JP6456725B2 - Polyolefin resin modifier - Google Patents

Description

  The present invention relates to a polyolefin resin modifier that imparts excellent wettability to a polyolefin resin substrate. More specifically, the present invention relates to a polyolefin resin modifier that imparts excellent wettability to a polyolefin resin substrate without impairing mechanical strength. Here and below, wettability means affinity for water and is evaluated by wet tension described later.

Polyolefin resins are excellent in moldability, rigidity, heat resistance, chemical resistance, electrical insulation, and the like, and are inexpensive, so they are widely used as films, fibers, and other shaped articles of various shapes. On the other hand, a polyolefin resin is a so-called nonpolar and extremely inert polymer substance having no polar group in the molecule. In addition, since it has high crystallinity and extremely low solubility in solvents, there are problems such as adhesion and paintability, and poor wettability with water and water repellent, so that water-based paint cannot be applied. It was.
Conventionally, as a method for improving wettability, a surface of a thermoplastic resin base material, for example, a polyolefin resin molded product, is subjected to corona treatment or plasma treatment (for example, see Patent Document 1), and a surfactant is added to the polyolefin resin composition. A method of adding and making this into a molded product (for example, see Patent Document 2) is known.

JP 2000-319426 A JP 2004-169014 A

However, the method of subjecting the surface of the molded product to corona treatment or plasma treatment has a problem that wettability decreases with the passage of time after treatment. In addition, in the method of adding a surfactant to a polyolefin resin composition and making this into a molded product, the mechanical strength inherent to the original molded product of the polyolefin resin substrate can be obtained by adding an amount sufficient to exert a modification effect. (Tensile modulus, impact resistance, etc., the same shall apply hereinafter) are impaired, and the surfactant may bleed out of the molded product, and improvements have been eagerly desired.
An object of the present invention is to provide a polyolefin resin modifier that imparts excellent wettability to water to a polyolefin resin substrate without impairing mechanical strength.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention relates to a modified polyolefin (X) having a polyolefin (A) and an unsaturated dicarboxylic acid (anhydride) (B) as structural units, and a polyoxy having one functional group reactive with the (X). A polyolefin resin modifier (K) comprising a polyoxyalkylene-modified polyolefin (Z) formed from an alkylene chain-containing compound (Y); comprising the (K) and the polyolefin resin (D) It is a polyolefin resin composition.

The modifier for polyolefin resin of the present invention and a molded product obtained by molding a polyolefin resin composition containing the modifier have the following effects.
(1) The modifier imparts excellent wettability to water to the polyolefin resin substrate without impairing the original mechanical strength.
(2) The molded article has excellent wettability with water and is excellent in its sustainability.

[Polyolefin (A)]
The polyolefin (A) in the present invention includes one or two or more (co) polymers of olefins, and one or more of olefins and one or more of other monomers. A polymer is included.
Examples of the olefin include alkenes having 2 to 30 carbon atoms (hereinafter sometimes abbreviated as C), such as ethylene, propylene, 1- and 2-butene, and isobutene, and C5-30 α-olefins (1- Hexene, 1-decene, 1-dodecene, etc.); Other monomers include C4-30 unsaturated monomers having copolymerizability with olefins, such as vinyl acetate.

Specific examples of (A) include ethylene unit-containing (propylene unit-free) (co) polymers such as high, medium and low density polyethylene, and ethylene and C4-30 unsaturated monomers [butene (1- Butene, etc.), C5-30 α-olefin (1-hexene, 1-dodecene, etc.), vinyl acetate, etc.] (weight ratio is the moldability of the polyolefin resin composition and the molecular end of (A) and From the viewpoint of the amount of double bonds in the molecular chain, preferably 30/70 to 99/1, more preferably 50/50 to 95/5), etc .; propylene unit-containing (ethylene unit-free) (co) polymer For example, a copolymer of polypropylene, propylene and C4-30 unsaturated monomer (same as above) (weight ratio is the same as above); ethylene / propylene copolymer (weight ratio is polyolefin resin group) From the viewpoint of the moldability of (A) and the amount of double bonds in the molecular ends and / or molecular chains, preferably 0.5 / 99.5 to 30/70, more preferably 2/98 to 20/80). A (co) polymer of C4 or higher olefins such as polybutene.
Among these, from the viewpoint of reactivity with the unsaturated dicarboxylic acid (anhydride) (B) described later, polyethylene, polypropylene, ethylene / propylene copolymer, propylene / C4-30 unsaturated monomer copolymer are preferable. Polymers, more preferably ethylene / propylene copolymers, and propylene / C4-30 unsaturated monomer copolymers.

  Number average molecular weight of (A) [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method described later. same as below. ] Is preferably 800 to 50,000, more preferably 1,000 from the viewpoint of the mechanical strength of the molded article of the composition containing the modifier (K) of the present invention and the productivity of the (K). ~ 45,000.

The measurement conditions of Mn by GPC in the present invention are as follows.
Apparatus: High-temperature gel permeation chromatograph
["Alliance GPC V2000", manufactured by Waters Corporation]
Detector: Refractive index detector Solvent: Orthodichlorobenzene reference material: Polystyrene sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm, MIXED-B 2 in series
[Made by Polymer Laboratories, Inc.]
Column temperature: 135 ° C

(A) preferably has a double bond in the molecular end and / or in the molecular chain from the viewpoint of reactivity with the below-mentioned unsaturated dicarboxylic acid (anhydride) (B).
The number of double bonds in the molecular end and / or molecular chain per 1,000 carbons (also referred to as 1,000 carbon atoms) of (A) is the reactivity between (A) and (B) and ( From the viewpoint of productivity of K), it is preferably 0.1-20, more preferably 0.3-18, and particularly preferably 0.5-15. Here, the number of double bonds can be determined from the spectrum of (A) ¹ H-NMR (nuclear magnetic resonance) spectroscopy. That is, the peak in the spectrum is assigned, and the number of double bonds in (A) and (A) are calculated from the integral value derived from double bonds and the integral value derived from (A) at 4.5 to 6 ppm in (A). Is calculated, and the number of double bonds in the molecular end and / or molecular chain per 1,000 carbon atoms in (A) is calculated. The number of double bonds in the examples described later followed this method.

  The production method of (A) includes polymerization methods (for example, those described in JP-A-59-206409) and degradation methods [thermal, chemical and mechanical degradation methods, etc. Examples of the formation method (hereinafter sometimes referred to as thermal degradation method) include those described in JP-B No. 43-9368, JP-B No. 44-29742, and JP-B No. 6-70094].

