming a repeating structure in the molecule and productivity of the block polymer (A) described below. It is more preferably 0.6 to 1.3, particularly preferably 0.7 to 1.2, and most preferably 0.8 to 1.1.
Among (a2-02), preferred from the viewpoint of ease of modification are low molecular weight polyolefins obtained by a thermal degradation method, and more preferred are low molecular weight polyolefins obtained by a thermal degradation method with an Mn of 3 ,000 to 20,000 polyethylene and/or polypropylene.
When using the method of obtaining low molecular weight polyolefins by thermal degradation, Mn is in the range of 6,000 to 30,000 and the average number of terminal double bonds per molecule is 1 to 1.5 (a2- 02) is obtained.
Since the low molecular weight polyolefin obtained by the thermal degradation method has the above-mentioned average number of terminal double bonds, it can be easily modified by introducing carboxyl groups, hydroxyl groups, amino groups, isocyanate groups, etc.

Note that (a2-01) and (a2-02) are usually obtained as a mixture thereof, but the mixture may be used as it is, or may be used after being purified and separated. Among these, mixtures are preferred from the viewpoint of manufacturing costs and the like.

Hereinafter, (a2-1) to (a2-4) having a carboxyl group, hydroxyl group, amino group or isocyanate group at both ends of the polyolefin (a2-01) will be explained. Regarding (a2-5) to (a2-8) having these groups, do the same as (a2-1) to (a2-4) with (a2-01) replaced with (a2-02). You can get it.

As the polyolefin (a2-1) having carboxyl groups at both ends of the polymer, the terminals of (a2-01) are α,β-unsaturated carboxylic acid (anhydride) (α,β-unsaturated carboxylic acid, its alkyl Polyolefin (a2-1-1), (a2-1-1) having a structure modified with (1 to 4 carbon atoms) ester or its anhydride; the same shall apply hereinafter) is dioxidized with lactam or aminocarboxylic acid. Polyolefins (a2-1-2), (a2-1-3), (a2-1-3) having a structure modified by oxidation or hydroformylation of polyolefins (a2-1-2), (a2-01) having a structure modified by lactam or Polyolefins (a2-1-4) having a structure secondarily modified with aminocarboxylic acids and mixtures of two or more thereof can be used.

(a2-1-1) can be obtained by modifying (a2-01) with an α,β-unsaturated carboxylic acid (anhydride).
Examples of the α,β-unsaturated carboxylic acid (anhydride) used for modification include monocarboxylic acids, dicarboxylic acids, alkyl (1 to 4 carbon atoms) esters of mono- or dicarboxylic acids, and anhydrides of mono- or dicarboxylic acids. Specifically, (meth)acrylic acid [(meth)acrylic acid means acrylic acid or methacrylic acid. Same below. ], methyl (meth)acrylate, butyl (meth)acrylate, maleic acid (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride), diethyl itaconate, and citraconic acid (anhydride). It will be done.
Among these, preferred from the viewpoint of ease of modification are dicarboxylic acids, alkyl esters of mono- or dicarboxylic acids, and anhydrides of mono- or dicarboxylic acids, and more preferred are maleic acid (anhydride) and fumaric acid. Particularly preferred is maleic acid (anhydride).

The amount of α,β-unsaturated carboxylic acid (anhydride) used for modification is determined based on the weight of polyolefin (a2-01), the ease of forming a repeating structure in the molecule, and the production of block polymer (A) described below. From the viewpoint of properties, the amount is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight.
Modification with an α,β-unsaturated carboxylic acid (anhydride) can be carried out, for example, by adding an α,β-unsaturated carboxylic acid to the terminal double bond of (a2-01) by either a solution method or a melt method. (anhydride) by addition reaction (ene reaction), and the reaction temperature is preferably 170 to 230°C.

(a2-1-1) can be obtained by secondarily modifying (a2-1) with a lactam or an aminocarboxylic acid.
Examples of the lactam used for secondary modification include lactams having 6 to 12 carbon atoms (preferably 6 to 8, more preferably 6), such as caprolactam, enantholactam, laurolactam, undecanolactam, etc. can be mentioned.
Examples of aminocarboxylic acids include aminocarboxylic acids having 2 to 12 carbon atoms (preferably 4 to 12 carbon atoms, more preferably 6 to 12 carbon atoms), and specifically, amino acids (glycine, alanine, valine, leucine, isoleucine). and phenylalanine, etc.), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
Among lactams and aminocarboxylic acids, preferred are caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, and more preferred are caprolactam, laurolactam, ω-Aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, particularly preferred are caprolactam and 12-aminododecanoic acid.

The amount of lactam or aminocarboxylic acid used for secondary modification is determined based on the weight of the substance to be modified (a2-1), from the viewpoint of ease of forming a repeating structure in the molecule and thermoplasticity of the block polymer (A). , preferably 0.5 to 200% by weight, more preferably 1 to 150% by weight, particularly preferably 2 to 100% by weight.

(a2-3) can be obtained by introducing a carboxyl group by oxidizing (a2-01) with oxygen and/or ozone (oxidation method) or by hydroformylation using the oxo method.
Introduction of a carbonyl group by an oxidation method can be carried out by a known method, for example, the method described in US Pat. No. 3,692,877. Introduction of a carbonyl group by hydroformylation can be carried out by various methods including those known in the art, for example, Macromolecules, Vol. 31, p. 5943.
(a2-4) can be obtained by secondarily modifying (a2-3) with a lactam or an aminocarboxylic acid.
Examples of the lactam and aminocarboxylic acid include those exemplified as the lactam and aminocarboxylic acid used in the secondary modification in (a2-1) above, and the preferred range and amount used are also the same.

Mn in (a2-1) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly Preferably it is 2,500 to 10,000.
Further, the acid value of (a2-1) is preferably 4 to 280 mgKOH/g, more preferably 4 to 100 mgKOH/g, particularly from the viewpoint of reactivity with (b) and thermoplasticity of block polymer (A). Preferably it is 5 to 50 mgKOH/g.

