JP2021017523A - Resin surface tension adjuster - Google Patents

Abstract

To provide a resin surface tension adjuster which imparts excellent wettability, adhesion, and persistence of these effects to a thermoplastic resin without impairing mechanical strength.SOLUTION: A resin surface tension adjuster (Y) contains a block polymer (X) having a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as constituent units. The block polymer (X) is preferably obtained by bonding the block of the hydrophobic polymer (a) and the block of the hydrophilic polymer (b) via an ester bond, an amide bond, an ether bond, an imide bond, a urethane bond or a urea bond.SELECTED DRAWING: None

Description

The present invention relates to a resin surface tension modifier. More specifically, the present invention relates to a resin surface tension modifier that imparts excellent wettability and adhesion (paintability) to paints, printing inks, adhesives, etc. to a thermoplastic resin without impairing the mechanical properties of the thermoplastic resin. ..
The wettability in the present invention means an affinity for paints, printing inks, adhesives, etc., and is evaluated by the wetting tension described later.

Thermoplastic resins, for example, polyolefin resins, have excellent moldability, rigidity, heat resistance, chemical resistance, light weight, electrical insulation, etc., and are widely used as molded products of various shapes such as films, fibers, hollow fiber membranes, etc. Has been done.
On the other hand, thermoplastic resins, which are so-called non-polar and extremely inactive polymer substances having no polar group in the molecule, particularly polyolefin resins, have high crystallinity and extremely low solubility in solvents. Therefore, there are problems in adhesiveness and paintability, for example, poor wettability and adhesion to paints, printing inks, adhesives, etc., and there is a problem that they cannot be applied without surface treatment of post-processing.
Conventionally, as a method for improving wettability and adhesion, 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 a surfactant on a polyolefin resin composition. Is known to be used as a molded product (see, for example, Patent Document 2).

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 problems that the number of steps increases and 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 inherent in the molded product of the original polyolefin resin base material is added when an addition amount that sufficiently exerts a modifying effect is added. There was a problem that (tensile elastic modulus, impact resistance, etc. The same applies hereinafter) was impaired.
An object of the present invention is to provide a resin surface tension modifier that imparts excellent wettability, adhesion, and sustainability of these effects 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 resin surface tension modifier (Y) containing a block polymer (X) having a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as constituent units.

The resin surface tension adjusting agent (Y) of the present invention has the following effects.
(1) The resin surface tension adjusting agent of the present invention is a thermoplastic resin without impairing the original mechanical strength (mechanical characteristics), and has modification characteristics (particularly resin surface tension adjusting characteristics), paint, printing ink and adhesive. It is possible to impart excellent wettability and adhesiveness (particularly the effect of improving paintability) to such substances, and the effect is excellent in sustainability.
(2) The resin composition of the present invention is excellent in wettability and adhesion (particularly the effect of improving paintability) to paints, printing inks, adhesives, etc., and is also excellent in sustainability of the effect.
(3) The molded product of the present invention has excellent mechanical properties and excellent wettability, as well as good paintability and printability.
(4) The molded article of the present invention has good adhesion to a coating film or the like.

<Hydrophobic polymer (a)>
Examples of the hydrophobic polymer (a) in the present invention include a polyolefin (a1) having a reactive group at both ends, a polyolefin (a2) having a reactive group at one end, and an alkyl (alkyl group having 4 to 32 carbon atoms). ) Poly (meth) acrylate (a3) containing (meth) acrylate as a constituent monomer can be mentioned.
The above (a) may be used alone or in combination of two or more.
The reactive group refers to a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, an amino group and an isocyanate group.

Among the hydrophobic polymers (a), the reactive group is preferable from the viewpoint of modifying properties of the molded product described later, modifying wettability, improving adhesion (improving coatability), and continuity of these effects. A polyolefin (a1) having both ends and a polyolefin (a2) having a reactive group at one end.
The hydrophobic polymer means a polymer having a water absorption rate (24 hours) of less than 0.1% by weight. The water absorption rate (24 hours) can be measured by a known measuring method. That is, the water absorption rate can be measured according to the method for determining the water absorption rate described in JIS K7209 (2000).

<Polyolefin having reactive groups at both ends (a1)>
Examples of (a1) include polyolefins (a1-1) having carboxyl groups or carboxylic acid anhydride groups at both ends of the polymer, polyolefins (a1-2) having hydroxyl groups at both ends of the polymer, and amino groups at both ends of the polymer. Examples thereof include the polyolefin (a1-3) having an isocyanate group and the polyolefin (a1-4) having an isocyanate group at both ends of the polymer. Of these, (a1-1) is preferable from the viewpoint of ease of modification and heat resistance during molding.
The term "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.

In (a1), for example, a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, an amino group or an isocyanate group is introduced into both ends of a polyolefin (a1-0) whose main component is a polyolefin whose both ends can be modified. Can be obtained by.
The "main component" means that the weight of the polyolefin whose both ends can be modified in the total weight of the polyolefin is 50% by weight or more of the total weight of the polyolefin.
However, even if the weight of the polyolefin that can be modified at both ends is less than 50% by weight of the total weight of the polyolefin, the total weight of the polyolefin that can be modified at both ends and the weight of the polyolefin that can be modified at one end, which will be described later. Is 50% by weight or more of the total weight of the polyolefin, and when the weight of the polyolefin having both ends modifiable is equal to or more than the weight of the polyolefin having one end modifiable, it is assumed to be (a1-0).

(A1-0) is obtained by (co) polymerization 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), and is derived from propylene. A polyolefin containing 30 mol% or more of the constituent units to be formed and a modified polyolefin {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 10,000 to 150,000] of polyolefin are mechanically and thermally prepared. Those that are physically or chemically reduced} are included. In addition, (co) polymerization means polymerization or copolymerization.

Of these, a modified polyolefin is preferable from the viewpoint of ease of modification and availability when introducing a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, an amino group or an isocyanate group. More preferably, it is a heat-decomposed polyolefin. According to thermal reduction, a low molecular weight polyolefin having 1 to 2 terminal double bonds per molecule can be easily obtained as described later, and the low molecular weight polyolefin has a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, and the like. It is easy to modify by introducing an amino group, an isocyanate group or the like.

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" [manufactured by Tosoh Corporation] (2)
"TSKgel Multipore HXL-M" [manufactured by Tosoh Corporation] (1 bottle)
Sample solution: 0.3 wt% orthodichlorobenzene solution Injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 135 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (TSKstandardPOLYSTYRENE)
12 points (molecular weight: 500, 1,050, 2,800, 5,970,
9,100,18,100,37,900,96,400,
190,000, 355,000, 1,090,000,
2,890,000) [manufactured by Tosoh Corporation]

Examples of the heat-decomposed polyolefin include those obtained by heating a high molecular weight polyolefin in an inert gas (for 0.5 to 10 hours at 300 to 450 ° C., for example, JP-A-3-62804). Examples thereof include those obtained by the method described) and those obtained by heating in air to reduce heat.

As the high molecular weight polyolefin used in the heat reduction method, 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 10,000 to 150,000, more preferably 15,000 to 70,000: melt flow rate (hereinafter abbreviated as MFR: unit is g / 10 min) is preferably 0.5 to 150, still more preferably. 1 to 100], such as those having a constituent unit derived from propylene in a polyolefin in an amount of 30 mol% or more. Here, the MFR is a numerical value indicating the melt viscosity of the resin, and the larger the numerical value, the lower the melt viscosity. The measurement of MFR conforms to the method specified in JIS K7210-1 (2014). 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, from the viewpoint of controlling the molecular weight, α-olefins having 2 to 12 carbon atoms, butadiene, isoprene and mixtures thereof are preferable, and more preferably 2 to 10 carbon atoms. Alpha-olefins, butadienes and mixtures thereof, with particular preference being ethylene and propylenes, which are α-olefins having 2-3 carbon atoms, and mixtures thereof.

The Mn of (a1-0) is preferably 800 to 20,000, more preferably 800 to 20,000, from the viewpoint of modifying the wettability of the molded product described later, improving the adhesion (improving the coatability), and sustaining these effects. Is 1,000 to 10,000, particularly preferably 1,200 to 6,000.

The average number of terminal double bonds per molecule of (a1-0) is the wettability modification of the molded product, the improvement of adhesion (improvement of coatability), the sustainability of these effects, and the block polymer (described later). From the viewpoint of ease of structural control and thermoplasticity of X), the number is preferably 1.1 to 2.5, more preferably 1.3 to 2.2, and particularly preferably 1.5 to 2.0. It is an individual.

When the 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 1.1 to 2.5 in the range of Mn 800 to 20,000 (a1-0). Is easily obtained.

<Polyolefin having a reactive group at one end (a2)>
Examples of (a2) include polyolefin (a2-1) having a carboxyl group or a carboxylic acid anhydride group at one end of the polymer, polyolefin (a2-2) having a hydroxyl group at one end of the polymer, and an amino group at one end of the polymer. Examples thereof include polyolefin (a2-3) having an isocyanate group at one end of the polymer, polyolefin (a2-4) having an isocyanate group at one end of the polymer, and polyolefin (a2-5) having both a carboxyl group and a hydroxyl group at one end of the polymer.
Of these, (a2-1) is preferable from the viewpoint of ease of modification and heat resistance during molding.
In addition, one end means one end in the main chain of a polymer.

(A2) can be obtained, for example, by introducing a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, an amino group or an isocyanate group into a polyolefin (a2-0) containing a polyolefin whose one end can be modified as a main component. Can be done.
The "main component" means that the weight of the polyolefin whose one end can be modified in the total weight of the polyolefin is 50% by weight or more of the total weight of the polyolefin.
However, even if the weight of the polyolefin that can be modified at one end is less than 50% by weight of the total weight of the polyolefin, the total weight of the polyolefin that can be modified at one end and the above-mentioned weight of the polyolefin that can be modified at both ends. Is 50% by weight or more of the total weight of the polyolefin, and when the weight of the polyolefin having one end modifiable is larger than the weight of the polyolefin having both ends modifiable, it is assumed to be (a2-0).

