JP2020164819A - Block polymer - Google Patents

Abstract

To provide a block polymer that has an excellent solvent solubility.SOLUTION: A block polymer (A), which is a block polymer having a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as a constituent unit, and in which the (a) is a polyolefin (a2) containing propylene as a constituent monomer, and the isotacticity of the propylene portion of (a2) is 1 to 50%. The number average molecular weight (Mn) of said (A) preferably is 5,000 to 200,000.SELECTED DRAWING: None

Description

The present invention relates to block polymers.

Polyolefins are commonly used as a general purpose material. Furthermore, modified polyolefins have been developed for widespread use. (For example, Patent Document 1).

JP-A-2016-156007

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

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 having a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as a constituent unit, wherein the (a) is a polyolefin containing propylene as a constituent monomer. (A2) is a block polymer (A) in which the isotacticity of the propylene moiety of (a2) is 1 to 50%.

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

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

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

By selecting a polyolefin having an isotacticity of the propylene moiety in the above range and binding to the block (b) of the hydrophilic polymer, the isotacticity of the propylene moiety of the polyolefin (a2) is in the above range. The 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 polyolefin, and the like. The isotacticity of the polyolefin used as a raw material and the isotacticity of the polyolefin (a2) can be confirmed by using ¹³ C-NMR (nuclear magnetic resonance spectroscopy). In general, side chain methyl groups are on both sides (triplet, triad), on both sides of the triplet (quintuplet, pentad), and on both sides of the quintuplet (seven-strand, heptad). It is known that peaks are observed at different chemical shifts under the influence of the configuration (meso or racemo) with the methyl group, and the evaluation of stereoregularity is generally performed for pentad. The isotacticity in is also able to be calculated based on the evaluation of the pentad.
That is, regarding the carbon peak derived from the side chain methyl group in propylene obtained by ¹³ C-NMR, each peak (H) of the pentad and the peak derived from the methyl group in the isotactic propylene in which the pentad is formed only by the meso structure. If the (H _a), isotacticity - is calculated by the following equation.
Isotacticity _{(%) = [(H a} ) / Σ (H)] × 100 (1)
However, where the H _a peak signal of isotactic (pentad is formed only in the mesostructure) height, H is a the peak height of the pentad.

As the polyolefin (a2), those containing ethylene and propylene as constituent monomers are preferable from an industrial point of view.
In that case, the weight ratio of the ethylene unit to the propylene unit [ethylene unit / propylene unit] 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 to 30/70.
The weight ratio [ethylene unit / propylene unit] can be calculated by, for example, ¹ H-MNR.

In the above (a2), other monomers other than ethylene and propylene may be used as constituent monomers. In that case, based on the weight of all the monomers constituting (a2), the weight of the other monomers is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less. Is.
Examples of the other monomer include 1- and 2-butene, isobutene, and 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 a polyolefin (a2-1) having a carboxyl group at both ends of the polymer, a polyolefin (a2-2) having a hydroxyl group at both ends of the polymer, and a polyolefin (a2) having an amino group at both ends of the polymer. -3) and polyolefin having an isocyanate group at both ends of the polymer (a2-4), polyolefin having a carboxyl group at one end of the polymer (a2-5), and polyolefin having a hydroxyl group at one end of the polymer (a2-6). , Polyolefin (a2-7) having an amino group at one end of the polymer, polyolefin (a2-8) having an isocyanate group at one end of the polymer, and the like. Of these, (a2-1) and (a2-5) having a carboxyl group at the terminal are preferable.
The terminal in the present invention means a terminal where the repeating structure of the monomer unit constituting the polymer is interrupted. Further, both ends mean both ends in the main chain of the polymer, and one end means one end in the main chain of the polymer.

As (a2-1), a polyolefin (a2) containing a polyolefin having both ends modifiable as a main component (preferably a content of 50% by weight or more, more preferably 75% by weight or more, particularly preferably 80 to 100% by weight). -01) with carboxyl groups introduced at both ends; (a2-2) with hydroxyl groups introduced at both ends of (a2-01); (a2-3) with (a2-01) Amino groups are introduced at both ends of (a2-4); and as (a2-4), those having isocyanate groups introduced at both ends of (a2-01) can be used.

As (a2-5) to (a2-8), instead of the polyolefin (a2-01), a polyolefin having a modifiable one end as a main component (preferably a content of 50% by weight or more, more preferably 75% by weight) is used. As described above, those in which a carboxyl group, a hydroxyl group, an amino group or an isocyanate group are introduced into one end of the polyolefin (a2-02), which is particularly preferably 80 to 100% by weight) can be used.

The polyolefin (a2-01) whose main component is a polyolefin whose both ends can be modified 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. The same applies below. ] The polyolefin (polymerization method) obtained and the modified polyolefin {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 50,000 to 150,000] polyolefin mechanically, thermally or chemically. (Decomposition method)} is included.
Of these, a modified polyolefin is preferable from the viewpoint of easiness of modification and availability when introducing a carboxyl group, a hydroxyl group, an amino group or an isocyanate group, and more preferable is heat. It is a reduced polyolefin. According to the thermal reduction, a low molecular weight polyolefin having an average number of terminal double bonds of 1.5 to 2 per molecule can be easily obtained as described later, and the low molecular weight polyolefin has a carboxyl group, a hydroxyl group, and an amino group. 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 by gel permeation chromatography (GPC) under the following conditions.
Equipment (example): "HLC-8120" [manufactured by Tosoh Corporation]
Column (example): "TSKgelGMHXL" (2)
"TSKgel Multipore HXL-M" (1)
Sample solution: 0.3 wt% orthodichlorobenzene solution Injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 135 ° C
Detection device: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 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 heat-decomposed polyolefin is not particularly limited, but is obtained by heating a high molecular weight polyolefin in an inert gas (300 to 450 ° C. for 0.5 to 10 hours, for example, JP-A-3-62804). Examples thereof include those obtained by the method described in the publication) and those obtained by heating in air to reduce the heat.

