JP6849354B2 - Hydrophilicity-imparting agent - Google Patents

Description

The present invention relates to a hydrophilicity imparting agent. More specifically, the present invention relates to a hydrophilicity imparting agent that imparts excellent wettability to a thermoplastic resin.
Here and below, the wettability means the affinity for water and is evaluated by the wet tension described later.

Thermoplastic resins, for example, polyolefin resins, have excellent moldability, rigidity, heat resistance, chemical resistance, electrical insulation, etc., and are widely and widely used as molded products of films, fibers, hollow fiber membranes, and other various shapes. Has been done.
On the other hand, the polyolefin resin is a so-called non-polar and extremely inert polymer substance having no polar group in the molecule. Furthermore, since it has high crystallinity and extremely low solubility in solvents, there are problems in adhesiveness, coatability, etc., and it also has problems such as poor wettability to water and the inability to apply water-based paints because it repels water. It was.
Conventionally, as a method for improving wettability, a method of applying corona treatment or plasma treatment to the surface of a thermoplastic resin, for example, a polyolefin resin molded product (see, for example, Patent Document 1), or adding a surfactant to a polyolefin resin composition is added. , A method of using this as a molded product (see, for example, Patent Document 2) and the like are known.

Japanese Unexamined Patent Publication No. 2000-319426 Japanese Unexamined Patent Publication No. 2004-169014

However, the method of applying the corona treatment or the plasma treatment to the surface of the molded product has a problem that the wettability decreases with the lapse of time after the treatment. Further, in the method of adding a surfactant to the polyolefin resin composition and using it as a molded product, the mechanical strength originally possessed by the molded product of the original polyolefin resin base material is added when an addition amount that sufficiently exerts a modifying effect is added. (Tensile modulus, impact resistance, etc. The same shall apply hereinafter) are impaired, and there are problems such as the surfactant bleeding out from the molded product, and it has been desired to solve these problems.
An object of the present invention is to provide a hydrophilicity imparting agent that imparts excellent wettability to water and excellent wettability to a thermoplastic resin without impairing mechanical strength.

The present inventors have arrived at the present invention as a result of diligent studies to solve the above problems. That is, the present invention is a hydrophilicity-imparting agent (Z) containing a block polymer (A) containing a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as a constituent unit. ..

The hydrophilicity-imparting agent of the present invention and a molded product of the hydrophilic thermoplastic resin composition containing the hydrophilicity-imparting agent have the following effects.
(1) The hydrophilicity-imparting agent imparts excellent wettability to water to the thermoplastic resin without impairing the original mechanical strength (mechanical characteristics).
(2) The molded product has excellent wettability with water and is excellent in its durability.

<Hydrophobic polymer (a)>
The hydrophobic polymer (a) in the present invention means a polymer having a volume specific resistance value exceeding ^{1 × 10 11 Ω · cm.} Specific examples thereof include polyamide (a1), polyolefin (a2) and polyamide-imide (a3), and two or more of these may be used in combination. Of (a), polyamide (a1) and polyolefin (a2) are preferable from the viewpoint of hydrophilicity, and polyolefin (a2) is more preferable.
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).

Examples of the polyamide (a1) include ring-opening polymerization or polycondensation of an amide-forming monomer (α), and a polycondensation product of a diamine (β) and a dicarboxylic acid (γ).

Examples of the amide-forming monomer (α) include lactam (α1-1) and aminocarboxylic acid (α1-2).
Examples of lactam (α1-1) include lactam having 4 to 20 carbon atoms (caprolactam, enantractam, laurolactam, undecanolactam, etc.).
Examples of the aminocarboxylic acid (α1-2) include aminocarboxylic acids having 2 to 20 carbon atoms (ω-aminocaproic acid, ω-aminoenant acid, ω-aminocapric acid, ω-aminopelargonic acid, ω-aminocapric acid, etc.). 11-Aminoundecanoic acid, 12-aminododecanoic acid and mixtures thereof, etc.) and the like.

As the diamine (β), aliphatic diamines having 2 to 20 carbon atoms (ethylene diamine, propylene diamine, hexamethylene diamine, decamethylene diamine, 1,12-dodecane diamine, 1,18-octadecane diamine and 1,20-eikosan) Diamine, etc.), alicyclic diamine with 5 to 20 carbon atoms [1,3- or 1,4-cyclohexanediamine, isophorone diamine, 4,4'-diaminocyclohexylmethane and 2,2-bis (4-aminocyclohexyl) Propane, etc.], aromatic diamines with 6 to 20 carbon atoms [p-phenylenediamine, 2,4- or 2,6-toluylene diamine and 2,2-bis (4,4'-diaminophenyl) propane, p- Alternatively, m-xylylene diamine, bis (aminoethyl) benzene, bis (aminopropyl) benzene, bis (aminobutyl) benzene, etc.] and the like can be mentioned.

As the dicarboxylic acid (γ), an aliphatic dicarboxylic acid having 2 to 20 carbon atoms (succinic acid, glutaric acid, adipic acid, pimelliic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid) , Fumaric acid and itaconic acid, etc.), aromatic dicarboxylic acid with 8 to 20 carbon atoms (phthalic acid, 2,6- or 2,7-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyetanedicarboxylic acid Acids, tolylene dicarboxylic acids, xylylene dicarboxylic acids and 5-sulfoisophthalic acid alkali metal salts, etc.), alicyclic dicarboxylic acids with 5 to 20 carbon atoms (cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexendicarboxylic acid) Acids, dicyclohexyl-4,4'-dicarboxylic acid, succinoic acid, etc.) and the like.

