JP7202209B2 - Resin modifier - Google Patents

Description

The present invention relates to resin modifiers. Specifically, wettability and adhesion to paints, printing inks, adhesives, etc. imparted to thermoplastic resins by surface treatments such as corona treatment, plasma treatment and flame treatment without impairing the mechanical properties of the thermoplastic resin composition. The present invention relates to a resin modifier that imparts durability of a surface modification effect such as property (improvement of paintability) to a thermoplastic resin.
The wettability in the present invention means the affinity for paints, printing inks, adhesives, etc., and is evaluated by wetting tension described later.

Thermoplastic resins, such as polyolefin resins, are excellent in moldability, rigidity, heat resistance, chemical resistance, lightness, electrical insulation, etc., and are widely used as films, fibers, hollow fiber membranes, and other molded products of various shapes. It is
On the other hand, thermoplastic resins, especially polyolefin resins, which are so-called non-polar and extremely inert polymeric substances having no polar group in the molecule, have high crystallinity and extremely low solubility in solvents. Therefore, there are problems in adhesiveness, paintability, etc. For example, there are problems such as poor wettability and adhesion to paints, printing inks, adhesives, etc., and cannot be applied without post-processing surface treatment.
Conventionally known methods for improving wettability and adhesion include a method of applying corona treatment or plasma treatment to the surface of a thermoplastic resin such as a polyolefin resin molded product (see, for example, Patent Document 1), and a method of flame treatment. ing.

JP-A-2000-319426

However, the method of simply subjecting the surface of the molded article to corona treatment, plasma treatment or flame treatment has the problem that wettability and adhesion deteriorate with the lapse of time after the treatment.
An object of the present invention is to improve surface properties such as wettability and adhesion imparted to thermoplastic resins by surface treatments such as corona treatment, plasma treatment and flame treatment without impairing the mechanical strength of the thermoplastic resin composition. To provide a resin modifier capable of sustaining its effect.

The present inventor arrived at the present invention as a result of intensive studies in order to solve the above problems. That is, the present invention has a block of polyolefin (a) having 30 mol% or more of structural units derived from propylene and a block of polyester (b) as structural units, and has the following molecular structures (1) to (3): a resin modifier (Y) containing a block polymer (X) having any structure of; a resin composition (Z) containing the resin modifier (Y) and a thermoplastic resin (C) a molded article obtained by molding the resin composition (Z);
(1) a linear (a)-(b) diblock structure;
(2) a linear (b)-(a)-(b) triblock structure;
(3) A branched structure in which 2 to 3 polyester (b) blocks are bonded to one end of a polyolefin (a) block.

The resin modifier of the present invention and a molded article of a thermoplastic resin composition containing the resin modifier of the present invention exhibit the following effects.
(1) The resin modifier of the present invention is a paint imparted to a thermoplastic resin by surface treatment such as corona treatment, plasma treatment and flame treatment without impairing the original mechanical strength (mechanical properties) of the thermoplastic resin. , the durability of the surface modification effect such as the wettability and adhesion (especially the paintability improvement effect) to printing inks and adhesives can be imparted to the thermoplastic resin.
(2) Molded articles of the thermoplastic resin composition of the present invention that have been surface-treated by corona treatment, plasma treatment, flame treatment, etc. have improved wettability and adhesion to paints, printing inks, adhesives, etc. (especially improved paintability) Effect) and other surface modification effects are excellent in durability.

The resin modifier (Y) of the present invention has a block of polyolefin (a) having 30 mol% or more of structural units derived from propylene and a block of polyester (b) as structural units, and has the following molecular structure: It contains a block polymer (X) having any one of structures (1) to (3).
(1) a linear (a)-(b) diblock structure;
(2) a linear (b)-(a)-(b) triblock structure;
(3) A branched structure in which 2 to 3 polyester (b) blocks are bonded to one end of a polyolefin (a) block.

<Polyolefin (a)>
Examples of the polyolefin (a) include polyolefins (a1-1) having carboxyl groups or carboxylic 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. A polyolefin (a1-3) having a terminal and a polyolefin (a1-4) having an isocyanate group at both ends of the polymer, a polyolefin (a1-5) having both a carboxyl group and a hydroxyl group at both ends of the polymer, a carboxyl group or a carboxylic group Polyolefin (a2-1) having an acid anhydride group at one end of the polymer, Polyolefin (a2-2) having a hydroxyl group at one end of the polymer, Polyolefin (a2-3) having an amino group at one end of the polymer and isocyanate Examples include polyolefin (a2-4) having a 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. Among these, (a1-1) and (a2-1) having a terminal carboxyl group or carboxylic anhydride group are preferred from the viewpoint of ease of modification and heat resistance during molding.
In the present invention, the terminal means the terminal portion where the repeating structure of the monomer units constituting the polymer is interrupted. Moreover, both ends mean both ends in the main chain of the polymer, and one end means either one end in the main chain of the polymer.

The polyolefin (a1-0) mainly composed of a polyolefin that can be modified at both ends contains one or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10 carbon atoms). (Co)polymerization of mixtures [(Co)polymerization means polymerization or copolymerization. Same below. ], Polyolefin containing 30 mol% or more of structural units derived from propylene in polyolefin (polymerization method) and degraded polyolefin {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 10,000 ~150,000] obtained by mechanically, thermally or chemically degrading polyolefin (degradation method)}.

Among these, degraded polyolefins are preferred from the viewpoint of ease of modification and availability when introducing a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group or an isocyanate group. More preferred are thermally degraded polyolefins. According to thermal degradation, a low-molecular-weight polyolefin having 1 to 2 terminal double bonds per molecule can be easily obtained as described later. It is easy to modify by introducing an amino group, an isocyanate group, or the like.

Mn of the polymer in the present invention can be measured using gel permeation chromatography (GPC) under the following conditions.
Apparatus (example): "HLC-8120" [manufactured by Tosoh Corporation]
Column (one example): "TSKgelGMHXL" [manufactured by Tosoh Corporation] (2 columns)
“TSKgel Multipore HXL-M” [manufactured by Tosoh Corporation] (1 piece)
Sample solution: 0.3% by weight ortho-dichlorobenzene solution Solution injection volume: 100 μl
Flow rate: 1 ml/min Measurement temperature: 135°C
Detection device: refractive index detector Reference material: standard polystyrene (TSKstandard POLYSTYRENE)
12 points (molecular weight: 500, 1,050, 2,800, 5,970,
9,100, 18,100, 37,900, 96,400,
190,000, 355,000, 1,090,000,
2,890,000) [manufactured by Tosoh Corporation]

The thermally degraded polyolefin is not particularly limited, but is obtained by heating a high-molecular-weight polyolefin in an inert gas (at 300 to 450° C. for 0.5 to 10 hours, e.g. JP-A-3-62804 obtained by the method described in the publication) and those thermally degraded by heating in air.

High-molecular-weight polyolefins used in the thermal degradation method include (co)polymers of one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms) [ Mn is preferably 12,000 to 100,000, more preferably 15,000 to 70,000; Melt flow rate (hereinafter abbreviated as MFR: unit is g/10min) is preferably 0.5 to 150, more preferably 1 to 100] and having 30 mol % or more of structural units derived from propylene in the polyolefin. Here, the MFR is a numerical value representing the melt viscosity of a resin, and the larger the numerical value, the lower the melt viscosity. Measurement of MFR conforms to the method specified in JIS K7210-1 (2014). For example, in the case of polypropylene, it is measured under conditions of 230° C. and a load of 2.16 kgf.
Examples of olefins having 2 to 30 carbon atoms include α-olefins having 2 to 30 carbon atoms and dienes having 4 to 30 carbon atoms.

Examples of α-olefins having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-icosene and 1- and tetracosene.
Examples of dienes having 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene and 1,11-dodecadiene.
Among the olefins having 2 to 30 carbon atoms, ethylene, propylene, α-olefins having 4 to 12 carbon atoms, butadiene, isoprene and mixtures thereof are preferable from the viewpoint of molecular weight control, and ethylene, Propylene, α-olefins having 4 to 10 carbon atoms, butadiene and mixtures thereof, particularly preferably ethylene, propylene and mixtures thereof.