The polyolefin (a2-2) having a hydroxyl group at both ends of the polymer includes a polyolefin having a hydroxyl group obtained by modifying the polyolefin (a2-1) having a carboxyl group at both ends of the polymer with an amine having a hydroxyl group, and these two. Mixtures of more than one species can be used.
Examples of amines having a hydroxyl group that can be used for modification include amines having a hydroxyl group having 2 to 10 carbon atoms, specifically 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-amino Mention may be made of butanol, 5-aminopentanol, 6-aminohexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol.
Among these, amines having a hydroxyl group having 2 to 6 carbon atoms (2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, and 6-aminobutanol) are preferable from the viewpoint of ease of modification. hexanol, etc.), more preferred are 2-aminoethanol and 4-aminobutanol, and particularly preferred is 2-aminoethanol.

The amount of amine having a hydroxyl group used for modification is preferably 0.5 to 0.5, based on the weight of the substance to be modified (a2-1), from the viewpoint of ease of forming a repeating structure in the molecule and adhesion to the substrate. The amount is 50% by weight, more preferably 1 to 40% by weight, particularly preferably 2 to 30% by weight.
Mn in (a2-2) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly Preferably it is 2,500 to 10,000.
The hydroxyl value of (a2-2) is preferably 4 to 280 mgKOH/g, more preferably 4 to 100 mgKOH/g, especially from the viewpoint of reactivity with (b) and thermoplasticity of block polymer (A). Preferably it is 5 to 50 mgKOH/g.

The polyolefin (a2-3) having amino groups at both ends of the polymer includes polyolefins having amino groups obtained by modifying the polyolefin (a2-1) having carboxyl groups at both ends of the polymer with diamine (Q1), and these polyolefins having amino groups at both ends of the polymer. A mixture of two or more of these can be used.
As the diamine (Q1), diamines having 2 to 12 carbon atoms can be used, and specific examples include ethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, and decamethylene diamine.
Among these, preferred are diamines having 2 to 8 carbon atoms (ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, etc.) from the viewpoint of ease of modification, and more preferred are ethylenediamine and hexamethylenediamine. Especially preferred is ethylenediamine.

The amount of (Q1) used for modification of (a2-1) is preferably 0.5% based on the weight of (a2-1) from the viewpoint of ease of forming a repeating structure in the molecule and adhesion to the substrate. 50% by weight, more preferably 1 to 40% by weight, particularly preferably 2 to 30% by weight. Note that the modification of (a2-1) with (Q1) is preferably 0.5 to 1,000% by weight, based on the weight of (a2-1), from the viewpoint of preventing polyamide (imide) formation, and further A preferred method is to use preferably 1 to 500% by weight, particularly preferably 2 to 300% by weight of (Q1), and then remove unreacted (Q1) at 120 to 230°C under reduced pressure.

Mn in (a2-3) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly Preferably it is 2,500 to 10,000.
The amine value of (a2-3) is preferably 4 to 280 mgKOH/g, more preferably 4 to 100 mgKOH/g, particularly from the viewpoint of reactivity with (b) and thermoplasticity of block polymer (A). Preferably it is 5 to 50 mgKOH/g.

The polyolefin (a2-4) having isocyanate groups at both ends includes polyolefins having isocyanate groups obtained by modifying (a2-2) with poly(2 to 3 or more) isocyanate (hereinafter abbreviated as PI), and these. Examples include mixtures of two or more of these.
As PI, aromatic PI having 6 to 20 carbon atoms (excluding carbon atoms in the NCO group, the same applies hereinafter), aliphatic PI having 2 to 18 carbon atoms, alicyclic PI having 4 to 15 carbon atoms, carbon It includes 8 to 15 aromatic aliphatic PIs, modified products of these PIs, and mixtures of two or more thereof.

Aromatic PIs include 1,3- or 1,4-phenylene diisocyanate, 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'-diisocyanatodiphenylmethane and 1, Examples include 5-naphthylene diisocyanate.

Aliphatic PIs include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis Examples include (2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Alicyclic PIs include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis(2-isocyanatoethyl). Examples thereof include -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

Examples of the araliphatic PI include m- or p-xylylene diisocyanate (XDI) and α, α, α', α'-tetramethylxylylene diisocyanate (TMXDI).

Examples of modified PI include urethane modified products, urea modified products, carbodiimide modified products, and uretdione modified products.
Among PIs, TDI, MDI and HDI are preferred, and HDI is more preferred.

The reaction between PI and (a2-2) can be carried out in the same manner as a normal urethanization reaction.
The molar equivalent ratio (NCO/OH) of PI and (a2-2) is preferably 1.8/1 to 3/1, more preferably 2/1.
In order to promote the urethanization reaction, a catalyst commonly used in urethanization reactions may be used if necessary. Catalysts include metal catalysts {tin catalysts [dibutyltin dilaurate and stannath octoate, etc.], lead catalysts [lead 2-ethylhexanoate, lead octenoate, etc.], other metal catalysts [metal salts of naphthenates (cobalt naphthenate, etc.) etc.) and phenylmercury propionate, etc.]; Amine catalysts {triethylenediamine, diazabicycloalkenes [1,8-diazabicyclo[5,4,0]undecene-7, etc.), dialkylaminoalkylamines (dimethylaminoethylamine and dimethylaminooctylamine, etc.), carbonates or organic acid (formic acid, etc.) salts of heterocyclic aminoalkylamines [2-(1-aziridinyl)ethylamine and 4-(1-piperidinyl)-2-hexylamine, etc.], N -methyl or ethylmorpholine, triethylamine and diethyl- or dimethylethanolamine, etc.}; and combination systems of two or more of these.
The amount of catalyst used is preferably 3% by weight or less, preferably 0.001 to 2% by weight, based on the total weight of PI and (a2-2).

Mn in (a2-4) is preferably 800 to 25,000, more preferably 1,000 to 20,000, especially Preferably it is 2,500 to 10,000.

From the viewpoint of solvent solubility and substrate adhesion, Mn of the polyolefin (a2) is preferably 200 to 25,000, more preferably 500 to 20,000, particularly preferably 1,000 to 15,000. be.

<Hydrophilic polymer (b)>
The hydrophilic polymer (b) in the present invention means a polymer having a volume resistivity of 1×10 ⁵ to 1×10 ¹¹ Ω·cm.
The volume resistivity value of (b) is preferably 1×10 ⁶ to 1×10 ⁹ Ω·cm, more preferably 1×10 ⁶ to 1×10 ⁸ Ω·cm. It is substantially difficult to obtain a material with a volume resistivity value of less than 1×10 ⁵ Ω·cm, and if it exceeds 1×10 ¹¹ Ω·cm, the antistatic property decreases.