  The polymerization method includes a method of (co) polymerizing one or more of the olefins, and a method of copolymerizing one or more of the olefins and one or more of the other monomers. It is.

  In the degradation method, a polyolefin (A0) having a high molecular weight [preferably Mn 30,000 to 400,000, more preferably 50,000 to 200,000] obtained by the polymerization method is thermally, chemically or mechanically used. The method of degrading is included.

Among the degradation methods, in the thermal degradation method, the polyolefin (A0) is continuously introduced for 0.5 to 10 hours at 300 to 450 ° C. in the absence of an organic peroxide under nitrogen aeration. Or a method of thermally degrading discontinuously and (2) a method of thermally degrading continuously or discontinuously at 180 to 300 ° C. for 0.5 to 10 hours in the presence of an organic peroxide. It is.
Among these, the method (1) in which a compound having a larger number of double bonds in the molecular terminal and / or molecular chain is easily obtained is preferable from the viewpoint of the copolymerizability between (A) and (B) obtained. is there.

  Among these production methods of (A), it is easy to obtain a compound having a larger number of double bonds in the molecular terminal and / or molecular chain, and the viewpoint that the copolymerization of (A) and (B) is easy Therefore, the degradation method is preferable, and the thermal degradation method is more preferable.

  Mn of (A) is preferably 800 to 50,000, more preferably 1,500 to 30,000 from the viewpoint of the mechanical strength of a molded product formed by molding a polyolefin resin described later and the productivity of (A). It is.

[Unsaturated dicarboxylic acid (anhydride) (B)]
The unsaturated dicarboxylic acid (anhydride) (B) in the present invention is a dicarboxylic acid (anhydride) having one polymerizable unsaturated group. In the present invention, the unsaturated dicarboxylic acid (anhydride) represents an unsaturated dicarboxylic acid or an unsaturated dicarboxylic acid anhydride.
The (B) includes C4-30, such as aliphatic (C4-24, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and their anhydrides), and alicyclic ones ( C8-24, for example, cyclohexanedicarboxylic acid, cycloheptenedicarboxylic acid). (B) may be used alone or in combination of two.
Of these, unsaturated dicarboxylic acid anhydride is preferred from the viewpoint of reactivity with (A), and maleic anhydride is more preferred.

  The weight ratio [(A) / (B)] of (A) and (B) is preferably 99/1 to 70/30 from the viewpoint of the productivity of the modified polyolefin (X) described later and the wettability of the molded product. More preferably, it is 98/2 to 80/20, and particularly preferably 95/5 to 90/10.

[Radical initiator (C)]
The modified polyolefin (X) in the present invention is obtained by copolymerizing the above (A) and (B) in the presence or absence of a radical generating source [radical initiator (C), heat, light, etc.]. It is done.
Examples of the radical initiator (C) include azo compounds [azobisisobutyronitrile, azobisisovaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile)], peroxides [monofunctional ( (Having one peroxide group in the molecule) (benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, dicumyl peroxide, etc.) and polyfunctional (having two or more peroxide groups in the molecule) [2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxyhexahydroterephthalate, diallyl peroxydicarbonate, etc.]] and the like.
Among these, from the viewpoint of the reactivity of (A) and (B), preferred are peroxides, more preferred are monofunctional peroxides, and particularly preferred are di-t-butyl peroxide, lauroyl peroxide, Dicumyl peroxide.

  The amount of (C) used is preferably 0.05 to 10%, more preferably 0.2 to 5%, based on the total weight of (A) and (B), from the viewpoint of reactivity and side reaction suppression. Especially preferably, it is 0.5 to 3%.

[Modified polyolefin (X)]
The modified polyolefin (X) in the present invention comprises the polyolefin (A) and the unsaturated dicarboxylic acid (anhydride) (B) as structural units.
The modified polyolefin (X) can be produced by copolymerizing the polyolefin (A) and the unsaturated dicarboxylic acid (anhydride) (B) in the presence or absence of the radical initiator (C).

The specific production method (X) includes the following methods [1] and [2].
[1] (A) and (B) are mixed with a suitable organic solvent [C3-18, such as hydrocarbon (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbon (di-, tri- , And tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methyl ethyl ketone, di-t-butyl ketone, etc.), ethers (ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.)] Suspended or dissolved, and if necessary, (C) [or a solution in which (C) is dissolved in an appropriate organic solvent (the same as above)], a chain transfer agent (t) described later, a polymerization inhibitor (f ) And heating and stirring (solution method);
[2] A method (melting method) in which (A), (B) and, if necessary, (C), (t), (f) are mixed in advance and melt-kneaded using an extruder, a Banbury mixer, a kneader or the like.

  The reaction temperature in the solution method may be a temperature at which (A) is dissolved in an organic solvent, and is preferably 50 to 220 ° C., more preferably 110 from the viewpoints of the reactivity and productivity of (A) and (B). It is -210 degreeC, Most preferably, it is 120-180 degreeC.

  The reaction temperature in the melting method may be a temperature at which (A) melts, and is preferably 120 to 260 ° C. from the viewpoint of the copolymerizability of (A) and (B) and the decomposition temperature of the reaction product. More preferably, it is 130-240 degreeC.

Examples of the chain transfer agent (t) include alcohol (C1-24, such as methanol, ethanol, 1-propanol, 2-butanol, allyl alcohol); thiol (C1-24, such as ethylthiol, propiothiol, 1- And 2-butylthiol, 1-octylthiol); ketones (C3-24, such as acetone, methyl ethyl ketone); aldehydes (C2-18, such as 2-methyl-2-propylaldehyde, 1- and 2-butyraldehyde, 1- Pentylaldehyde); phenol (C6-36, eg phenol, o-, m- and p-cresol); amine (C3-24, eg diethylmethylamine, triethylamine, diphenylamine); disulfide (C2-24, eg diethyl disulfide, G-1- B pill disulfide), and the like.
The amount of (t) used is usually 30% or less based on the total weight of (A) and (B) or the total weight of (A) and (B), (A), (B), or (A ) And (B) from the viewpoint of copolymerizability and productivity, it is preferably 0.1 to 20%.

Examples of the polymerization inhibitor (f) include catechol (C6-36, for example, 2-methyl-2-propylcatechol), quinone (C6-24, for example, p-benzoquinone), hydrazine (C2-36, for example, 1, 3, 5-triphenylhydrazine), nitro compounds (C3-24, such as nitrobenzene), stabilized radicals [C5-36, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2,6,6 -Tetramethyl-1-piperidinyl oxide (TEMPO)].
The amount used of (f) is usually 5% or less based on the total weight of (A) and (B), productivity, stability of (A) and (B) and reactivity of (A) and (B). From this viewpoint, the content is preferably 0.01 to 0.5%.