(A2-0) can be obtained in the same manner as in (a1-0), and Mn of (a2-0) can be used for modifying the wettability of the molded product, improving the adhesion (improving the coatability), and these. From the viewpoint of sustainability of the effect of the above, it is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000.

The average number of terminal double bonds per molecule of (a2-0) is the wettability modification of the molded product, the improvement of adhesion (improvement of coatability), the sustainability of these effects, and the block polymer (described later). From the viewpoint of ease of structural control and thermoplasticity of X), the number is preferably 0.5 to 1.4, more preferably 0.6 to 1.3, and particularly preferably 0.7 to 1.2. The number is, most preferably 0.8 to 1.1.

When the 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 0.5 to 1.4 (a2-) in the range of Mn of 800 to 20,000. 0) can be easily obtained.

Since the low molecular weight polyolefin obtained by the heat reduction method has an average number of the terminal double bonds, it is modified by introducing a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, an amino group, an isocyanate group, or the like. Is easy.

(A1-0) and (a2-0) are generally 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, (a1-1) to (a1-4) having a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, an amino group or an isocyanate group at both ends of (a1-0) will be described, but (a2-0). For (a2-1) to (a2-4) having these groups at one end of the above, (a1-1) to (a1-4) for those in which (a1-0) is replaced with (a2-0). ) Can be obtained in the same manner.

As (a1-1), polyolefins (a1-1-1) and (a1-1-1) having a structure in which the end of (a1-0) is modified with α, β-unsaturated carboxylic acid (anhydrous). The polyolefin (a1-1-2) having a structure secondaryly modified with lactam or aminocarboxylic acid, the polyolefin (a1-1-3) having a structure modified by oxidizing or hydroformulating (a1-0), (a1). A polyolefin (a1-1-4) having a structure in which -1-3) is secondarily modified with lactam or an aminocarboxylic acid, and a mixture of two or more thereof can be used.
The α, β-unsaturated carboxylic acid (anhydride) means an α, β-unsaturated carboxylic acid or an anhydride thereof.

(A1-1-1) can be obtained by modifying (a1-0) with α, β-unsaturated carboxylic acid (anhydride).
Examples of the α, β-unsaturated carboxylic acid (anhydride) used for the modification include monocarboxylic acid, dicarboxylic acid and mono- or dicarboxylic acid anhydride, and specific examples thereof include (meth) acrylic acid and maleic acid (meth) acrylic acid and maleic acid. (Anhydride), fumaric acid, itaconic acid (anhydride), citraconic acid (anhydride) and the like.
Of these, maleic anhydride and dicarboxylic acid of mono or dicarboxylic acid are preferable from the viewpoint of easiness of modification, maleic acid (anhydride) and fumaric acid are more preferable, and maleic acid is particularly preferable. (Anhydride).
In addition, (meth) acrylic acid means acrylic acid or methacrylic acid.

The amount of α, β-unsaturated carboxylic acid (anhydrous) used for modification is based on the weight of (a1-0), and the wettability of the molded product is modified, the adhesion is improved (coatability is improved), and the block polymer (block polymer). From the viewpoint of ease of structure control of X) and dispersibility of the block polymer (X) in the resin composition (Z) described later, the content is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight. %, Especially preferably 2 to 10% by weight.
Modification with α, β-unsaturated carboxylic acid (anhydrous) is performed by, for example, the terminal double bond of (a1-0) by either a solution method or a melting method. It can be carried out by subjecting (anhydrous) to an addition reaction (ene reaction). The reaction temperature of this addition reaction is preferably 170 to 230 ° C.

(A1-1-2) can be obtained by secondary modification of (a1-1-1) 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-aminoenanthic acid, ω-aminocapricic acid, ω-aminopelargonic 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 modification of (a1-1-1) is based on the weight of (a1-1-1), and the wettability of the molded product is modified and the adhesion is improved (paintability). (Improved), from the viewpoint of ease of structural control of the block polymer (X) and dispersibility of the block polymer (X) in the resin composition (Z) described later, it is preferably 0.5 to 100% by weight, and further. It is preferably 1 to 50% by weight, particularly preferably 2 to 25% by weight.

(A1-1-3) can be obtained by a method of oxidizing (a1-0) with oxygen and / or ozone (oxidation method), or by introducing a carboxyl group by hydroformylation by an oxo method.
The introduction of the carboxyl 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. The introduction of carboxyl 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.
(A1-1-4) can be obtained by secondary modification of (a1-1-3) with lactam or aminocarboxylic acid.
The lactam and aminocarboxylic acid used for the secondary modification of (a1-1-3) are the same as those exemplified as the lactam and aminocarboxylic acid used for the secondary modification of (a1-1-1). The same applies to the preferable range and the amount used.

The acid value of (a1-1) is preferably 4 to 100 mgKOH / g from the viewpoint of reactivity with the hydrophilic polymer (b), ease of structural control of the block polymer (X), and thermoplasticity. It is preferably 4 to 50 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
The acid value in the present invention is measured by titration using a KOH / methanol solution containing phenolphthalein as an indicator, and when the acid group is a carboxylic acid anhydride group, the half ester after being half-esterified with methanol. Measured as acid anhydride.

As (a1-2), a polyolefin having a hydroxyl group modified with an amine having a hydroxyl group and a mixture of two or more of these 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, 3-aminomethyl-3,5,5-trimethylcyclohexanol and the like can be mentioned.
Of these, amines having a hydroxyl group 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 amine having a hydroxyl group used for modification is based on the weight of (a1-1), and is easy to modify the wettability of the molded product, improve the adhesion (improve the coatability), and control the structure of the block polymer (X). From the viewpoint of dispersibility of the block polymer (X) in the resin composition (Z) described later, the content is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 2 to 2% by weight. It is 10% by weight.

The hydroxyl value of (a1-2) is preferably 4 to 100 mgKOH / g from the viewpoint of reactivity with the hydrophilic polymer (b), ease of structural control of the block polymer (X), and thermoplasticity. It is preferably 4 to 50 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.

As (a1-3), a polyolefin having an amino group modified with (a1-1) and a mixture of two or more thereof can be used.
As the diamine, 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 diamine used for the modification of (a1-1) includes modification of wettability of the molded product, improvement of adhesion (improvement of coatability), ease of structural control of the block polymer (X), and the resin composition (Z) described later. ), The block polymer (X) is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, particularly preferably 1 to 15% by weight, based on the weight of (a1-1). It is 2 to 10% by weight. The modification of (a1-1) with diamine is preferably 0.5 to 1,000% by weight, more preferably 0.5 to 1,000% by weight, based on the weight of (a1-1), from the viewpoint of preventing a cross-linking reaction between polymer molecules. Is preferably a method of using 1 to 500% by weight, particularly preferably 2 to 300% by weight of diamine, and then removing the unreacted diamine under reduced pressure at 120 to 230 ° C.

The amine value of (a1-3) is preferably 4 to 100 mgKOH / g from the viewpoint of reactivity with the hydrophilic polymer (b), ease of structural control of the block polymer (X), and thermoplasticity. It is preferably 4 to 50 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.

Examples of (a1-4) include polyolefins having an isocyanate group obtained by modifying (a1-2) with poly (2 to 3 or more) isocyanates, and mixtures of two or more thereof.
As the polyisocyanate, an aromatic polyisocyanate having 6 to 20 carbon atoms (excluding carbon atoms in the isocyanate group; the same applies hereinafter), an aliphatic polyisocyanate having 2 to 18 carbon atoms, and an alicyclic type having 4 to 15 carbon atoms. Includes polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms, modified versions of these polyisocyanates, and mixtures of two or more of these.

Aromatic polyisocyanates 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 , 5-Naftylene diisocyanate and the like.

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

Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanatoethyl). ) -4-Cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornene diisocyanate and the like.

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

Examples of the modified polyisocyanate include urethane modified products, urea modified products, carbodiimide modified products, and uretdione modified products.
Of the polyisocyanates, TDI, MDI and HDI are preferable, and HDI is more preferable.

The reaction between the polyisocyanate and (a1-2) can be carried out in the same manner as a general urethanization reaction.
The equivalent ratio (NCO: OH) of the isocyanate group of the polyisocyanate to the hydroxyl group of (a1-2) is preferably 1.8: 1-3: 1, and more preferably 2: 1.
In order to promote the urethanization reaction, a catalyst generally 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 catalyst {triethylenediamine, diazabicycloalkene [1,8-diazabicyclo [5,4,0] undecene-7, etc.], dialkylaminoalkylamine (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 the polyisocyanate and (a1-2).

As (a2-5), a polyolefin having a structure in which one end of (a2-0) is modified with α, β-unsaturated carboxylic acid anhydride is further modified with a diol amine, and a polyolefin having a structure secondarily modified (a2). -5-1) can be used.
Examples of the diol amine used for the secondary denaturation include diethanolamine.

Mn of (a1) and (a2) is from the viewpoint of dispersibility of the block polymer (X), mechanical properties of the molded product, wettability modifying effect, adhesion improvement (coatability improvement), and sustainability of these effects. , Each is preferably 1000 to 25,000, more preferably 1,500 to 12,000, and particularly preferably 2,000 to 7,000.

The amount of the structural unit derived from propylene in (a1) and (a2) is the mechanical properties of the resin composition (Z) (particularly when polypropylene resin is used), the wettability modifying effect, and the adhesion improvement (paintability). From the viewpoint of (improvement) and the sustainability of these effects, respectively, 30 to 100 mol%, preferably 35 to 100 mol%, still more preferably 50 to 100 mol%, particularly preferably 80 to 100 mol%, most preferably. It is 96 to 100 mol%.
(A1) and (a1) and (a1) and (a1) and (a1) and (a1) and (a1) and (a1) and (a2-0) contain a predetermined amount of propylene by using those having a content of a constituent unit derived from propylene in polyolefin of 30 to 100 mol%. a2) can be obtained.

In (a1) and (a2), from the viewpoint of the dispersibility of the block polymer (X), the mechanical properties of the molded product, the effect of modifying the wettability, the improvement of adhesion (improvement of coatability), and the sustainability of these effects. The isotacticity of the propylene moiety is preferably 90% to 100%.