Examples of the hydrophilic polymer (b) include hydrophilic polymers described in Japanese Patent No. 3488163, specifically, polyether (b1), polyether-containing hydrophilic polymer (b2), and cationic polymer (b3). and anionic polymer (b4).
Among the hydrophilic polymers (b), preferred are (b1) and (b2) from the viewpoint of solvent solubility and substrate adhesion.

Examples of the polyether (b1) include polyether diol (b1-1), polyether diamine (b1-2), and modified products thereof (b1-3).
Examples of the polyether diol (b1-1) include those obtained by addition-reacting alkylene oxide (hereinafter abbreviated as AO) to the diol (b0), and specifically, polyether diols represented by general formula (1). Examples include things that are done.

H-(OR ¹ ) _m -O-E ¹ -O-(R ² O) _n -H (1)

E ¹ in general formula (1) is a residue obtained by removing all hydroxyl groups from diol (b0).
Diols (b0) include aliphatic dihydric alcohols having 2 to 12 carbon atoms, alicyclic dihydric alcohols having 5 to 12 carbon atoms, aromatic dihydric alcohols having 6 to 18 carbon atoms, and diols containing tertiary amino groups. etc.
Examples of aliphatic dihydric alcohols having 2 to 12 carbon atoms include ethylene glycol (hereinafter abbreviated as EG), 1,2-propylene glycol (hereinafter abbreviated as PG), 1,4-butanediol (hereinafter abbreviated as 1, ), 1,6-hexanediol (hereinafter abbreviated as 1,6-HD), neopentyl glycol (hereinafter abbreviated as NPG), and 1,12-dodecanediol.

Examples of the alicyclic dihydric alcohol having 5 to 12 carbon atoms include 1,4-di(hydroxymethyl)cyclohexane and 1,5-di(hydroxymethyl)cycloheptane.
Examples of aromatic dihydric alcohols having 6 to 18 carbon atoms include monocyclic aromatic dihydric alcohols (xylylene diol, hydroquinone, catechol, resorcinol, urushiol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxy diphenyl-2,2-butane, dihydroxybiphenyl, etc.) and polycyclic aromatic dihydric alcohols (dihydroxynaphthalene, binaphthol, etc.).
Tertiary amino group-containing diols include aliphatic or alicyclic primary amines having 1 to 12 carbon atoms (methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, pentylamine, isopentylamine). , cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, dodecylamine, etc.) and aromatic primary amines having 6 to 12 carbon atoms (aniline, benzylamine, etc.) Examples include bishydroxyalkylated products.
Among these, preferred from the viewpoint of reactivity with bishydroxyalkylated products are aliphatic dihydric alcohols having 2 to 12 carbon atoms and aromatic dihydric alcohols having 6 to 18 carbon atoms, and more preferred are EG and bisphenol A.

R ¹ and R ² in general formula (1) are each independently an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include ethylene group, 1,2- or 1,3-propylene group, and 1,2-, 1,3-, 1,4- or 2,3-butylene group. It will be done.
m and n in general formula (1) are each independently a number from 1 to 300, preferably from 2 to 250, more preferably from 10 to 100.
When m and n in general formula (1) are each 2 or more, R ¹ and R ² may be the same or different, and the (OR ¹ ) _m and (R ² O) _n portions may be a random bond or a block bond. But that's fine.

Polyether diol (b1-1) can be produced by subjecting diol (b0) to an addition reaction with AO.
Examples of AO include AO having 2 to 4 carbon atoms [ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide (hereinafter abbreviated as PO), 1,2-, 1, 3-, 1,4-, 2,3- or butylene oxide (hereinafter abbreviated as BO), and a combination system of two or more of these are used, but if necessary, other AO [having 5 to 12 carbon atoms] may be used. [alpha]-olefin oxide, styrene oxide, epihalohydrin (such as epichlorohydrin)] can also be used in small proportions (30% by weight or less based on the total weight of AO).
The combination format when two or more types of AOs are used together may be either random combination or block combination. Preferred AOs are EO alone and EO in combination with other AOs.

The addition reaction of AO can be carried out by a known method, for example, in the presence of an alkali catalyst at a temperature of 100 to 200°C.
The content of (OR ¹ ) _m and (R ² O) _n based on the weight of the polyether diol (b1-1) represented by general formula (1) is preferably 5 to 99.8% by weight. , more preferably 8 to 99.6% by weight, particularly preferably 10 to 98% by weight.
The content of oxyethylene groups based on the weight of (OR ¹ ) _m and (R ² O) _n in general formula (1) is preferably 5 to 100% by weight, more preferably 10 to 100% by weight, particularly Preferably it is 50-100% by weight, most preferably 60-100% by weight.

Examples of the polyether diamine (b1-2) include those represented by general formula (2).

H ₂ NR ³ -(OR ⁴ ) _p -O-E ² -O-(R ⁵ O) _q -R ⁶ -NH ₂ (2)

E ² in general formula (2) is a residue obtained by removing all hydroxyl groups from diol (b0). Examples of the diol (b0) include those mentioned above, and the preferred ranges are also the same.
R ³ , R ⁴ , R ⁵ and R ⁶ in general formula (2) are each independently an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include those exemplified as R ¹ and R ² in general formula (1), and the preferred ranges are also the same.
p and q in general formula (2) are each independently a number from 1 to 300, preferably from 2 to 250, more preferably from 10 to 100.
In general formula (2), when p and q are each 2 or more, R ⁴ and R ⁵ may be the same or different, and the (OR ⁴ ) _p and (R ⁵ O) _q portions may be a random bond or a block bond. But that's fine.

Polyether diamine (b1-2) can be obtained by converting all hydroxyl groups of polyether diol (b1-1) into amino groups. For example, it can be produced by reacting (b1-1) with acrylonitrile and hydrogenating the resulting cyanoethylated product.

Modified products (b1-3) include aminocarboxylic acid modified products (terminal amino group), isocyanate modified products (terminal isocyanate group), and epoxy modified products (terminal epoxy group) of (b1-1) or (b1-2). etc.
The aminocarboxylic acid modified product can be obtained by reacting (b1-1) or (b1-2) with an aminocarboxylic acid or a lactam.
The isocyanate-modified product can be obtained by reacting (b1-1) or (b1-2) with a polyisocyanate, or by reacting (b1-2) with phosgene.
The epoxy modified product can be obtained by reacting (b1-1) or (b1-2) with diepoxide (epoxy resin such as diglycidyl ether, diglycidyl ester, and alicyclic diepoxide: epoxy equivalent: 85 to 600), or ( It can be obtained by reacting b1-1) with epihalohydrin (epichlorohydrin, etc.).