Mn of the polyolefin (a1-0) is preferably 800 to 20,000, more preferably 1,000, from the viewpoint of durability of surface modification effects such as improved wettability and improved adhesion (improved paintability). 000 to 10,000, particularly preferably 1,200 to 6,000.

The average number of terminal double bonds per molecule of (a1-0) is determined from the viewpoint of durability of surface modification effects such as improved wettability and improved adhesion (improved paintability), and the block polymer (X) described later. From the viewpoint of ease of structural control and thermoplasticity, the number is preferably 1.1 to 2.5, more preferably 1.3 to 2.2, particularly preferably 1.5 to 2.0. be.

When using a method of obtaining a low molecular weight polyolefin by thermal degradation, (a1-0) having an average number of terminal double bonds per molecule of 1.1 to 2.5 in the range of Mn 800 to 20,000 is easily obtained.

Polyolefin (a2-0) mainly composed of polyolefin that can be modified at one end can be obtained in the same manner as (a1-0), and Mn of (a2-0) improves wettability and adhesion. From the viewpoint of durability of the surface modification effect such as (improvement of paintability), it is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000. be.

The average number of double bonds per molecule of (a2-0) is determined from the viewpoint of durability of surface modification effects such as improved wettability and improved adhesion (improved paintability), and the block polymer (X) described later. From the viewpoint of ease of structural control and thermoplasticity, the number is preferably 0.5 to 1.4, more preferably 0.6 to 1.3, particularly preferably 0.7 to 1.2, most preferably The number is preferably 0.8 to 1.1.

When using the method of obtaining low molecular weight polyolefin by thermal degradation, the average number of terminal double bonds per molecule is 0.5 to 1.4 (a2- 0) is easily obtained.

Since the low-molecular-weight polyolefin obtained by the thermal degradation method has the average number of terminal double bonds, it can be modified by introducing a carboxyl group, a carboxylic 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, and the mixture may be used as it is or after purification and separation. Among these, a mixture is preferred from the viewpoint of production cost and the like.

Hereinafter, (a1-1) to (a1-5) having a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group or an isocyanate group at both ends of the polyolefin (a1-0) will be described. 0) having these groups at one end of (a2-1) to (a2-5), (a1-1) to (a1 -5) can be obtained in the same manner.

As the polyolefin (a1-1) having a carboxyl group or a carboxylic anhydride group at both ends of the polymer, the end of (a1-0) is an α,β-unsaturated carboxylic acid (anhydride) (α,β-unsaturated A polyolefin (a1-1-1) having a structure modified with a saturated carboxylic acid or an anhydride thereof; polyolefin (a1-1-2) having a structure modified by oxidation or hydroformylation of (a1-0), polyolefin (a1-1-3) (a1-1-3) with a lactam or aminocarboxylic acid, A polyolefin (a1-1-4) having a submodified structure, a mixture of two or more thereof, and the like can be used.
The α,β-unsaturated carboxylic acid (anhydride) means α,β-unsaturated carboxylic acid or its anhydride.

(a1-1-1) can be obtained by modifying (a1-0) with an α,β-unsaturated carboxylic acid (anhydride).
Examples of α,β-unsaturated carboxylic acids (anhydrides) used for modification include monocarboxylic acids, dicarboxylic acids and mono- or dicarboxylic anhydrides, specifically (meth)acrylic acid [(meth) Acrylic acid means acrylic acid or methacrylic acid. Same below. ], maleic acid (anhydride), fumaric acid, itaconic acid (anhydride) and citraconic acid (anhydride).
Among these, from the viewpoint of ease of modification, preferred are dicarboxylic acids and mono- or dicarboxylic acid anhydrides, more preferred are maleic acid (anhydride) and fumaric acid, and particularly preferred is maleic acid ( anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used for modification is based on the weight of polyolefin (a1-0), and the effect of improving wettability and adhesion (improving paintability) of molded products is maintained. from the viewpoints of properties, ease of structural control of the block polymer (X), and dispersibility of the block polymer (X) in the resin composition (Z) described later, preferably 0.5 to 20% by weight, and more preferably 0.5 to 20% by weight. is 1 to 15% by weight, particularly preferably 2 to 10% by weight.
Modification with an α,β-unsaturated carboxylic acid (anhydride) is performed, for example, on the terminal double bond of (a1-0) by either a solution method or a melt method, and an α,β-unsaturated carboxylic acid (Anhydride) can be subjected to an addition reaction (ene reaction), and the reaction temperature is preferably 170 to 230°C.

(a1-1-2) can be obtained by secondary modification of (a1-1-1) with a lactam or aminocarboxylic acid.
Lactams used for secondary modification include lactams having 6 to 12 carbon atoms (preferably 6 to 8, more preferably 6), and specific examples include caprolactam, enantholactam, laurolactam and undecanolactam. is mentioned.
Examples of aminocarboxylic acids include aminocarboxylic acids having 2 to 12 carbon atoms (preferably 4 to 12, more preferably 6 to 12 carbon atoms). Specifically, amino acids (glycine, alanine, valine, leucine, isoleucine, and phenylalanine, etc.), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Among the lactams and aminocarboxylic acids, preferred are caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, more preferred are caprolactam, laurolactam, ω-Aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, particularly preferred are caprolactam and 12-aminododecanoic acid.

The amount of lactam or aminocarboxylic acid used for secondary modification is based on the weight of the material to be modified (a1-1-1), and the effect of improving the wettability and adhesion (improving paintability) of the molded product can be maintained. from the viewpoints of properties, ease of structural control of the block polymer (X), and dispersibility of the block polymer (X) in the resin composition (Z) described later, preferably 0.5 to 100% by weight, more preferably is 1 to 50% by weight, particularly preferably 2 to 25% by weight.

(a1-1-3) can be obtained by oxidizing (a1-0) with oxygen and/or ozone (oxidation method) or by introducing a carboxyl group by hydroformylation by the oxo method.
Introduction of a carboxyl group by an oxidation method can be carried out by a known method such as the method described in US Pat. No. 3,692,877. Introduction of carboxyl groups by hydroformylation can be achieved by various methods including known methods, eg, Macromolecules, Vol. 31, page 5943 can be used.
(a1-1-4) can be obtained by secondary modification of (a1-1-3) with a lactam or aminocarboxylic acid.
Examples of the lactam and aminocarboxylic acid include those exemplified as the lactam and aminocarboxylic acid used in the secondary modification of (a1-1-1) above, and the preferred range and amount used are also the same. .

Further, the acid value of (a1-1) is preferably 4 to 100 mgKOH/g, more preferably 4, from the viewpoints of reactivity with (b), ease of structural control of the block polymer (X), and thermoplasticity. to 50 mg KOH/g, particularly preferably 5 to 30 mg KOH/g.
The acid value in the present invention is measured by titration using a KOH/methanol solution containing phenolphthalein as an indicator. Measured as oxidation number.

The polyolefin (a1-2) having hydroxyl groups at both ends of the polymer is obtained by modifying the polyolefin (a1-1) having carboxyl groups or carboxylic anhydride groups at both ends of the polymer with amines having hydroxyl groups. and mixtures of two or more of these can be used.
Amines having a hydroxyl group that can be used for modification include amines having a hydroxyl group having 2 to 10 carbon atoms, specifically 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-amino butanol, 5-aminopentanol, 6-aminohexanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol and the like.
Among these, amines having a hydroxyl group of 2 to 6 carbon atoms (2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-amino hexanol, etc.), more preferred are 2-aminoethanol and 4-aminobutanol, and particularly preferred is 2-aminoethanol.

The amount of amine having a hydroxyl group used for modification is based on the weight of the material to be modified (a1-1), and the durability of the effect of improving wettability and adhesion (improving paintability) of the molded product and the effect of block polymer (X ) and the dispersibility of the block polymer (X) in the resin composition (Z) described later, it is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight. %, particularly preferably 2 to 10% by weight.

