JP2007084688A - Coatability-improving agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coatability-improving agent which can improve the coatability of a resin in a small amount without deteriorating the physical properties of the resin, because a conventional known method for kneading a large amount of a modified polyolefin prepared by grafting polar functional groups to a polyolefin to improve the coatability (adhesiveness of coated films, or the like) of the polypropylene resin has problems such as the large deterioration of mechanical properties such as impact strength. <P>SOLUTION: This coatability-improving agent comprises a modified polyolefin which has a hydrophobic group comprising a polyolefin having a number-average mol. wt. of 1,500 to 100,000 and a hydrophilic group containing at least one amino group, and has a number-average mol. wt. of 400 to 50,000 per amino group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a paint improver. More specifically, the present invention relates to a paint improver that improves the adhesion of a coating film to a resin such as polyolefin.

Polypropylene is widely used as an injection molding material in the industrial parts field represented by automobile interior and exterior parts and home appliance parts. However, since polypropylene is nonpolar, it is usually inferior in paintability (here, paintability includes printability; the same shall apply hereinafter) and a paint film (here, the paint film includes a print film). (The same shall apply hereinafter.) For this reason, the primer is apply | coated to the surface of a polypropylene and the device which makes a coating film contact | adhere is made | formed. However, since the primer is expensive and the number of painting steps increases, there is a drawback that the painting cost is increased. For this reason, attempts have been made to reduce the coating cost by providing the coating film adhesion to polypropylene, omitting the primer coating step. For example, a method is known in which a modified polyolefin in which a polar functional group is grafted on a polyolefin is kneaded into polypropylene as a coating property improving agent, and a coating film is adhered without applying a primer (for example, see Patent Document 1). . In addition, for the purpose of improving the dyeability or impact resistance of polypropylene, a method is known in which a diamine compound reacted with maleic anhydride-modified polypropylene is added to polypropylene (see, for example, Patent Document 2).
Japanese Patent Laid-Open No. 9-048885 Japanese National Patent Publication No. 11-501069

However, in these methods, a large amount of modified polyolefin has to be added in order to adhere the coating film with a low concentration of polar functional groups, and mechanical properties such as impact strength are greatly reduced accordingly. Further, in the matrix of the polypropylene base resin, the polar functional groups are cross-linked to form a lump so that a sufficient effect of improving the paintability cannot be obtained.
The object of the present invention is to improve the paintability of a resin (coating adhesion, etc., the same shall apply hereinafter) without reducing the mechanical properties of the resin with a small amount of addition. It is providing the polyolefin resin composition made to contain in resin.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention has a hydrophobic group comprising a polyolefin (a) having a number average molecular weight of 1,500 to 100,000, a hydrophilic group containing at least one amino group (b), and (b) per one A coating property improver (A) comprising a modified polyolefin having a number average molecular weight of 400 to 50,000; a polyolefin resin composition comprising (A) in the polyolefin resin (B); and the composition. It is a molded product formed by molding.

[Polyolefin (a)]
The polyolefin (a) in the present invention includes one or more (co) polymers of olefins and copolymers of one or more olefins and one or more other monomers. In the following,% and ratio represent weight% and weight ratio, respectively, unless otherwise specified.
Examples of the olefin include alkenes having 2 to 30 carbon atoms (hereinafter abbreviated as C) (preferably 2 to 12, more preferably 2 to 4) such as ethylene, propylene, 1-, 2- and isobutene, and C5 30 α-olefins (1-hexene, 4-methylpentene-1,1-decene, 1-dodecene, etc.); other monomers include unsaturated monomers copolymerizable with olefins such as styrene, Vinyl acetate, (meth) acrylic acid and its alkyl (C1-30) esters are included.

Specific examples of (a) include ethylene polymers such as high density, medium density and low density polyethylene, ethylene and C4-30 unsaturated monomers [butene (1-butene, etc.), C5-30 α. -Copolymers with olefins (1-hexene, 1-dodecene, etc.), vinyl acetate, (meth) acrylic acid, etc.] [copolymerization ratio (weight ratio) 30/70 to 99/1, preferably 50/50 to 95/5] etc .; propylene polymers such as polypropylene, copolymers of propylene and C4-30 unsaturated monomers (same as above) [copolymerization ratio (weight ratio), same as above]; ethylene / propylene copolymer Copolymer [copolymerization ratio (weight ratio) 0.5 / 99.5 to 30/70, preferably 2/98 to 20/80]; C4 or higher olefin polymer, such as polybutene, poly-4-methylpentene 1 is included.
Among these, polyethylene, ethylene / propylene copolymer, propylene / unsaturated monomer (C4-20) copolymer, and particularly preferably polypropylene are preferable from the viewpoint of dispersibility in the polyolefin resin described later. .

Number average molecular weight of (a) [hereinafter abbreviated as Mn. It is the value measured by GPC method using high temperature GPC {made by Waters Co., Ltd., column: PLgel MIX ED-B, polymer Laboratories Co., Ltd.}. ] Has a lower limit of 1,500, preferably 2,000, more preferably 2,500, and an upper limit of 100,000, preferably 50,000, more preferably 15,000. When Mn is less than 1,500, the mechanical strength of a molded product described later deteriorates. When Mn exceeds 100,000, the adhesion of the coating film to the molded product deteriorates.

From the viewpoint of ease of modification in (a), the lower limit of the amount of double bonds per 1,000 carbon atoms in the molecular end and / or molecule of (a) is preferably 0.2, and more preferably 0. .3, particularly preferably 0.5, and the upper limit is preferably 10 from the industrial viewpoint, more preferably 6, and particularly preferably 5.

(A) includes a polyolefin produced by a polymerization method and a degraded polyolefin [a product obtained by mechanically, thermally and chemically degrading a high molecular weight polyolefin (preferably Mn 50,000 to 300,000)]. included. From the viewpoint of paintability, preferred is a degraded polyolefin, and more preferred is a thermally degraded polyolefin. The heat-degraded polyolefin is not particularly limited, but is heat-degraded by heating a high molecular weight polyolefin in an inert gas (usually at 300 to 450 ° C. for 0.5 to 10 hours) (for example, JP-A-3 -62804).

(A) is usually carboxy-modified in advance for constituting the hydrophobic group of the coating property improving agent (A) of the present invention, and the residue of the carboxy-modified polyolefin (ax) [part excluding the carboxyl group from (ax) ] Constitutes a hydrophobic group. The (ax) includes a polyolefin (ax1) obtained by carboxy-modifying (a) with an α, β-unsaturated carboxylic acid (anhydride) (m1) described later, and (ax1) further a carboxy-modifying agent. Polyolefin (ax2) modified by (m2) (secondary modification) and a mixture of two or more of these are included.

(Ax1) includes (i): a modified product obtained by reacting (a) with (m1), and (ii): a carboxyl group obtained by oxidizing (a) with an oxidizing agent (for example, oxygen and / or ozone). Is included.
The α, β-unsaturated carboxylic acid (anhydride) (m1) includes unsaturated mono- and dicarboxylic acids, and anhydrides thereof.
Unsaturated monocarboxylic acids include C3-18 (preferably 3-15, especially 3-10) aliphatic, alicyclic and aromatic monocarboxylic acids such as (meth) acrylic acid, (iso) crotonic acid , Cyclohexene monocarboxylic acid, cinnamic acid and the like.
Dicarboxylic acids (anhydrides) include aliphatic ones (C4-18, preferably C4-15, particularly preferably C4-12), such as (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, (anhydrous) Citraconic acid, mesaconic acid, allylmalonic acid, etc .; alicyclic ones (C7-24, preferably C8-16), such as 4-cyclohexene-1,2-dicarboxylic acid, etc .; those containing aromatic rings (C8-24, Preferably C8-16), for example phenylmaleic acid and the like are included. From the viewpoint of compatibility with (a) and reactivity, an anhydride of unsaturated dicarboxylic acid (especially aliphatic dicarboxylic acid), particularly maleic anhydride (hereinafter abbreviated as MA), is preferable.
The amount of (m1) used for modification is usually 0.5 to 40% based on the weight of (a), and preferably 1 to 30% from the viewpoint of the coating properties described later and the reactivity with (a).