The high molecular weight polyolefin used in the heat reduction 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; the unit is g / 10 min) is preferably 0.5 to 150, and more preferably 1 to 100. ] Etc. can be mentioned.
Here, MFR is a numerical value representing the melt viscosity of the resin, and the larger the value, the lower the melt viscosity. An extruded plastometer defined by JIS K6760 is used for the measurement of MFR, and the measuring method conforms to the method specified by JIS K7210 (1976). For example, in the case of polypropylene, it is measured under the conditions of 230 ° C. and a load of 2.16 kgf.
Examples of the olefin having 2 to 30 carbon atoms include an α-olefin having 2 to 30 carbon atoms and a diene 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-. Tetracosen and the like can be mentioned.
Examples of the diene having 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene and 1,11-dodecadien.
Among the olefins having 2 to 30 carbon atoms, ethylene, propylene, α-olefin having 4 to 12 carbon atoms, butadiene, isoprene and a mixture thereof are preferable from the viewpoint of molecular weight control, and ethylene is more preferable. Protin, α-olefins having 4 to 10 carbon atoms, butadiene and mixtures thereof, particularly preferred are ethylene, propylene, butadiene and mixtures thereof.

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

(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, and most preferably 1.8 to 2.2.

When a method for obtaining a low molecular weight polyolefin by a heat reduction method is used, it is easy (a2-01) to have an average number of terminal double bonds of 1.5 to 2 per molecule in the range of Mn 800 to 6,000. [Katsuhide Murata, Tadahiko Makino, Journal of the Japanese Society of Chemistry, p. 192 (1975)].

The polyolefin (a2-02) containing a polyolefin whose main component can be modified at one end can be obtained in the same manner as in (a2-01), and the Mn of (a2-02) is solvent-soluble and adheres to the substrate. From the viewpoint of sex, it is preferably 2,000 to 50,000, more preferably 2,500 to 30,000, and particularly preferably 3,000 to 20,000.
The number of double bonds per 1,000 carbon atoms of (a2-02) is preferably 0.3 to 20 and 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 the productivity of the block polymer (A) described later. It is more preferably 0.6 to 1.3, particularly preferably 0.7 to 1.2, and most preferably 0.8 to 1.1.
Of (a2-02), the low molecular weight polyolefin obtained by the heat reduction method is preferable from the viewpoint of easiness of denaturation, and the Mn obtained by the heat reduction method is 3 Thousands to 20,000 polyethylenes and / or polypropylenes.
When a method for obtaining a low molecular weight polyolefin by the heat reduction method is used, the average number of terminal double bonds per molecule is 1 to 1.5 (a2-) in the range of Mn of 6,000 to 30,000. 02) is obtained.
Since the low molecular weight polyolefin obtained by the heat reduction method has an average number of the terminal double bonds, it can be easily modified by introducing a carboxyl group, a hydroxyl group, an amino group, an isocyanate group or the like.

In addition, (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 purification and separation. Of these, a mixture is preferable from the viewpoint of manufacturing cost and the like.

Hereinafter, (a2-1) to (a2-4) having a carboxyl group, a hydroxyl group, an amino group or an isocyanate group at both ends of the polyolefin (a2-01) will be described, but one end of the polyolefin (a2-02) will be described. Regarding (a2-5) to (a2-8) having these groups, the one in which (a2-01) is replaced with (a2-02) is the same as (a2-1) to (a2-4). Can be obtained.

As the polyolefin (a2-1) having a carboxyl group at both ends of the polymer, the end of (a2-01) is α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, its alkyl. (1 to 4 carbon atoms) means an ester or an anhydride thereof. The same shall apply hereinafter.) Polymers (a2-1-1) and (a2-1-1) having a modified structure are mixed with lactam or aminocarboxylic acid. A polyolefin having a next modified structure (a2-1-2), a polyolefin having a structure obtained by modifying (a2-01) by oxidation or hydroformylation (a2-1-3), (a2-1-3) with lactam or A polyolefin (a2-1-4) having a structure secondarily modified with an aminocarboxylic acid and a mixture of two or more of these can be used.

(A2-1-1) can be obtained by modifying (a2-01) with α, β-unsaturated carboxylic acid (anhydride).
Examples of the α, β-unsaturated carboxylic acid (anhydrous) used for the modification include monocarboxylic acid, dicarboxylic acid, alkyl (1 to 4 carbon atoms) ester of mono or dicarboxylic acid, and anhydride of mono or dicarboxylic acid. Specifically, (meth) acrylic acid [(meth) acrylic acid means acrylic acid or methacrylic acid. The same applies below. ], Methyl (meth) acrylate, butyl (meth) acrylate, maleic anhydride (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride), diethyl itaconic acid and citraconic acid (anhydride). Be done.
Of these, from the viewpoint of easiness of modification, dicarboxylic acid, an alkyl ester of mono or dicarboxylic acid and an anhydride of mono or dicarboxylic acid are preferable, and maleic acid (anhydride) and fumaric acid are more preferable. , Particularly preferred is maleic acid (anhydride).