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

The polyolefin (a1-3) having amino groups at both ends of the polymer is a polyolefin having amino groups obtained by modifying the polyolefin (a1-1) having carboxyl groups or carboxylic anhydride groups at both ends of the polymer with a diamine. and mixtures of two or more of these can be used.
Diamines having 2 to 12 carbon atoms can be used as the diamine, and specific examples include ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine and decamethylenediamine.
Among these, preferred from the viewpoint of ease of modification are diamines having 2 to 8 carbon atoms (ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, etc.), and more preferred are ethylenediamine and hexamethylenediamine. Ethylenediamine is particularly preferred.

The amount of diamine used for modification of (a1-1) is determined for the durability of the wettability improvement effect and adhesion improvement (paintability improvement) effect of the molded product, the ease of structural control of the block polymer (X), and the resin described later. From the viewpoint of dispersibility of the block polymer (X) in the composition (Z), it is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, based on the weight of (a1-1). , particularly preferably 2 to 10% by weight. 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 cross-linking reaction between polymer molecules. is preferably 1 to 500% by weight, particularly preferably 2 to 300% by weight of diamine, and then removing unreacted diamine at 120 to 230° C. under reduced pressure.

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

Examples of the polyolefin (a1-4) having isocyanate groups at both ends include polyolefins having isocyanate groups obtained by modifying (a1-2) with poly(2 to 3 or more) isocyanates, and mixtures of two or more thereof. be done.
Examples of polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon atoms in the isocyanate (NCO) group; hereinafter the same), aliphatic polyisocyanates having 2 to 18 carbon atoms, and 4 to 15 carbon atoms. Alicyclic polyisocyanates, araliphatic polyisocyanates having 8 to 15 carbon atoms, modified products of these polyisocyanates, and mixtures of two or more thereof are included.

Aromatic polyisocyanates include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- or 4,4'-diphenylmethane Diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane and 1 , 5-naphthylene diisocyanate and the like.

Aliphatic polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and the like.

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

Aroaliphatic polyisocyanates include m- or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI).

Examples of modified polyisocyanate include urethane modified, urea modified, carbodiimide modified and uretdione modified.
Preferred among the polyisocyanates are TDI, MDI and HDI, more preferred is HDI.

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) between the isocyanate groups of the polyisocyanate and the hydroxyl groups of (a1-2) is preferably 1.8:1 to 3:1, more preferably 2:1.
In order to accelerate the urethanization reaction, a catalyst generally used for the urethanization reaction may be used, if necessary. As catalysts, metal catalysts {tin catalysts [dibutyltin dilaurate and stannus octoate, etc.], lead catalysts [lead 2-ethylhexanoate, lead octoate, etc.], other metal catalysts [metal naphthenate (cobalt naphthenate etc.) and phenylmercuric propionate etc.]}; amine catalyst {triethylenediamine, diazabicycloalkene [1,8-diazabicyclo[5,4,0]undecene-7 etc.], dialkylaminoalkylamine (dimethylaminoethylamine and dimethylaminooctylamine, etc.), carbonates or organic acid (formic acid, etc.) salts of heterocyclic aminoalkylamines [2-(1-aziridinyl)ethylamine and 4-(1-piperidinyl)-2-hexylamine, etc.], N -methyl or ethylmorpholine, triethylamine and diethyl- or dimethylethanolamine, etc.}; and combined systems of two or more of these.
The amount of catalyst used is preferably 3% by weight or less, preferably 0.001 to 2% by weight, based on the total weight of polyisocyanate and (a1-2).

As (a1-5), a polyolefin having a structure obtained by modifying one end of (a1-0) with an α,β-unsaturated carboxylic acid anhydride, and a polyolefin having a structure obtained by secondary modification with diolamine (a1 -5-1) can be used.
Diolamine used for secondary modification includes, for example, diethanolamine.

The Mn of the polyolefin (a) is preferably 1,000 to 1,000 from the viewpoint of the dispersibility of the block polymer (X), the mechanical properties of the molded product, the effect of improving wettability, and the durability of the effect of improving adhesion (improving paintability). 25,000, more preferably 1,500 to 12,000, particularly preferably 2,000 to 7,000.

The amount of structural units derived from propylene in the polyolefin (a) is the effect of improving the mechanical properties and wettability of the resin composition (Z) (especially when polypropylene resin is used) and the effect of improving adhesion (improving paintability). From the viewpoint of sustainability, it is 30 to 100 mol%, preferably 35 to 100 mol%, more preferably 50 to 100 mol%, particularly preferably 80 to 100 mol%, most preferably 96 to 100 mol%.
Polyolefin (a) containing a predetermined amount of propylene is obtained by using (a1-0) and (a2-0) having a content of structural units derived from propylene in the polyolefin of 30 to 100 mol%. Obtainable.

In the polyolefin (a), the isotacticity of the propylene portion is high from the viewpoint of the dispersibility of the block polymer (X), the mechanical properties of the molded product, the effect of improving wettability, and the durability of the effect of improving adhesion (improving paintability). It is preferably between 90% and 100%.

Isotacticity in the present invention can be calculated using, for example, ¹³ C-NMR (nuclear magnetic resonance spectroscopy). In general, side-chain methyl groups can be It is known that peaks are observed at different chemical shifts under the influence of the steric configuration (meso or racemo) with the methyl group. The isotacticity at can also be calculated based on the Pentad estimate.
That is, regarding the carbon peaks derived from the side chain methyl groups in propylene obtained by ¹³ C-NMR, each pentad peak (H) observed in the chemical shift range of 19.0 to 20.0 ppm, and the pentad is only a meso structure. When the carbon peak derived from the methyl group in the isotactic propylene to be formed is the methyl group peak (H _a ) observed at 21.8 ppm, the isotacticity is calculated by the following formula.
Isotacticity (%) = [(H _a )/Σ(H)] x 100 (1)
In the formula, H _a is the peak height of the isotactic (pentad is formed only by the mesostructure) signal, and H is each peak height of the pentad.

<Polyester (b)>
As the polyester (b) in the present invention, a polyester (b1) and a diol (f) or a monovalent and a polyester (b2) obtained by ring-opening polymerization of the alcohol (g) and the lactone monomer (h).

Examples of the dicarboxylic acid (e1) include a dicarboxylic acid (e11) having only a carboxyl group as an acid group and a dicarboxylic acid (e12) having a sulfo group. Dicarboxylic acid (e1) may be used alone or in combination of two or more.

Dicarboxylic acids (e11) having only a carboxyl group as an acid group include dicarboxylic acids having 2 to 20 carbon atoms [aliphatic dicarboxylic acids having 2 to 20 carbon atoms (succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid , azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid and itaconic acid, etc.), aromatic dicarboxylic acids having 8 to 20 carbon atoms (phthalic acid, 2,6- or 2,7-naphthalene dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, tolylenedicarboxylic acid, xylylenedicarboxylic acid and 5-sulfoisophthalic acid), alicyclic dicarboxylic acids having 5 to 20 carbon atoms (cyclo propanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, bicyclohexyl-4,4′-dicarboxylic acid, camphoric acid, etc.)] and the like.

Dicarboxylic acids having a sulfo group (e12) include aromatic dicarboxylic acids such as 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid and 4-sulfo-2,6-naphthalenedicarboxylic acid, and sulfosuccinic acid. and other aliphatic dicarboxylic acids.

The sulfo group possessed by (e12) is preferably a sulfonate group neutralized with a basic substance, from the viewpoint of durability of surface modification effects such as improved wettability and improved adhesion (improved paintability). .
Salts of sulfonic acid groups include alkali metal (lithium, sodium, potassium, etc.) salts, alkaline earth metal (magnesium, calcium, etc.) salts, ammonium salts, mono- and di- or amine salts such as triamines (mono-, di- or triethylamine, mono-, di- or triethanolamine and diethylethanolamine), quaternary ammonium salts of the above amines and amidinium (1-ethyl-3-methylimidazolium etc.) or guanidinium (2-dimethylamino-1,3,4-trimethylimidazolinium etc.) and the like.