The modification method and conditions are not particularly limited, but (m1) can be thermally added to the double bond contained in (a) by a melting method or a solution method. For example, (1) a method in which (m1) is mixed with (a) in a molten state and then, if necessary, in the presence of an organic peroxide, (2) after mixing (a), (m1) and a solvent If necessary, a method of heating in the presence of an organic peroxide and a method of adding the organic peroxide during (3) (a) and (m1) heating and kneading with a twin screw extruder may be mentioned.

Examples of the organic peroxide used in the above methods (1) to (3) include dicumyl peroxide, di-t-butyl peroxide, etc., and the amounts used thereof are those of (a) and (m1). It is usually 0.1 to 10% based on the total weight, and preferably 0.5 to 5% from the viewpoint of the added efficiency of (m1).
The reaction temperature can be varied within a wide range (for example, 80 to 260 ° C.) and is appropriately selected depending on the method. In the method (1), the reaction temperature is usually 100 to 220 ° C., preferably 140 to 200 ° C., and the method (2) is usually 80. It is -180 degreeC, Preferably it is 110-150 degreeC, and is 80-260 degreeC normally in a method (3), Preferably it is 120-240 degreeC, More preferably, it is 140-220 degreeC. Examples of the solvent in the method (2) include toluene and xylene.
Among these methods, the method (2) is preferable from the viewpoint that a uniform reaction is possible with few by-products. The introduction of the carboxyl group by oxidation can be carried out, for example, by the method described in US Pat. No. 3,692,877.

The carboxy modifier (m2) used for the production of (ax2) includes (m20) a precursor of (m21) described later [compound capable of forming (m21), the same applies hereinafter] lactam and lactone, (m21) aminocarboxylic A combination of an acid and a hydroxycarboxylic acid, a (m22) carboxy-reactive coupling agent and a polycarboxylic acid (referring to an acid or an ester-forming derivative thereof, the same applies hereinafter), and combinations of two or more thereof are included. The secondary modification of (ax1) can be performed by ring-opening addition (polymerization) of (m20), (poly) condensation of (m21), or a coupling reaction of (m22).

Examples of the aminocarboxylic acid of (m21) include those having C2-12, such as amino acids [glycine, alanine, valine, (iso) leucine, phenylalanine, etc.], ω-aminoalkanoic acids (for example, ω-aminocaprone, ω-aminoenanthate, ω-aminocapryl, ω-aminopergon, ω-aminocaprin, 11-aminoundecane, 12-aminododecanoic acid, etc.), aromatic aminocarboxylic acids (eg, o-, m- and p-aminobenzoic acid, etc.) Being;
(M20) lactams include those of C4-15 (preferably 6-12), such as caprolactam, enantolactam, laurolactam, undecanolactam, etc .; for lactones and hydroxycarboxylic acids, the above lactams and aminocarboxylic acids Corresponding (NH substituted with O) (for example, ε-caprolactone, γ-butyrolactone, γ-valerolactone, ω-hydroxycaproic acid, salicylic acid, p- and m-hydroxybenzoic acid, etc.), glycolic acid, glycerin Acids, tartronic acid, malic acid, tartaric acid, benzylic acid and the like are included. Preference is given to caprolactam and 12-aminododecanoic acid.
The amount of (m20) or (m21) is 1 to 10 moles or more, preferably 1 to 2 moles per unsaturated dicarboxylic acid (anhydride) group or carboxyl group of (ax1).

The carboxy-reactive coupling agent (m22) includes compounds having two or more carboxyl groups reactive with polycarboxylic acids, such as polyols, organic polyisocyanates (hereinafter abbreviated as PI), polyamines (hereinafter referred to as PI). Abbreviated PA), polyepoxides and epoxy alcohols. These polycarboxylic acids, polyol, PI, PA and polyepoxide include those described later, and epoxy alcohol includes glycidol and the like.

(Ax2) has a structure in which at least a part of the carboxyl group (carboxylic acid group or carboxylic anhydride group, hereinafter the same) in (ax1) is converted into, for example, a carboxy-containing group represented by the following general formula.
-E- (GLE) _n -GLE-OH
^{_{(-E-) p G-L 3}} [-G- (E-L 1 -E-G-L 2 -G) n -E-L 1 -E-OH] f
(-E-) _p GL ³ [-GE- (LG) _n -L ^1- (EGL) _n -E-OH] _f

In the formula, E is —CO— (carbonyl group); n is an integer of 0 or 1 or more (preferably 1 to 9 or more); L is a residue of aminocarboxylic acid or hydroxycarboxylic acid (amino group or hydroxyl group) Groups and carboxyl groups are removed), or lactam or lactone residues (amide or ester bonds are removed); L ¹ is a polycarboxylic acid residue (two carboxyl groups are removed); ² is a residue of diamine or diol (amino group or hydroxyl group is removed); f is 0 or an integer of 1 or more; L ³ is a residue of (1 + f) -valent PA, polyol or PI (amino group, Hydroxyl group or isocyanate group is removed), or epoxy ring-opening group (group formed by ring-opening of epoxide); p is 1 or 2; G is − - (L residues of hydroxy carboxylic acids or lactones, residues of L ² is a diol, when L ³ is residues or epoxy ring opening group of the polyol) or -NH- (L is an amino carboxylic acid or lactam residues Group, when L ² is a residue of diamine and L ³ is a residue of PA or PI) [when L ³ is a residue of PA and p is 2, G attached to p is> N -] [ie _(-E-) p G-represents an ester bond, an amide bond or imide bond. In the above and the following, each symbol in the case where there are a plurality thereof may be the same or different.
Epoxy ring opening groups are represented by —CH ₂ —CH (OH) —CH ₂ —, and polyepoxy ring opening groups such as the formula —CR ⁴ —CR ⁵ —J— (CR ⁵ —CR ⁴ —) _f. Wherein J is the residue of the polyepoxide (excluding the epoxy group); one of R ⁴ and R ⁵ (eg R ⁵ ) is OH and the other (eg R ⁴ ) is H Or they (for example, two R ^{4 s} ) may be bonded to each other or J to form a ring (when J is a residue of an alicyclic polyepoxide)].
Among the carboxy-modified polyolefins (ax), preferred are (ax1), particularly those modified with an unsaturated dicarboxylic acid (anhydride).

The degree of carboxy modification of (ax) is not particularly limited, but the acid value of (ax) is preferably 2 to 100 (mg KOH / g, the same applies hereinafter), more preferably, from the viewpoint of paintability and industrial viewpoint. 8 to 90, particularly preferably 15 to 70.

The polyol of (m22) is a divalent to octavalent or higher polymer polyol (having an OH equivalent of 250 or more), a low molecular polyol (having an OH equivalent of less than 250), and two of these A mixture of the above is included. The OH equivalent means the molecular weight per OH based on the OH value. Examples of the low molecular polyol include polyhydric alcohol, low molecular OH-terminated polymer [polyether polyol (hereinafter abbreviated as PT polyol), polyester polyol (hereinafter abbreviated as PS polyol) and the like] and the like.