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

(A2-1-1) can be obtained by secondary modification of (a2-1) with lactam or aminocarboxylic acid.
Examples of the lactam used for the secondary denaturation include lactam having 6 to 12 carbon atoms (preferably 6 to 8, more preferably 6), and specifically, caprolactam, enantractum, laurolactam, undecanolactam and the like. Can be mentioned.
Examples of the aminocarboxylic acid include aminocarboxylic acids having 2 to 12 carbon atoms (preferably 4 to 12, more preferably 6 to 12), and specifically, amino acids (glycine, alanine, valine, leucine, isoleucine). And phenylalanine, etc.), ω-aminocaproic acid, ω-aminoenantic acid, ω-aminocapric acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like.
Of the lactams and aminocarboxylic acids, caprolactam, laurolactam, glycine, leucine, ω-aminocapricic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and caprolactam, laurolactam, are more preferred. 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 the secondary denaturation is based on the weight of the object to be modified (a2-1), from the viewpoint of the ease of forming a repeating structure in the molecule and the thermoplasticity of the block polymer (A). It is preferably 0.5 to 200% by weight, more preferably 1 to 150% by weight, and particularly preferably 2 to 100% by weight.

(A2-3) can be obtained by a method of oxidizing (a2-01) with oxygen and / or ozone (oxidation method), or by introducing a carboxyl group by hydroformylation by an oxo method.
The introduction of the carbonyl group by the oxidation method can be carried out by a known method, for example, the method described in US Pat. No. 3,692,877. Introduction of carbonyl groups by hydroformylation can be carried out by a variety of methods, including known methods, such as Macromolecules, VOL. This can be done by the method described on pages 31, 5943.
(A2-4) can be obtained by secondary modification of (a2-3) with lactam or aminocarboxylic acid.
Examples of the lactam and the aminocarboxylic acid include the same as those exemplified as the lactam and the aminocarboxylic acid used for the secondary modification of (a2-1), and the preferable range and the amount used are also the same.

The Mn of (a2-1) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably 1,000 to 20,000, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. It is preferably 2,500 to 10,000.
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 the block polymer (A). It is preferably 5 to 50 mgKOH / g.

Examples of the polyolefin (a2-2) having hydroxyl groups at both ends of the polymer include polyolefins having hydroxyl groups obtained by modifying the polyolefins (a2-1) having hydroxyl groups at both ends of the polymer with amines having hydroxyl groups, and 2 of these. Mixtures of seeds and above can be used.
Examples of the amine having a hydroxyl group that can be used for modification include an amine having a hydroxyl group having 2 to 10 carbon atoms, and specifically, 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, and 4-amino. Butanol, 5-aminopentanol, 6-aminohexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol can be mentioned.
Of these, amines having hydroxyl groups having 2 to 6 carbon atoms (2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-amino) are preferable from the viewpoint of ease of modification. Hexanol, etc.), more preferred are 2-aminoethanol and 4-aminobutanol, and particularly preferred are 2-aminoethanol.

The amount of the amine having a hydroxyl group used for the modification is preferably 0.5 to 0.5 based on the weight of the object to be modified (a2-1) from the viewpoint of ease of forming a repeating structure in the molecule and adhesion to the substrate. It is 50% by weight, more preferably 1 to 40% by weight, and particularly preferably 2 to 30% by weight.
The Mn of (a2-2) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably 1,000 to 20,000, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. It is preferably 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, particularly from the viewpoint of reactivity with (b) and thermoplasticity of the block polymer (A). It is preferably 5 to 50 mgKOH / g.

Examples of the polyolefin (a2-3) having an amino group at both ends of the polymer include a polyolefin having an amino group obtained by modifying the polyolefin (a2-1) having a carboxyl group at both ends of the polymer with a diamine (Q1). Two or more mixtures of the above can be used.
As the diamine (Q1), a diamine having 2 to 12 carbon atoms can be used, and specific examples thereof include ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine and decamethylenediamine.
Of these, diamines having 2 to 8 carbon atoms (ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, etc.) are preferable from the viewpoint of ease of modification, and ethylenediamine and hexamethylenediamine are more preferable. Particularly preferred is ethylenediamine.

The amount of (Q1) used for the 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. It is ~ 50% by weight, more preferably 1 to 40% by weight, and particularly preferably 2 to 30% by weight. The modification of (a2-1) by (Q1) is preferably 0.5 to 1,000% by weight, more preferably 0.5 to 1,000% by weight, based on the weight of (a2-1) from the viewpoint of preventing polyamide (imide) formation. A method is preferably used in which 1 to 500% by weight, particularly preferably 2 to 300% by weight of (Q1) is used, and then the unreacted (Q1) is removed at 120 to 230 ° C. under reduced pressure.

The Mn of (a2-3) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably 1,000 to 20,000, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. It is preferably 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 the block polymer (A). It is preferably 5 to 50 mgKOH / g.

As the polyolefin (a2-4) having an isocyanate group at both ends, a polyolefin having an isocyanate group in which (a2-2) is modified with poly (2 to 3 or more) isocyanate (hereinafter abbreviated as PI) and these. A mixture of two or more of the above can be mentioned.
The PIs include aromatic PIs with 6 to 20 carbon atoms (excluding carbon atoms in the NCO group, the same applies hereinafter), aliphatic PIs with 2 to 18 carbon atoms, alicyclic PIs with 4 to 15 carbon atoms, and carbon. Includes numbers 8 to 15 aromatic aliphatic PIs, variants of these PIs and mixtures of two or more of these.

Aromatic PIs 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'-diisocyanatodiphenylmethane and 1, Examples thereof include 5-naphthylene diisocyanate.

As the aliphatic PI, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis Examples thereof include (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Examples of the alicyclic PI 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-norbornandiisocyanate.