From the viewpoint of heat resistance and reactivity with the hydrophobic polymer (a), Mn of the polyether (b1) is preferably 150 to 20,000, more preferably 300 to 18,000, particularly preferably 1, 000 to 15,000, most preferably 1,200 to 8,000.

As the polyether-containing hydrophilic polymer (b2), polyether ester amide (b2-1) having a segment of polyether diol (b1-1), polyether amide imide (b2-1) having a segment of (b1-1); 2), polyether ester (b2-3) having a segment of (b1-1), polyether amide (b2-4) having a segment of polyether diamine (b1-2) and (b1-1) or (b1 -2) polyether urethane (b2-5) having a segment.

From the viewpoint of moldability, the content of the polyether (b1) segment in the polyether-containing hydrophilic polymer (b2) is preferably 30 to 80% by weight, more preferably 40 to 80% by weight, based on the weight of (b2). It is 70% by weight.
From the viewpoint of antistatic properties, the content of oxyethylene groups in (b2) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight, based on the weight of (b2).
The lower limit of Mn in (b2) is preferably 800 from the viewpoint of heat resistance, and more preferably 1,000. The upper limit of Mn in (b2) is preferably 50,000, more preferably 30,000, from the viewpoint of reactivity with the hydrophobic polymer (a).

Examples of the cationic polymer (b3) include polymers having cationic groups separated by nonionic molecular chains within the molecule.
Nonionic molecular chains include a group consisting of divalent hydrocarbon groups, ether bonds, thioether bonds, carbonyl bonds, ester bonds, imino bonds, amide bonds, imide bonds, urethane bonds, urea bonds, carbonate bonds, and siloxy bonds. Examples include a divalent hydrocarbon group having one or more groups selected from the following, and a hydrocarbon group having a heterocyclic structure having a nitrogen atom or an oxygen atom.
Among the nonionic molecular chains, preferred are divalent hydrocarbon groups and divalent hydrocarbon groups having an ether bond.
Examples of the cationic group include groups having a quaternary ammonium salt or a phosphonium salt. Examples of the counter-anion forming the quaternary ammonium salt or phosphonium salt include super-strong acid anions and other anions.
Examples of the super strong acid anion include anions of super strong acids (such as tetrafluoroboric acid and hexafluorophosphoric acid) derived from a combination of a protonic acid and a Lewis acid, and anions such as trifluoromethanesulfonic acid.
Other anions include 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 above-mentioned protonic acids that induce super strong acids include hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide.
Examples of Lewis acids include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, and tantalum pentafluoride.
(b3) The number of cationic groups in one molecule is preferably 2 to 80, more preferably 3 to 60.

Specific examples of (b3) include cationic polymers described in JP-A No. 2001-278985.

Mn of (b3) is preferably 500 to 20,000, more preferably 1,000 to 15, from the viewpoint of substrate adhesion and reactivity with hydrophobic polymer (a) (a2). 000, particularly preferably 1,200 to 8,000.

The anionic polymer (b4) has a dicarboxylic acid (γ') having a sulfonyl group and a diol (b0) or a polyether (b1) as essential constituent units, and has 2 to 80 units, preferably 3 to 80 units in the molecule. It is a polymer with 60 sulfonyl groups.
Examples of (γ') include those in which a sulfonyl group is introduced into the dicarboxylic acid (γ), such as an aromatic dicarboxylic acid having a sulfonyl group, an aliphatic dicarboxylic acid having a sulfonyl group, and only a sulfonyl group forming a salt. Examples include aromatic dicarboxylic acids or aliphatic dicarboxylic acids having a sulfonyl group.

Examples of aromatic dicarboxylic acids having a sulfonyl group include 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalene dicarboxylic acid, and ester-forming derivatives thereof [alkyl (C1-4) esters (methyl ester, ethyl ester, etc.), acid anhydrides, etc.].
Examples of aliphatic dicarboxylic acids having a sulfonyl group include sulfosuccinic acid and its ester-forming derivatives [alkyl (1 to 4 carbon atoms) esters (methyl ester, ethyl ester, etc.), acid anhydrides, etc.].
Examples of salts forming aromatic dicarboxylic acids or aliphatic dicarboxylic acids having a sulfonyl group in which only the sulfonyl group is a salt include alkali metal (lithium, sodium, potassium, etc.) salts, alkaline earth metal (magnesium, calcium, etc.) salts. salts, ammonium salts, amine salts such as mono-, di- or triamines (mono-, di- or triethylamine, mono-, di- or triethanolamine, diethylethanolamine, etc.) having a hydroxyalkyl (2 to 4 carbon atoms) group; Examples include quaternary ammonium salts.
Among these, preferred are aromatic dicarboxylic acids having a sulfonyl group, more preferred are 5-sulfoisophthalates, and particularly preferred are 5-sulfoisophthalic acid sodium salt and 5-sulfoisophthalic acid potassium salt. .

Among (b0) or (b1) constituting (b4), preferred are alkanediols having 2 to 10 carbon atoms, EG, polyethylene glycol (hereinafter abbreviated as PEG) (degree of polymerization 2 to 20), bisphenol ( EO adducts (number of added moles: 2 to 60 moles) of bisphenol A, etc.) and mixtures of two or more thereof.
As for the manufacturing method of (b4), a normal polyester manufacturing method can be applied as is. The polyesterification reaction is carried out under reduced pressure in a temperature range of 150 to 240°C, and the reaction time is preferably 0.5 to 20 hours. Further, if necessary, a catalyst used in ordinary esterification reactions may be used. Esterification catalysts include antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide and dibutyltin oxide, etc.), titanium catalysts (tetrabutyl titanate, etc.), zirconium catalysts (tetrabutyl zirconate, etc.), and acetic acid metal salts. Examples include catalysts (zinc acetate, etc.).

Mn of (b4) is preferably 500 to 20,000, more preferably 1,000 to 15, from the viewpoint of substrate adhesion and reactivity with hydrophobic polymer (a) (a2). 000, particularly preferably 1,200 to 8,000.