The polyhydric alcohol includes the following.
Dihydric alcohols (C2-20 or higher), for example C2-12 aliphatic dihydric alcohols [(di) alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,3 -, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentanediol (hereinafter referred to as EG, DEG, PG, DPG, BD, HD, NPG and MPD, respectively) Abbreviation), dodecanediol, etc.], C6-10 alicyclic dihydric alcohol [1,4-cyclohexanediol, cyclohexanedimethanol, etc.], C8-20 araliphatic dihydric alcohol [xylylene glycol, bis (hydroxy Ethyl) benzene etc.] etc .;

Trihydric to octahydric or higher polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol, dipentaerythritol (hereinafter referred to as GR, respectively) Abbreviated as TMP, PE, SO and DPE), 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins, etc.], sugars and derivatives thereof such as sucrose, glucose, Fructose, mannose, lactose, glucoside (methyl glucoside, etc.)], nitrogen-containing polyol (tertiary amino group-containing polyol and quaternary ammonium group-containing polyol): for example nitrogen-containing diol, for example C ~ 12 aliphatic, cycloaliphatic and aromatic primary monoamines [methylamine, ethylamine, 1- and 2-propylamine, (iso) amylamine, hexylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine , 1-, 2- and 3-aminoheptane, nonylamine, decylamine, undecylamine, dodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, aniline, benzylamine and the like] [bishydroxyalkyl (C2-4) compound [ Bis (2-hydroxyethyl) compounds, bis (hydroxypropyl) compounds and the like, for example, tertiary nitrogen atom-containing polyols described in US Pat. No. 4,271,217], and quaternized products thereof [US Patents mentioned above] The quaternizing agent or dialkyl catalyst described in the specification Quaternized product by bonate (dimethyl carbonate or the like)], for example, quaternary nitrogen atom-containing polyol described in the above-mentioned US patent specification; trivalent to octavalent or higher nitrogen-containing polyol, for example, trialkanol (C2-4) amine (Triethanolamine etc.) and C2-12 aliphatic, cycloaliphatic, aromatic and heterocyclic PA [described later, eg ethylenediamine, tolylenediamine, aminoethylpiperazine etc.] polyhydroxyalkyl (C2-4) [Poly (2-hydroxyethyl) chloride, bis (hydroxypropyl) chloride, etc .: tetrakis (2-hydroxypropyl) ethylenediamine and pentakis (2-hydroxypropyl) diethylenetriamine], and quaternized compounds similar to those described above.

The low molecular OH-terminated polymer includes PT polyol, PS polyol and polyurethane (hereinafter abbreviated as PU) polyol [reaction product of PI and excess (1 mol per isocyanate group) polyhydric alcohol] as described below. And having an OH equivalent weight of less than 250. For example, a low-polymerization alkylene oxide (hereinafter abbreviated as AO) ring-opening polymer and a low-mol AO adduct of an active hydrogen atom-containing polyfunctional compound [for example, polyethylene glycol (PEG), polypropylene glycol (PPG), polytetra Methylene ether glycol (PTMG) and the like, EO (2-4 mol adducts of bis (hydroxyethoxy) benzene and bisphenol A), low-condensation condensed PS polyols and low-mol lactone adducts of polyols [polycarboxylic acid and excess (carboxyl group 1 1 mol per product) of a polyhydric alcohol condensate (eg dihydroxyethyl adipate) and EG caprolactone 1 mol adduct], and a low degree of PU polyol (eg reaction product of 1 mol TDI and 2 mol EG). Can be mentioned.

The polymeric polyol usually has an OH equivalent weight of 250 to 3,000 or more. The polyol usually has a Mn of 500 to 5,000 or more, preferably 700 to 4,500; preferably a weight average molecular weight of 500 to 6,000, particularly preferably 700 to 4,000 (measurement is GPC method (hereinafter abbreviated as Mw). Examples include OH-terminated polymers [PT, PS, polyamide (hereinafter abbreviated as PD), PU, vinyl polymer (hereinafter abbreviated as VP), polymer polyol (hereinafter abbreviated as P / P), etc.], and these Two or more mixtures are included.
The OH-terminated PT includes a ring-opening polymer of AO, an initiator having at least 2 (2 to 8 or more) active hydrogen atoms [the polyhydric alcohol, hydroxylamine, aminocarboxylic acid and hydroxy PT polyol (AO adduct) having a structure in which one or more kinds of AO are added to carboxylic acid; polyhydric phenol; and polycarboxylic acid (described later), and two molecules (the same or different) Alternatively, PT polyol obtained by coupling more than that with a coupling agent (polyhalide, epihalohydrin, polyepoxide, etc.) is included.
The AO includes C2-12 or more (preferably 2-4) AO such as ethylene oxide, 1,2-propylene oxide, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran and 3-methyl-tetrahydrofuran (hereinafter abbreviated as EO, PO, BO, THF and MTHF), 1,3-propylene oxide, isoBO, C5-12 α-olefin oxide, substituted AO such as styrene oxide and epihalohydrin (epichlorohydrin) Etc.), and combinations of two or more of these (random addition and / or block addition).

Examples of OH-terminated PT include PT diols such as polyalkylene glycol (hereinafter abbreviated as PAG) [eg polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol (hereinafter abbreviated as PEG, PPG and PTMG, respectively), poly-3 -Methyl tetramethylene ether glycol], copolymer polyoxyalkylene diol [EO / PO copolymer diol, THF / EO copolymer diol, THF / MTHF copolymer diol, etc. (weight ratio, for example, 1/9 to 9/1)], Aromatic ring-containing polyoxyalkylene diol [polyoxyalkylene bisphenol A (such as EO and / or PO adduct of bisphenol A)]; and a tri- or more functional PT polyol such as polyoxypropylene triol (PO adduct of GR) ); As well as those of one or more of these was coupled with methylene dichloride.

The OH-terminated PS includes condensed PS polyol, polylactone (hereinafter abbreviated as PL) polyol, castor oil-based polyol [castor oil (ricinoleic acid triglyceride) and a modified polyol thereof), polycarbonate polyol, and the like.
The condensed PS polyol is obtained by polycondensation of a polyol and a polycarboxylic acid (and optionally a hydroxycarboxylic acid) or by reaction of the polyol with a polycarboxylic acid anhydride and AO. By addition (or polycondensation of polyol and hydroxycarboxylic acid), a castor oil-based polyol modified product is obtained by a transesterification reaction between castor oil and polyol, and polycarbonate polyol is (1) an alkylene carbonate having a polyol as an initiator. It can be produced by ring-opening addition / polycondensation, (2) polycondensation (transesterification) of polyol and diphenyl or dialkyl carbonate, or (3) phosgenation of polyol or dihydric phenol (such as bisphenol A).
The polyol used for the production of PS usually has an OH equivalent of 1,000 or less, preferably 30 to 500. Examples thereof include the above polyhydric alcohol [diol (eg, EG, 1,4-BD, NPG, HD and DEG), trivalent or higher polyol (GR, TMP, PE, etc.)], the above PT polyol (PEG, PPG, PTMG, etc.), and mixtures of two or more thereof. Preferred for the production of the condensed PS polyol is a combination of a diol and a small proportion (for example, 10 equivalent% or less) of a trivalent or higher polyol.

The polycarboxylic acids include dicarboxylic acids and trivalent to tetravalent or higher polycarboxylic acids. Examples thereof include C2-30 or more (preferably C2-12) saturated and unsaturated aliphatic polycarboxylic acids such as C2-15 dicarboxylic acids (eg oxalic acid, succinic acid, malonic acid, adipic acid , Suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, itaconic acid, etc.), C6-20 tricarboxylic acid (for example, tricarballylic acid, hexanetricarboxylic acid, etc.)]; C8-15 aromatic poly Carboxylic acids such as dicarboxylic acids (eg terephthalic acid, isophthalic acid, phthalic acid etc.), tri- and tetra-carboxylic acids (eg trimellitic acid, pyromellitic acid etc.); C6-40 alicyclic polycarboxylic acids (dimers) Acid, etc.); sulfo group-containing polycarboxylic acid [one obtained by introducing a sulfo group into the above polycarboxylic acid, eg For example, sulfosuccinic acid, sulfomalonic acid, sulfoglutaric acid, sulfoadipic acid, sulfoisophthalic acid, and salts thereof [metal salts such as alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and Salts of Group IIB metals (such as zinc); ammonium salts; and amine salts and quaternary ammonium salts]]; and carboxy-terminated polymers.