Examples of the ester-forming derivative (e2) of the dicarboxylic acid (e1) include alkyl (C 1 to 4) esters (methyl esters, ethyl esters, etc.) of (e1) and acid anhydrides of (e1).

Among the dicarboxylic acid (e1) and its ester-forming derivative (e2), dicarboxylic acid having a sulfo group is preferable from the viewpoint of durability of surface modification effects such as improvement of wettability and adhesion (improvement of paintability). Acids (e12), dicarboxylic acids in which the sulfo group of (e12) forms a salt to form a sulfonic acid group, and ester-forming derivatives thereof, more preferably aromatic dicarboxylic acids having a sulfo group, sulfo Aromatic dicarboxylic acids and ester-forming derivatives thereof in which groups form salts, and particularly preferred are 5-sulfoisophthalic acid 1-ethyl-3-methylimidazolium salt, 5-sulfoisophthalic acid sodium salt, 5- Potassium sulfoisophthalic acid salts and their ester-forming derivatives.

The diol (f) used in the polyesters (b1) and (b2) is not particularly limited as long as it is a diol. 3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol) and diols having branched alkyl chains (1,2-propanediol, neopentyl glycol, 3-methyl- 1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,2-, 1,3- or 2,3-butanediol, etc.)]; Dihydric alcohol [1,4-bis(hydroxymethyl)cyclohexane and 2,2-bis(4-hydroxycyclohexyl)propane, etc.]; C2-C12 alkylene of the above C2-C10 aliphatic dihydric alcohol Oxide (hereinafter abbreviated as AO) adduct; aromatic ring-containing dihydric alcohol having 8 to 20 carbon atoms [m- or p-xylylene glycol, bis(hydroxyethyl)benzene, bis(hydroxyethoxy)benzene, bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.), AO adducts of dihydroxynaphthalene, bis(2-hydroxyethyl) terephthalate, etc.];

Examples of AO having 2 to 12 carbon atoms include ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, and 3-methyltetrahydrofuran. , styrene oxide and α-olefin oxide. In addition, AO may be used alone or two or more may be block-copolymerized or random-copolymerized.

Among these, from the viewpoint of durability of surface modification effects such as improved wettability and improved adhesion (improved paintability), dihydric alcohols having 2 to 10 carbon atoms and polyethylene glycol (hereinafter abbreviated as PEG) are preferable. ) (degree of polymerization: 2 to 20) and ethylene oxide side adducts of bisphenols (addition mole number: 2 to 60 mol).
Diol (f) may be used alone or in combination of two or more.

The monohydric alcohol (g) used in the polyester (b2) includes monohydric alcohols having 1 to 20 carbon atoms (methanol, ethanol, propanol, hexanol, octanol, decanol, dodecanol, eicosanol, etc.).

Examples of the lactone monomer (h) used in the polyester (b2) include lactone monomers having 3 to 12 carbon atoms (β-propiolactone, γ-butyrolactone, γ-valerolactone, ε-caprolactone, η-caprylolactone, 11 -undecanolactone and 12-tridecanoid, etc.).

Polyester (b) is a sulfonic acid (salt) group, that is, a sulfo group or a sulfone in which a sulfo group forms a salt, from the viewpoint of durability of surface modification effects such as improved wettability and improved adhesion (improved paintability). It is preferred to have an acid base. From the same point of view, the sulfonic acid (salt) group is preferably a sulfonic acid group, more preferably 1-ethyl-3-methylimidazolium salt of a sulfo group, sodium sulfo group and potassium sulfo group. be.
The amount of sulfonic acid (salt) groups in one molecule of the polyester (b) is 1 to 80 from the viewpoint of durability of surface modification effects such as improved wettability and improved adhesion (improved paintability). is preferred, more preferably 3 to 60.

By using a dicarboxylic acid having a sulfo group (e12), a dicarboxylic acid in which the sulfo group of (e12) forms a salt, or an ester-forming derivative thereof as an essential constituent monomer, a sulfonic acid (salt ) groups can be introduced. In the case of introducing a sulfo group, after producing (b) using dicarboxylic acid in which a sulfo group forms a salt, the neutralized salt can be converted to a sulfo group with an acid.

As a method for producing polyester (b), a general method for producing polyester can be applied as it is. The polyesterification reaction is carried out at a temperature range of 150 to 240° C. under reduced pressure, and the reaction time is preferably 0.5 to 20 hours. Also, if necessary, a catalyst generally used for esterification reaction may be used. Esterification catalysts include antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide, dibutyltin oxide, etc.), titanium catalysts (tetrabutyl titanate, etc.), zirconium catalysts (tetrabutyl zirconate, etc.) and metal acetate salts. Catalysts (such as zinc acetate) and the like are included.

From the viewpoint of structural control of the block polymer (X), polyester monool is preferably used as the polyester (b). Polyester monool is obtained by adjusting the molar ratio of dicarboxylic acid (e1) and diol (f); A method of obtaining by adjusting the molar ratio of (f); a method of ring-opening polymerization of a monohydric alcohol (g) with a lactone monomer (h), and the like.

Mn of the polyester (b) is preferably 500 to 10,000, more preferably 500 to 10,000, from the viewpoint of durability of the effect of improving wettability and adhesion (improving paintability) and reactivity with the polyolefin (a). is 1,000 to 6,000, particularly preferably 2,000 to 4,000.

<Block polymer (X)>
The block polymer (X) in the present invention has a block of polyolefin (a) having 30 mol % or more of structural units derived from propylene and a block of polyester (b) as structural units, and has the following molecular structure (1 ) to (3).
(1) a linear (a)-(b) diblock structure;
(2) a linear (b)-(a)-(b) triblock structure;
(3) A branched structure in which 2 to 3 polyester (b) blocks are bonded to one end of a polyolefin (a) block.

The structure of (X) is preferable from the viewpoint of the durability of the effect of improving wettability and adhesion (improving paintability) of the molded product, and the dispersibility of the block polymer (X) in the resin composition (Z) described later. is (a)-(b) diblock type structure or (b)-(a)-(b) triblock type structure, particularly preferred is (a)-(b) diblock type structure.

The block polymers having the above molecular structures (1) to (3) are not particularly limited, but can be obtained, for example, by the following method.

A block polymer having a linear (a)-(b) diblock type structure is, for example, a polyolefin (a2-1) having a carboxyl group or a carboxylic anhydride group at one end of the polymer and a polyester monool in 1: reacting at a molar ratio of 1; reacting a polyolefin (a2-1) having a carboxyl group or a carboxylic anhydride group at one end of the polymer with a polyester diol at a molar ratio of 1:1; Alternatively, it can be obtained by reacting a polyolefin (a1-1) having carboxylic acid anhydride groups at both ends of the polymer with a polyester monool at a molar ratio of 1:1.

A block polymer having a linear (b)-(a)-(b) triblock structure is, for example, a polyolefin (a1-1) having a carboxyl group or a carboxylic anhydride group at both ends of the polymer and a polyester monol can be obtained by reacting with at a molar ratio of 1:2.

A block polymer having a branched structure in which two blocks of polyester (b) are bonded to one end of a block of polyolefin (a) is, for example, a polyolefin having a carboxylic anhydride group at one end of the polymer and a monopolyester. and all in a molar ratio of 1:2.
In the above, an example of the combination of polyolefin (a) and polyester (b) when obtaining block polymer (X) having each structure is shown, but as described above, (a) and (b) can be various Since it has a functional group, any combination can be adopted as long as the functional group of (a) and the functional group of (b) can react with each other.

(X) preferably has a structure in which a block of polyolefin (a) and a block of polyester (b) are bonded via an ester bond, an amide bond or a urethane bond, for heat resistance and ease of production. From the viewpoint of , an ester bond or an amide bond is more preferable, and an ester bond is particularly preferable.

Mn of (X) is preferably from 3,000 to 14,000, more preferably from 4,000 to 11, more preferably from 3,000 to 14,000, from the durability of the wettability improvement effect and adhesion improvement (paintability improvement) effect of the molded product. 000, particularly preferably 5,000 to 8,000.