Specific examples of the polyamide (a1) include nylon 6,6, nylon 6,9, nylon 6,12, nylon 6, nylon 11, nylon 12, nylon 4,6, and a copolymer of nylon 6 and nylon 6,6. , A copolymer of nylon 6 and nylon 12, a copolymer of nylon 6 and nylon 6, 6 and nylon 12, and the like.

The polyolefin (a2) includes 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 the (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. ] And the modified polyolefin {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 50,000 to 150,000], mechanically, thermally or chemically. (Decomposition method)} is included.
Of these, a modified polyolefin (modified polyolefin) is preferable from the viewpoint of easy modification and availability when introducing a carboxyl group, a hydroxyl group, an amino group or an isocyanate group. More preferred is a heat-decomposed polyolefin (heat-decomposed 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 introduce an isocyanate group or the like to modify it.

The Mn of the polymer 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 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, 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 6, from the viewpoint of hydrophilicity of the molded product described later. It is 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, and particularly preferably 2 to 30 from the viewpoint of hydrophilicity of the molded product. There are 4 to 20 pieces.

(A2-01) The average number of terminal double bonds per molecule is preferably from the viewpoint of ease of forming a repeating structure in the molecule, hydrophilicity of the molded product, and thermoplasticity of the block polymer (A) described later. The number is 1.1 to 5, 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 to have an average number of terminal double bonds per molecule of 1.5 to 2 (a2-01) in the range of Mn 800 to 6,000. [Katsuhide Murata, Tadahiko Makino, Journal of the Japanese Society of Chemistry, p. 192 (1975)].

A polyolefin (a2-02) containing a polyolefin whose one end can be modified as a main component can be obtained in the same manner as in (a2-01), and Mn of (a2-02) is hydrophilic of a molded product described later. From the viewpoint of the above, 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 from the viewpoint of hydrophilicity of the molded product and molecular weight control of the block polymer (A). The number is preferably 0.5 to 15, particularly preferably 0.7 to 10.

(A2-02) The average number of double bonds per molecule is preferably 0 from the viewpoint of ease of forming a repeating structure in the molecule, hydrophilicity of the molded product, and thermoplasticity of the block polymer (A) described later. It is .5 to 1.4, 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 denaturation method is preferable from the viewpoint of easiness of denaturation, and more preferably Mn obtained by the heat denaturation 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.

Although (a2-01) and (a2-02) are usually obtained as a mixture thereof, 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 terminal 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, a mixture of two or more of these, and the like 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) acrylate [(meth) acrylate means acrylate or methacrylic acid. The same applies below. ], Methyl (meth) acrylate, butyl (meth) acrylate, maleic acid (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 (anhydrous) used for denaturation is based on the weight of the polyolefin (a2-01), the ease of forming a repeating structure in the molecule, the hydrophilicity of the molded product, and the hydrophilicity described later. From the viewpoint of dispersibility of the block polymer (A) in the hydrophilic resin composition, 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, enantractam, 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 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 the secondary denaturation is based on the weight of the object to be modified (a2-1), the ease of forming a repeating structure in the molecule, the hydrophilicity of the molded product, and the block polymer (A). From the viewpoint of thermoplasticity, 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 a hydroxyl group at both ends of the polymer include 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 two of these. A mixture of seeds or more 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 based on the weight of the object to be modified (a2-1), the ease of forming a repeating structure in the molecule, the hydrophilicity of the molded product, and the hydrophilic resin composition described later. From the viewpoint of dispersibility of the block polymer (A) and mechanical properties of the molded product, it is preferably 0.5 to 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 the ease of forming a repeating structure in the molecule, the hydrophilicity of the molded product, the dispersibility of the block polymer (A) in the hydrophilic resin composition, and the molded product. From the viewpoint of mechanical properties of (a2-1), it is preferably 0.5 to 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.

Examples of the polyolefin (a2-4) having an isocyanate group at both ends include 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 an aromatic PI having 6 to 20 carbon atoms (excluding carbon atoms in the NCO group, the same applies hereinafter), an aliphatic PI having 2 to 18 carbon atoms, an alicyclic PI having 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.

The aliphatic PI includes ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, and 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-norbornene diisocyanate.

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.

As the polyamide-imide (a3), a trivalent or tetravalent aromatic polycarboxylic acid or an anhydride thereof (δ) capable of forming at least one imide ring with the amide-forming monomer (α) and (α). A polymer having the above as a constituent monomer and a mixture thereof are included.

As (δ), trivalent carboxylic acid [monocyclic trivalent carboxylic acid (trimeric acid, etc.), polycyclic trivalent carboxylic acid (1,2,5- or 2,6,7-naphthalene tricarboxylic acid, 3, 3', 4-biphenyltricarboxylic acid, benzophenone-3,3', 4-tricarboxylic acid, diphenylsulfone-3,3', 4-tricarboxylic acid and diphenyl ether-3,3', 4-tricarboxylic acid, etc.) and their Anhydrous] and tetravalent carboxylic acid [monocyclic tetravalent carboxylic acid (pyromellitic acid, etc.), polycyclic tetravalent carboxylic acid (biphenyl-2,2', 3,3'-tetracarboxylic acid, benzophenone-2,2 ', 3,3'-tetracarboxylic acid, diphenylsulfone-2,2', 3,3'-tetracarboxylic acid and diphenyl ether-2,2', 3,3'-tetracarboxylic acid), and their anhydrides Things].

As a method for producing the polyamide-imide (a3), as in the case of the polyamide (a1), one or more selected from the diamine (β) and the dicarboxylic acid (γ) are used as the molecular weight adjuster. Then, a method of ring-opening polymerization or polycondensation of the amide-imide-forming monomer in the presence thereof can be mentioned.
The amount of the molecular weight adjusting agent used is preferably 2 to 80% by weight, more preferably 4 from the viewpoint of imparting hydrophilicity and heat resistance of the molded product, based on the total weight of the amidimide-forming monomer and the molecular weight adjusting agent. ~ 75% by weight.