Carboxy-terminated polymers include PT polycarboxylic acids such as carboxymethyl ethers of polyols [polyhydric alcohols, PT polyols etc. above] (obtained by reacting monochloroacetic acid in the presence of alkali); PD, PS and / or Or PU polycarboxylic acid, for example, polylactam polycarboxylic acid obtained by ring-opening polymerization of lactam or lactone (described above) using the above polycarboxylic acid as an initiator and PL polycarboxylic acid, or two or more of the above polycarboxylic acids. Reaction of condensed PS polycarboxylic acid and condensed PD polycarboxylic acid obtained by coupling (esterification or amidation) with polyol (described above) or PA or PI (described later), and the above polycarboxylic acids and polyol (urethanization) And esterification or amide ) Is allowed include PU polycarboxylic acids comprising.

Examples of ester-forming derivatives of polycarboxylic acids include acid anhydrides, lower alkyl (C1-4) esters, acid halides such as succinic acid, maleic acid, itaconic acid and phthalic anhydride, dimethyl terephthalate, malonyl dichloride, etc. Is included.

Preferred for the production of the condensed PS polyol is a combination of a dicarboxylic acid and a small proportion (for example, 10 equivalent% or less) of a trivalent to tetravalent or higher polycarboxylic acid.
Lactones and hydroxycarboxylic acids include those listed above.
Examples of the alkylene carbonate include those having a C2-6 alkylene group, such as ethylene carbonate and propylene carbonate.
Dialkyl carbonates include those having a C1-4 alkyl group, such as dimethyl, diethyl and di-i-propyl carbonate.

Specific examples of OH-terminated PS include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene / propylene adipate, polyethylene / butylene adipate, polybutylene / hexamethylene adipate, polydiethylene adipate, poly (poly Tetramethylene ether) adipate, polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol, polyhexamethylene carbonate diol and the like.
The OH-terminated PD includes poly (ester) amide polyols obtained by polycondensation of polycarboxylic acids (above) with hydroxylamine (above) or polyol (above) and PA (described later).

The OH-terminated PU includes an OH-terminated urethane prepolymer obtained by modifying a polyol with PI. Polyols include the polyhydric alcohols, polymer polyols (the above-mentioned OH-terminated PT and PS, and OH-terminated VP and P / P described later), and combinations of two or more of them as described above. Preference is given to high-molecular polyols (especially OH-terminated PS and especially PT) and combinations thereof with low-molecular polyols (especially polyhydric alcohols). The amount of the low molecular polyol to be used in combination can be appropriately changed according to the use and required performance, but is generally 0.01 to 0.5 equivalent, more preferably 0.02 to 1 equivalent of the polymer polyol. 0.4 equivalent is preferable, and 0.1 to 0.2 equivalent is particularly preferable.
In producing the OH-terminated urethane prepolymer, the equivalent ratio (OH / NCO ratio) between polyol and PI is usually 1.1 to 10, preferably 1.4 to 4, particularly preferably 1.4 to 2. The polyol and PI may be reacted in a single stage or in multiple stages (for example, after reacting a part of the polyol or PI, the remainder is reacted).

PI includes the following PI having 2 to 6 or more (preferably 2 to 3, particularly preferably 2) isocyanate groups, and mixtures of two or more thereof.
C (excluding carbon in the NCO group, the same shall apply hereinafter) 2-18 aliphatic PI: diisocyanate (hereinafter abbreviated as DI), for example, ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, decamethylene DI, dodecamethylene DI, 2,2,4- and / or 2,4,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethyl caproate, 2,6-diisocyanato Tilcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, etc .; trifunctional or higher functional PI (eg, triisocyanate), such as 1,6,11-undecane triisocyanate, 1,8 -Diisocyanate-4-isocyanate methyloctane, 1,3,6-hexa Tylene triisocyanate, lysine ester triisocyanate (phosgenation product of reaction product of lysine and alkanolamine, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl- 2,6-diisocyanatohexanoate etc.);

C4-15 alicyclic PI: DI, for example isophorone DI (IPDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane DI; tri- or higher functional PI (such as triisocyanate), such as bicycloheptane triisocyanate;
C8-15 araliphatic PI: m- and / or p-xylylene DI (XDI), diethylbenzene DI, α, α, α ′, α′-tetramethylxylylene DI (TMXDI);

C6-20 aromatic PI: DI, such as 1,3- and / or 1,4-phenylene DI, 2,4- and / or 2,6-tolylene DI (TDI), 4,4'- and / or 2,4′-diphenylmethane DI (MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3 , 3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene DI, etc .; trifunctional or higher functional PI (such as triisocyanate), such as crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate);

And modified products of PI: modified products of these PIs (for example, modified products having carbodiimide, urethane, urea, isocyanurate, uretoimine, allophanate, biuret, oxazolidone and / or uretdione groups), such as MDI, TDI, HDI, IPDI Urethane modified products (NCO-terminated urethane prepolymer obtained by reacting polyol with excess PI), biuret modified products, isocyanurate modified products, trihydrocarbyl phosphate modified products, and mixtures thereof.

Of the PIs, aliphatic PIs other than aromatic PIs, alicyclic PIs and araliphatic PIs, particularly aliphatic PIs, alicyclic PIs and combinations thereof are preferable from the viewpoint of light resistance.

OH-terminated VPs include polybutadiene-based polyols such as OH-terminated butadiene homopolymers and copolymers (styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, etc.) [those having 1,2-vinyl structures, 1,4-trans structures. Having 1,4-cis structure, and having two or more of these (molar ratio of 1,2-vinyl / 1,4-trans / 1,4-cis is 100 to 0/100 to 0/100 to 0, preferably 10 to 30/50 to 70/10 to 30), and hydrogenated products thereof (hydrogenation rate: eg 20 to 100%); acrylic polyols such as acrylic copolymers [alkyl ( C1-20) (meth) acrylate, or a copolymer of these with other monomers (styrene, acrylic acid, etc.) Obtained by introducing a hydroxyl group [introducing hydroxyl groups hydroxyethyl (meth) according acrylate primarily] in; includes partially saponified ethylene / vinyl acetate copolymers and the like.

P / P is obtained by in situ polymerization of an ethylenically unsaturated monomer in a polyol (previously OH-terminated PT and / or PS, or a mixture of this and the above polyhydric alcohol). Ethylenically unsaturated monomers include acrylic monomers such as (meth) acrylonitrile, alkyl (C1-20 or higher) (meth) acrylate (such as methyl methacrylate); hydrocarbon (hereinafter abbreviated as HC) monomers such as aromatic Unsaturated HC (such as styrene), aliphatic unsaturated HC (C2-20 or more alkenes, alkadienes, such as α-olefins, butadiene, etc.); and combinations of two or more of these [for example, acrylonitrile / styrene Combination (weight ratio 100/0 to 80/20)] is included.
P / P has a polymer content of, for example, 5 to 80% or more, preferably 30 to 70%.
Among the polymer polyols of the polyol (m22), PT polyol and PS polyol are preferable.