The isotacticity in the present invention can be calculated using, for example, 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, with respect to the carbon peak derived from the side chain methyl group in propylene obtained by ¹³ C-NMR, each peak (H) of the pentad observed in the chemical shift range of 19.0 to 20.0 ppm has only the meso structure. Assuming that the carbon peak derived from the methyl group in the propylene of the formed isotactic is the methyl group peak (Ha) observed at 21.8 ppm, the isotacticity is calculated by the following formula.
Isotacticity (%) = [(Ha) / Σ (H)] x 100 (1)
However, in the equation, Ha is the peak height of the isotactic (pentad is formed only by the meso structure) signal, and H is the peak height of the pentad.

<Poly (meth) acrylicate (a3) containing alkyl (alkyl group having 4 to 32 carbon atoms) (meth) acrylate as a constituent monomer>
(A3) is a poly (meth) acrylate containing an alkyl (alkyl group having 4 to 32 carbon atoms) (meth) acrylate as a constituent monomer.

Examples of the alkyl group of the alkyl (alkyl group having 4 to 32 carbon atoms) (meth) acrylate of the constituent monomer include n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-. Octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-octadecyl group, n- Nonadesyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n- Examples thereof include a nonacosyl group, an n-triacontyl group, an n-gentriacontyl group and an n-dotriacontyl group.

Of (a3), a linear or branched alkyl having 12 to 32 carbon atoms is preferable from the viewpoint of modifying the wettability of the molded product described later, improving the adhesion (improving the coatability), and sustaining these effects. Alkyl (meth) acrylates having a group are more preferable, and alkyl (meth) acrylates having a linear or branched alkyl group having 16 to 32 carbon atoms are particularly preferable, and a branched alkyl group having 20 to 32 carbon atoms is particularly preferable. It is an alkyl (meth) acrylate having.

The Mn of (a3) is preferably 800 to 20,000, and more preferably 1 from the viewpoint of modifying the wettability of the molded product described later, improving the adhesion (improving the coatability), and sustaining these effects. It is 000 to 10,000, particularly preferably 1,200 to 6,000.
As a method for introducing a reactive functional group into the terminal of the poly (meth) acrylate, for example, a hydroxyl group or an epoxy group can be introduced as the reactive functional group by a known method such as living radical polymerization.

<Hydrophilic polymer (b)>
Examples of the hydrophilic polymer (b) in the present invention include polyether (b1), polyether-containing hydrophilic polymer (b2), cationic polymer (b3), anionic polymer (b4), and polyglycerin (b5). Polyvinyl alcohol (b6) can be mentioned.
The above (b) may be used alone or in combination of two or more.

Among the hydrophilic polymers (b), (b1) and (b1) are preferable from the viewpoints of modification characteristics of the molded product, wettability modification, improvement of adhesion (improvement of coatability) and continuity of these effects, which will be described later. b2), (b3) and (b4) are more preferable, (b1) and (b2) are more preferable, and (b1) is particularly preferable.
The hydrophilic polymer means a polymer having a water absorption rate (24 hours) of 0.1% by weight or more.

The Mn of the hydrophilic polymer (b) is preferably 500 to 10,000 from the viewpoint of modifying the wettability of the molded product described later, improving the adhesion (improving the coatability), and the reactivity with the hydrophobic polymer (a). It is more preferably 1,000 to 6,000, and particularly preferably 2,000 to 4,000.

<Polyether (b1)>
As (b1), from the viewpoint of structural control of the block polymer (X), polyether monool (b1-1), polyether monoamine (b1-2) and modified products (b1-3) thereof may be used. preferable.

Examples of (b1-1) include polyether monool represented by the general formula (1).

R ¹ and R ² in the general formula (1) are each independently a hydrocarbon group having 1 to 12 carbon atoms, Q ¹ represents an oxygen atom or a nitrogen atom, when Q ¹ is oxygen atom, h is 0 Yes, when Q ¹ is a nitrogen atom, h is 1, R ³ and R ⁴ each independently represent an alkylene group having 1 to 4 carbon atoms, and a plurality of (R ³ O) are the same but different. The combination format may be block format or random format, and i represents an integer of 10 to 250.

As R ¹ and R ² in the general formula (1), aliphatic hydrocarbons having 1 to 12 carbon atoms are preferable from the viewpoint of wettability modifying effect, adhesion improvement (coatability improvement) and continuity of these effects. Hydrogen groups and aromatic hydrocarbon groups having 6 to 12 carbon atoms are more preferable, aliphatic hydrocarbon groups and phenyl groups having 1 to 6 carbon atoms are particularly preferable, and methyl groups and hexyl groups are particularly preferable. The most preferred is the methyl group.

As a plurality of (R ³ O) in the general formula (1), oxyethylene group alone and oxyethylene are preferable from the viewpoint of wettability modifying effect, adhesion improvement (coatability improvement) and continuity of these effects. The group is used in combination with another oxyalkylene group, and more preferably the oxyethylene group alone.
As R ⁴ in the general formula (1), an ethylene group is preferable from the viewpoint of wettability modifying effect, adhesion improvement (coatability improvement), and continuity of these effects.

Among the polyether monools represented by the general formula (1), those in which R ³ is a methylene group are cyclic compounds having formaldehyde or an oxymethylene structure as a repeating unit in the presence of monool having 1 to 12 carbon atoms. (1,3,5-trioxane, tetramer 1,3,5,7-tetraoxane, pentameric 1,3,5,7,9-pentaoxane, etc.) with cations such as boron trifluoride A method of polymerizing or ring-opening polymerization using a polymerization initiator, or a cyclic compound using methylal (CH ₃ OCH ₂ OCH ₃ ) as a chain transfer agent and having an oxymethylene structure as a repeating unit, and ethylene oxide or 1,3-dioxolane. By carrying out the copolymerization, it can be obtained by a method of end-capping the polymer terminal with a methoxy group by a chain transfer reaction or the like.

Among the polyether monools represented by the general formula (1), those in which R ³ is an alkylene group having 2 to 4 carbon atoms are monools having 1 to 12 carbon atoms or secondary amines having 2 to 24 carbon atoms. It can be obtained by subjecting to an addition reaction of an alkylene oxide having 2 to 4 carbon atoms (hereinafter abbreviated as AO).

Examples of monools having 1 to 12 carbon atoms include aliphatic monohydric alcohols having 1 to 12 carbon atoms (methanol, ethanol, propanol, butanol, hexanol, neopentyl alcohol, dodecanemonool, etc.) and fats having 5 to 12 carbon atoms. Cyclic monohydric alcohols [mono (hydroxymethyl) cyclohexane, mono (hydroxymethyl) cycloheptane, etc.] and monovalent phenol compounds with 6 to 12 carbon atoms (phenols, phenols with alkyl groups 1 to 6 carbon atoms and naphthol). Etc.) etc.

Of these, aliphatic monohydric alcohols having 1 to 12 carbon atoms and 6 to 12 carbon atoms are preferable from the viewpoint of wettability modifying effect, adhesion improvement (coatability improvement), and continuity of these effects. It is a monovalent phenol compound, more preferably an aliphatic monohydric alcohol having 1 to 6 carbon atoms and phenol, particularly preferably methanol and hexanol, and most preferably methanol.

Secondary amines having 2 to 24 carbon atoms include dimethylamine, diethylamine, ethylmethylamine, di-n-propylamine, diisopropylamine, isopropylethylamine, di-sec-butylamine, di-t-butylamine, dicyclohexylamine and isopropyl. Examples thereof include cyclohexylamine, diphenylamine and carbazole.

Examples of the AO to be added to the monool having 1 to 12 carbon atoms or the secondary amine having 2 to 24 carbon atoms include AO having 2 to 4 carbon atoms [ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3. -Propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3-, 1,4- or 2,3-butylene oxide (hereinafter abbreviated as BO) and a combination system of two or more of these are used. If necessary, other AOs [α-olefin oxide having 5 to 12 carbon atoms, styrene oxide, epichlorohydrin, etc.] may be used in small proportions (30% by weight or less based on the total weight of AO). it can.
The combination format when two or more types of AOs are used in combination may be either a random format or a block format. From the viewpoint of modifying the wettability of the molded product, improving the adhesion (improving the coatability), and the continuity of these effects as AO, it is preferable to use EO alone or EO in combination with other AOs, which is particularly preferable. Is EO alone.

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 (R ³ O) based on the weight of the polyether monool represented by the general formula (1) is the wettability modification, the adhesion improvement (coatability improvement), and these effects of the molded product described later. From the viewpoint of continuity, it is preferably 5 to 99.8% by weight, more preferably 8 to 99.6% by weight, and particularly preferably 10 to 98% by weight.
Therefore, the preferable range of i in the general formula (1) is the range of i which is the preferable range of the content of the above (R ³ O).

The content of the oxyethylene group based on the weight of (R ³ O) in the general formula (1) is the viewpoint of modifying the wettability of the molded product, improving the adhesion (improving the coatability), and the continuity of these effects, which will be described later. Therefore, it is preferably 70 to 100% by weight, more preferably 85 to 100% by weight, particularly preferably 95 to 100% by weight, and most preferably 100% by weight.

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

R ⁵ and R ⁶ in the general formula (2) are each independently a hydrocarbon group having 1 to 12 carbon atoms, Q ² represents an oxygen atom or a nitrogen atom, when Q ² is an oxygen atom, j is 0 Yes, when Q ² is a nitrogen atom, j is 1, R ⁷ represents an alkylene group having 1 to 4 carbon atoms, R ⁸ represents an alkylene group having 2 to 4 carbon atoms, and there are a plurality of them (R ⁷ O). ) May be the same or different, and the combined form may be a block form or a random form, and k represents an integer of 10 to 250.

The polyether monoamine represented by the general formula (2) can be obtained by converting the hydroxyl group of the polyether monoamine represented by the general formula (1) into an alkylamino group. For example, it can be produced by reacting a polyether monool represented by the general formula (1) with acrylonitrile and hydrogenating the obtained cyanoethylated product.

Examples of R ⁵ , R ⁶ and R ⁷ in the general formula (2) include those similar to those exemplified in R ¹ , R ² and R ³ in the general formula (1), respectively, and preferable ones are also the same. ..
In addition, the preferable ranges of the contents of (R ⁷ O), k, and (R ⁷ O) in the general formula (2) and the content of the oxyethylene group in (R ⁷ O) are in the general formula (1), respectively. It is the same as the preferable range of the content of (R ³ O), i, (R ³ O) and the content of ethyleneoxy group in (R ³ O).