The Mn of (a3) is preferably 200 to 5,000, more preferably 500 to 4,000, from the viewpoint of moldability and the production of the hydrophilicity-imparting agent.

The Mn of the hydrophobic polymer (a) is preferably 200 to 25,000, more preferably 500 to 25,000, and particularly preferably 500 to 25,000, from the viewpoint of the dispersibility of the block polymer (A) and the mechanical properties of the molded product. It is 2,000 to 25,000.

<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 hydrophilicity of the molded product described later decreases.

Examples of the hydrophilic polymer (b) include the hydrophilic polymer described in 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.

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.
Examples of aromatic dihydric alcohols having 6 to 18 carbon atoms include monocyclic aromatic dihydric alcohols (xylylenediol, hydroquinone, catechol, resorcin, ursiol, 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.
^{R 1} and R ² when m and n in the general formula (1) are 2 or more, respectively, may be the same or different, and the (OR ¹ ) _m and (R ² O) _n portions may be randomly combined or block connected. 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 combination in a small proportion (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 -OE ^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) _n 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 can be prepared by reacting (b1-1) or (b1-2) with a diepoxide (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 500 to 20,000, more preferably 700 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.

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

The polyether ester amide (b2-1) is composed of a polyamide (a1) having a carboxyl group at both ends and a polyether diol (b1-1).
Examples of (a1') include a ring-opening polymer of the lactam (α1-1), a polycondensate of the aminocarboxylic acid (α1-2), and a polyamide of the diamine (β) and the dicarboxylic acid (γ). Can be mentioned.
Of (a1'), the ring-opening polymer of caprolactam, the polycondensate of 12-aminododecanoic acid, and the polyamide of adipic acid and hexamethylenediamine are preferable from the viewpoint of hydrophilicity, and more preferable. It is a ring-opening polymer of caprolactam.

The polyetheramideimide (b2-2) is composed of a polyamide-imide (a3) having at least one imide ring and a polyetherdiol (b1-1).
(A3) is an aminocarboxylic acid (a3), which is a polymer composed of lactam (α1-1) and a trivalent or tetravalent aromatic polycarboxylic acid (δ) capable of forming at least one imide ring. Examples thereof include a polymer composed of α1-2) and (δ), a polymer composed of polyamide (a1') and (δ), and a mixture thereof.

Examples of the polyether ester (b2-3) include those composed of polyester (Q) and polyether diol (b1-1).
Examples of (Q) include polyesters containing a dicarboxylic acid (γ) and a diol (b0).
Examples of the polyether amide (b2-4) include those composed of a polyamide (a1) and a polyether diamine (a212).
Examples of the polyether urethane (b2-5) include the diisocyanate in the PI, the polyether diol (b1-1) or the polyether diamine (b1-2), and if necessary, the chain extender [the diol (b0) and the diamine. (Β) etc.].

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 hydrophilicity and moldability.
The lower limit of Mn in (b2) is preferably 500, 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, and particularly preferably 20,000, 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, a hydrocarbon group having a heterocyclic structure having a nitrogen atom or an oxygen atom, and the like.

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 superacid include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide and the like.
Examples of 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 15,000, and particularly preferably 1 from the viewpoint of imparting hydrophilicity and reactivity with the hydrophobic polymer (a). , 200-8,000.

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 a hydroxyalkyl (2-4 carbon atoms) group (mono, di or triethylamine, mono, di or triethanolamine, diethylethanolamine, etc.) and the amines. Quaternary ammonium salt and the like can be mentioned.
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 ( It is an EO adduct (number of moles added: 2 to 60 mols) of (bisphenol A, etc.) and a mixture of two or more thereof.
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 antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide, dibutyltin oxide, etc.), titanium catalysts (tetrabutyl titanate, etc.), zirconium catalysts (tetrabutylzirconate, etc.) and metal acetates. Examples include catalysts (zinc acetate, etc.).

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

Further, among the above (b1) to (b4), (b1) and (b2) are preferable, and (b1) is more preferable, from the viewpoint of imparting hydrophilicity and dispersibility of (A).
The number average molecular weight (Mn) of the (b) is preferably 500 to 20,000 from the viewpoint of imparting hydrophilicity and mechanical properties.

<Block polymer (A)>
The block polymer (A) in the present invention contains the block of the hydrophobic polymer (a) and the block of the hydrophilic polymer (b) as constituent units.

Of (A), the following (A1) and / or (A2) are preferable from the viewpoint of hydrophilicity [hydrophilicity-imparting property], and (A2) is more preferable.
(A1): (a) is a polyamide (a1), (b) is a polyether (b1) or a polyether-containing hydrophilic polymer (b2), and (a1) and (b1) and / or ( A polyether ester amide obtained by reacting b2).
(A2): (a) is polyolefin (a2), and the block of (a2) and the block of hydrophilic polymer (b) are ester bond, amide bond, ether bond, imide bond, urethane bond and urea. A block polymer having a structure bonded via at least one bond selected from the group consisting of bonds.

The weight ratio of the block (a) constituting (A) to the block (b) is preferably 10/90 to 80/20, more preferably 20/80, from the viewpoint of hydrophilicity and water resistance. ~ 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).
As the structure of the block polymer (A), [(a)-(b)] n-type in which (a)-(b)] are repeatedly and alternately bonded from the viewpoint of hydrophilicity imparting property and anchoring effect on the target resin. Is preferable.
[(A)-(b)] n in the n-type structure is preferably 2 to 50, more preferably 2.3, from the viewpoint of imparting hydrophilicity, mechanical properties of the molded product, and anchoring effect on the resin. ~ 30, particularly preferably 2.7 to 20, and most preferably 3 to 10. n can be determined by Mn of the block polymer (A) and Mn of (a) and (b), ^{1 1} H-NMR analysis.