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

When (X) has a structure in which blocks (a) and (b) are linked via an ester bond or an amide bond, for example, (a) and (b) are placed in a reaction vessel. Then, while stirring, at a reaction temperature of 100 to 250° C. and a pressure of 0.003 to 0.1 MPa, water generated in the amidation reaction or esterification reaction (hereinafter abbreviated as generated water) is removed from the reaction system. It can be produced by a method of reacting for 1 to 50 hours.

For the esterification reaction, it is preferred to use 0.05 to 0.5% by weight of catalyst based on the weight of (a) and (b) in order to promote the reaction. Catalysts include inorganic acids (sulfuric acid, hydrochloric acid, etc.), organic sulfonic acids (methanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, etc.), antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide and dibutyl tin oxide, etc.), titanium catalysts (tetrabutyl titanate, bistriethanolamine titanate, potassium oxalate titanate, etc.), zirconium catalysts (tetrabutyl zirconate, zirconyl acetate, etc.), zinc catalysts (zinc acetate, etc.), etc. mentioned. When a catalyst is used, the catalyst can be neutralized, if necessary, and treated with an adsorbent to remove and purify the catalyst after the completion of the esterification reaction.
Methods for removing the generated water out of the reaction system include the following methods.
[1] A method of using an organic solvent that is incompatible with water (e.g., toluene, xylene, cyclohexane, etc.) and azeotroping the organic solvent and generated water under reflux to remove only the generated water from the reaction system. .
[2] A method of blowing a carrier gas (for example, air, nitrogen, helium, argon, carbon dioxide, etc.) into the reaction system to remove the generated water out of the reaction system together with the carrier gas.
[3] A method of reducing the pressure in the reaction system to remove the generated water out of the reaction system.

When (X) has a structure in which a block of (a) and a block of (b) are bonded via a urethane bond, for example, (b) is put into a reaction vessel and stirred for 30 to 30 minutes. After heating to 100° C., (a) is added and reacted at the same temperature for 1 to 20 hours.
To promote the reaction, it is preferred to use 0.001 to 5% by weight of catalyst based on the weight of (a) and (b). Examples of catalysts include organometallic compounds (dibutyltin dilaurate, dioctyltin dilaurate, lead octanoate, bismuth octanoate, etc.), tertiary amines {triethylenediamine, trialkylamines having an alkyl group having 1 to 8 carbon atoms (trimethylamine, tributylamine and trioctylamine, etc.), diazabicycloalkenes [1,8-diazabicyclo[5,4,0]undecene-7], etc.}; and combinations of two or more thereof.

<Resin modifier (Y)>
The resin modifier (Y) of the present invention contains the block polymer (X) described above.
The resin modifier (Y) can be suitably used as a resin modifier for the thermoplastic resin (C) described below.
The resin modifier (Y) includes a colorant (D1), a release agent (D2), an antioxidant (D3), a flame retardant (D4), an ultraviolet absorber (D5), an antibacterial agent (D6), and Additives (D) such as compatibilizers (D7), fillers (D8) and transesterification inhibitors (D9) may be included.

<Resin composition (Z)>
The resin composition (Z) of the present invention contains the resin modifier (Y) of the present invention and a thermoplastic resin (C).
The weight ratio [(Y):(C)] of the resin modifier (Y) and the thermoplastic resin (C) is the durability of the effect of improving mechanical properties and wettability and adhesion (improving paintability). From the point of view, it is preferably 1:99 to 50:50, more preferably 5:95 to 20:80, and particularly preferably 10:90 to 15:85.

The thermoplastic resin (C) includes polyolefin resin (C1) [polypropylene (PP), ethylene/propylene copolymer, polyethylene (PE), etc.]; fluororesin (C2) [PTFE (polytetrafluoroethylene), ETFE ( ethylene-tetrafluoroethylene copolymer), PFA (perfluoroalkoxyalkane (copolymer of tetrafluoroethylene (C ₂ F ₄ ) and perfluoroalkoxyethylene) and PVDF (polyvinylidene fluoride resin)]; polystyrene resin (C3) [A vinyl group-containing aromatic hydrocarbon alone and a copolymer containing a vinyl group-containing aromatic hydrocarbon and at least one selected from the group consisting of butadiene as structural units; polystyrene], etc.; and mixtures of two or more of these.
Among these, PVDF of (C1) and (C2) is preferred, and more preferred is (C1), particularly preferred are polypropylenes within (C1) (homotype polypropylene, block-type polypropylene and ethylene/propylene copolymers), most preferred is homotype polypropylene.

The resin composition (Z) may optionally contain a colorant (D1), a release agent (D2), an antioxidant (D3), a flame retardant (D4), and an ultraviolet absorber as long as the effects of the present invention are not impaired. Additives (D) such as (D5), antibacterial agents (D6), compatibilizers (D7), fillers (D8) and transesterification inhibitors (D9) can be included. Each additive may be used alone or in combination of two or more.

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

Release agents (D2) include lower alcohol esters of higher fatty acids (having 1 to 4 carbon atoms) (butyl stearate, etc.), and polyvalent (divalent to tetravalent or higher) fatty acids (having 2 to 18 carbon atoms). Examples thereof include alcohol esters (hardened castor oil, etc.), glycol (C2-8) esters of fatty acids (2-18 carbon atoms) (ethylene glycol monostearate, etc.), and liquid paraffin.

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

Flame retardants (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 UV absorbers (D5) include benzotriazole [2-(2'-hydroxy-5'-methylphenyl)benzotriazole, etc.], benzophenone (2-hydroxy-4-methoxybenzophenone, etc.), salicylate (phenylsalicylate etc.) and acrylates (2-ethylhexyl-2-cyano-3,3-diphenyl acrylate etc.).

Antibacterial agents (D6) include benzoic acid, sorbic acid, halogenated phenols, organic iodine, nitriles (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylenebisthianocyanate), N-halo Alkylthioimides, copper agents (8-oxyquinoline copper, etc.), benzimidazoles, benzothiazoles, trihaloallyls, triazoles, organic nitrogen-sulfur compounds (Suraof 39, etc.), quaternary ammonium compounds and pyridine compounds.

Examples of the compatibilizer (D7) include modified vinyl polymers having at least one functional group (polar group) selected from the group consisting of carboxyl groups, epoxy groups, amino groups, hydroxyl groups and polyoxyalkylene groups; , a polymer described in JP-A-3-258850, and a block polymer having a modified vinyl polymer having a sulfonic acid group and a polyolefin portion and an aromatic vinyl polymer portion described in JP-A-6-345927. A coalescence etc. are mentioned.

Examples of the filler (D8) include inorganic fillers (calcium carbide, talc, clay, etc.) and organic fillers (urea, calcium stearate, etc.).
Examples of transesterification inhibitors (D9) include phosphate [bisphenol A bis(diphenyl phosphate), monooctadecyl phosphate and dioctadecyl phosphate] and phosphite [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 effects of each additive and the mechanical properties of the molded product. , More preferably 0.01 to 35% by weight; From the same viewpoint, the content of each (D) is preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight; (D2) is preferably 0.01 to 3 wt%, more preferably 0.05 to 1 wt%; (D3) is preferably 0.01 to 3 wt%, more preferably 0.05 to 1 wt%; (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, more preferably 0.05 to 1% by weight; ) is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight; (D7) is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight; (D8) is preferably 0.5-10% by weight, more preferably 1-5% by weight; (D9) is 0.01-3% by weight, more preferably 0.05-1% by weight.

The resin composition (Z) of the present invention can be obtained by melt mixing the resin modifier (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 modifier (Y) may be added to the resin composition (Z).
As a method of melt-mixing, in general, pelletized or powdered components are mixed in an appropriate mixer (Henschel mixer, etc.), and then melt-mixed in an extruder to pelletize. can.
There are no particular restrictions on the order of addition of each component during melt mixing, but for example,
[1] A method of melt-mixing (C) and (Y) and then, if necessary, adding (D) all at once and melt-mixing;
[2] When melt-mixing (C) and (Y), part of (C) is melt-mixed in advance to prepare a high-concentration composition (masterbatch resin composition) of (Y), and then the remaining A method of melt mixing (C) and optionally (D) (masterbatch method or master pellet method);
etc.
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) is easily dispersed in (C) efficiently.