Examples of (b1-3) include the carboxylic acid-modified product (terminal carboxyl group), isocyanate-modified product (terminal isocyanate group), aminocarboxylic acid-modified product (terminal amino group) of (b1-1) or (b1-2), and Examples thereof include an epoxy-modified product (terminal epoxy group).
The isocyanate-modified product can be obtained by reacting (b1-1) or (b1-2) with polyisocyanate or reacting (b1-2) with phosgene.
The modified aminocarboxylic acid can be obtained by reacting (b1-1) or (b1-2) with an aminocarboxylic acid or lactam.
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.).

<Polyester-containing hydrophilic polymer (b2)>
Examples of (b2) include the polyether ester amide (b2-1) having the segment of (b1-1), the polyether amide imide (b2-2) having the segment of (b1-1), and (b1-1). A polyether ester having a segment (b2-3), a polyether amide having a segment of (b1-2) (b2-4), and a polyether urethane having a segment of (b1-1) or (b1-2). (B2-5) can be mentioned.

(B2-1) is composed of a polyamide having a carboxyl group at both ends and (b1-1) among the polyamides [12 nylon, 6 nylon, etc.].
Examples of the polyamide having a carboxyl group at both ends include a ring-opening polymer of lactam, a polycondensate of aminocarboxylic acid, and a polyamide of diamine and a dicarboxylic acid having 2 to 12 carbon atoms of a linear hydrocarbon.
Among the polyamides having carboxyl groups at both ends, from the viewpoint of dispersibility of the block polymer (X) in the resin composition (Z) described later, the ring-opening polymer of caprolactam, 12-aminododecanoic acid, is preferable. A polycondensate and a polyamide of adipic acid and hexamethylenediamine are more preferable, and a ring-opening polymer of caprolactam is more preferable.

(B2-2) is composed of a polyamide-imide having at least one imide ring and (b1-1).
As the polyamide imide, a polymer composed of lactam and a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring described above, an aminocarboxylic acid and a trivalent or tetravalent aromatic polycarboxylic acid. Examples thereof include a polymer composed of a carboxylic acid, a polymer composed of a polyamide and a trivalent or tetravalent aromatic polycarboxylic acid, and a mixture thereof.

Examples of (b2-3) include those composed of polyester and (b1-1).
Examples of the polyester include a polyester containing a dicarboxylic acid and a diol.

Examples of (b2-4) include those composed of polyamide and (b1-2).

Examples of (b2-5) include diisocyanate among polyisocyanates, (b1-1) or (b1-2) and, if necessary, a chain extender [straight-chain or branched aliphatic diol (ethylene) having 2 to 12 carbon atoms. Glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc.) and the above diamine, etc.].

The content of the segment of the polyether portion in (b2) is preferably 70 to 99% by weight based on the weight of (b2) from the viewpoint of modifying the wettability of the molded product and improving the adhesion (improving the coatability). Yes, more preferably 90-99% by weight.

From the viewpoint of structural control of the block polymer (X), a polyether diol in which Q ¹ is an oxygen atom and R ¹ is a hydrogen atom in the general formula (1) cannot be used, but (a1-2) and (a2-). A block produced using the polyether monool represented by the general formula (1) by reacting 2) with AO having 2 to 4 carbon atoms, formaldehyde, or a cyclic compound having the oxymethylene structure as a repeating unit. It is possible to produce a polymer in which Q ¹ is an oxygen atom and R ¹ is a hydrogen atom, that is, a polymer having a hydroxyl group at the end of the molecule.

Either the polyether monool represented by the general formula (1) or the polyether monoamine represented by the general formula (2) is reacted with (a1) by the method described below, or (a1-2) or (a2-2). ) Is subjected to an addition reaction with the above AO having 2 to 4 carbon atoms, or a cyclic compound having formaldehyde or the above oxymethylene structure as a repeating unit is (ring-opened) polymerized to give the block polymer (X) the general formula (3). ) Can be introduced.

Q ³ in the general formula (3) represents an oxygen atom or a nitrogen atom, and when Q ³ is an oxygen atom, m is 0 and R ⁹ represents a hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms, and Q ³ When is a nitrogen atom, m is 1 and R ⁹ and R ¹⁰ independently represent hydrocarbon groups having 1 to 12 carbon atoms, and R ¹¹ and R ¹² independently represent alkylene groups having 1 to 4 carbon atoms. The plurality of (R ¹¹ O) may be the same or different, and the combined form may be a block form or a random form, and n represents an integer of 10 to 250.

As R ⁹ and R ¹⁰ in the general formula (3), aliphatic hydrocarbons having 1 to 12 carbon atoms are preferable from the viewpoint of wettability modifying effect, adhesion improvement (coatability improvement) and continuity of these effects. Hydrogen groups and aromatic hydrocarbon groups having 6 to 12 carbon atoms are more preferable, aliphatic hydrocarbon groups and phenyl groups having 1 to 6 carbon atoms are particularly preferable, methyl groups and hexyl groups are particularly preferable, and most preferably. It is a methyl group.

As a plurality of (R ¹¹ O) in the general formula (3), ethyleneoxy group alone and ethyleneoxy are preferable from the viewpoint of wettability modifying effect, adhesion improvement (coatability improvement) and continuity of these effects. The group is used in combination with another alkyleneoxy group, and more preferably the ethyleneoxy group alone.
As R ¹² in the general formula (3), an ethylene group is preferable from the viewpoint of wettability modifying effect, adhesion improvement (coatability improvement), and continuity of these effects.

The content of (R ¹¹ O) based on the weight of the polyether monool represented by the general formula (3) is the wettability modification, the adhesion improvement (coatability improvement) and the effects thereof of the molded product described later. From the viewpoint of continuity, it is preferably 5 to 99.8% by weight, more preferably 8 to 99.6% by weight, and particularly preferably 10 to 98% by weight.
Therefore, the preferable range of n in the general formula (3) is the range of n which is the preferable range of the content of the above (R ¹¹ O).

The content of ethyleneoxy groups based on the weight of (R ¹¹ O) in the general formula (3) is the viewpoint of modifying the wettability of the molded product, improving the adhesion (improving the coatability), and the continuity of these effects, which will be described later. Therefore, it is preferably 70 to 100% by weight, more preferably 85 to 100% by weight, particularly preferably 95 to 100% by weight, and most preferably 100% by weight.

<Cationic polymer (b3)>
Examples of (b3) include those described in Japanese Patent No. 3488163 and 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.

<Anionic polymer (b4)>
As (b4), for example, those described in Japanese Patent No. 3488163, a dicarboxylic acid (γ') having a sulfonyl group (for example, 5-sulfoisophthalic acid) and a diol (b0) or (b1) are used as essential constituent units. , And a polymer having 2 to 80, preferably 3 to 60 sulfonyl groups in the molecule.

<Polyglycerin (b5), polyvinyl alcohol (b6)>
Examples of (b5) and (b6) include known ones.

<Block polymer (X)>
The block polymer (X) in the present invention has a block of the hydrophobic polymer (a) and a block of the hydrophilic polymer (b) as constituent units.
In the present specification, the block of the hydrophobic polymer (a) refers to a structural unit of a polymer composed of one hydrophobic polymer (a), and the block of the hydrophilic polymer (b) is hydrophilic. Sex polymer (b) Refers to the structural unit of a polymer composed of one.

As the block polymer (X), the block polymer (X1) having a molecular structure according to any one of the following (1) to (3) is preferable from the viewpoint of modification characteristics and mechanical properties.
(1) Linear (a)-(b) diblock type structure;
(2) Linear (b)-(a)-(b) triblock structure;
(3) A branched structure in which two or three blocks (b) are connected to one end of the block (a).

As the structure of (X), it is preferable from the viewpoint of modifying the wettability of the molded product, improving the adhesion (improving the coatability), and the dispersibility of the block polymer (X) in the resin composition (Z) described later. A)-(b) diblock type structure or (b)-(a)-(b) triblock type structure, particularly preferably (a)-(b) diblock type structure.

The block polymers (X) having the above molecular structures (1) to (3) can be obtained, for example, by the following methods.

The linear (a)-(b) diblock type block polymer reacts, for example, (a2-1) with (b1-1) or (b1-2) in a molar ratio of 1: 1. It can also be obtained by reacting (a1-1) with (b1-1) or (b1-2) at a molar ratio of 1: 1.
Further, by adding AO to (a2-2), a linear block polymer having a linear (a)-(b) diblock type structure having a hydroxyl group at the end of the block of (b1) can be obtained.

A block polymer having a linear (b)-(a)-(b) triblock structure contains, for example, (a1-1) and (b1-1) or (b1-2) in a ratio of 1: 2. It can be obtained by reacting with a ratio.
Further, by adding AO to (a2-1), a linear block polymer having a linear (b)-(a)-(b) triblock structure having a hydroxyl group at the end of the block of (b1) can be obtained. be able to.

The block polymer having a branched structure in which two blocks of polyether (b1) are bonded to one end of the block of (a2) is, for example, one end of the polymer having a carboxylic acid anhydride group in (a2-1). It can be obtained by reacting the polyolefin contained in (b1-1) with a molar ratio of 1: 2.
Since the carboxylic acid anhydride group present at the end of the polymer can be regarded as a dehydration condensation of the dicarboxylic acid in the molecule, it reacts with a double amount of the reactive group without breaking the main chain of the polymer to form a bond. Can be formed. Therefore, the carboxylic acid anhydride group existing at the end of the polymer is bonded to two (b1-1) to form a block polymer having a branched structure.
In the above, an example of the combination of the hydrophobic polymer (a) and the hydrophilic polymer (b) for obtaining the block polymer (X) having each structure is shown, but as described above, the hydrophobic polymer (a) And the hydrophilic polymer (b) have various functional groups, so any combination can be used as long as the functional group of the hydrophobic polymer (a) and the functional group of the hydrophilic polymer (b) can react with each other. be able to.