The Mn of (A) is preferably 2,000 to 1,000,000, more preferably 4,000 to 500,000, and particularly preferably 10 from the viewpoint of mechanical properties and hydrophilicity of the molded product described later. It is 000 to 100,000.

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 hydrophilicity and water resistance.

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 can be mentioned. 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, 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 the generated water is removed from the reaction system together with the carrier gas.
(3) A method in which the inside of the reaction system is depressurized 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 hydrophilicity and water resistance.

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 octanoate, 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.

<Hydrophilicity-imparting agent>
The hydrophilicity-imparting agent (Z) of the present invention contains a block polymer (A) containing a block of the hydrophobic polymer (a) and a block of the hydrophilic polymer (b) as constituent units.
The (Z) can be suitably used as a hydrophilicity-imparting agent (wetting property-imparting agent) for the thermoplastic resin (C) described later.

<Hydrophilic improver (D)>
The hydrophilicity imparting agent (Z) can further contain the hydrophilicity improving agent (D) as long as the effect of the present invention is not impaired.
Examples of the hydrophilicity preventive agent (D) include alkali metal or alkaline earth metal salt (D1), quaternary ammonium salt (D2), surfactant (D3) and ionic liquid (D4). (D1) to (D4) may be used in combination of two or more.

Examples of the alkali metal or alkaline earth metal salt (D1) include alkali metals (lithium, natriu, potassium, etc.) or alkaline earth metals (magnesium, calcium, etc.)] and organic acids [mono or dicarboxylic having 1 to 7 carbon atoms. Acids (foric acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), sulfonic acids having 1 to 7 carbon atoms (methanesulfonic acid, p-toluenesulfonic acid, etc.) and thiosian acids], and the organic acids. Examples thereof include salts of inorganic acids [hydrohalogenate (hydrochloric acid, hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.).

Examples of the quaternary ammonium salt (D2) include amidinium (1-ethyl-3-methylimidazolium, etc.) or guanidium (2-dimethylamino-1,3,4-trimethylimidazolinium, etc.) and the organic acid or inorganic acid. Examples include salts with acids.

Examples of the surfactant (D3) include known nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and the like.

The ionic liquid (D4) is a compound excluding the above (D1) to (D3), has a melting point of 25 ° C. or lower, at least one of the constituent cations or anions is an organic ion, and has an initial conductivity. A molten salt having a value of 1 to 200 ms / cm (preferably 10 to 200 ms / cm) can be mentioned, and specific examples thereof include the molten salt exemplified in WO95 / 15572.

The content of each of (D1) to (D4) based on the weight of the hydrophilicity-imparting agent (Z) is preferably 10% by weight from the viewpoint of providing a resin molded product having good appearance without precipitation on the resin surface and hydrophilicity. It is less than or equal to, more preferably 0.01 to 5% by weight, and particularly preferably 0.1 to 3% by weight.
The total content of (D) when two or more of (D1) to (D4) are used in combination is preferably 10 from the viewpoint of imparting hydrophilicity and giving a resin molded product having a good appearance without precipitating on the resin surface. It is not more than% by weight, more preferably 0.01 to 5% by weight, and particularly preferably 0.1 to 3% by weight.

As a method of incorporating (D) in the hydrophilicity-imparting agent (Z) of the present invention, a method of pre-dispersing the hydrophilicity-imparting agent (Z) in the hydrophilicity-imparting agent (Z) in order not to impair the appearance of the molded product described later Preferably, the method of containing (D) at the time of producing the block polymer (A) is more preferable. The time when (D) is contained in the production of (A) is not particularly limited and may be contained before, during or after polymerization, but it is preferably contained in the raw material before polymerization.

<Hydrophilic resin composition>
The hydrophilic resin composition of the present invention contains the hydrophilicity-imparting agent and the thermoplastic resin (C).

Examples of (C) include polyphenylene ether resin (C1) (PPE); polyolefin resin (C2) [polypropylene (PP), polyethylene (PE), ethylene-vinyl acetate copolymer resin (EVA) and ethylene-ethyl acrylate copolymer resin). Etc.]; Poly (meth) acrylic resin (C3) [Polymethyl methacrylate, etc.]; Polystyrene resin (C4) [Vinyl group-containing aromatic hydrocarbon alone, vinyl group-containing aromatic hydrocarbon, and (meth) acrylic acid A copolymer whose constituent unit is one or more selected from the group consisting of ester, (meth) acrylonitrile and butadiene; for example, polystyrene (PS), styrene / acrylonitrile copolymer (AN resin), and acrylonitrile / butadiene / styrene. Polymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin) and styrene / methyl methacrylate copolymer (MS resin)], etc .; polyester resin (C5) [polyethylene terephthalate, polybutylene terephthalate, Polycyclohexanedimethylene terephthalate, polybutylene adipate and polyethylene adipate]; Copolymer resin (C6) [Nylon 66, Nylon 69, Nylon 612, Nylon 6, Nylon 11, Nylon 12, Nylon 46, Nylon 6/66 and Nylon 6/12 Etc.]; Polycarbonate resin (C7) [Polycarbonate and polycarbonate / ABS alloy resin (PC / ABS), etc.]; Polyacetal resin (C8), polyvinylidene fluoride resin (C9), and a mixture of two or more thereof.
Of these, (C1), (C2), (C3), (C4), (C7), and (C9) are more preferable from the viewpoint of imparting mechanical properties and hydrophilicity to the molded product described later. Is (C2), (C9), and (C9) is particularly preferable.