<Molded product>
The molded article of the present invention is obtained by molding the resin composition (Z) of the present invention. Examples of molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding and film molding (cast method, tenter method, inflation method, etc.). It can be molded by any method including means such as molding, multi-layer molding or foam molding.

The molded article of the present invention has excellent mechanical properties, wettability improvement effect and adhesion improvement effect (improvement of paintability), and has good paintability and printability. Alternatively, a molded article can be obtained by printing.
Examples of methods for coating the molded article include air spray coating, airless spray coating, electrostatic spray coating, dip coating, roller coating and brush coating, but are not limited to these.
As the paint, paints generally used for coating plastics can be used, and specific examples include polyester melamine resin paints, epoxy melamine resin paints, acrylic melamine resin paints, and acrylic urethane resin paints.
The coating film thickness (dry film thickness) can be appropriately selected depending on the purpose, but is preferably 10 to 50 μm.

As a method for printing on a molded product or a coated surface of a molded product, any printing method generally used for printing plastics can be used, such as gravure printing, flexographic printing, screen printing, and pad printing. , dry offset printing and offset printing.
As the printing ink, those generally used for printing on plastics can be used, including gravure ink, flexographic ink, screen ink, pad ink, dry offset ink and offset ink.

The resin modifier (Y) of the present invention is excellent in the persistence of the surface-modifying effect imparted to the molded product by surface treatment, so it is useful for resin molded products surface-treated by corona treatment, plasma treatment or flame treatment. It is suitably used as an agent for improving the durability of wettability or as an agent for improving the durability of adhesion of resin molded articles surface-treated by corona treatment, plasma treatment or flame treatment.
The surface-treated molded article of the present invention containing (Y) has excellent wettability and its durability, and therefore can be suitably used for the following applications. That is, improvement of liquid wettability of PP for battery separators, improvement of liquid wettability of PE and PVDF for water treatment membranes, improvement of liquid wettability of short fiber polyolefin for fiber reinforcement, improvement of liquid wettability of vinyl houses (plastic houses), It is also suitable for improving the liquid wettability of automobile interior and exterior materials and the liquid wettability of food packaging films.

Examples of the present invention will be described below, but the present invention is not limited to these. In the following, parts indicate parts by weight. In the following, Examples 8, 11, 12, 16, 28, 31, 32, and 36 are referred to as Reference Examples 1 to 8, respectively.

<Production Example 1> [Single-terminal acid-modified ethylene-propylene random copolymer (a-1)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=32 mol %) at 410±0.1° C. under nitrogen flow (80 mL/min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200° C. over 3 hours to obtain a polyolefin (a-1) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The Mn of (a-1) was 4,000, the propylene content was 32 mol %, and the isotacticity of the propylene portion was 40%.

<Production Example 2> [One-terminal acid-modified ethylene-propylene random copolymer (a-2)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermally degrading a polymer (propylene content=52 mol %) at 410±0.1° C. under nitrogen flow (80 mL/min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200° C. over 3 hours to obtain a polyolefin (a-2) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The Mn of (a-2) was 4,000, the propylene content was 52 mol %, and the isotacticity of the propylene portion was 60%.

<Production Example 3> [One-end acid-modified 1-butene-propylene random copolymer (a-3)]
A low molecular weight 1-butene-propylene random copolymer [1-butene- Obtained by thermally degrading a propylene random copolymer (propylene content = 82 mol%) at 410 ± 0.1°C for 16 minutes under nitrogen flow (80 mL/min). Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200° C. over 3 hours to obtain a polyolefin (a-3) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The Mn of (a-3) was 4,000, the propylene content was 82 mol %, and the isotacticity of the propylene portion was 80%.

<Production Example 4> [Single-terminal acid-modified ethylene-propylene random copolymer (a-4)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=96 mol %) at 410±0.1° C. under nitrogen flow (80 mL/min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200° C. over 3 hours to obtain a polyolefin (a-4) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
(a-4) had an Mn of 4,000, a propylene content of 96 mol %, and an isotacticity of the propylene portion of 90%.

<Production Example 5> [Single-end acid-modified homotype polypropylene (a-5)]
A low-molecular-weight homotype polypropylene obtained by a thermal degradation method [homotype polypropylene at 410 ± 0.1 ° C , obtained by thermal degradation for 16 minutes under nitrogen bubbling (80 mL/min). Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin (a-5) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The Mn of (a-5) was 4,000, the propylene content was 100 mol %, and the isotacticity of the propylene portion was 99%.

<Production Example 6> [Both-terminal acid-modified ethylene-propylene random copolymer (a-6)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=96 mol %) at 410±0.1° C. under nitrogen flow (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 charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin (a-6) having carboxylic anhydride groups at both ends of the polymer. 95 parts were obtained.
The Mn of (a-6) was 4,000, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 7> [Single-terminal acid-modified ethylene-propylene random copolymer (a-7)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=96 mol %) at 410±0.1° C. under nitrogen flow (80 mL/min) for 16 minutes. Mn: 1,400, Average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene are charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin (a-7) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The Mn of (a-7) was 1,500, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 8> [Single-terminal acid-modified ethylene-propylene random copolymer (a-8)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=96 mol %) at 410±0.1° C. under nitrogen flow (80 mL/min) for 16 minutes. Mn: 2,400, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were added, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin (a-8) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The Mn of (a-8) was 2,500, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 9> [Single-terminal acid-modified ethylene-propylene random copolymer (a-9)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=96 mol %) at 410±0.1° C. under nitrogen flow (80 mL/min) for 16 minutes. Mn: 10,000, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene are charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200° C. over 3 hours to obtain a polyolefin (a-9) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The Mn of (a-9) was 10,000, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 10> [Both-terminal acid-modified ethylene-propylene random copolymer (a-10)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=96 mol %) at 410±0.1° C. under nitrogen flow (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 are charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin (a-10) having carboxylic anhydride groups at both ends of the polymer. 95 parts were obtained.
The Mn of (a-10) was 10,000, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 11> [Both-terminal acid-modified ethylene-propylene random copolymer (a-11)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=96 mol %) at 410±0.1° C. under nitrogen flow (80 mL/min) for 16 minutes. Mn: 1,400, average number of double bonds per molecule: 2.0] 90 parts, 20 parts of maleic anhydride and 30 parts of xylene are charged, mixed uniformly, replaced with nitrogen, and stirred while sealed. The temperature was raised to 200° C. while melting, and the mixture was reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin (a-11) having carboxylic anhydride groups at both ends of the polymer. 95 parts were obtained.
The Mn of (a-11) was 1,500, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 12> [One-terminal amino-modified ethylene-propylene random copolymer (a-12)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=96 mol %) at 410±0.1° C. under nitrogen flow (80 mL/min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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. over 3 hours to obtain 95 parts of a polyolefin having a carboxylic anhydride group at one end of the polymer. .
Next, 90 parts of the above-mentioned polyolefin having a carboxylic anhydride group at one end of the polymer and 10 parts of bis(2-aminoethyl) ether were charged into the same pressure-resistant reaction vessel as in Production Example 1, and under a nitrogen gas atmosphere, The temperature was raised to 200° C. while stirring, and the reaction was carried out at the same temperature for 2 hours. Excess bis(2-aminoethyl) ether was distilled off under reduced pressure (0.013 MPa or less) at 200° C. over 2 hours to obtain modified polyolefin (a-12) having an amino group at one end.
The Mn of (a-12) was 4,000, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 13> [One-end hydroxyl group-modified ethylene-propylene random copolymer (a-13)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=96 mol %) at 410±0.1° C. under nitrogen flow (80 mL/min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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. over 3 hours to obtain 95 parts of a polyolefin having a carboxylic anhydride group at one end of the polymer. .
Next, 90 parts of the above polyolefin having a carboxylic anhydride group at one end of the polymer and 5 parts of ethanolamine were charged into the same pressure-resistant reaction vessel as in Production Example 1, and heated to 180° C. under a nitrogen gas atmosphere with stirring. 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. over 2 hours to obtain a polyolefin (a-13) having a hydroxyl group at one end of the polymer.
The Mn of (a-13) was 4,000, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 14>
120 parts of ε-caprolactone and 5-sulfoisophthalic acid dimethyl ester of 1-ethyl-3-methylimidazolium salt are placed in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating/cooling device, nitrogen inlet tube and pressure reducing device. 360 parts and 0.2 parts of dibutyl tin oxide were charged, the temperature was raised to 190° C. under a reduced pressure of 0.067 MPa, and the resulting methanol was distilled off while the transesterification reaction was carried out at the same temperature for 6 hours. A polyester monool (b-1) having an average of one sodium sulfonate base was obtained.
(b-1) had a hydroxyl value of 112 mgKOH/g, an acid value of 112 mgKOH/g, and an Mn of 500.