  Mn of (X) is preferably 1,500 to 70,000, more preferably 2,000 to 60,000, particularly preferably 2,500 to 50,000, from the viewpoint of mechanical strength and moldability of the molded product. It is.

The acid value of (X) is preferably from 1 to 250 mg KOH / g (hereinafter, only numerical values are shown), from the viewpoint of the wettability of the molded product and the affinity between the polyolefin resin (D) and the modifier (K) described later. Is from 5 to 200, particularly preferably from 10 to 100. The acid value here is a value obtained by measurement according to the following procedures (i) to (iii) according to JIS K0070.
(I) 1 g of (X) is dissolved in 100 g of xylene adjusted to 100 ° C.
(Ii) Titration is performed with a 0.1 mol / L potassium hydroxide ethanol solution [trade name “0.1 mol / L ethanolic potassium hydroxide solution”, manufactured by Wako Pure Chemical Industries, Ltd.] using phenolphthalein as an indicator.
(Iii) The amount of potassium hydroxide required for titration is converted to mg, and the acid value (unit: mgKOH / g) is calculated.
In the above measurement, the carboxyl group and the acid anhydride group were measured equivalently, and the acid values in Examples described later were in accordance with this method.

Examples of the method of bringing the acid value of (X) into the above range include a method of suspending or dissolving in an appropriate organic solvent and copolymerizing the structural units of (A) and (B) under the condition of heating and stirring. It is done.
Specifically, (A) and (B) are mixed with a suitable organic solvent [C3-18, such as hydrocarbon (hexane, heptane, octane, decane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbon (di- -, Tri- and tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methyl ethyl ketone, diethyl ketone, di-t-butyl ketone, etc.), ethers (ethyl-n-propyl ether, di-i-propyl ether, di-n-) Butyl ether, di-t-butyl ether, dioxane, etc.)], and if necessary, (C) [or a solution in which (C) is dissolved in an appropriate organic solvent (the same as above)], The chain transfer agent (t) and the polymerization inhibitor (f) can be added and heated and stirred.

[Polyoxyalkylene chain-containing compound (Y)]
The polyoxyalkylene chain-containing compound (Y) in the present invention is a compound having one functional group reactive with (X).
Examples of the functional group include a hydroxyl group, an amino group, and an epoxy group.
Specific examples include alkylene oxide adducts (Y1), aminopolyoxyalkylene monoalkyl ethers (Y2), and modified products (Y3) of compounds having one active hydrogen.

Examples of the alkylene oxide adduct (Y1) of a compound having one active hydrogen include those obtained by subjecting a compound having one active hydrogen to an addition reaction of alkylene oxide (hereinafter abbreviated as AO). Examples of the compound include those represented by the general formula (1).

R ¹ O— (R ² O) _m —H (1)

R ¹ in the general formula (1) represents a residue obtained by removing one active hydrogen from the compound (Y0) having one active hydrogen.
As (Y0), C1-C50 saturated aliphatic monohydric alcohol (Y01), C1-C50 unsaturated aliphatic monohydric alcohol (Y02), C7-C50 monohydric phenol (Y03) ), Secondary amines having 2 to 50 carbon atoms (Y04), and the like.

(Y01) includes methanol, ethanol, n-propanol, isopropanol n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, pentyl alcohol, hexyl alcohol, cyclohexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, Examples include decyl alcohol, tetradecyl alcohol, hexadecyl alcohol, icosa alcohol, triaconta alcohol, pentacontacohol, benzyl alcohol, and diphenylmethyl alcohol.
(Y02) includes ethenyl alcohol, propenyl alcohol, isopropenyl alcohol, 3-butenyl alcohol, 3-butynyl alcohol, 4-hexenyl alcohol, 7-octenyl alcohol, 9-decenyl alcohol, oleyl alcohol, etc. Is mentioned.
(Y03) includes phenol, nonylphenol and the like.
Examples of (Y04) include dimethylamine, diethylamine, dioctylamine, diphenylamine, and ethylmethylamine.

Of the above (Y0), (Y01), (Y03), (Y04) are preferable from the viewpoint of wettability of a molded article described later and an industrial viewpoint, and more preferable are (Y01) to (Y01) to (Y01) to (C25). Y04), particularly preferably (Y01) having 1 to 20 carbon atoms.
(Y0) may be used alone or in combination of two or more.

R ² in the general formula (1) is an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include ethylene group, 1,2- or 1,3-propylene group, 1,2-, 1,3-, 1,4- or 2,3-butylene group, and the like, and These 2 or more types of mixtures are mentioned.
M in General formula (1) is a number of 2-20, Preferably it is 3-18, More preferably, it is 5-18.

The alkylene oxide adduct (Y1) of a compound having one active hydrogen can be produced by adding AO to (Y0).
As AO, C2-C4 AO [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, but other AO [alpha of 5 to 12 carbon atoms] is used if necessary. -Olefin oxide, styrene oxide and epihalohydrin (such as epichlorohydrin) can be used in a small proportion (30 wt% or less based on the total weight of AO).
When two or more kinds of AO are used in combination, the coupling method may be either random coupling or block coupling. From the viewpoint of the wettability of the molded product described later, EO alone or a combination of EO and other AO is preferred, and EO alone is more preferred.

The addition reaction of AO can be performed by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst.
The content of (R ² O) m based on the weight of (Y1) represented by the general formula (1) is preferably 5 to 99.8% from the viewpoint of wettability and mechanical strength of a molded product described later. More preferably, it is 10 to 98%, and particularly preferably 20 to 90%.

Examples of the aminopolyoxyalkylene alkyl ether (Y2) include those represented by the general formula (2).

R ¹ O— (R ² O) _n —R ³ —NH ₂ (2)

R ¹ in the general formula (2) is the same as R ¹ in the general formula (1), R ² and R ³ is an alkylene group having 2 to 4 carbon atoms, R ¹ and R in the general formula (1) ^{The same} as those exemplified as ² can be mentioned, and the preferred range is also the same.
N in General formula (2) is a number of 2-20, Preferably it is 3-18, More preferably, it is 5-15.

  The aminopolyoxyalkylene alkyl ether (Y2) can be obtained by converting all the hydroxyl groups of the (Y1) into amino groups. For example, it can be produced by reacting (Y1) with acrylonitrile and hydrogenating the obtained cyanoethylated product.