The weight ratio [(Z) / (C)] of (Z) to (C) in the hydrophilic resin composition is preferably 1/99 to 50/50 from the viewpoint of hydrophilicity and mechanical properties of the molded product. It is more preferably 3/97 to 40/60, and particularly preferably 5/95 to 30/70.

The hydrophilic resin composition of the present invention may contain other additives (E) as long as the effects of the present invention are not impaired. Examples of (E) include a colorant (E1), a mold release agent (E2), an antioxidant (E3), a flame retardant (E4), an ultraviolet absorber (E5), an antibacterial agent (E6), and a dispersant (E7). And the filler (E8) and the like. (E) may be used in combination of two or more.

Coloring agents (E1) include inorganic pigments (white pigments, cobalt compounds, iron compounds, sulfides, etc.), organic pigments (azo pigments, polycyclic pigments, etc.) and dyes (azo-based, indigoid-based, sulfide-based, alizarin). System, aclysine system, thiazole system, nitro system, aniline system, etc.) and the like.

The release agent (E2) includes an alkyl (1 to 4 carbon atoms) ester of a fatty acid having 12 to 18 carbon atoms (butyl stearate, etc.) and a glycol (2 to 8 carbon atoms) ester of a fatty acid having 2 to 18 carbon atoms. Examples thereof include (ethylene glycol monostearate, etc.), polyvalent (trivalent or higher) alcohol esters of fatty acids having 2 to 18 carbon atoms (hardened castor oil, etc.), liquid paraffins, and the like.

Examples of the antioxidant (E3) include phenol compounds [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.)) and bisphenol [2,2'-methylenebis (4-methyl-6-t-butylphenol). ) Etc.] and polycyclic phenol [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc.], etc.], sulfur compounds (dilauryl- 3,3'-thiodipropionate, etc.), phosphorus compounds (triphenylphosphite, etc.), amine compounds (octylated diphenylamine, etc.) and the like.

Examples of the flame retardant (E4) include a halogen-containing flame retardant, a nitrogen-containing flame retardant, a sulfur-containing flame retardant, a silicon-containing flame retardant, and a phosphorus-containing flame retardant.

Examples of the ultraviolet absorber (E5) include benzotriazole [2- (2'-hydroxy-5'-methylphenyl) benzotriazole, etc.], benzophenone (2-hydroxy-4-methoxybenzophenone, etc.), salicylate (phenylsalicylate, etc.). Etc.) and acrylates (2-ethylhexyl-2-cyano-3, 3'1-diphenyl acrylate, etc.) and the like.

Examples of the antibacterial agent (E6) include benzoic acid, sorbic acid, phenol halide, organic iodine, nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylenebistianocyanate, etc.), N- Examples thereof include haloalkylthioimides, copper agents (8-oxyquinolin copper, etc.), benzimidazoles, benzothiazoles, trihaloallyl, triazoles, organic nitrogen-sulfur compounds (suraoff 39, etc.), quaternary ammonium compounds, and pyridine compounds.

The dispersant (E7) is a modified vinyl polymer having one or more functional groups (polar groups) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group (for example, specially. Polymers described in Kaihei 3-258850, modified vinyl polymers having a sulfonic acid group described in JP-A-6-345927, block polymers having a polyolefin moiety and an aromatic vinyl polymer moiety, etc.), etc. Can be mentioned.

Examples of the filler (E8) include inorganic fillers (calcium carbonate, talc, clay, etc.) and organic fillers (urea, calcium stearate, etc.) and the like.

The total content of (E) based on the weight of the thermoplastic resin (C) is preferably 45% by weight or less, more preferably 0.001 to 40% by weight, and particularly preferably 0.001 to 40% by weight, from the viewpoint of mechanical properties of the molded product. Is 0.01 to 35% by weight.
The content of (E1) based on the weight of the thermoplastic resin (C) is preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, from the viewpoint of the mechanical properties of the molded product. is there.
The contents of (E2), (E3), and (E5) based on the weight of the thermoplastic resin (C) are preferably 0.01 to 3% by weight, more preferably 0.01 to 3% by weight, from the viewpoint of the mechanical properties of the molded product. Is 0.05 to 1% by weight.
The contents of (E4) and (E6) based on the weight of the thermoplastic resin (C) are preferably 0.5 to 20% by weight, more preferably 1 to 10 from the viewpoint of mechanical properties of the molded product. By weight%.
The contents of (E7) and (E8) based on the weight of the thermoplastic resin (C) are preferably 0.5 to 10% by weight, more preferably 1 to 5 from the viewpoint of mechanical properties of the molded product. By weight%.

The hydrophilic resin composition of the present invention can be obtained by melt-mixing the hydrophilicity-imparting agent (Z) of the present invention, the thermoplastic resin (C), and if necessary, (D) and (E). As a method of melt-mixing, generally, a method of mixing pellet-shaped or powder-shaped components with an appropriate mixer (Henschel mixer, etc.) and then melt-mixing with an extruder to pelletize is applied. it can.
The order of addition of each component during melt mixing is not particularly limited, but for example,
[1] A method in which (Z) is melt-mixed, and then (C), and if necessary, (D) and (E) are collectively added and melt-mixed.
[2] After melt-mixing (Z), a part of (C) is melt-mixed in advance to prepare a high-concentration composition (masterbatch resin composition) of (Z), and then the remaining (C) and A method of melting and mixing (D) and (E) as needed (master batch method or master pellet method).
And so on.
The concentration of (Z) in the masterbatch resin composition in the method [2] is preferably 40 to 80% by weight, more preferably 50 to 70% by weight.
Of the methods [1] and [2], the method [2] is preferable from the viewpoint that (Z) can be easily dispersed in (C) efficiently.

<Molded product>
The molded product of the present invention is a molded product of the hydrophilic resin composition of the present invention. 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.