As (X), the block of the hydrophobic polymer (a) [preferably (a1)] and the block of the hydrophilic polymer (b) [preferably (b1), (b2)] are ester-bonded or amide-bonded. , Ether bond, imide bond, urethane bond or urea bond is preferable, and ester bond or imide bond is more preferable from the viewpoint of heat resistance and ease of production. Is particularly preferable.

The Mn of the block polymer (X) is preferably 3,000 to 14,000, more preferably 4 from the viewpoint of mechanical properties of the molded product, which will be described later, modification of wettability, and improvement of adhesion (improvement of coatability). It is 000 to 11,000, particularly preferably 5,000 to 8,000.

The weight ratio [(b) / (X)] of the block of the hydrophilic polymer (b) to the block polymer (X) is determined from the viewpoint of improving the mechanical properties and wettability of the molded product and improving the adhesion (improving the coatability). From the viewpoint of dispersibility of the block polymer (X) in the resin composition (Z), it is preferably 20 to 60% by weight, more preferably 25 to 50% by weight, and particularly preferably 30 to 40% by weight.

When (X) 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, for example, the hydrophobic polymer (a). ) And the hydrophilic polymer (b) are put into a reaction vessel, and water produced by an amidation reaction, an esterification reaction or an imidization reaction at a reaction temperature of 100 to 250 ° C. and a pressure of 0.003 to 0.1 MPa under stirring. It can be produced by a method of reacting for 1 to 50 hours while removing (hereinafter abbreviated as produced water) from the reaction system.

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 weight of the hydrophobic polymer (a) and the hydrophilic polymer (b) in order to accelerate the reaction. Examples of catalysts include inorganic acids (sulfuric acid, hydrochloric acid, etc.), organic sulfonic acids (methanesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, etc.), antimony catalysts (antimonite trioxide, etc.), tin catalysts (monobutyltin). Oxide and dibutyltin oxide, etc.), titanium catalyst (tetrabutyl titanate, bistriethanolamine titanate, potassium titanate oxalate, etc.), zirconium catalyst (tetrabutylzirconate, zirconyl acetate, etc.), zinc catalyst (zinc acetate, etc.), etc. 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 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 of removing the generated water from the reaction system by reducing the pressure inside the reaction system.

When (X) has a structure in which the block of the hydrophobic polymer (a) and the block of the hydrophilic polymer (b) are bonded via a urethane bond or a urea bond, for example, the hydrophilic polymer (b). ) Is put into a reaction vessel, heated to 30 to 100 ° C. with stirring, and then the hydrophobic polymer (a) is put in and reacted at the same temperature for 1 to 20 hours.
In order to accelerate the reaction, it is preferable to use 0.001 to 5% by weight of the catalyst based on the weight of the hydrophobic polymer (a) and the hydrophilic polymer (b). Examples of the catalyst include organic metal compounds (dibutyltin dilaurate, dioctyltin dilaurate, lead octanate and bismuth octanate, 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.

<Block polymer (X2)>
The block polymer (X2) in the present invention is hydrophobic except for the block polymer whose molecular structure is any of (1) to (3) [may be described as a block polymer (X1)]. It has a block of the sex polymer (a) and a block of the hydrophilic polymer (b) as constituent units.

The molecular structure of the block polymer (X2) is preferably any of the following from the viewpoint of modifying properties and mechanical properties. That is, the total number of blocks of the multi-block type structure [(a) and (b) consisting of the repetition of (a) and (b) is, for example, 3 to 20, preferably 4 to 15, and more preferably 6 to 12. ], (A) is a main chain and (b) is a side chain, whichever is preferable.

As the structure of (X2), a multi-block type structure is preferable from the viewpoint of dispersibility of the block polymer (X) and (X2) in the resin composition (Z) described later.

As (X2), a structure in which a block of the hydrophobic polymer (a) and a block of the hydrophilic polymer (b) are bonded via an ester bond, an amide bond, an ether bond, an imide bond, a urethane bond or a urea bond. It is preferable to have an ester bond or an imide bond from the viewpoint of heat resistance and ease of production.

The Mn of the block polymer (X2) is preferably 10,000 to 100,000, more preferably 20,000 to 70,000, and particularly preferably 40,000 to 40,000 from the viewpoint of mechanical properties of the molded product described later. It is 50,000.

The weight ratio of the block of the hydrophilic polymer (b) to the block polymer (X2) [(b) / (X2)] is the same as that of the block polymer (X) to the resin composition (Z) from the viewpoint of mechanical properties of the molded product. From the viewpoint of dispersibility of (X2), it is preferably 20 to 60% by weight, more preferably 25 to 50% by weight, and particularly preferably 30 to 40% by weight.

The block polymer (X2) can be produced by the method described above in the section of the block polymer (X).

When the block polymer (X1) and (X2) are used in combination, the weight ratio [(X1) / (X2)] of (X1) and (X2) is determined by the block polymer (Z) to the resin composition (Z) described later. From the viewpoint of the dispersibility of X) and the mechanical properties of the molded product, it is preferably 50/50 to 90/10, more preferably 60/40 to 80/20, and particularly preferably 65/35 to 75/25. ..

<Resin surface tension adjuster (Y)>
The resin surface tension modifier (Y) of the present invention contains the block polymer (X). The resin surface tension adjuster (Y) imparts excellent wettability and adhesion (improvement of paintability) to paints, printing inks, adhesives, etc. to the thermoplastic resin without impairing the mechanical properties of the thermoplastic resin. can do.
From the above, the resin surface tension adjusting agent (Y) can be suitably used as a resin surface tension adjusting agent for the thermoplastic resin (C) described later.
The resin surface tension adjusting agent (Y) includes a colorant (D1), a mold release agent (D2), an antioxidant (D3), a flame retardant (D4), an ultraviolet absorber (D5), and an antibacterial agent (D6), which will be described later. , Additives (D) such as compatibilizer (D7), filler (D8) and ester exchange inhibitor (D9) can be contained.

Examples of the colorant (D1) include inorganic pigments [white pigments, cobalt compounds, iron compounds, sulfides, etc.], organic pigments [azo pigments, polycyclic pigments, etc.], dyes [azo-based, indigoid-based, sulfide-based, alizarin, etc.] System, aclysine system, thiazole system, nitro system, aniline system, etc.] and the like.

As the release agent (D2), a lower (1 to 4 carbon atoms) alcohol ester of a higher fatty acid (butyl stearate, etc.) and a polyvalent fatty acid (2 to 18 carbon atoms) (divalent to tetravalent or higher) Examples thereof include alcohol esters (hardened castor oil and the like), glycols (2 to 8 carbon atoms) of fatty acids (2 to 18 carbon atoms), and liquid paraffins (ethylene glycol monostearate and the like).

Examples of the antioxidant (D3) include phenol compounds [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.)) and bisphenol [2,2'-methylenebis (4-methyl-6-t-butylphenol). ) Etc.], Polycyclic phenol [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc.], etc.], Sulfur compound (dilauryl 3) , 3'-thiodipropionate, etc.), phosphorus compounds (triphenylphosphite, etc.), amine compounds (octylated diphenylamine, etc.) and the like.

Examples of the flame retardant (D4) include halogen-containing flame retardants, nitrogen-containing flame retardants, sulfur-containing flame retardants, silicon-containing flame retardants, and phosphorus-containing flame retardants.

Examples of the ultraviolet absorber (D5) 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-diphenylacrylate, etc.) and the like.

Examples of the antibacterial agent (D6) include benzoic acid, sorbic acid, phenol halide, organic iodine, nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylenebistianocyanate), and N-halo. Examples thereof include alkylthioimides, copper agents (8-oxyquinoline copper, etc.), benzimidazoles, benzothiazoles, trihaloallyl, triazoles, organic nitrogen-sulfur compounds (suraoff 39, etc.), quaternary ammonium compounds, and pyridine compounds.

Examples of the compatibilizer (D7) include a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group: for example. , The polymer described in JP-A-3-258850, and the modified vinyl polymer having a sulfonic acid group and the polyolefin moiety and the aromatic vinyl polymer moiety described in JP-A-6-345927. Coalescence and the like can be mentioned.

Examples of the filler (D8) include inorganic fillers (calcium carbide, talc, clay, etc.) and organic fillers (urea, calcium stearate, etc.) and the like.
Examples of the transesterification inhibitor (D9) include phosphate esters [bisphenol A bis (diphenyl phosphate), monooctadecyl phosphate, dioctadecyl phosphate, etc.] and phosphite esters [Tris (2,4-di-t-butylphenyl). ) Phosphite, etc.] and the like.

The total content of (D) based on the weight of the thermoplastic resin (C) is generally 45% by weight or less, preferably 0.001 to 40% by weight from the viewpoint of the effect of each additive and the mechanical properties of the molded product. , More preferably 0.01 to 35% by weight; the content of each (D) is preferably 0.1 to 3% by weight, still more preferably 0.2 to 2% by weight from the same viewpoint; (D2) is preferably 0.01 to 3% by weight, more preferably 0.05 to 1% by weight; (D3) is preferably 0.01 to 3% by weight, still more preferably 0.05 to 1% by weight; (D4) is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight; (D5) is preferably 0.01 to 3% by weight, still more preferably 0.05 to 1% by weight; (D6). ) Is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight; (D7) is preferably 0.5 to 10% by weight, still more preferably 1 to 5% by weight; (D8) is preferably. 0.5 to 10% by weight, more preferably 1 to 5% by weight; (D9) is 0.01 to 3% by weight, still more preferably 0.05 to 1% by weight.

<Resin composition (Z)>
The resin composition (Z) of the present invention contains the resin surface tension adjusting agent (Y) of the present invention and the thermoplastic resin (C).
The weight ratio [(Y): (C)] of the resin surface tension adjuster (Y) and the thermoplastic resin (C) is the mechanical properties, wettability modification, adhesion improvement (coatability improvement), and their effects. From the viewpoint of sustainability, it is preferably 1:99 to 50:50, more preferably 5:95 to 20:80, and particularly preferably 10:90 to 15:85.