PA includes primary and / or secondary PA, for example, corresponding to the above-mentioned PI (NCO replaced with NH ₂ ), aliphatic (C2-18), alicyclic (C4-15), aromatic fat Group (C8-15) and aromatic (C6-20) PA; polyalkylene (C2-6) PA (degree of polymerization 2-10 or more), for example polyethylene PA (diethylenetriamine, triethylenetetramine, tetraethylenepentamine) And the like, and the corresponding polypropylene PA; polymerized fatty acid PA [PA derived from a polymer of fatty acid (linoleic acid, linolenic acid, oleic acid, etc.) (such as dimer acid) (formed by hydrogenation of its amide or nitrile)] Amino-terminated polymers (below); partial PA (C1-10) and / or hydroxyalkyl (C2-4) products of these PAs; (N-alkyl diamines, N, N′-dialkyl diamines, N-hydroxyalkyl diamines, N, N′-dihydroxyalkyl diamines, etc.); and heterocyclic PAs such as piperazine, imidazolidine, pyrazolidine, etc., and their N— Aminoalkyl- and N, N′-diaminoalkyl substituents (such as aminoethylpiperazine) are included.

Amino-terminated polymers include amino-terminated PT, such as C3-10 (preferably C3) aminoalkyl ethers of the above polyols (polyhydric alcohols, PT polyols, etc.) [hydrides of cyanoalkylates (cyanoethylates, etc.)]; PD, for example, amino-terminated condensed PD [obtained by polycondensation of the above PA and polycarboxylic acids (supra)], amino-terminated polylactam [ring-opening addition with lactam or aminocarboxylic acid (supra) using the above PA as an initiator or Obtained by polycondensation].
Preferred PA is diamine (hereinafter abbreviated as DA), particularly aliphatic DA. Further preferred are those of C2-12 [ethylene DA (hereinafter abbreviated as EDA), hexamethylene DA, heptamethylene DA, octamethylene DA and decamethylene DA], particularly EDA.

The polyepoxide includes the following.
(1) Aliphatic polyepoxide: polyglycidyl ether of an aliphatic polyol [the above-mentioned dihydric to octahydric or higher polyhydric alcohol and PT polyol] (glycidyl ether is hereinafter abbreviated as GE): diGE [for example, EG, PG, 1,4-BD, HD, MPD, DEG, NPG, PEG (Mn 150-200,000) and PPG (Mn 134-200,000) diGE], tri-GE [e.g., GR and TMP tri-GE, etc.], and Polyglycidyl esters of tetravalent or higher GE [e.g., PE tetra GE and SO hexa GE]; aliphatic polycarboxylic acids (divalent to trivalent or higher aliphatic polycarboxylic acids listed for PS production) (Glycidyl ester is abbreviated as GS hereinafter) [for example, oxalic acid and adipic acid diGS, tricarbari TriGS, etc.], glycidyl (meth) acrylate polymer, glycidyl (meth) acrylate and other monomers [eg unsaturated HC (aliphatic HC, alicyclic HC, aromatic HC, etc.), alkyl (meth) acrylate [C1 Having up to 50 alkyl groups such as methyl, ethyl, propyl, butyl, 2-ethylhexyl, dodecyl, hexadecyl, heptadecyl and eicosyl (meth) acrylate], carbonyl, ether and / or sulfur containing unsaturated monomers [eg Saturated ester, unsaturated ether, vinyl ketone, sulfide bond-containing monomer, sulfone group-containing monomer, etc., preferably alkyl (meth) acrylate] (Mn is preferably 300 to 10,000, particularly 500 to 5 , 000; copolymerization ratio [ Rishijiru (meth) acrylate / other monomer] is preferably 2 / 98-80 / 20, in particular 5 / 95-50 / 50); epoxidized animal and vegetable oils (e.g., epoxidized soybean oil);

(2) Alicyclic polyepoxides: those of C8-20, such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, EG bisepoxydicyclopentyl ether, 3, 4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and the aromatic ring-containing polyepoxide described below. Nuclear hydrogenated product;
(3) Heterocycle-containing polyepoxide: C5-20, such as trisglycidyl melamine;

(4) Aromatic ring-containing polyepoxide: polyphenol (the above divalent to trivalent or higher polyhydric phenol) or AO adduct polyGE: divalent phenol diGE (bisphenol F, A, B, AD) And S di-GE, catechol di-GE, resorcinol di-GE, hydroquinone di-GE, 1,5-dihydroxynaphthalene di-GE, dihydroxybiphenyl di-GE, di-GE obtained by reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin) Tri-phenol tri-GE (pyrogallol tri-GE, etc.); and poly-phenol poly-tetra- or higher valence (GE of phenol or cresol novolac resin, polyphenol obtained by condensation reaction of phenol and glyoxal, glutaraldehyde or formaldehyde Poly GE, resorcin and poly GE of polyphenols obtained by condensation reaction such as acetone) and the like.

Among these, from the viewpoint of reactivity with (ax1), aliphatic polyepoxides and aromatic ring-containing polyepoxides, particularly polymers of TMP triGE and glycidyl (meth) acrylate [glycidyl (meth) acrylate 10 to 100% And other monomers [the above alkyl (meth) acrylates, especially dodecyl methacrylate] 0-90% (co) polymers, Mn 500-5,000] and bisphenol A diGE.
Further, among the polyepoxides, those having an epoxy equivalent of 50 to 500, particularly 60 to 200 are more preferable.

[Hydrophilic group]
In the present invention, the hydrophilic group containing at least one amino group (b) is a functional group (primary or secondary amino group, hydroxyl group, unsaturated group, etc.) capable of reacting with a carboxyl group in the molecule and an amino group (b ) Having a compound (b01). Examples of the amino group (b) include a primary, secondary or tertiary amino group.

(B01) has a primary or secondary amino group and another 1, 2 or tertiary amino group [C2-69, such as ethylenediamine, N-methyl- and -ethylethylenediamine, 1,3-propane Diamine, N-methyl-, -ethyl- and -butyl-1,3-propanediamine, p-phenylenediamine, N-methyl- and -ethyl-p-phenylenediamine, N, N'-dimethylethylenediamine, N, N '-Dimethyl-1,3-propanediamine, N, N'-dimethyl-p-phenylenediamine, N, N'-diethylethylenediamine, N, N'-diethyl-1,3-propanediamine, N, N'- Diethyl-p-phenylenediamine, N, N'-dibutyl-1,3-propanediamine, N, N-dimethyl-, -diethyl-o Bi-dibutyl-1,3-propanediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N, N′-trimethyl-1,3-propanediamine]; Those having a hydroxyl group and an amino group [C4-69, such as 2-dimethylaminoethanol, 2-diethylaminoethanol, m-dimethylaminophenol, N-methyldiethanolamine]; those having an unsaturated group and an amino group [C2-51, Examples include vinylamine, N-methyl and -ethylvinylamine, N, N-dimethylvinylamine, allylamine, N-methyl and -ethylallylamine, N, N-dimethylallylamine, dimethylaminoethyl (meth) acrylate.

Of the above (b01), those having a primary or secondary amino group and another 1, 2, or tertiary amino group are preferred from the viewpoints of paintability and reactivity of (ax) and (b01), and Those having an unsaturated group and an amino group, more preferably a primary or secondary amino group, and another having a 1, 2 or tertiary amino group, particularly preferably a primary or secondary amino group It has another secondary amino group.

Among the above hydrophilic groups in the present invention, those represented by the following general formula (1) are preferable from the viewpoint of the mechanical strength and paintability of the molded product described later.