The molded product of the present invention has excellent mechanical properties and excellent hydrophilicity, and also has good paintability and printability, and a molded product can be obtained by painting and / or printing the molded product.
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 usually 10 to 50 μm.

As a method of printing on a molded product or a painted surface of the molded product, any printing method generally used for printing plastic can be used, and gravure printing, flexo printing, screen printing, pad printing can be used. , Dry offset printing, offset printing and the like.
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.

Examples of the present invention will be described below, but the present invention is not limited thereto. In the following, parts indicate parts by weight.

<Manufacturing Example 1> [Manufacturing of Polyamide (a1-1)]
In a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device, 173 parts of ε-caprolactam, 33.2 parts of terephthalic acid, antioxidant ["Irganox 1010", Ciba Made by Specialty Chemicals Co., Ltd.] 0.4 part and 10 parts of water were added, and after nitrogen replacement, the temperature was raised to 220 ° C with stirring under sealing, and the same temperature (pressure: 0.2 to 0.3 MPa). Was stirred for 4 hours to obtain a polyamide (a1-1) having a carboxyl group at both ends. The acid value of (a1-1) was 111, and Mn was 1,000.

<Production Example 2> [Production of polyolefin (a2-1-1α) having carboxyl groups at both ends]
In the same pressure-resistant reaction vessel as in Production Example 1, low molecular weight polypropylene [polypropylene (MFR: 10 g / 10 min) obtained by the thermal decomposition method was placed at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Obtained by heat reduction. 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 denatured at both ends: 90 weight %) 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were added, mixed uniformly, replaced with nitrogen, heated to 200 ° C. with stirring under sealing, melted, and reacted at the same temperature for 10 hours. I let you. Next, excess maleic anhydride and xylene were distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to form a polyolefin (a2-1-1α) 95 having carboxyl groups at both ends of the polymer. I got a part. The acid value of (a2-1-1α) was 27.5, and Mn was 3,600.

<Production Example 3> [Production of polyolefin (a2-1-2) obtained by secondary modification of (a2-1-1α)]
88 parts of (a2-1-1α) and 12 parts of 12-aminododecanoic acid were put into the same pressure-resistant reaction vessel as in Production Example 1, mixed uniformly, and then heated to 200 ° C. with stirring in a nitrogen gas atmosphere. Then, the reaction was carried out at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours to obtain 96 parts of polyolefin (a2-1-2) obtained by secondary modification of (a2-1-1α). The acid value of (a2-1-2) was 24.8, and Mn was 4,000.

<Production Example 4> [Production of polyolefin (a2-2) having hydroxyl groups at both ends]
In Production Example 2, 90 parts of low molecular weight polypropylene and 10 parts of maleic anhydride obtained by the heat reduction method were used, and 94 parts of low molecular weight ethylene / propylene random copolymer and maleic anhydride 6 obtained by the heat reduction method were used. 98 parts of polyolefin (a2-1-1β) having carboxyl groups at both ends of the polymer was obtained in the same manner as in Production Example 2 except that the parts were changed to parts. The acid value of (a2-1-1β) was 9.9, and Mn was 10,200. The low molecular weight ethylene / propylene random copolymer (Mn: 10,000, number of double bonds per 1,000 carbon atoms: 2.5, 2 per molecule) obtained by the above thermal modification method. The average number of double bonds: 1.8, content of polyolefin that can be modified at both ends: 90% by weight) is 410 for ethylene / propylene random copolymer (ethylene content: 2% by weight, MFR: 10 g / 10 min). It was obtained by heat-polymerizing at ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 14 minutes.
Next, 97 parts of (a2-1-1β) and 5 parts of ethanolamine were put into the same pressure-resistant reaction vessel as in Production Example 1, and the temperature was raised to 180 ° C. with stirring under a nitrogen gas atmosphere, and 2 at the same temperature. Reacted for time. Excess ethanolamine was distilled off under reduced pressure (0.013 MPa or less) at 180 ° C. for 2 hours to obtain a polyolefin (a2-2) having hydroxyl groups at both ends of the polymer. The hydroxyl value of (a2-2) was 9.9, the amine value was 0.01, and Mn was 10,200.

<Production Example 5> [Production of modified polyolefin (a2-4) having amino groups at both ends]
In Production Example 2, 90 parts of low molecular weight polypropylene and 10 parts of maleic anhydride obtained by the heat reduction method were changed to 80 parts of low molecular weight polypropylene and 20 parts of maleic anhydride obtained by the heat reduction method. In the same manner as in Production Example 2, 92 parts of polyolefin (a2-1-1γ) having carboxyl groups at both ends of the polymer was obtained. The acid value of (a2-1-1γ) was 64.0 and Mn was 1,700. The low molecular weight polypropylene (Mn: 1,500, number of double bonds per 1,000 carbon atoms: 17.8, average number of double bonds per molecule:: 1.94, content of polyolefin that can be modified at both ends: 98% by weight) is an ethylene / propylene random copolymer (ethylene content: 3% by weight, MFR: 7 g / 10 min) at 410 ± 0.1 ° C. It was obtained by heat-reducing for 18 minutes.
Next, 90 parts of (a2-1-1γ) and 10 parts of bis (2-aminoethyl) ether were put into the same pressure-resistant reaction vessel as in Production Example 1, and the temperature was raised to 200 ° C. with stirring under a nitrogen gas atmosphere. Then, the reaction was carried out at the same temperature for 2 hours. Excess bis (2-aminoethyl) ether was distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 2 hours to obtain a modified polyolefin (a2-4) having amino groups at both ends. The amine value of (a2-4) was 64.0, and Mn was 1,700.