<Thermoplastic resin (C)>
Examples of the thermoplastic resin (C) include polyolefin resin (C1) [polypropylene (PP), ethylene / propylene copolymer, polyethylene (PE), etc.]; fluororesin (C2) [PTFE (polytetrafluoroethylene), ETFE ( Ethylene-tetrafluoroethylene copolymer), PFA (perfluoroalkoxyalkane (copolymer of ethylene tetrafluoroethylene (C2F4) and perfluoroalkoxyethylene) and PVDF (polyvinylidene fluoride resin)]; polystyrene resin (C3) [Copolymers containing vinyl group-containing aromatic hydrocarbons alone and vinyl group-containing aromatic hydrocarbons, and one or more selected from the group consisting of butadiene; for example, polystyrene (PS) and impact-resistant polystyrene] Etc .; and mixtures of two or more of these.
Of these, PVDF among (C1) and (C2) is preferable from the viewpoint of mechanical properties of the molded product, which will be described later, modification of wettability, improvement of adhesion (improvement of coatability), and sustainability of these effects. More preferably, (C1) is particularly preferable, polypropylene (homotype polypropylene, block type polypropylene and ethylene / propylene copolymer) in (C1) is particularly preferable, and homotype polypropylene is most preferable.

The resin composition (Z) contains a colorant (D1), a mold release agent (D2), an antioxidant (D3), a flame retardant (D4), and an ultraviolet absorber, if necessary, as long as the effects of the present invention are not impaired. Additives (D) such as (D5), antibacterial agent (D6), compatibilizer (D7), filler (D8) and ester exchange inhibitor (D9) can be contained. Each additive may be used alone or in combination of two or more.

The resin composition (Z) of the present invention can be obtained by melt-mixing the resin surface tension adjusting agent (Y) of the present invention, the thermoplastic resin (C) and, if necessary, the additive (D).
At this time, the same additive (D) as the additive (D) contained in the resin surface tension adjusting agent (Y) may be added to the resin composition (Z).
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 (C) and (Y) are melt-mixed, and then (D) is added all at once and melt-mixed if necessary;
[2] When melt-mixing (C) and (Y), a part of (C) is melt-mixed in advance to prepare a high-concentration composition (masterbatch resin composition) of (Y), and then the rest. (C) and, if necessary, a method of melting and mixing (D) (masterbatch method or master pellet method);
And so on.
The concentration of (Y) in the masterbatch resin composition in the method [2] is preferably 20 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 (Y) can be easily dispersed in (C).

<Molded product>
The molded product of the present invention is a molded product of the resin composition (Z) of the present invention. Examples of the molding method include injection molding, compression molding, calender molding, slush molding, rotary molding, extrusion molding, blow molding and 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, wettability, adhesion (paintability) and durability thereof, and also has good paintability and printability, so that the molded product can be painted and / or printed. By applying, a molded article can be obtained.
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 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 generally 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 resin surface tension modifier (Y) of the present invention is preferably used as a wettability modifier.
Since the molded product of the present invention containing (Y) has excellent wettability, it can be suitably used for the following applications. That is, improvement of liquid wettability of PP for battery separator, improvement of liquid wettability of PE and PVDF of water treatment film, improvement of liquid wettability of short fiber polyolefin for fiber reinforcement, improvement of liquid wettability of vinyl house (plastic house), etc. It is also suitable for improving the liquid wettability of food packaging films.

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.

<Production Example 1> [One-terminal acid-modified ethylene-propylene random copolymer (a-1)]
Low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer] obtained by heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. A product obtained by thermally reducing the coalescence (propylene content = 33 mol%) at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, replaced with nitrogen, and sealed. The temperature was raised to 200 ° C. with stirring to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. The excess maleic anhydride and xylene are then distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to have a carboxylic acid anhydride group at one end of the polymer, one-terminal acid-modified ethylene. -95 parts of propylene random copolymer (a-1) was obtained.
The Mn of (a-1) was 4,000, the propylene content was 33 mol%, the isotacticity of the propylene moiety was 40%, and the water absorption rate (24 hours) was 0.03%.

<Production Example 2> [One-terminal acid-modified ethylene-propylene random copolymer (a-2)]
Low molecular weight ethylene-epylene random copolymer obtained by the heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device [Ethylene-propylene random copolymer] A polymer (propylene content = 52 mol%) obtained by heat-declining at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, replaced with nitrogen, and sealed. The temperature was raised to 200 ° C. with stirring to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. The excess maleic anhydride and xylene are then distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to have a carboxylic acid anhydride group at one end of the polymer, one-terminal acid-modified ethylene. -95 parts of propylene random copolymer (a-2) was obtained.
The Mn of (a-2) was 4,000, the propylene content was 52 mol%, the isotacticity of the propylene moiety was 60%, and the water absorption rate (24 hours) was 0.03%.

<Production Example 3> [One-terminal acid-modified 1-butene-propylene random copolymer (a-3)]
Low molecular weight 1-butene-propylene random copolymer [1-butene-] obtained by the heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. A propylene random copolymer (propylene content = 82 mol%) obtained by heat-decomposing for 16 minutes at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min). Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, replaced with nitrogen, and sealed. The temperature was raised to 200 ° C. with stirring to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. Next, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to have a carboxylic acid anhydride group at one end of the polymer, and one end acid modification 1 95 parts of -butene-propylene random copolymer (a-3) was obtained.
The Mn of (a-3) was 4,000, the propylene content was 82 mol%, the isotacticity of the propylene moiety was 80%, and the water absorption rate (24 hours) was 0.03%.

<Production Example 4> [One-terminal acid-modified ethylene-propylene random copolymer (a-4)]
Low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer] obtained by heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. A product obtained by thermally reducing the coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, replaced with nitrogen, and sealed. The temperature was raised to 200 ° C. with stirring to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. The excess maleic anhydride and xylene are then distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to have a carboxylic acid anhydride group at one end of the polymer, one-terminal acid-modified ethylene. -95 parts of propylene random copolymer (a-4) was obtained.
The Mn of (a-4) was 4,000, the propylene content was 96 mol%, the isotacticity of the propylene moiety was 90%, and the water absorption rate (24 hours) was 0.02%.

<Production Example 5> [One-terminal acid-modified homotype polypropylene (a-5)]
Low molecular weight homotype polypropylene obtained by the heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device [Homotype polypropylene at 410 ± 0.1 ° C. , Obtained by heat reduction for 16 minutes under nitrogen aeration (80 mL / min). Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, replaced with nitrogen, and sealed. The temperature was raised to 200 ° C. with stirring to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. The excess maleic anhydride and xylene are then distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to have a carboxylic acid anhydride group at one end of the polymer, a one-terminal acid modified homo. 95 parts of type polypropylene (a-5) was obtained.
The Mn of (a-5) was 4,000, the propylene content was 100 mol%, the isotacticity of the propylene moiety was 99%, and the water absorption rate (24 hours) was 0.01%.

<Production Example 6> [Both-terminal acid-modified ethylene-propylene random copolymer (a-6)]
Low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer] obtained by heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. A product obtained by thermally reducing the coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 2.0] 90 parts, 20 parts of maleic anhydride and 30 parts of xylene were added, mixed uniformly, replaced with nitrogen, and sealed. The temperature was raised to 200 ° C. with stirring to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. Excess maleic anhydride and xylene are then distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to have bi-terminal acid-modified ethylene having carboxylic acid anhydride groups at both ends of the polymer. 95 parts of -propylene random copolymer (a-6) was obtained.
The Mn of (a-6) was 4,000, the propylene content was 96 mol%, the isotacticity of the propylene moiety was 90%, and the water absorption rate (24 hours) was 0.02%.

<Production Example 7> [One-terminal acid-modified ethylene-propylene random copolymer (a-7)]
Low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer] obtained by heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. A product obtained by thermally reducing the coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 1,400, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, replaced with nitrogen, and sealed. The temperature was raised to 200 ° C. with stirring to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. The excess maleic anhydride and xylene are then distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to have a carboxylic acid anhydride group at one end of the polymer, one-terminal acid-modified ethylene. 95 parts of -propylene random copolymer (a-7) was obtained.
The Mn of (a-7) was 1,500, the propylene content was 96 mol%, the isotacticity of the propylene moiety was 90%, and the water absorption rate (24 hours) was 0.05%.

<Production Example 8> [One-terminal acid-modified ethylene-propylene random copolymer (a-8)]
Low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer] obtained by heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. A product obtained by thermally reducing the coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 2,400, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, replaced with nitrogen, and sealed. The temperature was raised to 200 ° C. with stirring to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. The excess maleic anhydride and xylene are then distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to have a carboxylic acid anhydride group at one end of the polymer, one-terminal acid-modified ethylene. -95 parts of propylene random copolymer (a-8) was obtained.
The Mn of (a-8) was 2,500, the propylene content was 96 mol%, the isotacticity of the propylene moiety was 90%, and the water absorption rate (24 hours) was 0.03%.

<Production Example 9> [One-terminal acid-modified ethylene-propylene random copolymer (a-9)]
Low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer] obtained by heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. A product obtained by thermally reducing the coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 10,000, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride (10 parts) and xylene (30 parts) were added, mixed uniformly, replaced with nitrogen, and sealed. The temperature was raised to 200 ° C. with stirring to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. The excess maleic anhydride and xylene are then distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to have a carboxylic acid anhydride group at one end of the polymer, one-terminal acid-modified ethylene. -95 parts of propylene random copolymer (a-9) was obtained.
The Mn of (a-9) was 10,000, the propylene content was 96 mol%, the isotacticity of the propylene moiety was 90%, and the water absorption rate (24 hours) was 0.01%.

<Production Example 10> [Both-terminal acid-modified ethylene-propylene random copolymer (a-10)]
Low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer] obtained by heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. A product obtained by thermally reducing the coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 10,000, average number of double bonds per molecule: 2.0] 90 parts, 20 parts of maleic anhydride and 30 parts of xylene were added, mixed uniformly, replaced with nitrogen, and sealed. The temperature was raised to 200 ° C. with stirring to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. Excess maleic anhydride and xylene are then distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to have bi-terminal acid-modified ethylene having carboxylic acid anhydride groups at both ends of the polymer. 95 parts of -propylene random copolymer (a-10) was obtained.
The Mn of (a-10) was 10,000, the propylene content was 96 mol%, the isotacticity of the propylene moiety was 90%, and the water absorption rate (24 hours) was 0.02%.