Examples of the modified product (Y3) include aminocarboxylic acid modified products (terminal amino groups), isocyanate modified products (terminal isocyanate groups), and epoxy modified products (terminal epoxy groups) of (Y1) and (Y2).
The aminocarboxylic acid-modified product can be obtained by reacting (Y1) or (Y2) with aminocarboxylic acid or lactam.
The isocyanate-modified product can be obtained by reacting (Y1) or (Y2) with polyisocyanate or reacting (Y2) with phosgene.
The epoxy-modified product is obtained by reacting (Y1) or (Y2) with a diepoxide (epoxy resin such as glycidyl ether, glycidyl ester and alicyclic diepoxide: epoxy equivalent 85 to 600), or (Y1) and epihalohydrin (epi It can be obtained by reacting with chlorohydrin or the like).

Mn of the polyoxyalkylene chain-containing compound (Y) is 150 to 20,000, more preferably 300 to 10,000, from the viewpoint of the wettability of the molded product described later and the reactivity with the modified polyolefin (X). Particularly preferred is 500 to 5,000.
Of the above (Y1) to (Y3), (Y1) is preferable from an industrial viewpoint.

[Polyoxyalkylene-modified polyolefin (Z)]
The polyoxyalkylene-modified polyolefin (Z) in the present invention is formed from the modified polyolefin (X) and the polyoxyalkylene group-containing compound (Y).
That is, (Z) is one in which (X) and (Y) are preferably bonded by an ester bond, an imide bond, an amide bond, an epoxy ring-opening bond, and more preferably an ester bond.

The weight ratio [(X) / (Y)] of (X) and (Y) in (Z) is 30/70 to 99/1 from the viewpoint of the mechanical strength and wettability of the molded product described later. Preferably they are 50 / 50-95 / 5, Most preferably, it is 70 / 30-90 / 10.
The equivalent ratio [(X) / (Y)] of (X) and (Y) is preferably 1.0 to 2.0, more preferably from the viewpoint of wettability and mechanical strength of the molded product. 1.6-2.0.
The equivalent ratio [(X) / (Y)] can be calculated from the amount of carboxyl groups derived from the dicarboxylic acid (anhydride) possessed by (X) and the amount of reactive functional groups possessed by (Y).
The content of the polyoxyalkylene unit in (Z) is preferably 0.1 to 60% by weight, more preferably 1 to 55% by weight, and particularly preferably 5 from the viewpoints of wettability and mechanical strength of the molded product. ~ 50% by weight.
Further, the Mn (number average molecular weight) of (Z) is preferably 3,000 to 100,000, more preferably 5,000 to 70,000, particularly preferably, from the viewpoint of mechanical strength and moldability of the molded product. Is 10,000 to 50,000.

The polyoxyalkylene-modified polyolefin (Z) can be produced by reacting the modified polyolefin (X) with the polyoxyalkylene chain-containing compound (Y).
As a specific production method of (Z), (1) the dicarboxylic acid (anhydride) of the modified polyolefin (X) is reacted with the hydroxyl group, amino group, and epoxy group of the polyoxyalkylene group-containing compound (Y). A method is included, in which (X) and (Y) are charged into a reaction vessel, and agitated, esterified and imidized at a reaction temperature of 100 to 250 ° C. and a pressure of 0.003 to 0.1 MPa while stirring. Then, a method of reacting for 1 to 50 hours while removing water generated (hereinafter abbreviated as “generated water”) from the reaction system as necessary is mentioned.
In the case of the esterification reaction, it is preferable to use 0.05 to 0.5% by weight of catalyst based on the total weight of (X) and (Y) in order to promote the reaction. Catalysts include inorganic acids (such as sulfuric acid and hydrochloric acid), organic sulfonic acids (such as methane sulfonic acid, paratoluene sulfonic acid, xylene sulfonic acid, and naphthalene sulfonic acid), and organometallic compounds (dibutyltin oxide, tetraisopropoxy titanate, bistrimethyl). Ethanolamine titanate and potassium oxalate titanate). When a catalyst is used, the catalyst can be neutralized as necessary after completion of the esterification reaction 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.
(I) A method in which an organic solvent incompatible with water (for example, toluene, xylene, cyclohexane, etc.) is used to azeotrope the organic solvent and product water under reflux, and only the product water is removed from the reaction system. .
(Ii) A method in which a carrier gas (for example, air, nitrogen, helium, argon, carbon dioxide, etc.) is blown into the reaction system, and the produced water is removed from the reaction system together with the carrier gas.
(Iii) A method of removing the generated water from the reaction system by reducing the pressure in the reaction system.

[Modifier for polyolefin resin (K)]
The polyolefin resin modifier (K) of the present invention is a polyoxyalkylene formed from a polyoxyalkylene group-containing compound (Y) having one functional group reactive with the modified polyolefins (X) and (X). It contains a modified polyolefin (Z).
The modifier (K) of the present invention is used as a modifier for the polyolefin resin (D) described later.

[Polyolefin resin composition]
The polyolefin resin composition of the present invention comprises the modifier (K) and the polyolefin resin (D).
(D) includes a polymerization method exemplified as the production method of (A), or a degradation (thermal, chemical and mechanical degradation) method of a high molecular weight polyolefin (preferably Mn 80,000 to 400,000). For example, an ethylene unit-containing (propylene unit-free) (co) polymer, a propylene unit-containing (ethylene-unit-free) (co) polymer, an ethylene / propylene copolymer, and (Co) polymers of C4 or higher olefins are included.

  As a combination of (D) and (K), the case where the structural unit of (D) and the structural unit of the polyolefin (A) constituting (K) are the same or similar is the case of (D) and (K) It is preferable from the viewpoint of compatibility. For example, when (D) is a propylene unit-containing (ethylene unit-free) (co) polymer, (A) constituting (K) is also a propylene unit-containing (ethylene unit-free) (co) polymer. Some cases are preferred.

  Mn in (D) is preferably 10,000 to 500,000, more preferably 20,000 to 400,000 from the viewpoint of mechanical strength of the polyolefin resin substrate and compatibility with (K).

The polyolefin resin composition of the present invention can further contain various additives (G) as necessary within a range not inhibiting the effects of the present invention.
(G) includes colorant (G1), flame retardant (G2), filler (G3), lubricant (G4), antistatic agent (G5), dispersant (G6), antioxidant (G7), and ultraviolet light. The 1 type (s) or 2 or more types chosen from the group which consists of an absorber (G8) are mentioned.

Examples of the colorant (G1) include pigments and dyes.
Examples of the pigment include inorganic pigments (alumina white, graphite and the like); organic pigments (azo lake type and the like).
Examples of the dye include azo series and anthraquinone series.