Examples of the aromatic aliphatic PI include m- or p-xylene diisocyanate (XDI) and α, α, α', α'-tetramethylxylene diisocyanate (TMXDI).

Examples of the modified PI include urethane modified products, urea modified products, carbodiimide modified products and uretdione modified products.
Of the PIs, TDI, MDI and HDI are preferred, and HDI is even 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 / 1-3 / 1, and more preferably 2/1.
In order to promote the urethanization reaction, a catalyst usually used for the urethanization reaction may be used, if necessary. Examples of the catalyst include metal catalysts {tin catalysts [dibutyltin dilaurate and stanas octoate, etc.], lead catalysts [lead 2-ethylhexanoate, lead octenoate, etc.], and other metal catalysts [metal salts of naphthenate (cobalt naphthenate, etc.). Etc.) and phenylmercury propionate, etc.]}; amine catalysts {triethylenediamine, diazabicycloalkene [1,8-diazabicyclo [5,4,0] undecene-7, etc.], dialkylaminoalkylamines (dimethylaminoethylamine and Dimethylaminooctylamine, etc.), heterocyclic aminoalkylamine [2- (1-aziridinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine, etc.] carbonate or organic acid (gilic acid, etc.) salt, N -Methyl or ethylmorpholine, triethylamine and diethyl- or dimethylethanolamine, etc.}; and a combination system of two or more of these.
The amount of the 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).

The Mn of (a2-4) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably 1,000 to 20,000, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. It is preferably 2,500 to 10,000.

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

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

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

Examples of the polyether (b1) include a polyether diol (b1-1), a polyether diamine (b1-2) and a modified product thereof (b1-3).
Examples of the polyether diol (b1-1) include those obtained by subjecting the diol (b0) to an addition reaction of an alkylene oxide (hereinafter abbreviated as AO), and specific examples thereof are represented by the general formula (1). There are things that are done.

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

E ¹ in the general formula (1) is a residue obtained by removing all hydroxyl groups from the diol (b0).
Examples of the diol (b0) include an aliphatic dihydric alcohol having 2 to 12 carbon atoms, an alicyclic dihydric alcohol having 5 to 12 carbon atoms, an aromatic dihydric alcohol having 6 to 18 carbon atoms, and a tertiary amino group-containing diol. And so on.
Examples of the aliphatic dihydric alcohol having 2 to 12 carbon atoms include ethylene glycol (hereinafter abbreviated as EG), 1,2-propylene glycol (hereinafter abbreviated as PG), and 1,4-butanediol (hereinafter 1,1). Examples thereof include 4-BD (abbreviated as 4-BD), 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.
Aromatic dihydric alcohols having 6 to 18 carbon atoms include monocyclic aromatic dihydric alcohols (xylylenediol, hydroquinone, catechol, resorcin, urushiol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxy. Diphenyl-2,2-butane and dihydroxybiphenyl, etc.) and polycyclic aromatic dihydric alcohols (dihydroxynaphthalene, binaphthol, etc.) and the like.
Examples of the tertiary amino group-containing diol 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 (aniline, benzylamine, etc.) with 6 to 12 carbon atoms. Bishydroxyalkylated products can be mentioned.
Of these, from the viewpoint of reactivity with the bishydroxyalkylated product, an aliphatic dihydric alcohol having 2 to 12 carbon atoms and an aromatic dihydric alcohol having 6 to 18 carbon atoms are preferable, and EG is more preferable. And bisphenol A.

R ¹ and R ² in the general formula (1) are independently alkylene groups having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a 1,2- or 1,3-propylene group and a 1,2-, 1,3-, 1,4- or 2,3-butylene group. Be done.
M and n in the general formula (1) are independently numbers 1 to 300, preferably 2 to 250, and more preferably 10 to 100.
When m and n in the general formula (1) are 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 randomly combined or block-combined. But it may be.

The polyether diol (b1-1) can be produced by subjecting the diol (b0) to an addition reaction with AO.
As AO, 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 AOs [with 5 to 12 carbon atoms] are used. α-olefin oxide, styrene oxide, epichlorohydrin (epichlorohydrin, etc.), etc.] can also be used in small proportions (30% by weight or less based on the total weight of AO).
When two or more types of AO are used in combination, the binding form may be either random binding or block binding. Preferable 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 alkaline 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 the general formula (1) is preferably 5 to 99.8% by weight. More preferably, it is 8 to 99.6% by weight, and particularly preferably 10 to 98% by weight.
The content of the oxyethylene group based on the weights of (OR ¹ ) _m and (R ² O) _{n in} the general formula (1) is preferably 5 to 100% by weight, more preferably 10 to 100% by weight, particularly. It is preferably 50 to 100% by weight, most preferably 60 to 100% by weight.

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

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

E ² in the general formula (2) is a residue obtained by removing all hydroxyl groups from the diol (b0). Examples of the diol (b0) include those similar to those described above, and the preferred range is also the same.
R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula (2) are independently alkylene groups having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include those similar to those exemplified as R ¹ and R ² in the general formula (1), and the preferable range is also the same.
P and q in the general formula (2) are independently numbers 1 to 300, preferably 2 to 250, and more preferably 10 to 100.
R ⁴ and R ⁵ when p and q in the general formula (2) are 2 or more, respectively, may be the same or different, and the (OR ⁴ ) _p and (R ⁵ O) _q portions may be randomly combined or block connected. But it may be.