<Block polymer (A)>
The block polymer (A) of the present invention is a block polymer having a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as constituent units, wherein the above (a) is propylene as a constituent monomer. The polyolefin (a2) contains polyolefin (a2) as a body, and the isotacticity of the propylene moiety of (a2) is 1 to 50%.
Although the block polymer (A) can be applied to various uses, it can be particularly suitably used in the coating agent (X) and resin composition (Y) described below.

The isotacticity of the propylene moiety in the above (a2) can be adjusted as appropriate by the isotacticity of the propylene moiety of the polyolefin before thermal degradation, for example, when (a2) is performed by a thermal degradation method.
Examples of the polyolefin as a raw material (preferably before thermal degradation) include the product under the trade name "Vistamaxx6202, 3980" manufactured by Exxonmobil; can.

In a preferred form of the block polymer, the block of (a2) and the block of hydrophilic polymer (b) are at least one selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond, a urethane bond, and a urea bond. It is a block polymer having a structure connected through one type of bond.
The weight ratio of the block (a) to the block (b) constituting (A) is preferably 10/90 to 80/20, more preferably 10/90 to 80/20 from the viewpoint of solvent solubility and substrate adhesion. It is from 20/80 to 75/25.

Structures in which blocks (a) and blocks (b) constituting (A) are combined include (a)-(b) type, (a)-(b)-(a) type, and (b) type. )-(a)-(b) type and [(a)-(b)]n type (n represents the average number of repetitions).
From the viewpoint of solvent solubility and substrate adhesion, the block polymer (A) has an n-type structure [(a)-(b)] in which (a) and (b) are repeatedly and alternately bonded. preferable.
[(a)-(b)] n in the n-type structure is preferably 2 to 20, more preferably 2.3 to 15, particularly preferably 2, from the viewpoint of solvent solubility and substrate adhesion. .7 to 10, most preferably 3 to 7. n can be determined by Mn and ¹ H-NMR analysis of the block polymer (A).

From the viewpoint of substrate adhesion and solvent solubility, Mn in (A) is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, particularly preferably 15, 000 to 50,000.

When (A) has a structure in which the block (a) and the block (b) are bonded via an ester bond, amide bond, ether bond, or imide bond, it may be produced by the following method. I can do it.
(a) and (b) are put into a reaction container, and under stirring, at a reaction temperature of 100 to 250°C and a pressure of 0.003 to 0.1 MPa, the water produced by the amidation reaction, esterification reaction, or imidization reaction ( A method of reacting for 1 to 50 hours while removing water (hereinafter abbreviated as produced water) from the reaction system can be mentioned. The weight ratio of (a) and (b) is 10/90 to 80/20, more preferably 20/80 to 75/25, from the viewpoint of solvent solubility and substrate adhesion.

In the case of the esterification reaction, it is preferred to use 0.05 to 0.5% by weight of catalyst, based on the weight of (a) and (b), to accelerate the reaction. Examples of catalysts include inorganic acids (sulfuric acid and hydrochloric acid, etc.), organic sulfonic acids (methanesulfonic acid, p-toluenesulfonic acid, xylene sulfonic acid, naphthalenesulfonic acid, etc.), and organometallic compounds (dibutyltin oxide, tetraisopropoxy titanate, bistrichloride, etc.). ethanolamine titanate, potassium oxalate titanate, etc.). When a catalyst is used, the catalyst can be neutralized if necessary after the esterification reaction is completed, and treated with an adsorbent to remove and purify the catalyst. Examples of methods for removing produced water from the reaction system include the following methods.
(1) A method in which an organic solvent that is incompatible with water (e.g. toluene, xylene, cyclohexane, etc.) is used to azeotrope the organic solvent and the produced water under reflux, and only the produced water is removed from the reaction system. .
(2) A method in which a carrier gas (for example, air, nitrogen, helium, argon, carbon dioxide, etc.) is blown into the reaction system and produced water is removed from the reaction system together with the carrier gas.
(3) A method in which the pressure inside the reaction system is reduced to remove produced water from the reaction system.

When (A) has a structure in which the block (a) and the block (b) are bonded via a urethane bond or a urea bond, it can be produced by the following method.
An example of a method is to charge (a) into a reaction vessel, heat it to 30 to 100°C with stirring, then add (b) and react at the same temperature for 1 to 20 hours. The weight ratio of (a) and (b) is 10/90 to 80/20, more preferably 20/80 to 75/25, from the viewpoint of solvent solubility and substrate adhesion.
To accelerate the reaction, it is preferred to use 0.001 to 5% by weight of catalyst, based on the weight of (a) and (b). Examples of catalysts include organometallic compounds (dibutyltin dilaurate, dioctyltin dilaurate, lead octoate, bismuth octoate, etc.), tertiary amines {triethylenediamine, trialkylamines having an alkyl group having 1 to 8 carbon atoms (trimethylamine, tributylamine, etc.), , trioctylamine, etc.), diazabicycloalkenes [1,8-diazabicyclo[5,4,0]undecene-7], etc.}; and combinations of two or more of these.

<Coating agent (X)>
The coating agent (X) of the present invention contains the block polymer (A). Preferably, it contains the above (A) and a solvent (S). Examples of the solvent (S) include known solvents, but aromatic hydrocarbons (toluene, xylene, etc.) are preferable.
In that case, the weight ratio [(A)/(S)] between the (A) and the (S) is preferably 5/95 to 50/50, more preferably 10/90 to 40/60.

The coating agent (X) has excellent solvent solubility and stability after being dissolved in the solvent. Therefore, it can be suitably used in various coating applications, especially antistatic coating applications.

<Resin composition (Y)>
The resin composition (Y) of the present invention contains the block polymer (A) and a thermoplastic resin (B). This resin composition (Y) can be preferably used for molded articles.
The weight ratio [(A)/(B)] between the block polymer (A) and the thermoplastic resin (B) is determined by the antistatic property, the adhesion to the base material, and the mechanical strength (tensile strength, etc.) of the molded product. From this point of view, the ratio is preferably 1/99 to 30/70, more preferably 3/97 to 20/80, and particularly preferably 5/95 to 15/85.