[In the formula, R ¹ and R ² may be the same or different, and each may have a substituent selected from the group consisting of H or a hydroxyl group and an amino group; A group; X represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent selected from the group consisting of a hydroxyl group and an amino group; Z represents N constituting an amide group or an imide group. ]

Examples of the hydrocarbon group having 1 to 20 carbon atoms in R ¹ and R ² include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, and the like, for example, a methyl group, an ethyl group, a propyl group, and a butyl group. And a phenyl group.
As a C1-C20 bivalent hydrocarbon in X, an alkylene group, a bivalent aromatic group, etc. are mentioned, For example, an ethylene group, a propylene group, a phenylene group etc. are mentioned.
In the formula, when R ¹ and R ² are hydrocarbon groups, they are preferably C1 to 15 and more preferably C1 to 4 from the viewpoint of mechanical strength and paintability of the molded product. Of these combinations of R ¹ and R ² , R ¹ is preferably H, R ² is H or an alkyl group, and more preferably R ¹ is H and R ² is an alkyl group, from the viewpoint of the paintability of the molded product. It is a combination.
The divalent hydrocarbon group represented by X is preferably C1-15, more preferably C1-4, from the viewpoint of mechanical strength and paintability of the molded product. Among these hydrocarbon groups, a hydrocarbon group having no substituent is preferable from the viewpoint of the mechanical strength of the molded product.
Further, N constituting the amide group or imide group represented by Z is preferably N constituting the imide group from the viewpoint of the paintability of the molded product.

[Modified polyolefin]
The modified polyolefin in the present invention has a hydrophobic group comprising the polyolefin (a) and a hydrophilic group containing at least one amino group (b), and (b) 400 to 50,000, preferably 450 It has a Mn of ˜20,000, more preferably 550 to 12,000, particularly preferably 650 to 6,000. If the Mn is less than 400, the mechanical strength of the molded product is lowered, and if it exceeds 50,000, the paintability is deteriorated.
The Mn per (b) of the modified polyolefin can be determined from the formula of [(KOH formula weight) × 10 ³ / amine value] from the amine value of the modified polyolefin and the formula quantity of KOH.

The modified polyolefin can be produced, for example, by reacting carboxy-modified polyolefin (ax) and (b01).
In the above production method, the functional group equivalent ratio [COOH / (primary or secondary amino group, hydroxyl group and / or unsaturated group)] in the reaction of (ax) and (b01) is the paintability of the molded product and the machine From the viewpoint of strength, it is preferably 1 / 0.2 to 1/8, more preferably 1 / 0.5 to 1/4.

The amine value of the modified polyolefin is usually from 1 to 140, preferably from 5 to 120, more preferably from 10 to 100, and particularly preferably from 15 to 80, from the viewpoints of paintability and mechanical properties of the molded product described later. Here, the amine value means the number of mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize the amine contained in 1 g of the sample, the sample is dissolved in xylene, bromcresol green is used as an indicator, hydrogen chloride Is a value obtained by neutralization titration with a methanol solution (unit: mg KOH / g, shown only in this specification).

The paintability improving agent (A) of the present invention comprises the modified polyolefin.

[Polyolefin resin composition]
The polyolefin resin composition of the present invention comprises the polyolefin resin (B) containing the paintability improving agent (A) of the present invention. The amount of (A) used in the resin composition is preferably from 0.01 to 30%, more preferably from the viewpoint of maintaining the coating properties and mechanical properties of (B), based on the weight of (B). It is 1 to 25%, particularly preferably 1 to 20%.

Examples of (B) include polyolefin resins obtained by (co) polymerizing at least one olefin selected from the group consisting of ethylene, propylene, and C4-12 α-olefins. Examples of the C4-12 α-olefin include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like.
Mn in (B) is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, from the viewpoint of mechanical strength of the molded product.

The polyolefin resin composition of the present invention may further contain various additives (C) as necessary as long as the effects of the present invention are not impaired.
(C) includes plasticizer (C1), lubricant (C2), adhesion, dispersibility and / or compatibility imparting agent (C3), antioxidant (C4), ultraviolet absorber (C5), colorant ( Examples thereof include one or two or more additives selected from the group consisting of C6), filler (C7), flame retardant (C8) and antistatic agent (C9).

The following are mentioned as a plasticizer (C1).
(C11) Monocarboxylic acid ester aliphatic carboxylic acid ester [C10-96, such as butyl stearate (BS), methoxyethyl oleate (MEO), methyl acetylricinoleate (MAR), ethyl acetylricinoleate (EAR), acetyl Methoxyethyl ricinoleate (MEAR), glycerin triheptanoate, etc.], aromatic (aliphatic) carboxylic acid ester [C7-96, such as butyl benzoate, octyl benzoate, butyl phenylacetate, hexyl phenylacetate, etc.], alicyclic Formula carboxylic acid ester [C5-96, such as methyl cyclopropanecarboxylate, butyl cyclopropanecarboxylate, methoxyethyl cyclobutanecarboxylate, ethyl cyclopentanecarboxylate, butyl cyclopentanecarboxylate, cyclohexanecarbox Methyl acid, cyclohexanecarboxylic acid methoxyethyl, cyclohexanecarboxylic acid octyl];

(C12) Dicarboxylic acid ester aliphatic dicarboxylic acid ester [C10-96, such as adipic acid ester [eg, di-2-ethylhexyl adipate (DOA), diisodecyl adipate (DIDA), di (methylcyclohexyl) adipate, etc.], Azelaic acid esters [eg azelaic acid di-n-hexyl (DNHZ), azelaic acid di-2-ethylhexyl (DOZ) etc.], sebacic acid esters [eg dibutyl sebacate (DBS), di-2-ethylhexyl sebacate (DOS) And the like]], aromatic (aliphatic) dicarboxylic acid esters [C10-96, such as phthalic acid esters [eg, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), heptylnonyl phthalate (HNP]). ), Di-2-phthalate Tylhexyl (DOP), di-n-octyl phthalate (DNOP), di-i-octyl phthalate (DIOP), di-s-octyl phthalate (DCapP), di (79 alkyl) phthalate (D79P), phthalate Acid-i-decyl (DIDP), ditridecyl phthalate (DTDP), dicyclohexyl phthalate (DCHP), butyl benzyl phthalate (BBP), ethyl phthalyl ethyl glycolate (EPEG), butyl phthalyl butyl glycolate (BPBG) etc]〕;

(C13) Tricarboxylic acid ester aliphatic tricarboxylic acid ester [C5-96, for example, citrate ester [for example, triethyl citrate (TEC), tributyl citrate (TBC), acetyl triethyl citrate (ATEC), acetyl citrate tributyl (ATBC) ), Acetyl citrate tricyclohexyl, trioctyl citrate, tri (octyldecyl) citrate]], aromatic (aliphatic) tricarboxylic acid esters [C10-96, such as ethyl benzenetricarboxylate, octyl benzenetricarboxylate, etc.];
(C14) Epoxy series C10-96, such as epoxidized soybean oil (ESO), 4,5-epoxycyclohexane-1,2-dicarboxylate di-2-ethylhexyl (E-PS) and the like;

(C15) Phosphate esters C3 to 96, such as tributyl phosphate (TBP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), diphenyl monocresyl phosphate, 2-ethylhexyldiphenyl phosphate, phosphoric acid Tripropylene glycol, tributoxyethyl phosphate, trichloroethyl phosphate, triethyl phosphate, trixylyl phosphate, etc .;
(C16) Chlorinated hydrocarbons C10 to 96, such as chlorinated paraffin, chlorinated aromatic hydrocarbon (for example, chlorinated naphthalene, chlorinated biphenyl, etc.) and the like.

Of these, (C11) to (C13) are preferable from the viewpoint of the functional expression of (A) and (C1), and aliphatic di- and tricarboxylic acid esters and aromatic dicarboxylic acid esters are particularly preferable. Di-2-ethylhexyl adipate (DOA), citrate ester and phthalate ester.