<Production Example 15>
630 parts of PEG (Mn: 200), 500 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and dibutyl tin are placed in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating/cooling device, nitrogen inlet tube and pressure reducing device. 0.2 part of oxide is added, the temperature is raised to 190° C. under a reduced pressure of 0.067 MPa, and the resulting methanol is distilled off while the transesterification reaction is performed at the same temperature for 6 hours to form a sodium sulfonate base in one molecule. A polyester monool (b-2) having an average of 2 was obtained.
(b-2) had a hydroxyl value of 55 mgKOH/g, an acid value of 55 mgKOH/g, and an Mn of 1,000.

<Production Example 16>
800 parts of diethylene glycol, 1700 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 parts of dibutyltin oxide are placed in a stainless steel pressure-resistant reactor equipped with a stirrer, thermometer, heating/cooling device, nitrogen inlet tube and pressure reducing device. was added, the temperature was raised to 190°C under a reduced pressure of 0.067 MPa, and the resulting methanol was distilled off while transesterification was performed at the same temperature for 6 hours. Polyester having an average of 6 sodium sulfonate bases in one molecule Monol (b-3) was obtained.
(b-3) had a hydroxyl value of 28 mgKOH/g, an acid value of 28 mgKOH/g, and an Mn of 2,000.

<Production Example 17>
210 parts of PEG (Mn: 300), 200 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and dibutyltin are placed in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating/cooling device, nitrogen inlet tube and pressure reducing device. 0.2 part of oxide is added, the temperature is raised to 190° C. under a reduced pressure of 0.067 MPa, and the resulting methanol is distilled off while the transesterification reaction is performed at the same temperature for 6 hours to form a sodium sulfonate base in one molecule. A polyester monool (b-4) having an average of 7 was obtained.
(b-4) had a hydroxyl value of 14 mgKOH/g, an acid value of 14 mgKOH/g, and an Mn of 4,000.

<Production Example 18>
55 parts of diethylene glycol, 15 parts of hexanol, 150 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and dibutyltin oxide are placed in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating/cooling device, nitrogen inlet tube and pressure reducing device. 0.2 part was added, the temperature was raised to 190° C. under a reduced pressure of 0.067 MPa, and the resulting methanol was distilled off while the transesterification reaction was performed at the same temperature for 6 hours. A polyester monool (b-5) having 5 groups was obtained.
(b-5) had a hydroxyl value of 28 mgKOH/g, an acid value of 0 mgKOH/g, and an Mn of 2,000.

<Production Example 19>
45 parts of diethylene glycol, 80 parts of PEG (Mn: 200), 35 parts of terephthalic acid, and dimethyl 5-sulfoisophthalate are placed in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating/cooling device, nitrogen inlet tube, and pressure reducing device. 55 parts of the sodium salt of the ester and 0.2 parts of dibutyltin oxide are added, the temperature is raised to 190°C under a reduced pressure of 0.067 MPa, and the resulting methanol is distilled off while the transesterification reaction is performed at the same temperature for 6 hours, A polyester diol (b-6) having an average of two sodium sulfonate groups in one molecule was obtained.
(b-6) had a hydroxyl value of 56 mgKOH/g, an acid value of 0.5 mgKOH/g, and an Mn of 2,000.

<Production Example 20>
120 parts of PEG (Mn: 300), 80 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and dibutyltin oxide are placed in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating/cooling device, nitrogen inlet tube and pressure reducing device. 0.2 part is added, the temperature is raised to 190° C. under a reduced pressure of 0.067 MPa, and the transesterification reaction is performed at the same temperature for 6 hours while methanol is distilled off, and an average of 5 sodium sulfonate bases in one molecule. A polyester diol (b-7) having
(b-7) had a hydroxyl value of 56 mgKOH/g, an acid value of 1 mgKOH/g, and an Mn of 2,000.

<Comparative Production Example 1> [Single-terminal acid-modified ethylene-propylene random copolymer (a'-1)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=20 mol %) at 410±0.1° C. under nitrogen gas (80 mL/min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin (a'-1 ) to give 95 parts.
The Mn of (a′-1) was 4,000, the propylene content was 20 mol %, and the isotacticity of the propylene portion was 10%.

<Comparative Production Example 2> [Graft acid-modified ethylene-propylene random copolymer (a'-2)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=96 mol %) at 410±0.1° C. under nitrogen flow (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 100 parts of xylene are charged, and after purging with nitrogen, the temperature is raised to 140°C under nitrogen ventilation. and uniformly dissolved. A solution prepared by dissolving 2.0 parts of dicumyl peroxide [trade name “Percumyl D”, manufactured by NOF Corporation] in 10 parts of xylene was added dropwise thereto over 10 minutes, and then stirring was continued for 3 hours while refluxing xylene. rice field. Thereafter, xylene and unreacted maleic anhydride are distilled off under reduced pressure (1.5 kPa, hereinafter the same) to obtain 95 parts of polyolefin (a'-2) in which carboxylic anhydride groups are grafted onto the polymer. rice field.
(a′-2) had an Mn of 10,000, a propylene content of 96 mol %, and an isotacticity of the propylene portion of 90%.

<Example 1>
100 parts of (a-1) obtained in Production Example 1, 50 parts of polyester monool (b-1) obtained in Production Example 14 and oxidation 0.3 parts of the inhibitor "Irganox 1010" was added, the temperature was raised to 210°C while stirring, and the mixture was reacted at the same temperature under reduced pressure (0.013 MPa or less) for 5 hours to obtain a block polymer having an Mn of 6,000. A resin modifier (Y-1) containing (X-1) was obtained.

Table 1 shows a list of symbols and compositions of raw materials used in the examples.

<Examples 2 to 20, Comparative Examples 1 to 3>
In the same manner as in Example 1 except that the raw materials used and the amount used were changed to those shown in Table 2 or Table 3, resin modifiers (Y-2) to (Y-20) and (RY-1) ~ (RY-3) was obtained.

The physical properties and compositions of the resin modifiers (Y-1) to (Y-20) and (RY-1) to (RY-3) obtained in Examples 1 to 20 and Comparative Examples 1 to 3 are shown in Table 2 and Table 3 shows.

<Examples 21 to 49, Comparative Examples 4 to 11>
According to the formulation (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 vented twin-screw extruder at 100 rpm, 220 ° C., and a residence time of 5 minutes. As a result, resin compositions (Z-1) to (Z-29) and (RZ-1) to (RZ-8) were obtained.

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

For each resin composition obtained, using an injection molding machine ["PS40E5ASE", manufactured by Nissei Plastic Industry Co., Ltd.], a molding test piece was prepared at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C., and the following performance test was performed. Tables 4 and 5 show the results of evaluation by .
In the following evaluations (3) to (6), the molded test pieces were evaluated using test pieces subjected to surface treatment (corona treatment) under the following equipment and conditions.
・Equipment: Corona scanner ASA-4 manufactured by Shinko Denki Keiso Co., Ltd.
・Processing conditions: processing power 12.5 kV, processing speed 70 mm/s, room temperature

<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 abnormality (equivalent to thermoplastic resin containing no resin modifier)
x: Rough surface, blisters, etc. are observed.