In the present invention, thermoplastic resins (B) include polyphenylene ether (PPE) resins (B1); vinyl resins [polyolefin resins (B2)] such as polypropylene (PP), polyethylene (PE), ethylene- Vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin], poly(meth)acrylic resin (B3) [e.g. polymethyl methacrylate], polystyrene resin (B4) [vinyl group-containing aromatic hydrocarbon alone or A copolymer containing a vinyl group-containing aromatic hydrocarbon and at least one member selected from the group consisting of (meth)acrylic acid ester, (meth)acrylonitrile, and butadiene, such as polystyrene, high-impact polystyrene (HIPS), etc. ), styrene/acrylonitrile copolymer (AN resin), acrylonitrile/butadiene/styrene copolymer (ABS resin), methyl methacrylate/butadiene/styrene copolymer (MBS resin), styrene/methyl methacrylate copolymer ( MS resin)]; Polyester resin (B5) [e.g. polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polybutylene adipate, polyethylene adipate]; Polyamide resin (B6) [e.g. nylon 66, nylon 69, nylon 612 , nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12]; polycarbonate resin (B7) [e.g. polycarbonate (PC), polycarbonate (PC)/ABS alloy resin]; polyacetal resin (B8 ), and mixtures of two or more thereof.
Among the thermoplastic resins (B), polyolefin resins (B2) are preferred from the viewpoint of antistatic properties and adhesion to substrates.

<Molded product (Z)>
The molded article (Z) of the present invention is obtained by molding the resin composition (Y). Molding methods include injection molding, compression molding, calendar molding, slush molding, rotation molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), and depending on the purpose, single layer molding It can be molded by any method including molding, multilayer molding, foam molding, or the like.
Among the above molding methods, film molding is preferred.

The molded article of the present invention has antistatic properties and good paintability and printability, and a molded article can be obtained by painting and/or printing the molded article.
Methods for painting the molded article include, but are not limited to, air spray painting, airless spray painting, electrostatic spray painting, dip painting, roller painting, and brush painting.
As the paint, paints commonly used for painting plastics can be used, and specific examples include polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint.
The coating film thickness (dry film thickness) can be appropriately selected depending on the purpose, but is preferably 10 to 50 μm.

As a method for printing on the molded product or the painted surface of the molded product, any known printing method used for printing on plastics can be used, including gravure printing, flexo printing, screen printing, pad printing, Examples include dry offset printing and offset printing.
As the printing ink, those commonly used for printing plastics can be used, and examples include gravure ink, flexo ink, screen ink, pad ink, dry offset ink, and offset ink.

The block polymer (A) of the present invention has excellent solvent solubility, substrate adhesion, and antistatic properties, and is suitable for various uses, preferably as a modifier for resins, an antistatic agent, an emulsion raw material, a coating agent, and a primer. It is extremely useful because it can be suitably used for.

Examples of the present invention will be described below, but the present invention is not limited thereto.

<Manufacture example 1>
[Production of acid-modified polyolefin (a1-1-1)]
A low molecular weight ethylene/propylene random copolymer (ethylene content: 15 wt. %, Mn: 10,000, number of double bonds per 1,000 carbon atoms: 2.5, average number of double bonds per molecule: 1.8, content of polyolefin that can be modified at both ends: 90 94 parts by weight (% by weight, isotacticity of propylene portion 40%), 6 parts by weight of maleic anhydride, and 30 parts by weight of xylene were mixed uniformly, and then heated at 200°C with stirring under a nitrogen gas atmosphere (closed). It was melted and reacted for 10 hours.
Thereafter, excess maleic anhydride and xylene were distilled off at 200°C over 3 hours under reduced pressure (1.3 kPa or less) to obtain 98 parts by weight of acid-modified polyolefin (a1-1-1). The acid value of (a1-1-1) was 9.9, the Mn was 10,200, and the isotacticity of the propylene moiety was 40%.

<Manufacture example 2>
[Production of acid-modified polyolefin (a1-1-2)]
A low molecular weight ethylene/propylene random copolymer (ethylene content: 22 wt. %, Mn: 3,400, number of double bonds per 1,000 carbon atoms: 7.0, average number of double bonds per molecule: 1.8, content of polyolefin that can be modified at both ends: 90 90 parts by weight (% by weight, isotacticity of propylene portion 4%), 10 parts by weight of maleic anhydride, and 30 parts by weight of xylene were mixed uniformly, and then heated at 200°C with stirring under a nitrogen gas atmosphere (closed). It was melted and reacted for 10 hours.
Thereafter, excess maleic anhydride and xylene were distilled off at 200°C over 3 hours under reduced pressure (1.3 kPa or less) to obtain 95 parts by weight of acid-modified polyolefin (a1-1-2). The acid value of (a1-1-2) was 27.5, the Mn was 3,600, and the isotacticity of the propylene moiety was 4%.

<Manufacture example 3>
[Production of secondary modified acid-modified polyolefin (a1-2)]
88 parts by weight of (a1-1-2) and 12 parts by weight of 12-aminododecanoic acid were charged into a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating/cooling device, a nitrogen introduction tube, and a pressure reducing device, and nitrogen The mixture was melted at 200° C. with stirring in a gas atmosphere and reacted for 3 hours under reduced pressure (1.3 kPa or less) to obtain 96 parts by weight of secondarily modified acid-modified polyolefin (a1-2).
The acid value of (a1-2) was 24.8, the Mn was 4,000, and the isotacticity of the propylene moiety was 4%.

<Manufacture example 4>
[Production of modified polyolefin (a1-3) having hydroxyl groups at both ends]
Add 5 parts by weight of 2-aminoethanol to 97 parts by weight of (a1-1-1) in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating/cooling device, nitrogen introduction tube, and pressure reducing device, and place in a nitrogen gas atmosphere. The mixture was melted at 180° C. and reacted for 2 hours. Thereafter, excess 2-aminoethanol was distilled off under reduced pressure (1.3 kPa or less) at 180° C. over 2 hours to obtain a modified polyolefin (a1-3) having hydroxyl groups at both ends.
The hydroxyl value of (a1-3) was 9.9, the amine value was 0.01, the Mn was 10,200, and the isotacticity of the propylene moiety was 40%.

<Manufacture example 5>
[Production of modified polyolefin (a1-4) having amino groups at both ends]
Add 88 parts by weight of (a1-1-2) and 10 parts by weight of bis(2-aminoethyl) ether to a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating/cooling device, nitrogen inlet tube, and pressure reducing device. The mixture was melted at 200° C. with stirring under a nitrogen gas atmosphere, and reacted for 2 hours. Thereafter, excess bis(2-aminoethyl) ether was distilled off at 200°C for 2 hours under reduced pressure (1.3 kPa or less) to obtain a modified polyolefin (a3-1) having amino groups at both ends. Ta.
The amine value of (a1-4) was 22.4, the Mn was 4,200, and the isotacticity of the propylene moiety was 4%.