<Production Example 11> [Both-terminal acid-modified ethylene-propylene random copolymer (a-11)]
Low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer] obtained by heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. A product obtained by thermally reducing the coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 1,400, average number of double bonds per molecule: 2.0] 90 parts, maleic anhydride 20 parts and xylene 30 parts were added, mixed uniformly, replaced with nitrogen, sealed and stirred. The temperature was raised to 200 ° C. to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. Excess maleic anhydride and xylene are then distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to have bi-terminal acid-modified ethylene having carboxylic acid anhydride groups at both ends of the polymer. 95 parts of -propylene random copolymer (a-11) was obtained.
The Mn of (a-11) was 1,500, the propylene content was 96 mol%, the isotacticity of the propylene moiety was 90%, and the water absorption rate (24 hours) was 0.07%.

<Production Example 12> [One-terminal amino group-modified ethylene-propylene random copolymer (a-12)]
Low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer] obtained by heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. A product obtained by thermally reducing the coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, replaced with nitrogen, and sealed. The temperature was raised to 200 ° C. with stirring to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene were distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to obtain 95 parts of a polyolefin having a carboxylic acid anhydride group at one end of the polymer. ..
Next, 90 parts of the above-mentioned polyolefin and 10 parts of bis (2-aminoethyl) ether having a carboxylic acid anhydride group at one end of the polymer were put into the same pressure-resistant reaction vessel as in Production Example 1 under a nitrogen gas atmosphere. The temperature was raised to 200 ° C. with stirring, and the reaction was carried out at the same temperature for 2 hours. Excess bis (2-aminoethyl) ether is distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 2 hours, and one-terminal amino group-modified ethylene-propylene random copolymer having an amino group at one end. A coalescence (a-12) was obtained.
The Mn of (a-12) was 4,000, the propylene content was 96 mol%, the isotacticity of the propylene moiety was 90%, and the water absorption rate (24 hours) was 0.08%.

<Production Example 13> [One-terminal hydroxyl-modified ethylene-propylene random copolymer (a-13)]
Low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer] obtained by heat reduction method in a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device. A product obtained by thermally reducing the coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, replaced with nitrogen, and sealed. The temperature was raised to 200 ° C. with stirring to melt the mixture, and the mixture was reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene were distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to obtain 95 parts of a polyolefin having a carboxylic acid anhydride group at one end of the polymer. ..
Next, 90 parts of the above-mentioned polyolefin and 5 parts of ethanolamine having a carboxylic acid anhydride group at one end of the polymer were put into the same pressure-resistant reaction vessel as in Production Example 1 and brought to 180 ° C. with stirring under a nitrogen gas atmosphere. The temperature was raised and the reaction was carried out at the same temperature for 2 hours. Excess ethanolamine was distilled off under reduced pressure (0.013 MPa or less) at 180 ° C. for 2 hours, and a single-ended hydroxyl group-modified ethylene-propylene random copolymer having a hydroxyl group at one end of the polymer (a-13). Got
The Mn of (a-13) was 4,000, the propylene content was 96 mol%, the isotacticity of the propylene moiety was 90%, and the water absorption rate (24 hours) was 0.08%.

<Production Example 14> [One-ended hydroxyl group-modified alkyl polyacrylate (a-14)]
Toluene (1,000 ml) and CuBr (10 g) are placed in a glass 5 L Kolben container equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device, deoxidized by liquid phase injection of nitrogen, and then nitrogen. Below, 1,000 g of 2-n-tetradecyl-n-heptadecyl (meth) acrylate and 20 g of N-propyl-2-pyridylmethaneimine were added, uniformly dissolved with stirring, and removed by liquid phase blowing of nitrogen. Oxygen was applied.
Then, after raising the temperature to 90 ° C., 10 ml of 2-hydroxyethyl 2-bromoisobutyrate was added under nitrogen to carry out a polymerization reaction. After 8 hours, the solvent was removed under reduced pressure to obtain a single-ended hydroxyl group-modified alkyl polyacrylate (a-14) having a hydroxyl group at one terminal of the polymer.
The Mn of (a-14) was 4,000, the propylene content was 0 mol%, and the water absorption rate (24 hours) was 0.09%.

<Production Example 15> [Production of polyolefin (a-15) obtained by secondary modification of (a-6)]
440 parts (a-6) and 60 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 under a nitrogen gas atmosphere. The reaction was carried out at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours to obtain 480 parts of polyolefin (a-15) obtained by secondary modification of (a-6). The Mn of (a-15) was 4,500, the propylene content was 96 mol%, the isotacticity of the propylene moiety was 90%, and the water absorption rate (24 hours) was 0.05%.

<Production Example 16> [Both-terminal hydroxyl-modified cationic polymer (b3-1)]
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. Then, methanol was distilled off under reduced pressure to obtain a double-ended hydroxyl group-modified cationic polymer (b3-1) having an average of 12 quaternary ammonium groups.
(B3-1) had a hydroxyl value of 28.1, an acid value of 0.5, Mn: 4,000, and a water absorption rate (24 hours): 1.50%.

<Production Example 17> [Anionic polymer (b4-1)]
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, the ester exchange reaction was carried out at the same temperature for 6 hours while distilling off methanol to obtain an anionic polymer (b4-1) having an average of 6 sodium sulfonate bases in one molecule. (B4-1) had a hydroxyl value of 48, an acid value of 0.6, Mn: 2,000, and a water absorption rate (24 hours): 2.10%.

<Production Example 18> [Production of anionic polymer (b4-2)]
67 parts of PEG (Mn: 300, polyethylene glycol), 49 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 amount was 0.067 MPa. The temperature was raised to 190 ° C. under reduced pressure, and the ester exchange reaction was carried out at the same temperature for 6 hours while distilling off methanol to obtain an anionic polymer (b4-2) having an average of 5 sodium sulfonate bases in one molecule. ..
(B4-2) had a hydroxyl value of 28, an acid value of 0.4, Mn: 4,000, and a water absorption rate (24 hours): 1.30%.

<Example 1>
In a reaction vessel equipped with a stirrer, a thermometer and a heating / cooling device, 100 parts of (a-1) obtained in Production Example 1 and the polyethylene glycol (Mn = 2000) monomethyl ether (b-3) shown in Table 1 ) 50 parts and 0.3 part of the antioxidant "Irganox 1010" were added, the temperature was raised to 210 ° C. with stirring, and the reaction was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 5 hours, and Mn was 6 A resin surface tension modifier (Y-1) containing 000 block polymers (X-1) was obtained.

Table 1 shows a list of raw material symbols and compositions used in the examples.
Note that (b-5) in Table 1 shows a monomethyl ether of polyethylene glycol (Mn = 2000) introduced with a 2-carboxyethyl group.
Further, (b-7) is obtained by reacting a monomethyl ether of polyethylene glycol (Mn = 2000) with ethylene diisocyanate to introduce a 2-isocyanatoethyl group.
Further, the description of "(ethylene oxide 45 molar adduct)" in (b-8) refers to the polyether obtained by adding poly (45) ethylene oxide to the hydroxyl group of the polyolefin (a-13) in Example 20 below. It represents the relevant part.

<Examples 2 to 19, Examples 21 to 34, Comparative Example 1>
The same procedure as in Example 1 was carried out except that the raw materials used and the amounts used thereof were replaced with those shown in Table 2 or Table 3, and the resin surface tension adjusting agents (Y-2) to (Y-19), (Y-21). )-(Y-34) were obtained.
As the resin surface tension adjusting agent (RY-1) of Comparative Example 1, a commercially available surfactant [stearic acid monoester of glycerin] was used as it was.

<Example 20>
In an autoclave, 100 parts of the one-terminal hydroxyl group-modified ethylene-propylene random copolymer (a-13) obtained in Production Example 13 and 1 part of lithium hydroxide monohydrate were charged, subjected to nitrogen substitution, and then 150. The temperature was raised to ° C. Then, 50 parts of ethylene oxide was added dropwise at 130 to 150 ° C. and a reaction pressure of 0.2 MPa or less for 24 hours to react, and poly (45) ethylene oxide was added to the terminal hydroxyl group of (a-13) to add Mn. A resin surface tension modifier (Y-20) containing 6,000 block polymers (X-20) was obtained.

Physical properties and compositions of the resin surface tension modifiers (Y-1) to (Y-34) and (RY-1) obtained in Examples 1 to 2 and Comparative Examples 1 to 2 and the following (1) to (3). The structures of the block polymers shown in Tables 2 and 3 are shown in Tables 2 and 3. The structure of the block polymers of Examples 33 and 34 was a multi-block structure represented by [-(a)-(b)-] n (the average number of n is 3 and 6).
(1) Linear (a)-(b) Diblock type structure (2) Linear (b)-(a)-(b) Tri-block type structure (3) One of the blocks of (a) A branched structure in which two or three blocks (b) are connected to the end of.

<Examples 41 to 85, Comparative Examples 11 to 16>
According to the compounding formulations (parts) shown in Tables 4 and 5, each compounding component was 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. Then, resin compositions (Z-1) to (Z-45) and (RZ-1) to (RZ-6) were obtained.

The contents of the thermoplastic resins shown in Tables 4 and 5 are as follows.
(C-1): Homotype polypropylene [Product name "SunAllomer PM900A", manufactured by SunAllomer Ltd.]
(C-2): Block type polypropylene ["PM771M", manufactured by SunAllomer Ltd.]
(C-3): Ethylene-propylene copolymer [trade name "SunAllomer PB222A", manufactured by SunAllomer Ltd.]
(C-4): Polyethylene [Product name "Novatec HJ490", manufactured by Japan Polyethylene Corporation]
(C-5): Impact-resistant polystyrene resin ["HIPS 433", manufactured by PS Japan Corporation]
(C-6): Polyvinylidene fluoride resin ["KYNAR741", manufactured by Arkema Co., Ltd.]
(C-7): Olefin-based thermoplastic elastomer ["Esporex 901", manufactured by Sumitomo Chemical Co., Ltd.]