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

The modified product (b1-3) includes an aminocarboxylic acid modified product (terminal amino group), an isocyanate modified product (terminal isocyanate group) and an epoxy modified product (terminal epoxy group) of (b1-1) or (b1-2). And so on.
The modified aminocarboxylic acid can be obtained by reacting (b1-1) or (b1-2) with an aminocarboxylic acid or lactam.
The isocyanate-modified product can be obtained by reacting (b1-1) or (b1-2) with polyisocyanate or reacting (b1-2) with phosgene.
The epoxy-modified product is prepared by reacting (b1-1) or (b1-2) with a diepoxyd (epoxy resin such as diglycidyl ether, diglycidyl ester and alicyclic diepoxy: epoxy equivalent 85-600). It can be obtained by reacting b1-1) with epihalohydrin (epichlorohydrin, etc.).

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

As the polyether-containing hydrophilic polymer (b2), a polyether ester amide having a segment of a polyether diol (b1-1) (b2-1) and a polyether amide imide having a segment of (b1-1) (b2-) 2) Polyether ester (b2-3) with segments of (b1-1), polyetheramide (b2-4) with segments of polyetherdiamine (b1-2) and (b1-1) or (b1) Examples thereof include polyether urethane (b2-5) having the segment of -2).

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 40% by weight, based on the weight of (b2) from the viewpoint of moldability. It is 70% by weight.
The content of the oxyethylene group in (b2) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight, based on the weight of (b2) from the viewpoint of antistatic property.
The lower limit of Mn in (b2) is preferably 800, more preferably 1,000, from the viewpoint of heat resistance. 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 a cationic group separated by a nonionic molecular chain in the molecule.
The nonionic molecular chain is a group consisting of a divalent hydrocarbon group, an ether bond, a thioether bond, a carbonyl bond, an ester bond, an imino bond, an amide bond, an imide bond, a urethane bond, a urea bond, a carbonate bond and a syroxy bond. Examples thereof include a divalent hydrocarbon group having one or more groups selected from the above, and a hydrocarbon group having a heterocyclic structure having a nitrogen atom or an oxygen atom.
Of the nonionic molecular chains, a divalent hydrocarbon group and a divalent hydrocarbon group having an ether bond are preferable.
Examples of the cationic group include a group having a quaternary ammonium salt or a phosphonium salt. Examples of the counter anion forming the quaternary ammonium salt or the phosphonium salt include superacid anions 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 such as trifluoromethanesulfonic acid.
Other anionic, halogen ions ^{(F -, Cl -, Br} - and I ^{-, _{etc.), OH -, PO 4 -}} , CH 3 OSO 4 -, C 2 H 5 OSO 4 -, and ClO ₄ ^- and the like 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 the Lewis acid 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-2001-278985.

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

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

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

Of the (b0) or (b1) constituting (b4), alkanediols having 2 to 10 carbon atoms, EG, polyethylene glycol (hereinafter abbreviated as PEG) (degree of polymerization 2 to 20), bisphenol ( An EO adduct (number of moles added: 2 to 60 mols) of bisphenol A, etc., and a mixture of two or more of these.
As the manufacturing method of (b4), a normal polyester manufacturing method can be applied as it 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 for a normal esterification reaction may be used. Examples of the esterification catalyst include an antimony catalyst (antimony trioxide, etc.), a tin catalyst (monobutyltin oxide, dibutyltin oxide, etc.), a titanium catalyst (tetrabutyl titanate, etc.), a zirconium catalyst (tetrabutylzirconate, etc.), and a metal acetate. Examples include catalysts (zinc acetate, etc.).

The Mn of (b4) is preferably 500 to 20,000, more preferably 1,000 to 15, from the viewpoint of substrate adhesion and reactivity with the 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 block polymer (a) constitutes a propylene. The polyolefin (a2) contained as a body has an isotacticity of 1 to 50% of the propylene moiety of (a2).
The block polymer (A) can be applied to various uses, and can be particularly preferably used for the coating agent (X) and the resin composition (Y) described later.

The isotacticity of the propylene moiety of the above (a2) can be appropriately adjusted by, for example, when (a2) is based on the heat-decomposition method, the isotacticity of the propylene moiety of the polyolefin before the heat-decomposition.
Examples of the raw material (preferably before heat aging) polyolefin include trade names “Vistamaxx6202, 3980” and ExxonMobil, and are produced by a known production method, for example, a method according to Japanese Patent No. 4620205. it can.

As a preferable form of the block polymer, at least the block of (a2) and the block of the hydrophilic polymer (b) are 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 bonded via one type of bond.
The weight ratio of the block (a) and 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.

The structure in which the block (a) constituting (A) and the block (b) are combined includes (a)-(b) type, (a)-(b)-(a) type, and (b). )-(A)-(b) type and [(a)-(b)] n type (n represents the average number of repetitions).
The structure of the block polymer (A) is [(a)-(b)] n-type in which (a) and (b) are repeatedly and alternately bonded from the viewpoint of solvent solubility and substrate adhesion. preferable.
[(A)-(b)] n in the n-type structure is preferably 2 to 20, more preferably 2.3 to 15, and 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 1} H-NMR analysis of the block polymer (A).