  Examples of the flame retardant (G2) include organic flame retardants [nitrogen-containing compounds [salts such as urea compounds and guanidine compounds], sulfur-containing compounds [sulfuric esters, sulfamic acids, and their salts, esters, amides, etc.], silicon-containing compounds Compound [polyorganosiloxane etc.], phosphorus-containing [phosphate ester etc.]]; inorganic flame retardant [antimony trioxide, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, etc.] and the like.

  Fillers (G3) include carbonates (magnesium carbonate, calcium carbonate, etc.), sulfates (aluminum sulfate, etc.), sulfites (calcium sulfite, etc.), metal sulfides (molybdenum disulfide, etc.), silicates (aluminum silicate) Etc.), diatomaceous earth, quartzite powder, talc, silica, zeolite, woody materials (wood flour, etc.) and mixtures thereof.

  Examples of the lubricant (G4) include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), and higher fatty acid amides (such as stearic acid amide).

As the antistatic agent (G5), the following surfactant (G51) and nonionic, cationic, anionic and amphoteric compounds described in US Pat. Nos. 3,929,678 and 4,331,447 are used. These surfactants may be mentioned.
(1) Nonionic surfactant Alkylene oxide (hereinafter abbreviated as AO) addition type nonionics, for example, active hydrogen atom-containing compound having a hydrophobic group (C8-24 or more) [saturated and unsaturated, higher alcohol (C8-18), higher aliphatic amines (C8-24) and higher fatty acids (C8-24) etc.] (poly) oxyalkylene derivatives (higher fatty acid mono- and di-esters of AO adducts and polyalkylene glycols) A (poly) oxyalkylene derivative of a higher fatty acid (C8-24) ester of a polyhydric alcohol (C3-60) (Tween type nonionics, etc.); a (poly) oxyalkylene derivative of a (alkanol) amide of a higher fatty acid (above) A (poly) oxyalkylene of a polyhydric alcohol (above) alkyl (C3-60) ether Derivatives; and polyoxypropylene polyols [polyoxypropylene derivatives of polyhydric alcohols and polyamines (C2-10) (pluronic and tetronic nonionics)]; polyhydric alcohols (above) type nonionics (for example of polyhydric alcohols) Fatty acid esters, polyhydric alcohol alkyl (C3-60) ethers, and fatty acid alkanolamides); and amine oxide type nonionics [eg (hydroxy) alkyl (C10-18) di (hydroxy) alkyl (C1-3) amine oxide ].

(2) Cationic surfactants Quaternary ammonium salt-type cationix [tetraalkyl ammonium salt (C11-100) alkyl (C8-18) trimethylammonium salt and dialkyl (C8-18) dimethylammonium salt etc.]; trialkyl Benzylammonium salt (C17-80) (lauryldimethylbenzylammonium salt etc.); alkyl (C8-60) pyridinium salt (cetylpyridinium salt etc.); (poly) oxyalkylene (C2-4) trialkylammonium salt (C12-100) ) (Polyoxyethylene lauryl dimethyl ammonium salt, etc.); and acyl (C8-18) aminoalkyl (C2-4) or acyl (C8-18) oxyalkyl (C2-4) tri [(hydroxy) alkyl (C1-4 ]] Ammoni Um salts (sapamine type quaternary ammonium salts) [these salts include, for example, halides (chlorides, bromides, etc.), alkyl sulfates (methosulphate, etc.) and organic acids (below); and amine salt types Cationics: 1-3 primary amines [for example, higher aliphatic amines (C12-60), polyoxyalkylene derivatives of aliphatic amines (methylamine, diethylamine, etc.) [ethylene oxide (hereinafter abbreviated as EO) adducts, etc.], and acyl Aminoalkyl or acyloxyalkyl (above) di (hydroxy) alkyl (above) amine (such as stearoyloxyethyl dihydroxyethylamine, stearamide ethyl diethylamine)], inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc.) salt and organic Acid (C2-22) salt.

(3) Anionic surfactant Higher fatty acid (above) salt (such as sodium laurate), ether carboxylic acid [carboxymethylated product of EO (1-10 mol) adduct, etc.], and salts thereof; sulfate salt ( Alkyl and alkyl ether sulfates, etc.), sulfated oils, sulfated fatty acid esters and sulfated olefins; sulfonates [alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfosuccinic acid dialkyl ester types, α-olefins (C12-18) Sulfonates, N-acyl-N-methyl taurine (Igepon T type, etc.)], and phosphate ester salts (alkyl, alkyl ethers, alkylphenyl ether phosphates, etc.)

(4) Amphoteric surfactant:
Carboxylic acid (salt) type amphoterics [amino acid type amphoterics (such as laurylaminopropionic acid (salt)) and betaine type amphoterics (such as alkyldimethylbetaine and alkyldihydroxyethylbetaine)]; sulfuric acid Ester (salt) type amphoterics [sulfuric ester (salt) of laurylamine, hydroxyethyl imidazoline sulfate ester (salt), etc.]; sulfonic acid (salt) type amphoterics [pentadecyl sulfotaurine, imidazoline sulfonic acid ( Salt) etc.], and phosphate ester (salt) type amphoterics etc. [phosphate ester (salt) etc. of glycerol lauryl ester].

  Salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and group IIB metals (zinc, etc.); Ammonium salts; and amine salts and quaternary ammonium salts.

  Examples of the dispersant (G6) include polymers having Mn of 1,000 to 20,000, such as vinyl resin {polyolefin (polyethylene, polypropylene, etc.), modified polyolefin [polyethylene oxide (polyethylene oxide oxidized with ozone, etc., carboxyl group, carbonyl group and And / or those having a hydroxyl group introduced therein), and vinyl resins other than the above polyolefins (polyhalogenated vinyl [polyvinyl chloride, polyvinyl bromide, etc.], polyvinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly (meta ) Acrylic acid, poly (meth) acrylic acid ester [poly (meth) methyl acrylate etc.] and styrene resin [polystyrene, acrylonitrile / styrene (AS) resin etc.] etc .; polyester resin [polyethylene terephthalate etc.], polyamid Examples include resins [6,6-nylon, 12-nylon, etc.], polyether resins [polyethersulfone, etc.], polycarbonate resins [polycondensates of bisphenol A and phosgene, etc.], and block copolymers thereof. .

  Antioxidants (G7) include hindered phenol compounds [pt-amylphenol-formaldehyde resin, nordihydroguaiaretic acid (NDGA), 2,6-di-tert-butyl-4-methylphenol (BHT). ), 2-t-butyl-4-methylphenol (BHA), 6-t-butyl-2,4, -methylphenol (24M6B), 2,6-di-t-butylphenol (26B) and the like];

  Sulfur-containing compounds [N, N'-diphenylthiourea, dimyristylthiodipropionate, etc.];

  Phosphorus-containing compound [2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, dioctadecyl-4-hydroxy-3,5-di- t-butylbenzylphosphonate and the like] and the like.