<Manufacture example 6>
[Production of cationic polymer (b3-1)]
41 parts by weight of N-methyldiethanolamine, 49 parts by weight of adipic acid, and 0.3 parts by weight of zirconyl acetate were charged into a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating/cooling device, a nitrogen introduction tube, and a pressure reducing device. After purging with nitrogen, the temperature was raised to 220° C. over 2 hours, and the pressure was reduced to 0.13 kPa over 1 hour to carry out a polyesterification reaction. After the reaction was completed, the mixture was cooled to 50° C., and 100 parts by weight of methanol was added to dissolve the mixture. While stirring, the temperature in the reaction vessel was maintained at 120° C., 31 parts by weight of dimethyl carbonate was gradually added dropwise over 3 hours, and the mixture was aged at the same temperature for 6 hours. After cooling to room temperature, 100 parts by weight of a 60% by weight aqueous hexafluorophosphoric acid solution was added, and the mixture was stirred at room temperature for 1 hour.
Next, methanol was distilled off under reduced pressure to obtain a cationic polymer (b3-1) having an average of 12 quaternary ammonium groups (hydroxyl value: 30.1, acid value: 0.5, volume resistivity: 1×10 ⁵ Ω).・cm) was obtained.

<Manufacture example 7>
[Production of anionic polymer (b4-1)]
67 parts by weight of PEG (Mn: 300), 49 parts by weight of sodium salt of dimethyl 5-sulfoisophthalate and 0.2 parts by weight of dibutyltin oxide was added, the temperature was raised to 190°C under a reduced pressure of 0.67 kPa, and transesterification was carried out for 6 hours while methanol was distilled off, so that an average of 5 sodium sulfonate bases were present in one molecule. anionic polymer (b4-1) (hydroxyl value: 29.6, acid value: 0.4, volume resistivity: 2×10 ⁶ Ω・cm
) was obtained.

<Comparative manufacturing example 1>
[Production of acid-modified polyolefin (a1-1-3)]
A low molecular weight ethylene/propylene random copolymer (ethylene content: 2 wt. %, Mn: 3,400, amount of double bonds per 1,000 carbon atoms: 7.0, average number of double bonds per molecule: 1.8, content of polyolefin that can be modified at both ends: 90 parts by weight (propylene portion isotacticity 85%), 10 parts by weight of maleic anhydride, and 30 parts by weight of xylene were added, and after uniform mixing, the mixture was heated at 200°C under a nitrogen gas atmosphere (closed) with stirring. The mixture was melted and reacted for 10 hours.
Thereafter, excess maleic anhydride and xylene were distilled off at 200°C over 3 hours under reduced pressure (1.3 kPa or less) to obtain 95 parts by weight of acid-modified polyolefin (a1-1-3).
The acid value of (a1-1-3) was 27.5, the Mn was 3,600, and the isotacticity of the propylene moiety was 85%.

<Example 1>
70.7 parts by weight of acid-modified polyolefin (a1-1-1) and α,ω-diamino PEG (Mn : 4,000, volume resistivity value: 1×10 ⁷ Ωcm) (b1-1) 28.3 parts by weight, antioxidant [trade name "Irganox 1010", manufactured by BASF Japan Co., Ltd.] 0. 4 parts by weight and 0.6 parts by weight of zirconyl acetate were added and polymerized for 3 hours at 220° C. under reduced pressure of 0.13 kPa or less to obtain a viscous polymer. This polymer is taken out in strand form on a belt and pelletized to produce block polymer (A-1) (Mn: 42,000) consisting of blocks (a1-1-1) and blocks (b1-1). Obtained.

<Example 2>
In Example 1, except that 46.9 parts by weight of (a1-1-2) and 52.1 parts by weight of (b1-1) were used instead of 70.7 parts by weight of (a1-1-1). In the same manner as in Example 1, a block polymer (A-2) (Mn: 23,000) consisting of a block (a1-1-2) and a block (b1-1) was obtained.

<Example 3>
In Example 1, instead of 70.7 parts by weight of (a1-1-1), 56.6 parts by weight of secondary modified acid-modified polyolefin (a1-2), PEG (Mn: 3,000, volume resistivity) Value: 1×10 ⁷ Ω・cm) (b1-2) From the block of (a1-2) and the block of (b1-2) in the same manner as in Example 1 except that 42.4 parts by weight was used. A block polymer (A-3) (Mn: 28,000) was obtained.

<Example 4>
In Example 1, instead of 70.7 parts by weight of (a1-1-1), 69.3 parts by weight of modified polyolefin (a1-3) having hydroxyl groups at both ends, and 25 parts by weight of cationic polymer (b3-1). In the same manner as in Example 1 except that 7 parts by weight and 4.0 parts by weight of dodecanedioic acid were used, a block polymer consisting of the block of (a1-3), the block of (b3-1) and dodecanedioic acid ( A-4) (Mn: 28,000) was obtained.

<Example 5>
In Example 1, instead of 70.7 parts by weight of (a1-1-1), 47.8 parts by weight of modified polyolefin (a1-4) having amino groups at both ends, and 43 parts by weight of anionic polymer (b4-1) A block polymer consisting of the block of (a1-4), the block of (b4-1) and dodecanedioic acid was prepared in the same manner as in Example 1 except that .2 parts by weight and 8.0 parts by weight of dodecanedioic acid were used. (A-5) (Mn: 32,000) was obtained.

<Example 6>
In Example 1, instead of 70.7 parts by weight of (a1-1-1), 68.3 parts by weight of secondarily modified acid-modified polyolefin (a1-2), polytetramethylene glycol (Mn 1,800, volume specific) Resistance value 1×10 ¹¹ Ω・cm) (b1-3) From the block (a1-2) and the block (b1-3) in the same manner as in Example 1 except that 30.7 parts by weight was used. A block polymer (A-6) (Mn: 23,000) was obtained.

<Example 7>
In Example 1, instead of 70.7 parts by weight of (a1-1-1), 66.0 parts by weight of secondarily modified acid-modified polyolefin (a1-2), bisphenol A ethylene oxide adduct (Mn 2,000, The block of (a1-2) and the block of (b1-4) were prepared in the same manner as in Example 1 except that 33.0 parts by weight of volume resistivity (1×10 ⁷ Ωcm) (b1-4) was used. A block polymer (A-7) (Mn: 24,000) consisting of blocks was obtained.