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

When (A) has a structure in which the block of (a) and the block of (b) are bonded via an ester bond, an amide bond, an ether bond or an imide bond, it is produced by the following method. Can be done.
Water (a) and (b) produced by amidation reaction, esterification reaction or imidization reaction at a reaction temperature of 100 to 250 ° C. and a pressure of 0.003 to 0.1 MPa under stirring. Hereinafter, a method of reacting for 1 to 50 hours while removing the generated 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 preferable to use 0.05 to 0.5% by weight of the catalyst based on the weights of (a) and (b) in order to accelerate the reaction. As catalysts, inorganic acids (sulfuric acid, hydrochloric acid, etc.), organic sulfonic acids (methanesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, etc.) and organic metal compounds (dibutyltin oxide, tetraisopropoxytitanate, bistri). Ethanolamine titanate, potassium titanate oxalate, etc.) and the like. When a catalyst is used, after the esterification reaction is completed, the catalyst can be neutralized if necessary and treated with an adsorbent to remove and purify the catalyst. Examples of the method for removing the produced water from the reaction system include the following methods.
(1) A method in which an organic solvent incompatible with water (for example, toluene, xylene, cyclohexane, etc.) is used to azeotrope the organic solvent and the produced water under reflux to remove only the produced water 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 the generated 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 the generated 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.
Examples thereof include a method in which (a) is charged into a reaction vessel, heated to 30 to 100 ° C. with stirring, and then (b) is charged and reacted 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.
In order to accelerate the reaction, it is preferable to use 0.001 to 5% by weight of the catalyst based on the weights of (a) and (b). Examples of the catalyst include organic metal compounds (dibutyltin dilaurate, dioctyltin dilaurate, lead octanate and bismuth octanoate, etc.), tertiary amines {triethylenediamine, trialkylamines having an alkyl group having 1 to 8 carbon atoms (trimethylamine, tributylamine). , And trioctylamine, etc.), diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7], etc.}; and a combination of two or more of these.

<Coating agent (X)>
The coating agent (X) of the present invention contains the block polymer (A). It preferably contains the above (A) and the 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)] of the (A) to the (S) is preferably 5/95 to 50/50, more preferably 10/90 to 40/60.

The coating agent (X) is excellent in solvent solubility and stability after solvent dissolution. Therefore, it can be suitably used for various coating applications, especially antistatic coating applications.

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

Examples of the thermoplastic resin (B) in the present invention include polyphenylene ether (PPE) resin (B1); vinyl resin [polystyrene resin (B2) [for example, polypropylene (PP), polyethylene (PE), ethylene-) other than the above (A). Vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin], poly (meth) acrylic resin (B3) [for example, polymethyl methacrylate], polystyrene resin (B4) [vinyl group-containing aromatic hydrocarbon alone or Copolymers containing a vinyl group-containing aromatic hydrocarbon and at least one selected from the group consisting of (meth) acrylic acid ester, (meth) acrylonitrile and butadiene as a constituent unit, for example, polystyrene, impact-resistant polystyrene (HIPS). ), Styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), styrene / methyl methacrylate copolymer () MS resin)] etc.]; Polyester resin (B5) [for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate]; polyamide resin (B6) [for example, nylon 66, nylon 69, nylon 612] , Nylon 6, Nylon 11, Nylon 12, Nylon 46, Nylon 6/66, Nylon 6/12]; Polystyrene resin (B7) [for example, Polystyrene (PC), Polystyrene (PC) / ABS alloy resin]; Polyacetal resin (B8) ), And a mixture of two or more of these.
Among the thermoplastic resins (B), the polyolefin resin (B2) is preferable from the viewpoint of antistatic property and substrate adhesion.

<Molded product (Z)>
The molded product (Z) of the present invention is a molded product (Y) of the resin composition. Examples of the molding method include injection molding, compression molding, calender molding, slush molding, rotary molding, extrusion molding, blow molding, film molding (cast method, tenter method, inflation method, etc.), and a single layer depending on the purpose. It can be molded by any method incorporating means such as molding, multi-layer molding or foam molding.
Of the above molding methods, film molding is preferable.

The molded article of the present invention has antistatic properties, as well as good coatability and printability, and a molded article can be obtained by applying coating and / or printing to the molded article.
Examples of the method for coating the molded product include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating.
As the paint, a paint generally used for painting plastics can be used, and specific examples thereof 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 intended purpose, but is preferably 10 to 50 μm.

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

The block polymer (A) of the present invention is excellent in solvent solubility, substrate adhesion, and antistatic property, and is used in various applications, preferably resin modifiers, antistatic agents, emulsion raw materials, coating agent applications, and primer applications. 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.

<Manufacturing example 1>
[Manufacture of Acid-Modified Polyolefin (a1-1-1)]
Low molecular weight ethylene / propylene random copolymer obtained by the heat reduction method (ethylene content: 15 weight) in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. %, 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 polyolefins that can be modified at both ends: 90 94 parts by weight, isotacticity of propylene portion 40%), 6 parts by weight of maleic anhydride and 30 parts by weight of xylene were added, and after uniform mixing, the mixture was uniformly mixed and then at 200 ° C. with stirring in a nitrogen gas atmosphere (sealed). It was melted and reacted for 10 hours.
Then, excess maleic anhydride and xylene were distilled off under reduced pressure (1.3 kPa or less) at 200 ° C. for 3 hours to obtain 98 parts by weight of the acid-modified polyolefin (a1-1-1). The acid value of (a1-1-1) was 9.9, Mn was 10,200, and the isotacticity of the propylene moiety was 40%.

<Manufacturing example 2>
[Manufacture of Acid-Modified Polyolefin (a1-1-2)]
Low molecular weight ethylene / propylene random copolymer obtained by the heat reduction method (ethylene content: 22 weight) in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. %, 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 polyolefins that can be modified at both ends: 90 90 parts by weight, isotacticity of propylene portion 4%), 10 parts by weight of maleic anhydride and 30 parts by weight of xylene were added, and after uniform mixing, the mixture was uniformly mixed and then at 200 ° C. with stirring in a nitrogen gas atmosphere (sealed). It was melted and reacted for 10 hours.
Then, excess maleic anhydride and xylene were distilled off under reduced pressure (1.3 kPa or less) at 200 ° C. for 3 hours to obtain 95 parts by weight of an acid-modified polyolefin (a1-1-2). The acid value of (a1-1-2) was 27.5, Mn was 3,600, and the isotacticity of the propylene moiety was 4%.