(2) Decrease rate of mechanical strength (Izod impact strength and flexural modulus) The strength and flexural modulus were evaluated. In addition, since the rate of decrease in mechanical strength varies depending on the amount of resin modifier (Y) blended, in order to clarify the rate of decrease depending on the type of resin modifier (Y), the rate of decrease at a specific amount was divided by the blended weight % of the resin modifier (Y) at that time.
That is, evaluation was made according to the following evaluation criteria using the rate of decrease in mechanical strength (%/% by weight) obtained by the following formula.
[Degradation rate of mechanical strength (% / wt%)] = {[mechanical strength before blending] - [mechanical strength after blending]} / [mechanical strength before blending] / [resin modifier Compounding weight] × 100 (%)
For example, when homotype polypropylene (Izod impact strength = 2.0 J / m) is blended with 10% by weight of the resin modifier (Y), and the Izod impact strength after blending is 1.8 J / m, the calculation The formula is as follows.
[Mechanical strength reduction rate (%/wt%)] = [2.0 (J/m) - 1.8 (J/m)]/2.0 (J/m)/10 (wt%) x 100 (%) = 1.0 (%/% by weight)

<Evaluation Criteria>
◎: [decrease rate] ≤ 0.5
○: 0.5 < [decrease rate] ≤ 1.5
○ ^- : 1.5 < [decrease rate] ≤ 2.5
△: 2.5 < [decrease rate] ≤ 5.5
×: 5.5 < [decrease rate]
(2-1) Izod impact strength (unit: J/m)
Measured according to ASTM D256 Method A (notched, 3.2 mm thick).
(2-2) Flexural modulus (unit: MPa)
Measured according to ASTM D638.

(3) Wettability after surface treatment (unit: dyn/cm)
The wettability of the surface-treated (corona-treated) test piece was evaluated by measuring the wetting tension in accordance with JIS K6768 (1999). The higher the wetting tension, the higher the wettability to paints and adhesives, and the better the wettability.

(4) Sustainability of wettability-enhancing effect of surface treatment A surface-treated (corona-treated) test piece was allowed to stand under conditions of room temperature of 25°C and humidity of 50% RH, and wettability was measured after one week. It was confirmed by the evaluation method described above and evaluated according to the following criteria.
<Evaluation Criteria>
◎: Compared to the wettability before the passage of time, no decrease in wetting tension is observed ○: Compared to the wettability before the passage of time, the decrease in wetting tension is 1 dyn / cm
○ ^- : Wetting tension decreased by 2 dyn/cm compared to the wettability before immersion in water.
×: Wetting tension decreased by 3 dyn/cm or more compared to the wettability before the passage of time

(5) Adhesion to paint after surface treatment The paintability (wettability and adhesion to paint) was evaluated based on the adhesion of urethane-based paint. A urethane-based paint was applied to a surface-treated (corona-treated) test piece (100 x 100 x 2 mm) with an applicator so that the film thickness after drying was 30 µm, and the coated surface was dried at 80°C for 30 minutes. A cross-cut peel test was performed using a transparent pressure-sensitive adhesive tape in accordance with JIS K 5600-5-6. Among 100 grids, the number of portions where the coating film was not peeled was counted and evaluated according to the following criteria.
<Evaluation Criteria>
◎: The number that did not peel is 100
○ ⁺ : 95 to 99 that did not peel off
○: The number that did not peel is 90 to 94
○ ^- : 81 to 89 that did not peel off
△: 50 to 80 not peeled
×: The number that did not peel off is 0 to 49

(6) Sustainability of adhesion improvement effect of surface treatment A test piece subjected to surface treatment (corona treatment) was allowed to stand under conditions of room temperature 25 ° C. and humidity 50% RH, and adhesion was confirmed after 1 week. It was evaluated by the above-described method for evaluating adhesion.

From Tables 4 and 5, the resin modifier (Y) of the present invention imparts excellent wettability and persistence of adhesion to the thermoplastic resin without impairing its mechanical properties as compared with the comparative one. I know you can.

The resin modifier (Y) of the present invention does not impair the mechanical strength and good appearance of the thermoplastic resin molded product, and the wettability imparted to the molded product by surface treatment such as corona treatment, plasma treatment and flame treatment. and adhesion (paintability) and other surface modification effects can be maintained, so an agent for improving the durability of wettability of resin molded products surface-treated by corona treatment, plasma treatment or flame treatment, or corona treatment, plasma It is particularly useful as an adhesive persistence improver for resin molded articles surface-treated by treatment or flame treatment. In addition, since the wettability is improved, it is possible to improve the liquid wettability of PP for battery separators, improve the liquid wettability of PE and PVDF for water treatment membranes, improve the liquid wettability of short fiber polyolefin for fiber reinforcement, and improve the liquid wettability of vinyl houses (plastic It is also suitable for improving the liquid wettability of houses), improving the liquid wettability of automotive interior and exterior materials, and improving the liquid wettability of food packaging films.

The resin composition (Z) using the resin modifier (Y) of the present invention has good paintability and durability of printability when surface-treated molded articles using the resin composition (Z), so various molding methods can be used. [Injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding, film molding (cast method, tenter method and inflation method), etc.] , game machines and office equipment, etc.), plastic container materials [trays (IC trays, etc.) used in clean rooms and other containers, etc.], various cushioning materials, covering materials (packaging films, protective films, etc.), flooring materials It can be widely used as a material for sheets, artificial turf, mats, tape substrates (for semiconductor manufacturing processes, etc.), and various molded products (automobile parts, etc.), and is extremely useful.
The molded article of the present invention has excellent mechanical properties as well as excellent wettability, paintability, printability, and durability thereof. Molded articles with good properties are obtained.

Claims (10)

A block of polyolefin (a) having 30 mol% or more of structural units derived from propylene and a block of polyester (b) as structural units, and having a molecular structure of any one of the following (1) to (3) wherein the polyester (b) has a number average molecular weight (Mn) of 500 to 10,000, and the (b) contains 1 to 7 sulfonic acids per molecule (salt) group, the block polymer (X) has a number average molecular weight of 3,000 to 14,000, and the weight ratio of the block of the polyester (b) to the block polymer (X) [(b )/(X)] is 20 to 60% by weight, a resin modifier (Y) for polyolefin resin (C1 ).
(1) a linear (a)-(b) diblock structure;
(2) a linear (b)-(a)-(b) triblock structure;
(3) A branched structure in which 2 to 3 polyester (b) blocks are bonded to one end of a polyolefin (a) block. 2. The resin modifier according to claim 1, wherein the isotacticity of the propylene portion in said polyolefin (a) is 90% to 100%. 3. The resin modifier according to claim 1 or 2 , wherein the block polymer (X) is formed by bonding the polyolefin (a) block and the polyester (b) block via an ester bond, an amide bond or a urethane bond. pawn. The resin modifier according to any one of claims 1 to 3, wherein the block polymer (X) is a (a)-(b) diblock type polymer. As an agent for improving durability of wettability of resin molded products surface-treated by corona treatment, plasma treatment or flame treatment, or as an agent for improving durability of adhesion of resin molded products surface-treated by corona treatment, plasma treatment or flame treatment The resin modifier according to any one of claims 1 to 4, which is used. A resin composition containing the resin modifier (Y) according to any one of claims 1 to 5 and a thermoplastic resin (C) , wherein the thermoplastic resin (C) is a polyolefin resin (C1) ( Z). 7. The resin composition according to claim 6 , wherein the resin modifier (Y) and the thermoplastic resin (C) have a weight ratio [(Y):(C)] of 1:99 to 50:50. A molded article obtained by molding the resin composition (Z) according to claim 6 or 7 . A molded product obtained by subjecting the molded product according to claim 8 to corona treatment, plasma treatment or flame treatment. A molded article obtained by subjecting the molded article according to claim 9 to at least one treatment selected from the group consisting of coating, printing and adhesive application.