  Examples of the ultraviolet absorber (G8) include salicylate compounds [phenyl salicylate and the like]; benzophenone compounds [2,4-dihydroxyzenzophenone and the like]; benzotriazole compounds [2- (2′-hydroxy-5′-methylphenyl). ) -Benzotriazole and the like].

The total content of (G) in the polyolefin resin composition is usually 20% or less based on the total weight of the composition, preferably 0.05 to 10 from the viewpoint of functional expression of each (G) and an industrial viewpoint. %, More preferably 0.1 to 5%.
The amount of each additive used based on the total weight of the composition is as follows: (G1) is usually 5% or less, preferably 0.1 to 3%; (G2) is usually 8% or less, preferably 1 to 3%; (G3) is usually 5% or less, preferably 0.1 to 1%; (G4) is usually 8% or less, preferably 1 to 5%; (G5) is usually 8% or less, preferably 1 to 3%; (G6) is usually 1% or less, preferably 0.1 to 0.5%; (G7) is usually 2% or less, preferably 0.05 to 0.5%; (G8) is usually 2% or less, preferably Is 0.05 to 0.5%.

  When the additive is the same and overlaps between the above (G1) to (G8), the amount of each additive having the corresponding additive effect is not used as it is, but the effect as the other additive is simultaneously achieved. Considering what is obtained, the usage amount is adjusted according to the purpose of use.

As a production method of the polyolefin resin composition of the present invention,
(1) A method (collective method) in which (D), (K) and, if necessary, (G) are mixed at once to obtain a polyolefin resin composition;
(2) A masterbatch polyolefin resin composition containing a high concentration of (K) is prepared by mixing a part of (D), the total amount of (K), and if necessary, a part or all of (G). Then, a method (masterbatch method) in which the remaining (D) and, if necessary, the remaining (G) are added and mixed to obtain a polyolefin resin composition is included.
The method (2) is preferable from the viewpoint of the mixing efficiency of (K).

The weight ratio [(K) / (D)] of (K) and (D) in the polyolefin resin composition of the present invention is preferably 1/2 from the viewpoint of wettability to water and mechanical strength of a molded product described later. 99-40 / 60, more preferably 2 / 98-30 / 70, particularly preferably 5 / 95-25 / 75, most preferably 10 / 90-20 / 80.
Moreover, the modification | reformation effect can be heightened more by adding the said surfactant (G51) to the polyolefin resin composition of this invention. Of these (G51), from the viewpoint of the modification effect, nonionic surfactants are preferred, (Y) is more preferred, and (Y1) is particularly preferred.
The amount of (G51) based on the total weight of the composition is preferably 0.5 to 5%, more preferably 1 based on the weight of (Z), from the viewpoint of the modification properties and the mechanical strength of the molded product. ~ 3%.

As a specific mixing method in the manufacturing method of the polyolefin resin composition, (i) each component to be mixed is, for example, a powder mixer [“Henschel mixer” [trade name “Henschel mixer FM150L / B”, Mitsui Mining] Manufactured by Co., Ltd.], “Nauter Mixer” [trade name “Nauter Mixer DBX3000RX”, manufactured by Hosokawa Micron Co., Ltd.], “Banbury Mixer” [trade name “MIXTRON BB-16MIXER”, manufactured by Kobe Steel Co., Ltd.], etc. ] And then kneading usually at 120 to 220 ° C. for 2 to 30 minutes using a melt kneader [batch kneader, continuous kneader (single screw kneader, biaxial kneader, etc.), etc.];
(Ii) A method of directly kneading the components to be mixed under the same conditions using the same melt-kneading apparatus as described above without mixing powders in advance.
Among these methods, the method (i) is preferable from the viewpoint of mixing efficiency.

The modifier (K) of the present invention or the polyolefin resin composition containing the (K) has a polarity such as a low-polarity plastic such as polyolefin and a polyurethane because (K) has the carboxyl group and the like. It also has a feature that it has excellent affinity for any of the high plastics.
Therefore, in the adhesion between plastics having different polarities (such as when one is a base material and the other is a paint), the modifier (K) of the present invention, or the polyolefin resin composition containing the (K), It can also be applied for use as a primer for plastic molded products.

[Molded articles and molded articles]
The molded product of the present invention is formed by molding the polyolefin resin composition.
Examples of molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), etc., depending on the purpose. Molding, multilayer molding, foam molding and the like can be performed by any method that incorporates means. Examples of the form of the molded product include a plate shape, a sheet shape, a film, and a fiber (including a nonwoven fabric).
Since the molded article of the present invention contains the modifier (K) having the polyoxyalkylene group or the like, it has excellent wettability with water, and has a relatively high polarity paint, ink, etc. as described later. Excellent affinity.

The molded article of the present invention has excellent mechanical strength and good paintability and printability, and a molded article can be obtained by coating and / or printing the molded article.
Examples of the method for coating the molded product include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating.
Examples of the paint include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, acrylic urethane resin paint, and these so-called relatively high-polarity paints, Further, paints with low polarity (such as olefins) can also be used.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm.

Further, as a method for further printing after coating the molded product or the molded product, any printing method generally used for plastic printing can be used. For example, gravure printing, flexographic printing, Examples include printing, screen printing, pad printing, dry offset printing, and offset printing.
As the printing ink, those usually used for printing plastics, for example, gravure ink, flexographic ink, screen ink, pad ink, dry offset ink and offset ink can be used.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the examples, “part” means “part by weight” and “%” other than mol% means “% by weight”. Hereinafter, Examples 4 to 6, 10 to 13, 16, and 18 to 19 are referred to as Reference Examples 1 to 10, respectively.

[Polyolefin (A)]
Production Example 1
Polyolefin (A0-1) having a structural unit of 98 mol% propylene and 2 mol% ethylene in a reaction vessel [trade name “Sun Allomer PZA20A”, manufactured by Sun Allomer Co., Ltd., Mn 100,000, molecules per 1,000 carbons The number of double bonds in the terminal and / or molecular chain is 0, and so on. 100 parts were charged in a nitrogen atmosphere, heated and melted with a mantle heater while nitrogen was passed through the gas phase portion, and subjected to heat degradation at 360 ° C. for 70 minutes while stirring to obtain polyolefin (A-1). . In (A-1), the number of double bonds in the molecular ends and / or molecular chains per 1,000 carbon atoms was 6.8, and Mn was 4,000.