<Manufacturing 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 put into 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, and nitrogen was added. It was melted at 200 ° C. with stirring under a gas atmosphere and reacted under reduced pressure (1.3 kPa or less) for 3 hours to obtain 96 parts by weight of a secondary modified acid-modified polyolefin (a1-2).
The acid value of (a1-2) was 24.8, Mn was 4,000, and the isotacticity of the propylene moiety was 4%.

<Manufacturing example 4>
[Manufacture 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 decompression device, and nitrogen gas atmosphere. Below, it was melted at 180 ° C. and reacted for 2 hours. Then, excess 2-aminoethanol was distilled off under reduced pressure (1.3 kPa or less) at 180 ° C. for 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, Mn was 10,200, and the isotacticity of the propylene moiety was 40%.

<Production 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 introduction tube and decompression device. , Melted at 200 ° C. with stirring under a nitrogen gas atmosphere, and reacted for 2 hours. Then, excess bis (2-aminoethyl) ether was distilled off under reduced pressure (1.3 kPa or less) at 200 ° C. for 2 hours to obtain a modified polyolefin (a3-1) having amino groups at both ends. It was.
The amine value of (a1-4) was 22.4, Mn was 4,200, and the isotacticity of the propylene moiety was 4%.

<Manufacturing example 6>
[Manufacturing 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 put into a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. After nitrogen substitution, the temperature was raised to 220 ° C. over 2 hours and reduced to 0.13 kPa over 1 hour for the polyesterification reaction. After completion of the reaction, the mixture was cooled to 50 ° C., and 100 parts by weight of methanol was added to dissolve the mixture. The temperature in the reaction vessel was maintained at 120 ° C. with stirring, 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 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 cationic polymer (b3-1) having an average of 12 quaternary ammonium groups (hydroxyl value: 30.1, acid value: 0.5, volume specific resistance value: 1 × 10 ⁵ Ω). · Cm) was obtained.

<Manufacturing example 7>
[Manufacturing of anionic polymer (b4-1)]
67 parts by weight of PEG (Mn: 300), 49 parts by weight of sodium salt of 5-sulfoisophthalic acid dimethyl ester, and 49 parts by weight of PEG (Mn: 300) 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. 0.2 part by weight of dibutyltin oxide was added, the temperature was raised to 190 ° C. under a reduced pressure of 0.67 kPa, and the ester exchange reaction was carried out for 6 hours while distilling off methanol, and an average of 5 sodium sulfonate bases were contained in one molecule. Anionic polymer (b4-1) (hydroxyl value: 29.6, acid value: 0.4, volume specific resistance value: 2 × 10 ⁶ Ω · cm
) Was obtained.

<Comparative manufacturing example 1>
[Manufacture of Acid-Modified Polyolefin (a1-1-3)]
Low molecular weight ethylene / propylene random copolymer obtained by heat reduction method (ethylene content: 2 weights) in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. %, 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 polyolefins that can be modified at both ends: 90 parts by weight, isotacticity of propylene portion 85%) 90 parts by weight, 10 parts by weight of maleic anhydride and 30 parts by weight of xylene were added, and after uniform mixing, the temperature was 200 ° C. with stirring under a nitrogen gas atmosphere (sealed). And reacted for 10 hours.
Then, excess maleic anhydride and xylene were distilled off under reduced pressure (1.3 kPa or less) at 200 ° C. for 3 hours to obtain 95 parts by weight of the acid-modified polyolefin (a1-1-3).
The acid value of (a1-1-3) was 27.5, 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), α, ω-diaminoPEG (Mn) in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. : 4,000, volume specific resistance value: 1 × 10 ⁷ Ω · cm) (b1-1) 28.3 parts by weight, antioxidant [trade name “Irganox 1010”, manufactured by BASF Japan Ltd.] 0. 4 parts by weight and 0.6 parts by weight of zirconyl acetate were added and polymerized at 220 ° C. under a reduced pressure of 0.13 kPa or less for 3 hours to obtain a viscous polymer. This polymer is taken out in a strand shape on a belt and pelletized to obtain a block polymer (A-1) (Mn: 42,000) composed of a block of (a1-1-1) and a block of (b1-1). Obtained.

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

<Example 3>
In Example 1, instead of (a1-1-1) 70.7 parts by weight, 56.6 parts by weight of the secondary modified acid-modified polyolefin (a1-2), PEG (Mn: 3,000, volume specific resistance) 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. 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 a modified polyolefin (a1-3) having a hydroxyl group at both ends, and a cationic polymer (b3-1) 25. A block polymer composed of the block of (a1-3), the block of (b3-1) and the dodecanedioic acid 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-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 a modified polyolefin (a1-4) having an amino group at both ends, an anionic polymer (b4-1) 43. A block polymer composed of the block of (a1-4), the block of (b4-1) and the dodecanedioic acid 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 the secondary modified acid-modified polyolefin (a1-2), polytetramethylene glycol (Mn1,800, volume specific). From the block (a1-2) and the block (b1-3) in the same manner as in Example 1 except that the resistance value 1 × 10 ¹¹ Ω · cm) (b1-3) 30.7 parts by weight was used. 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 the secondary modified acid-modified polyolefin (a1-2), a bisphenol A ethylene oxide adduct (Mn2,000, Volume specific resistance value 1 × 10 ⁷ Ω · cm) (b1-4) In the same manner as in Example 1 except that 33.0 parts by weight was used, the block of (a1-2) and (b1-4). A block polymer (A-7) (Mn: 24,000) composed of blocks was obtained.