Examples of the lubricant (C2) include hydrocarbons [eg liquid paraffin, natural paraffin, microwax, polyethylene wax (Mn100 to 10,000), etc.]; higher fatty acids [C8 to 48, eg lauric acid, palmitic acid, stearic acid, olein Acid, linoleic acid, linolenic acid, esyl acid, etc.]; higher fatty acid amides [C8-48, such as palmitic acid amide, stearic acid amide, oleic acid amide, esylic acid amide, erucic acid amide, methylene bisstearamide, etc.]; Higher fatty acid esters [C8-48 such as butyl stearate, octyl stearate, ethylene glycol monooctylate, ethylene glycol monostearate, etc.]; higher alcohols [C8-48 such as cetyl alcohol, stearyl alcohol, oleyl alcohol Metal soaps [C8-48, such as higher fatty acid (above) metals, such as alkali metal salts (such as sodium, potassium, etc.), alkaline earth metals (such as calcium, magnesium, etc.), lead, aluminum, etc. ]]. Of these, higher fatty acids, higher fatty acid amides and higher fatty acid esters are preferred from the viewpoints of compatibility with (A), functional expression of (A) and functional expression of (C2) as a lubricant.

Examples of the adhesion, dispersibility and / or compatibility imparting agent (C3) include polymers having a Mn of 1,000 to 100,000, such as vinyl resins {for example, polyolefins [for example, polyethylene, polypropylene, ethylene / butene copolymers [copolymerization weight]. 1-99 / 1-99], propylene / butene copolymer [copolymerization weight ratio 1-99 / 1-99], ethylene / propylene / butene copolymer [copolymerization weight ratio 1-98 / 1-98 / 1-98], modified polyolefins (excluding the modified polyolefins of the present invention) [for example, polyethylene oxide (polyethylene is oxidized with ozone or the like to introduce carboxyl groups, carbonyl groups and / or hydroxyl groups, etc.), polypropylene oxide ( In the above oxidized polyethylene, polyethylene can be obtained in the same way instead of polypropylene. , Epoxy-modified polyethylene (epoxy equivalent 100 to 20,000), epoxy-modified polypropylene (epoxy equivalent 100 to 20,000), hydroxyl-modified polyethylene (hydroxyl value 0.1 to 60), hydroxyl-modified polypropylene (hydroxyl value 0.1 to 0.1) 60), hydroxyl-modified ethylene / butene copolymer (hydroxyl value 0.1-60, copolymer weight ratio 1-99 / 99-1), hydroxyl-modified propylene / butene copolymer (hydroxyl value 0.1-60, Copolymer weight ratio of 1 to 99/99 to 1), etc.], vinyl resins other than the above polyolefins [eg, polyvinyl halides [eg, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyiodide, etc.], poly Vinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly (meth) ac Phosphoric acid, poly (meth) acrylic acid esters [eg poly (meth) acrylic acid-methyl, -ethyl, -n- and i-propyl and -n- and t-butyl], styrene resins [eg polystyrene, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin, etc.]]};

Polyester resin [for example, polyalkylene (C2-24) terephthalate [for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc.], polyalkylene (C2-24) isophthalate [for example, polyethylene isophthalate, polybutylene isophthalate, etc.] , Poly-p-phenylene ester [eg poly-p-phenylene malonate, poly-p-phenylene adipate, poly-p-phenylene terephthalate, etc.]]; polyamide resin [eg polycapramide (6-nylon), polyhexamethylene adipate Amide (6,6-nylon), polyhexamethylene sebacamide (6,10-nylon), polyundecanamide (11-nylon), poly-ω-aminoheptanoic acid (7-nylon), poly-ω-aminonona Acid (9-nylon) etc.]; polyether resin [eg polyoxymethylene, polyoxyethylene, polyoxyphenylene, poly-1,3-dioxolane etc.]; polycarbonate resin; polyphenylene resin (PPO); A copolymer is mentioned.
Of these, modified polyolefins and (A) and (C3) are preferred from the viewpoints of compatibility, (A) function expression, and (C3) adhesion, dispersibility, and / or function expression as a compatibility imparting agent. Polyester resin.

Examples of the antioxidant (C4) include hindered phenols [for example, pt-amylphenol-formaldehyde resin, 2,6-bis (1-methylheptadecyl) -p-cresol, butylated cresol, styrenated cresol. 4,4′-butylidenebis (6-t-butyl-m-cresol), 4,4′-cyclohexylidenebis (2-cyclohexylphenol), 2 (2′-hydroxy-5′-methylphenyl) benzotriazole , Octadecyl-3,5-di-t-butyl-4-hydroxycinnamate, butylated hydroxyanisole, propyl gallate, 2,4,5-trihydroxybutyrophenone, nordihydroguaiaretic acid (NDGA), 2,6 -Di-t-butyl-4-methylphenol (BHT), 2-t-butyl 4-methylphenol (BHA), 6-t-butyl-2,4-dimethylphenol (24M6B), 2,6-di-t-butylphenol (26B), 2-t-butyl-4-ethylphenol, 2, 6-di-t-butyl-4-ethylphenol, n-octadecyl-3- (4′-hydroxy-3,5-di-t-butylphenyl) propionate, 4,4′-butylidenebis (6-t-butyl) -3-methylphenol), 4,4'-methylenebis (6-t-butylphenol), 4,4'-bis (2,6-di-t-butylphenol), 2,2'-methylenebis (4-methyl-) 6-tert-butylphenol), 2,2′-thiobis (6-tert-butyl-4-hydroxy-2-methylphenol), 1,6-bis (3,5-di-tert-butyl-4-hydro Cis-2-methylphenyl) butane, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) mesitylene, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tetrakis [β- (3,5-di-t-butyl- 4-hydroxyphenyl) propionyloxymethyl] methane etc.];

Sulfur-containing systems (for example, N, N′-diphenylthiourea, dimyristylthiodipropionate, dilaurylthiodipropionate, 4,4′-thiobis (6-t-butyl-m-cresol), distearylthiodipropio 6- (4-oxy-3,5-di-t-butylanilino) 2,4-bis (n-octylthio) -1,3,5-triazine, 4,4′-thiobis (6-t-butyl) -3-methylphenol), 4,4′-thiobis (6-t-butyl-o-cresol) and the like]; phosphorus-containing systems [for example, 2-t-butyl-α- (3-t-butyl-4-hydroxy) Phenyl) -p-cumenylbis (p-nonylphenyl) phosphite, phosphite ester resin, tris (nonylphenyl) phosphite, dioctadecyl-4-hydroxy-3,5- Etc. -t- butyl benzyl phosphonate], and the like.

Examples of the ultraviolet absorber (C5) include salicylates (for example, phenyl salicylate, 4-t-butylphenyl salicylate, p-octylphenyl salicylate, etc.); benzophenones (for example, 2,4-dihydroxyzenzo). Phenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone ( Trihydrate), 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5- Chloro-2 Hydroxybenzophenone, etc.]; benzotriazole [such as 2- (2'-hydroxy-5'-methylphenyl) - benzotriazole, etc.] and the like.

Examples of the colorant (C6) include white pigments (eg, titanium oxide, zinc white, barium sulfate, calcium carbonate, etc.), black pigments (eg, carbon black, iron black, aniline black, etc.), yellow pigments (eg, yellow lead, cadmium yellow). Iron oxide yellow, benzidine yellow, Hansa yellow, oil yellow 2G, etc.), orange pigment (eg red lead yellow lead, chrome vermilion, cadmium orange, pyrazolone orange, etc.), red pigment (eg Bengala, cadmium red, permanent red, lake red) C, Carmine 6B, Pigment Scarlet 3B, Permanent Red F5R, Quinacridone Red, Thioindigo Maroon, etc., Purple Pigment (eg, Cobalt Violet, Mineral Violet, etc.), Blue Dyeing Pigment (eg, Ultramarine Blue, Bituminous Blue, Cobalt Blue, Phthalose) Nburu etc.), a green pigment (e.g. phthalocyanine green, chrome green, etc.), metal powder pigments (e.g. aluminum powder, bronze powder, pearl essence and the like) and the like.