<Production Example 6> [Production of cationic polymer (b3)]
41 parts of N-methyldiethanolamine, 49 parts of adipic acid and 0.3 part of zirconyl acetate were put into the same pressure-resistant reaction vessel as in Production Example 1, and after nitrogen substitution, the temperature was raised to 220 ° C. over 2 hours and 1 hour. The pressure was reduced to 0.013 MPa and the polyesterification reaction was carried out. After completion of the reaction, the mixture was cooled to 50 ° C. and 100 parts of methanol was added to dissolve the reaction. The temperature in the reaction vessel was maintained at 120 ° C. with stirring, 31 parts of dimethyl carbonate was added dropwise over 3 hours, and the mixture was aged at the same temperature for 6 hours. After cooling to room temperature, 100 parts of a 60 wt% hexafluorophosphoric acid aqueous solution was added, and the mixture was stirred at room temperature for 1 hour. Next, methanol was distilled off under reduced pressure, and a cationic polymer (b3) 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.

<Production Example 7> [Production of anionic polymer (b4α)]
114 parts of diethylene glycol, 268 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 parts of dibutyltin oxide were put into a pressure resistant reaction vessel similar to that of Production Example 1, and the temperature was raised to 190 ° C. under a reduced pressure of 0.067 MPa. After warming and transesterifying at the same temperature for 6 hours while distilling off methanol, an anionic polymer (b4α) having an average of 6 sodium sulfonate bases in one molecule (hydroxyl value is 49, acid value is 0.6). , volume resistivity was obtained ^{3 × 10 8 Ω · cm)} .

<Production Example 8> [Production of anionic polymer (b4β)]
67 parts of PEG (Mn: 300), 49 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 part of dibutyltin oxide were put into a pressure resistant reaction vessel similar to that of Production Example 1 under a reduced pressure of 0.067 MPa. The temperature was raised to 190 ° C., and the ester exchange reaction was carried out at the same temperature for 6 hours while distilling off methanol, and an anionic polymer (b4β) having an average of 5 sodium sulfonate bases in one molecule (hydroxyl value: 29.6, Acid value: 0.4, volume specific resistance value: 2 × 10 ⁶ Ω · cm) was obtained.

<Example 1>
199 parts of (a1-1) and EO adduct of bisphenol A (Mn: 4,000, volume specific resistance value: 2 × 10 ⁷ Ω · cm) in a reaction vessel equipped with a stirrer, a thermometer and a heating / cooling device. 780 parts and 0.6 parts of zirconyl acetate were added, the temperature was raised to 240 ° C. with stirring, and the mixture was polymerized under reduced pressure (0.013 MPa or less) at the same temperature for 6 hours to contain a block polymer (A1-1). A hydrophilicity-imparting agent (Z-1) was obtained.
The Mn of (A1-1) was 24,000.

<Example 2>
In the same pressure-resistant reaction vessel as in Example 1, 143 parts of (a1-1), 320 parts of (b4α) and 0.3 part of the antioxidant "Irganox 1010" were put and heated to 240 ° C. with stirring. , Polymerized under reduced pressure (0.013 MPa or less) at the same temperature for 5 hours to obtain a hydrophilicity-imparting agent (Z-2) containing a block polymer (A1-2).
The Mn of (A1-2) was 21,000.

<Example 3>
In the same pressure-resistant reaction vessel as in Example 1, 67.1 parts of (a2-1-1α), polyether diamine (b1-2) [α, ω-diaminoPEG (Mn: 2,000, volume specific resistance value:): 1 x 10 ⁷ Ω · cm)] 32.9 parts, 0.3 part of the antioxidant "Irganox 1010" and 0.5 part of zirconyl acetate are added, the temperature is raised to 220 ° C. with stirring, and the pressure is reduced (1 × 10 7 Ω · cm)] Polymerization was carried out at the same temperature for 3 hours (0.013 MPa or less) to obtain a hydrophilicity-imparting agent (Z-3) containing a block polymer (A2-1).
The Mn of (A2-1) was 50,000.

<Example 4>
In Example 3, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 60.1 parts of (a2-1-2) and polyetherdiol (b1-1α) [PEG. (Mn: 3,000, volume specific resistance value: 1 × 10 ⁷ Ω · cm)] The block polymer (A2-2) was contained in the same manner as in Example 3 except that it was changed to 39.9 parts. (Z-4) was obtained.
The Mn of (A2-2) was 30,000.

<Example 5>
In Example 3, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 48.0 parts of (a2-2), 48.0 parts of (b3) and dodecanedioic acid 4 A hydrophilicity-imparting agent (Z-5) containing a block polymer (A2-3) was obtained in the same manner as in Example 3 except that the portion was changed.
The Mn of (A2-3) was 100,000.

<Example 6> [Block polymer (A2-4)]
In Example 3, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 31.6 parts of (a2-4), 68.4 parts of (b4β) and 8 dodecanedioic acid. A hydrophilicity-imparting agent (Z-6) containing a block polymer (A2-4) was obtained in the same manner as in Example 3 except that the portion was changed.
The Mn of (A2-4) was 10,000.

<Example 7>
In Example 3, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 71.5 parts of (a2-1-2) and polyetherdiol (b1-1β) [poly The block polymer (A2-5) was contained in the same manner as in Example 3 except that the tetramethylene glycol (Mn: 1,800, volume specific resistance value: 1 × 10 ^{11 Ω · cm) was changed to 28.5 parts.} A hydrophilic imparting agent (Z-7) was obtained.
The Mn of (A2-5) was 40,000.

<Example 8>
In Example 3, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 48.0 parts of (a2-2), 48.0 parts of (b3) and hexamethylene diisocyanate ( A hydrophilicity-imparting agent (Z-8) containing a block polymer (A2-6) was obtained in the same manner as in Example 3 except that the HDI) was changed to 3 parts.
The Mn of (A2-6) was 100,000.