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

Each of the obtained block polymers (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) 10 g of each obtained block polymer (A) is placed in a container, 90 g of xylene at 25 ° C is stirred at 25 ° C for 3 hours, and then at room temperature (25 ° C). It was allowed to stand for one day. After standing, the contents of the container were observed, and the solvent solubility was evaluated according to the following <evaluation criteria>.

<Evaluation criteria>
⊚: Transparent.
◯: There is a slight haze.
Δ: There are some undissolved polymers.
X: Almost not dissolved.

<2> Solvent solubility at high temperature 10 g of each of the obtained block polymers (A) and 90 g of xylene are placed in a container, heated to 80 ° C., stirred for 3 hours, allowed to cool to 25 ° C., and allowed to stand for 1 day. did. After standing, the contents of the container were observed, and the solvent solubility was evaluated according to the following <evaluation criteria>.

<Evaluation criteria>
⊚: The solution is transparent and has fluidity.
◯: The solution is slightly hazy and fluid.
Δ: The solution is hazy and has no fluidity.
X: Almost not dissolved.

<3> Adhesion to base material The contents of the container after the evaluation of <2> above are placed on a polyester film [manufactured by Toray Industries, Inc., trade name "Lumirror" type T] base material so that the film thickness becomes 10 μm after drying. And dried at 80 ° C. for 10 minutes. The coating film was subjected to an adhesion test (a grid test) by a grid tape method based on JIS K5400.
The number of portions of the grid 100 where the coating film has not peeled off is represented by 0 to 100, and the larger the value, the better the adhesion between the base material and the coating film.
In the above <2>, those having Δ and × were not evaluated because they could not be coated.

<4> Surface specific resistance value (antistatic property)
After the coating film dried in <3> above is allowed to stand for 48 hours under the conditions of 23 ° C. and 50% humidity RH, it is subjected to a super insulation meter [model number "R8340A", manufactured by Advantest Co., Ltd.] under the same conditions. It was measured.

<Examples 11 to 17, Comparative Example 11>
According to the compounding composition (parts by weight) shown in Table 2, the compounding components were blended with a Henschel mixer for 3 minutes, and then using an inflation molding machine equipped with a twin-screw extruder with a vent, 100 rpm, 170 ° C., and a residence time of 5 minutes. After melt-kneading under the conditions to obtain each resin composition (Y), the film obtained by extrusion molding from a die whose temperature was adjusted at 170 ° C. was 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 with a winder. 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 [Compliant with ASTMD257 (1984)]
Evaluated by surface specific resistance value (unit is Ω). Using a test piece (100 x 100 mm) cut out from a film, let the test piece stand for 48 hours under the conditions of 23 ° C. and 50% humidity, and then use a super insulation meter [model number "R8340A", manufactured by Advantest Co., Ltd.]. The measurement was performed under the same conditions.

<6> Heat seal strength (evaluation of substrate adhesion)
The films cut to a width of 1.5 cm are laminated, heat-sealed at sealing temperature: 120 ° C and 130 ° C, sealing pressure: 0.2 MPa, and sealing time: 1.0 second, and the T-shaped peel strength is pulled. The heat seal strength was measured with a testing machine under an atmosphere of a tensile speed of 100 mm / min, 23 ° C., and a humidity of 50% RH.

The contents of the symbols in Table 2 are as follows.
B-1: High-pressure method low-density polyethylene [Product name: Novatec LF128, manufactured by Japan Polyethylene Corporation]
B-2: Linear 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 is excellent in solvent solubility at room temperature, solvent solubility at high temperature, substrate adhesion, and antistatic property as compared with the comparative one. Further, from the results in Table 2, it can be seen that the molded product (Z) of the resin composition (Y) of the present invention is excellent in antistatic property and excellent substrate adhesion as compared with the comparative one.

The block polymer (A) of the present invention is excellent in solvent solubility, substrate adhesion, and antistatic property, and is used in various applications, preferably resin modifiers, antistatic agents, emulsion raw materials, coating agent applications, and primer applications. It is extremely useful because it can be suitably used for.

Claims (10)

A block polymer having a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as a constituent unit, wherein the (a) is a polyolefin (a2) containing propylene as a constituent monomer. , The block polymer (A) in which the isotacticity of the propylene moiety of (a2) is 1 to 50%. The block polymer according to claim 1, wherein the weight ratio [ethylene unit / propylene unit] of the ethylene unit to the propylene unit of (a2) is 2/98 to 50/50. The block polymer according to claim 1 or 2, wherein (b) is at least one selected from the group consisting of polyethers, cationic polymers and anionic polymers. Any of claims 1 to 3 in which the (a) and (b) are bonded via 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. The block polymer described.
.. The block polymer according to any one of claims 1 to 4, wherein the number average molecular weight (Mn) of (A) is 5,000 to 200,000. The invention according to any one of claims 1 to 5, wherein the (A) has a [(a)-(b)] n-type structure (n = 2 to 20) in which (a) and (b) are alternately coupled. Block polymer A coating agent (X) containing the block polymer (A) according to any one of claims 1 to 6. A resin composition (Y) containing the block polymer (A) according to any one of claims 1 to 6 and a thermoplastic resin (B). A molded product (Z) obtained by molding the resin composition (Y) according to claim 8. A molded article obtained by painting and / or printing the molded article (Z) according to claim 9.