For each of the obtained resin compositions, a molding test piece was prepared at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. using an injection molding machine [“PS40E5ASE”, manufactured by Nissei Resin Industry Co., Ltd.], and the following performance test was performed. The results evaluated by Table 4 and Table 5 are shown.

<Performance test>
(1) Appearance The appearance of the surface of the test piece (80 × 80 × 2 mm) was visually observed and evaluated according to the following criteria.
◯: Good without any abnormality (equivalent to thermoplastic resin not containing resin surface tension adjuster)
X: Rough surface, blisters, etc. are observed.
(2) Reduction rate of mechanical strength (Izot impact strength and flexural modulus) The reduction rate of mechanical strength when the resin surface tension adjusting agent (Y) of the present invention is blended with the thermoplastic resin (C) is determined by Izot. The impact strength and flexural modulus were evaluated. Since the rate of decrease in mechanical strength also differs depending on the amount of the resin surface tension adjusting agent (Y) blended, in order to clarify the rate of decrease depending on the type of the resin surface tension adjusting agent (Y), a specific blending amount is used. The rate of decrease was evaluated using a value obtained by dividing the rate of decrease by the blending weight% of the resin surface tension adjusting agent (Y) at that time.
That is, the evaluation was performed according to the following evaluation criteria using the reduction rate (% / weight%) of the mechanical strength obtained by the following formula.
[Reduction rate of mechanical strength (% / weight%)] = {[Mechanical strength before compounding]-[Mechanical strength after compounding]} / [Mechanical strength before compounding] / [Resin surface tension modifier] Blended weight] x 100 (%)
For example, when 10% by weight of the resin surface tension adjusting agent (Y) is blended with homotype polypropylene (Izod impact strength = 2.0 J / m) and the Izod impact strength after blending is 1.8 J / m. The calculation formula is as follows.
[Reduction rate of mechanical strength (% / weight%)] = [2.0 (J / m) -1.8 (J / m)] /2.0 (J / m) / 10 (weight%) × 100 (%) = 1.0 (% / weight%)
<Evaluation criteria>
⊚: [Decrease rate] ≤ 0.5
◯: 0.5 <[decrease rate] ≤ 1.5
◯-: 1.5 << [decrease rate] ≤ 2.5
Δ: 2.5 << [decrease rate] ≤ 5.5
X: 5.5 << [decrease rate]
(2-1) Izod impact strength (unit: J / m)
Measurements were made according to ASTM D256 Method A (notched, 3.2 mm thick).
(2-2) Flexural modulus (unit: MPa)
Measured according to ASTM D638.

(3) Wetting property (unit: dyne / cm) (surface tension)
Wetness was evaluated by measuring the wetting tension according to JIS K6768 (1999). The larger the wetting tension, the higher the wettability to the paint or the adhesive, and the better the wettability.
(4) Sustainability of wettability After immersing the above test piece in water at 25 ° C for 24 hours, pull it up, wipe the surface with a cotton cloth, and in a constant temperature and humidity chamber where the humidity is 50 RH% and the temperature is kept at 23 ° C. The temperature was adjusted for 24 hours, the wet tension was measured in the same manner as above, and the evaluation was made according to the following criteria.
<Evaluation criteria>
⊚: No decrease in wetting tension is observed as compared with the wettability before the treatment of immersion in water.
◯: The decrease in wetting tension is 1 dyn / cm as compared with the wettability before the treatment of immersing in water.
◯ −: The decrease in wetting tension is 2 dyn / cm as compared with the wettability before the treatment of immersion in water.
X: The decrease in wetting tension is 3 dyn / cm or more as compared with the wettability before the treatment of immersion in water.
-: Since the wettability of the resin composition after blending is the same as that of the resin before blending and there is no effect of modifying the wettability, the durability of the wettability is not evaluated.

(5) Adhesion to paint The paintability (wetting property and adhesion to paint) was evaluated by the adhesion of urethane-based paint. Apply urethane-based paint on the test piece (100 x 100 x 2 mm) with an applicator so that the film thickness after drying is 30 μm, and on the painted surface after drying at 80 ° C for 30 minutes, JIS K 5600-5-6. In accordance with (1999), a grid peeling test was performed using a transparent pressure-sensitive adhesive tape. Of the 100 grids, the number of portions where the coating film did not peel off was measured and evaluated according to the following criteria.
⊚: The number that did not peel off is 100
○ +: The number that did not peel off was 95 to 99
◯: The number that did not peel off was 90 to 94.
◯-: The number that did not peel off was 81-89
Δ: The number that did not peel off was 50 to 80.
X: The number that did not peel off was 0 to 49

From Tables 4 and 5, the resin surface tension adjusting agent of the present invention has excellent wettability (resin surface tension adjusting characteristic) to the thermoplastic resin without impairing its mechanical properties, as compared with those of the comparative example. It can be seen that the durability and adhesion can be imparted.

The resin surface tension adjusting agent (Y) of the present invention has excellent wettability (particularly sustained wettability) and adhesiveness (coatability) to the molded product without impairing the mechanical strength and good appearance of the thermoplastic resin molded product. ) And these sustainability can be imparted, which is particularly useful as a wettability modifier and / or a coatability improver, and since the wettability is improved, the liquid wettability of the PP for the battery separator is improved. Improved wettability of PE and PVDF of water treatment film, improved wettability of short fiber polyolefin for fiber strengthening, improved wettability of vinyl house (plastic house), improved wettability of automobile interior and exterior materials, food It is also suitable for improving the wettability of the packaging film.
Since the resin composition (Z) of the present invention has good coatability and printability, various molding methods [injection molding, compression molding, calender molding, slush molding, rotary molding, extrusion molding, blow molding, foam molding and Housing products (for home appliances / OA equipment, game equipment, office equipment, etc.) molded by film molding (cast method, tenter method, inflation method, etc.), plastic container materials [Trays used in clean rooms (IC trays, etc.) And other containers, etc.], various cushioning materials, covering materials (packaging materials, protective films, etc.), flooring sheets, artificial turf, mats, tape base materials (for semiconductor manufacturing processes, etc.) and various molded products (automobile parts, etc.) Etc.) It can be widely used as a material and is extremely useful.
The molded product of the present invention has excellent mechanical properties and excellent wettability, as well as good paintability and printability, and by applying coating and / or printing to this molded product, it adheres to a coating film or the like. A molded article having good properties can be obtained.
The molded article of the present invention has good adhesion to a coating film or the like.

Claims (16)

A resin surface tension modifier (Y) containing a block polymer (X) having a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as constituent units. The resin surface tension adjusting agent according to claim 1, wherein the molecular structure of the block polymer (X) is the block polymer (X1) having any of the following structures (1) to (3).
(1) Linear (a)-(b) Diblock type structure (2) Linear (b)-(a)-(b) Tri-block type structure (3) One of the blocks of (a) A branched structure in which two or three blocks (b) are connected to the end of. The hydrophobic polymer (a) is a polyolefin (a1) having a reactive group at both ends, a polyolefin (a2) having a reactive group at one end, and an alkyl (alkyl group having 4 to 32 carbon atoms) (meth) acrylate. The resin surface tension adjusting agent according to claim 1 or 2, which is at least one selected from the group consisting of poly (meth) acrylicate (a3) containing as a constituent monomer. The resin surface tension adjusting agent according to any one of claims 1 to 3, wherein the hydrophobic polymer (a) is a polyolefin having 30 mol% or more of a structural unit derived from propylene. The resin surface tension adjusting agent according to claim 4, wherein the isotacticity of the propylene portion in the polyolefin is 90% to 100%. The hydrophilic polymer (b) is a polyether (b1), a polyether-containing hydrophilic polymer (b2), a cationic polymer (b3), an anionic polymer (b4), a polyglycerin (b5), and a polyvinyl alcohol (b6). The resin surface tension adjusting agent according to any one of claims 1 to 5, which is at least one selected from the group consisting of. The resin surface tension adjusting agent according to any one of claims 1 to 6, wherein the block of the hydrophilic polymer (b) is a block represented by the general formula (3).

[In the formula, Q ³ represents an oxygen atom or a nitrogen atom; when Q ³ is an oxygen atom, m is 0 and R ⁹ represents a hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms; Q ³ is nitrogen. In the case of an atom, m is 1 and R ⁹ and R ¹⁰ independently represent hydrocarbon groups having 1 to 12 carbon atoms; R ¹¹ and R ¹² each independently represent an alkylene group having 1 to 4 carbon atoms. The plurality (R ¹¹ O) may be the same or different. ; N represents an integer of 10 to 250. ] The resin surface tension modifier according to any one of claims 1 to 7, wherein the block polymer (X) has a number average molecular weight of 3,000 to 14,000. The resin surface tension according to any one of claims 1 to 8, wherein the weight ratio [(b) / (X)] of the block of the hydrophilic polymer (b) to the block polymer (X) is 20 to 60% by weight. Regulator. The block polymer (X) has a block of the hydrophobic polymer (a) and a block of the hydrophilic polymer (b) via an ester bond, an amide bond, an ether bond, an imide bond, a urethane bond or a urea bond. The resin surface tension adjusting agent according to any one of claims 1 to 9, which is bonded. The block polymer (X1) and the block polymer (X2) are contained, and the (X2) has a block of the hydrophobic polymer (a) and a block of the hydrophilic polymer (b) as constituent units. The molecular structure is any one of claims 2 to 10 which is a multi-block structure composed of the repetition of (a) and (b) and / or a graft structure having (a) as a main chain and (b) as a side chain. Described resin surface tension modifier A resin composition (Z) containing the resin surface tension adjusting agent (Y) according to any one of claims 1 to 11 and a thermoplastic resin (C). The resin composition according to claim 12, wherein the thermoplastic resin (C) is a polyolefin. The resin composition according to claim 12 or 13, wherein the weight ratio [(Y): (C)] of the resin surface tension adjusting agent (Y) and the thermoplastic resin (C) is 1:99 to 50:50. Stuff. A molded product obtained by molding the resin composition (Z) according to any one of claims 12 to 14. A molded article obtained by subjecting the molded article according to claim 15 to at least one treatment selected from the group consisting of painting, printing and adhesive application.