Production Examples 2-6
Except having performed thermal degradation according to Table 1 in the manufacture example 1, it carried out similarly to the manufacture example 1 and obtained polyolefin (A-2)-(A-6). The results are shown in Table 1.

[Modified polyolefin (X)]
Production Example 7
A reaction vessel was charged with 100 parts of (A-1), 11 parts of maleic anhydride (B-1), and 100 parts of xylene, and after purging with nitrogen, it was heated to 140 ° C. under nitrogen flow and dissolved uniformly. . A solution prepared by dissolving 2.0 parts of dicumyl peroxide [trade name “Park Mill D”, manufactured by NOF Corporation] (C-1) in 10 parts of xylene was added dropwise over 10 minutes, and then refluxed with xylene. Stirring was continued for 3 hours. Thereafter, xylene and unreacted maleic anhydride were distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter) to obtain a modified polyolefin (X-1). (X-1) had an acid value of 52 and Mn of 7,000.

Production Examples 8-12
In Production Example 7, modified polyolefins (X-2) to (X-6) were obtained in the same manner as in Production Example 7 except that each used raw material was used according to Table 2. The results are shown in Table 2.

[Polyoxyalkylene chain-containing compound (Y)]
Production Example 13
A glass autoclave was charged with 268 parts of oleyl alcohol and 1 part of lithium hydroxide monohydrate, and after nitrogen substitution, the temperature was raised to 110 ° C. Thereafter, 440 parts of EO was dropped for 24 hours in the range of 70 to 90 ° C. and a reaction pressure of 0.2 MPa or less to obtain a polyoxyalkylene chain-containing compound (Y-1). In (Y-1), Mn was 600.

Production Example 14
In Production Example 13, a polyoxyalkylene chain-containing compound (Y-2) was obtained in the same manner as in Production Example 13 except that EO 880 parts was used instead of EO 440 parts. In (Y-2), Mn was 1,000.

Production Example 15
In Production Example 13, a polyoxyalkylene chain-containing compound (Y-3) was obtained in the same manner as in Production Example 13, except that 32 parts of methanol was used instead of 268 parts of oleyl alcohol. In (Y-3), Mn was 450.

Production Example 16
In Production Example 13, a polyoxyalkylene chain-containing compound (Y-4) was obtained in the same manner as in Production Example 13 except that 268 parts of oleyl alcohol and 358 parts of pentacontanol and 580 parts of PO were used instead of 440 parts of EO. . In (Y-4), Mn was 900.

Production Example 17
In Production Example 13, a polyoxyalkylene chain-containing compound (Y-5) was obtained in the same manner as in Production Example 13, except that EO 220 parts and PO 290 parts were used instead of EO 440 parts. In (Y-5), Mn was 750.

Production Example 18
In Production Example 13, a polyoxyalkylene chain compound (Y-6) was obtained in the same manner as in Production Example 13, except that EO 2200 parts were used instead of EO 440 parts. In (Y-6), Mn was 2400.

Production Example 19
In a reaction vessel, 100 parts of (Y-1), 100 parts of toluene, 0.5 part of potassium hydroxide, and 2 parts of water were charged. After purging with nitrogen, the temperature was raised to 30 ° C. under nitrogen flow and 60 parts of acrylonitrile was added. After dropwise addition in minutes, stirring was continued for 2 hours. Thereafter, toluene and unreacted acrylonitrile were distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter), and then 100 parts of methanol, 2 parts of ammonia, and 0.01 part of Raney nickel were charged at 20 ° C. under 1.5 MPa. Hydrogen gas was added and hydrogenation reaction was performed for 24 hours to obtain a polyoxyalkylene chain-containing compound (Y-7). In (Y-7), Mn was 650.

Production Example 21
In Production Example 19, (Y-1) 100 parts, instead of acrylonitrile 8 parts, except that (Y-3) 100 parts, acrylonitrile 10 parts were used. Compound (Y-8) was obtained. In (Y-8), Mn was 500.

Production Example 22
In Production Example 19, (Y-1) 100 parts, instead of acrylonitrile 8 parts, except that (Y-4) 100 parts, acrylonitrile 6 parts were used, the same as Production Example 19, and containing polyoxyalkylene chain Compound (Y-9) was obtained. In (Y-9), Mn was 950.

Production Example 23
In Production Example 19, in the same manner as in Production Example 19 except that (Y-5) 100 parts and acrylonitrile 8 parts were used instead of (Y-1) 100 parts and acrylonitrile 8 parts, containing polyoxyalkylene chain Compound (Y-10) was obtained. In (Y-10), Mn was 800.

Production Example 24
In Production Example 19, (Y-1) 100 parts, instead of acrylonitrile 8 parts, except that (Y-6) 100 parts, acrylonitrile 2 parts were used. Compound (Y-11) was obtained. In (Y-11), Mn was 2,450.

Production Example 25
In Production Example 13, a polyoxyalkylene chain-containing compound (Y-12) was obtained in the same manner as in Production Example 13, except that 220 parts of nonylphenol was used instead of 268 parts of oleyl alcohol. In (Y-12), Mn was 550.

Production Example 26
In Production Example 13, a polyoxyalkylene chain-containing compound (Y-13) was obtained in the same manner as in Production Example 13, except that 268 parts of oleyl alcohol was used and 58 parts of isopropenyl alcohol was used. In (Y-13), Mn was 400.

Production Example 27
In Production Example 13, a polyoxyalkylene chain-containing compound (Y-14) was obtained in the same manner as in Production Example 13, except that 45 parts of dimethylamine was used instead of 268 parts of oleyl alcohol. In (Y-14), Mn was 400.

Production Example 28
A reaction vessel was charged with 100 parts of (Y-1) and 35 parts of 12-aminododecanoic acid, and after substitution with nitrogen, a dehydration condensation reaction was carried out at 200 ° C. for 3 hours under reduced pressure to obtain a polyoxyalkylene chain-containing compound (Y-15). Got. In (Y-15), Mn was 850.

Production Example 29
In a reaction vessel, 100 parts of (Y-1) and 28 parts of hexamethylene diisocyanate were charged. After purging with nitrogen, the mixture was heated to 70 ° C. under nitrogen flow and stirred for 6 hours to give a polyoxyalkylene chain-containing compound (Y— 16) was obtained. In (Y-16), Mn was 800.