<Comparative example 1>
In Example 1, except that 46.9 parts by weight of (a1-1-3) and 52.1 parts by weight of (b1-1) were used instead of 70.7 parts by weight of (a1-1-1). In the same manner as in Example 1, a block polymer (ratio A-1) (Mn: 23,000) consisting of a block (a1-1-3) and a block (b1-1) was obtained.

Each obtained block polymer (A) was evaluated according to the following performance evaluation method. The results are shown in Table 1.

<1> Solvent solubility at room temperature (25°C) 10g of each obtained block polymer (A) was placed in a container, 90g of xylene at 25°C was stirred at 25°C for 3 hours, and then dissolved at room temperature (25°C). It was left to stand for one day. After standing still, the contents of the container were observed and the solvent solubility was evaluated using the following <Evaluation Criteria>.

<Evaluation criteria>
◎: Transparent.
○: There is slight haze.
Δ: There is a small amount of undissolved polymer.
×: Hardly dissolved.

<2> Solvent solubility at high temperatures 10 g of each obtained block polymer (A) and 90 g of xylene were placed in a container, heated to 80°C, stirred for 3 hours, cooled to 25°C, and left to stand for 1 day. did. After standing still, the contents of the container were observed and the solvent solubility was evaluated using the following <Evaluation Criteria>.

<Evaluation criteria>
◎: The solution is transparent and has fluidity.
○: The solution is slightly hazy and has fluidity.
△: There is haze in the solution and there is no fluidity.
×: Hardly dissolved.

<3> Substrate adhesion The contents of the container after the evaluation in <2> above are applied to a polyester film [manufactured by Toray Industries, Inc., trade name "Lumirror" Type T] substrate so that the film thickness after drying is 10 μm. and dried at 80°C for 10 minutes. The coating film was subjected to an adhesion test (checkerboard test) using a checkerboard tape method in accordance with JIS K5400.
The number of areas where the coating film did not peel off out of a grid of 100 is expressed as 0 to 100, and the larger the number, the better the adhesion between the substrate and the coating film.
Note that in <2> above, those marked Δ and × were not evaluated because they could not be coated.

<4> Surface specific resistance value (antistatic property)
The coating film after drying in <3> above was left to stand for 48 hours at 23°C and 50% RH, and then measured under the same atmosphere using a super megohmmeter [model number "R8340A", manufactured by Advantest Co., Ltd.]. It was measured.

<Examples 11 to 17, Comparative Example 11>
According to the formulation composition (parts by weight) shown in Table 2, the ingredients were blended for 3 minutes using a Henschel mixer, and then heated at 100 rpm, 170°C, and a residence time of 5 minutes using an inflation molding machine equipped with a vented twin-screw extruder. After melt-kneading to obtain each resin composition (Y), the resulting film was extruded from a die controlled at 170°C and air-cooled at a take-up speed of 10 m/min and a blow ratio of 2.0. After that, each molded product [film] (Z) having a thickness of 80 μm was obtained by winding it up using a winding machine. Each of the obtained molded products (Z) was evaluated according to the following <5> and <6>. The results are shown in Table 2.

<5> Antistatic property [based on ASTM D257 (1984)]
Evaluated by surface specific resistance value (unit: Ω). Using a test piece (100 x 100 mm) cut out from the film, the test piece was allowed to stand for 48 hours at 23°C and 50% RH, and then measured using a super megohmmeter (model number "R8340A", manufactured by Advantest Co., Ltd.). Measurements were made under the same atmosphere conditions.

<6> Heat seal strength (evaluation of base material adhesion)
Films cut into 1.5 cm widths were stacked and heat sealed at sealing temperatures of 120°C and 130°C, sealing pressure: 0.2 MPa, and sealing time: 1.0 seconds, and the T-peel strength was determined by tensile strength. The heat seal strength was measured using a testing machine at a tensile speed of 100 mm/min, at 23° C., and in an atmosphere of 50% RH.

The contents of the symbols in Table 2 are as follows.
B-1: High-pressure low-density polyethylene [Product name: Novatec LF128, manufactured by Japan Polyethylene Co., Ltd.]
B-2: Straight chain short chain branched polyethylene [Product name: 2515HF, manufactured by Ube Industries, Ltd.]

From Table 1, it can be seen that the block polymer (A) of the present invention has excellent solvent solubility at room temperature, solvent solubility at high temperature, substrate adhesion, and antistatic property compared to the comparative ones. Moreover, from the results in Table 2, it can be seen that the molded product (Z) of the resin composition (Y) of the present invention has excellent antistatic properties and excellent adhesion to a substrate as compared to the comparative products.

The block polymer (A) of the present invention has excellent solvent solubility, substrate adhesion, and antistatic properties, and is suitable for various uses, preferably as a modifier for resins, an antistatic agent, an emulsion raw material, a coating agent, and a primer. It is extremely useful because it can be suitably used for.

Claims (9)

A block polymer having a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as constituent units, wherein (a) is a polyolefin (a2) containing propylene as a constituent monomer. , a block polymer in which the propylene portion of (a2) has an isotacticity of 1 to 50%, and the weight ratio of the ethylene units to propylene units in (a2) [ethylene units/propylene units] is 5/95 to Block polymer (A) which is 40/60 . The block polymer (A ) according to claim 1 , wherein the (b) is at least one selected from the group consisting of polyether, cationic polymer, and anionic polymer. 3. The above (a) and (b) are bonded through at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, a urethane bond, and an imide bond. block polymer (A) . The block polymer (A) according to any one of claims 1 to 3 , wherein the number average molecular weight (Mn) of the block polymer (A) is 5,000 to 200,000. 5. The structure according to claim 1 , wherein the (A) has an n-type structure (n=2 to 20) in which (a) and (b) are alternately bonded [(a)-(b)]. Block polymer (A). A coating agent (X) comprising the block polymer (A) according to any one of claims 1 to 5 . A resin composition (Y) comprising the block polymer (A) according to any one of claims 1 to 5 and a thermoplastic resin (B). A molded article (Z) obtained by molding the resin composition (Y) according to claim 7 . A molded article obtained by painting and/or printing the molded article (Z) according to claim 8 .