<Comparative example 1>
A commercially available surfactant [aliphatic ester nonionic surfactant, trade name "Chemistat 1100", manufactured by Sanyo Chemical Industries, Ltd.] is used as it is, and a hydrophilicity-imparting agent (ratio Z-1) for comparison is used. ).

<Examples 9 to 27, Comparative Examples 2 to 8>
According to the compounding composition (part) shown in Table 1, the compounding components were blended with a Henschel mixer for 3 minutes, and then melt-kneaded with a twin-screw extruder with a vent at 100 rpm, 220 ° C., and a residence time of 5 minutes. A hydrophilic resin composition (X) was obtained.

The contents of the symbols in Tables 1 and 2 are as follows.
(C-1): Impact resistant PS resin ["HIPS 433", manufactured by PS Japan Corporation]
(C-2): ABS resin ["Sevian 680SF", manufactured by Daicel Polymer Co., Ltd.]
(C-3): PC / ABS resin ["Psycholoy C6600", manufactured by SABIC Innovative Plastics Japan GK]
(C-4): Modified PPE resin ["Noril V-095", manufactured by SABIC Innovative Plastics Japan GK]
(C-5): PP resin ["PM771M", manufactured by SunAllomer Ltd.]
(C-6): Polyvinylidene fluoride resin ["KYNAR741", manufactured by Arkema Co., Ltd.]

Using an injection molding machine [“PS40E5ASE”, manufactured by Nissei Resin Industry Co., Ltd.], each of the obtained hydrophilic resin compositions was used to prepare a molding test piece at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C., as described below. It was evaluated by a performance test. The results are shown in Tables 1 and 2.

<Performance test>
(1) Wetness (unit: °)
The wettability was evaluated by measuring the water contact angle in accordance with JIS R2357. The smaller the water contact angle, the better the hydrophilicity-imparting effect and the better the wettability.
(2) Persistence of wettability (unit: °)
The film was immersed in water, the surface was washed with a cotton cloth, and then dried under reduced pressure (1 kPa, 80 ° C., 1 hour). The temperature of this test piece was adjusted (23 ° C., 50 RH%, 24 hours), and the above 3. The water contact angle was measured in the same manner as in.
(3) Izod impact strength (unit: J / m)
Measured according to ASTM D256 Method A (notched, 3.2 mm thick).

(4) Appearance Surface appearance The appearance of the surface of the test piece (100 × 100 × 2 mm) was visually observed and evaluated according to the following criteria.
[Evaluation criteria]
◯: Good without any abnormality (equivalent to a thermoplastic resin that does not contain a hydrophilicity imparting agent)
×: Rough surface, blisters, etc. are observed.

From Table 1, it can be seen that the hydrophilicity-imparting agent of the present invention imparts excellent hydrophilicity and its durability to the thermoplastic resin as compared with the comparative one, without impairing the mechanical properties.

The hydrophilicity-imparting agent of the present invention can impart excellent hydrophilicity, particularly sustained hydrophilicity, to the molded product without impairing the mechanical strength and good appearance of the thermoplastic resin molded product. Therefore, various molding methods [injection molding] , Compression molding, Calender molding, Slash molding, Rotation molding, Extrusion molding, Blow molding, Foam molding and film molding (cast method, tenter method and inflation method), etc.] Housing products (home appliances / OA equipment, game equipment) And office equipment, etc.), plastic container materials [tray used in clean rooms (IC trays, etc.) and other containers, etc.], various cushioning materials, covering materials (packaging materials, protective films, etc.), flooring sheets, It can be widely used as a material for artificial turf, mats, tape base materials (for semiconductor manufacturing processes, etc.) and various molded products (automobile parts, etc.), and is extremely useful.

Claims (10)

And a block of a hydrophobic polymer (a), and also contains a block polymer (A) containing as a structural unit and a block of hydrophilic polymer (b), the block polymer (A) is in the following (A2) A hydrophilicity-imparting agent (Z) for a polyvinylidene fluoride resin .
( A2): (a) is polyolefin (a2), and the block of (a2) and the block of hydrophilic polymer (b) are ester bond, amide bond, ether bond, imide bond, urethane bond and urea. A block polymer having a structure bonded via one or more bonds selected from the group consisting of bonds. The hydrophilicity-imparting agent according to claim 1, wherein the weight ratio of the block (a) constituting the block polymer (A) to the block (b) is 10/90 to 80/20. (B) constituting the (A2) is one or more selected from the group consisting of a polyether (b1), a polyether-containing hydrophilic polymer (b2), a cationic polymer (b3) and an anionic polymer (b4). The hydrophilicity-imparting agent according to claim 1 or 2. The hydrophilicity-imparting agent according to any one of claims 1 to 3, wherein the block polymer (A) has a number average molecular weight of 10,000 to 100,000. The hydrophilicity-imparting agent according to any one of claims 1 to 4, wherein the hydrophobic polymer (a) has a number average molecular weight of 2,000 to 25,000. The hydrophilicity-imparting agent according to any one of claims 1 to 5, wherein the hydrophilic polymer (b) has a number average molecular weight of 500 to 20,000. The hydrophilicity-imparting agent (Z) according to any one of claims 1 to 6 and the thermoplastic resin (C) are contained, and the thermoplastic resin (C) is a polyvinylidene fluoride resin (C9). Sex resin composition (X). The hydrophilic resin composition according to claim 7, wherein the weight ratio [(Z) / (C)] of (Z) to (C) is 1/99 to 50/50. A molded product obtained by molding the hydrophilic resin composition (X) according to claim 7 or 8. A molded article obtained by painting and / or printing the molded article according to claim 9.