Production Example 30
In a reaction vessel, 100 parts of (Y-1) and 50 parts of 50 wt% aqueous sodium hydroxide solution were charged. After purging with nitrogen, the temperature was adjusted to 25 ° C. under nitrogen flow, and 17 parts of epichlorohydrin was added dropwise for 3 hours. Stir for hours. Then, extraction was performed using 1000 parts of toluene, and after toluene was distilled off under reduced pressure, a polyoxyalkylene chain-containing compound (Y-17) was obtained. In (Y-17), Mn was 660.

Production Example 31
In Production Example 13, a polyoxyalkylene chain-containing compound (Y-18) was obtained in the same manner as in Production Example 13, except that EO 6600 parts were used instead of EO 440 parts. In (Y-18), Mn was 6,500.

Comparative production example 1
In Production Example 13, a polyoxyalkylene chain-containing compound (RY-1) was obtained in the same manner as in Production Example 13, except that 58 parts of ethylene glycol was used instead of 268 parts of oleyl alcohol. In (RY-1), Mn was 400.

Comparative production example 2
In Production Example 13, a polyoxyalkylene chain-containing compound (RY-2) was obtained in the same manner as in Production Example 13, except that 92 parts of glycerin was used instead of 268 parts of oleyl alcohol. In (RY-2), Mn was 450.

[Polyoxyalkylene-modified polyolefin (Z)]
Example 1
The reaction vessel was charged with 100 parts of (X-1) and 90 parts of (Y-1), and after nitrogen substitution, heated to 180 ° C. under nitrogen flow to dissolve uniformly, and then under reduced pressure (1.5 kPa) The same applies to the following), and the reaction was carried out for 5 hours while distilling off the generated water to obtain a polyolefin resin modifier (K-1) containing the polyoxyalkylene-modified polyolefin (Z-1). In (Z-1), Mn was 17,000.

Examples 2-19, Comparative Examples 1-4
In Example 1, according to Table 3, except using each use raw material, it carries out similarly to Example 1, and the modifier for polyolefin resins (K-2)-(K-19), (RK-1)- (RK-4) was obtained. The results are shown in Table 3.

[Polyolefin resin composition, molded product]
Examples 20-47, Comparative Examples 5-14
Modifiers (K-1) to (K-19), (RK-1) to (RK-4), thermal degradation product (A-1), modified polyolefin (X-1), polyoxyalkylene chain Containing compound (Y-1), commercially available polypropylene (D-1) [trade name “Sun Allomer PL500A”, manufactured by Sun Allomer Co., Ltd.], commercially available polyethylene (D-2) [trade name “Novatech HJ490”, Nippon Polyethylene ( Co., Ltd., Mn 300,000] and commercially available ethylene / propylene copolymer (D-3) [trade name “Sun Allomer PB222A”, Sun Allomer Co., Ltd., Mn 350,000], Table 4 In accordance with the above, each blended for 3 minutes with a Henschel mixer, then melt-kneaded in a twin-screw extruder with a vent at 180 ° C., 100 rpm, residence time 5 minutes. To obtain a resin composition.
Each resin composition was molded at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. using an injection molding machine [trade name “PS40E5ASE”, Nissei Plastic Industry Co., Ltd.], and a predetermined test piece was prepared. Evaluation was made according to the method. The results are shown in Table 4.

<Evaluation method>
1. Impact resistance (Unit: J / m ² )
Izod impact values were measured according to ASTM D256.
2. Tensile modulus (unit: MPa)
The measurement was performed according to JIS K7161.
3. Wettability (Unit: °)
The water contact angle was measured according to JIS R2357 for evaluation of wettability. A smaller water contact angle indicates better wettability.
4). Persistence of wettability (unit: °)
The film was immersed in water and the surface was washed with a cotton cloth, and then dried under reduced pressure (1 kPa, 80 ° C., 1 hour). This test piece was temperature-controlled (23 ° C., 50 RH%, 24 hours), and the above 3. Similarly, the water contact angle was measured.

From the results of Table 4, the polyolefin resin modifier (K) of the present invention imparts wettability to water without impairing the mechanical strength of the molded article of the polyolefin resin composition, as compared with the comparative one.
In addition, it is clear that the polyolefin resin composition is excellent in moldability and superior in mechanical strength, wettability to water, and sustainability as compared with the comparative one.

  The modifier (K) comprising the polyoxyalkylene-modified polyolefin (Z) of the present invention is excellent in imparting wettability to water without lowering the mechanical strength of the molded article, and the modifier Molded products made by molding polyolefin resin compositions containing (K) have a good balance between wettability and mechanical strength, so they are used for electrical and electronic equipment, packaging materials, transport materials, and household materials. It can be suitably applied to a wide range of fields such as for building materials.

Claims (14)

A polyolefin (A) having 0.1 to 20 double bonds per 1,000 carbon atoms and being an ethylene / propylene copolymer [weight ratio: 0.5 / 99.5 to 30/70] and It is formed from a modified polyolefin (X) having an unsaturated dicarboxylic acid (anhydride) (B) as a structural unit and a polyoxyalkylene chain-containing compound (Y) having one functional group reactive with the (X). A polyolefin resin modifier (K) comprising the polyoxyalkylene-modified polyolefin (Z). The modifier according to claim 1 , wherein (A) is a heat-degraded polyolefin having a number average molecular weight of 30,000 to 400,000. The modifier for polyolefin resin according to claim 1 or 2, wherein Mn (number average molecular weight) of (Z) is 3,000 to 100,000.   The modifier according to any one of claims 1 to 3, wherein the reactive functional group possessed by (Y) is at least one selected from the group consisting of a hydroxyl group, an amino group, and an epoxy group.   (X) and (Y) are bonded via at least one bond selected from the group consisting of an ester bond, an imide bond, an amide bond, and an epoxy ring-opening bond. The modifier described.   The weight ratio [(X) / (Y)] of (X) and (Y) is 30/70 to 99/1, The modifier according to any one of claims 1 to 5.   The modifier according to any one of claims 1 to 6, wherein the polyoxyalkylene unit content in (Z) is 0.1 to 60% by weight.   The modifier according to any one of claims 1 to 7, wherein (Y) is an alkylene oxide adduct of a compound having one active hydrogen.   The modifier according to claim 8, wherein the alkylene oxide addition mole number of (Y) is 3-18.   A polyolefin resin composition comprising the modifier (K) according to any one of claims 1 to 9 and a polyolefin resin (D).   The composition according to claim 10, wherein the weight ratio [(K) / (D)] of (K) to (D) is from 1/99 to 60/40.   The composition according to claim 11 or 12, further comprising a surfactant (G51).   A molded article formed by molding the composition according to claim 10. A molded article obtained by coating and / or printing the molded article according to claim 13.