Examples of the filler (C7) include metal powder (eg, aluminum powder), metal oxide (eg, alumina, wollastonite, silica, talc, mica, kaolin clay, calcined kaolin, etc.), metal hydroxide (eg, water). Aluminum oxide, etc.), metal salts (eg, calcium carbonate, calcium silicate, etc.), fibers [eg, inorganic fibers (carbon fiber, fiber, α-fiber, glass fiber, asbestos, etc.) and organic fibers (eg, cotton fiber, jute) Fiber, nylon fiber, acrylic fiber, rayon fiber, etc.)], microballoon (eg, glass, shirasu, phenol resin, etc.), carbon (eg, carbon black, graphite, etc.), metal sulfide (eg, molybdenum disulfide, etc.), organic powder (For example, wood powder etc.), inorganic powder (for example, coal powder etc.), etc. are mentioned.

Examples of the flame retardant (C8) include organic [eg, phosphorus-containing [eg, phosphate ester (eg, tricresyl phosphate)], bromine-containing (eg, tetrabromobisphenol A, decabromobiphenyl ether, etc.), Chlorine-containing (eg, chlorinated paraffin, anhydrous heptic acid)] and inorganic (eg, antimony trioxide, magnesium hydroxide, borate, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus, magnesium hydroxide) , Ammonium polyphosphate, etc.].

Examples of the antistatic agent (C9) include nonionic, cationic, anionic and amphoteric surfactants described below and in US Pat. Nos. 3,929,678 and 4,331,447. .
1) Nonionic surfactant:
AO-added nonionics, for example, active hydrogen atom-containing compounds having a hydrophobic group (C8-24 or higher) [saturated and unsaturated, higher alcohols (C8-18), higher aliphatic amines (C8-24), (Poly) oxyalkylene derivatives of higher fatty acids (C8-24) and the like: for example, alkyl or alkenyl (dodecyl, stearyl, oleyl, etc.) alcohol and amine, alkanoic acid or alkenoic acid (lauric acid, stearic acid, oleic acid, etc.) (Poly) oxyalkylene derivatives of higher fatty acid (above) esters of polyhydric alcohols (as described above, for example, GR, PE, sorbitan, etc.) (molecular weight of 320 or more and Mn30, 000 or less; Tween type nonionics, etc.); higher fat (Poly) oxyalkylene derivative of (alkanol) amide of (above) (molecular weight of 330 or more and Mn of 30,000 or less); (poly) oxyalkylene derivative of polyhydric alcohol (above) alkyl (C3-60) ether (molecular weight of 180 And Mn 30,000 or less); polyoxypropylene polyol [polyoxypropylene derivative of polyhydric alcohol (above) and polyamine (above PA)] (Mn 1,000 to 30,000) [for example, Pluronic type Polyhydric alcohol (C3-60) type nonionics, for example, higher fatty acid (above) esters of polyhydric alcohol (above), polyhydric alcohol (above) alkyl (C3-60) ether, Higher fatty acid (above) alkanolamine Etc .; amine oxide Nonionikkusu, for example (hydroxy) alkyl (C10-18), di (hydroxy) alkyl (C1 -3) amine oxide.

2) Cationic surfactant:
Quaternary ammonium salt-type cationics such as tetraalkylammonium salts (C11-100); trialkylbenzylammonium salts (C17-80); alkyl (C8-60) pyridinium salts; (poly) oxyalkylenes (C2-4, Degree of polymerization 1-100 or higher) Trialkylammonium salt (C12-100); Acyl (C8-18) aminoalkyl (C2-4) or Acyl (C8-18) oxyalkyl (C2-4) tri [(hydroxy ) Alkyl (C1-4)] ammonium salts [These salts include, for example, halides (chloride, bromide, etc.), alkyl sulfates (methosulphate, etc.), salts of organic acids (below), etc .; Cathonics: 1st to 3rd class amines [eg higher aliphatic amines, higher fats Inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid) of polyoxyalkylene derivatives of amine (above) (above; EO adducts, etc.), acylaminoalkyl or acyloxyalkyl (above) di (hydroxy) alkyl (above) amine] Etc.) Salt or organic acid (C2-22: acetic acid, propionic acid, lauric acid, oleic acid, succinic acid, adipic acid, azelaic acid, benzoic acid, etc.) salt.

3) Anionic surfactant:
Carboxylic acids (salts) such as higher fatty acids (above), ether carboxylic acids [higher alcohols (above) or AO adducts thereof], and salts thereof; sulfate salts such as sulfuric acids of the above higher alcohols or AO adducts thereof Ester salts, sulfated fatty acid esters and sulfated olefins (salts neutralized by sulfation of C12-18 olefins); sulfonates such as alkylbenzene sulfonates, N-acyl-N-methyltaurines (Igepon T type, etc.) ); Phosphoric acid ester salts such as the above higher alcohols or AO adducts thereof or phosphoric acid ester salts of alkyl (C4-60) phenol AO adducts (same as above).

4) Amphoteric surfactant:
Carboxylic acid (salt) type amphoterics, such as amino acid type amphoterics, betaine type amphoterics, etc .; sulfate (salt) type amphoterics, such as hydroxyalkyl (C2-4) imidazoline sulfate ( Salt); sulfonic acid (salt) type amphoterics; phosphate ester (salt) type amphoterics.

Examples of the 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.), group IIB metals (zinc, etc.), etc. Ammonium salts; amine salts; quaternary ammonium salts and the like.
The amines constituting the salts include C1-20 amines such as hydroxylamines, tertiary amino group-containing diols, primary monoamines, secondary monoamines, and their alkylation (C1-4) and / or hydroxyalkylation ( C2-4) products (AO adducts): for example mono-, di- and tri- (hydroxy) alkyl (amines) (mono-, di- and tri-ethanolamine and ethylamine, diethylethanolamine, morpholine, N-methyl Morpholine, N-hydroxyethylmorpholine and the like). The quaternary ammonium salt includes a quaternized product of these amines [a quaternizing agent described in US Pat. No. 4,271,217 or a quaternized product with a dialkyl carbonate (described above)].

The total amount of (C) used in the polyolefin resin composition of the present invention is usually 30% or less based on the weight of (B), preferably from 0.01 to 25% from the viewpoint of the effect of (C) and economy. More preferably, it is 0.1 to 20%.
The amounts of (C1) to (C9) used based on the weight of (B) are usually (C1), (C2), (C3) and (C9) 15% or less, and the effects and economics of (C) From the viewpoint of, preferably 0.01 to 10%, more preferably 0.1 to 5%; (C4), (C5) and (C8) are usually 10% or less, and from the same viewpoint, preferably 0.01 to 10%. %, More preferably 0.1 to 3%; (C6) and (C7) are usually 30% or less, preferably from 0.01 to 25%, more preferably from 0.1 to 20% from the same viewpoint.

In the method for producing the polyolefin resin composition of the present invention, (1) (A) and (B) and, if necessary, (C) are all melt-mixed, (2) (A) and a small amount of (B) And, if necessary, a part or all of (C) is melt-mixed to prepare a masterbatch resin composition, and then the remaining (B) and, if necessary, the remaining (C) are added and melt-mixed; and (3) A part of (A), a small amount of (B), and if necessary, part or all of (C) are melt-mixed to prepare a masterbatch resin composition, and then the remaining (B), the remaining A method of adding (A) and, if necessary, the remaining (C) and melt-mixing [(2) and (3) is a master batch method] is included. The melting temperature is preferably 40 to 300 ° C, more preferably 90 to 280 ° C, from the viewpoint of the melting temperature and decomposition temperature of (A) and (B).
Among the above methods, the method (2) is preferable from the viewpoint of paintability.
Examples of the melt mixing apparatus include batch kneaders (for example, Banbury [trade name, manufactured by Farrel Co., Ltd.], kneader, etc.), continuous kneaders (for example, FCM [trade name, manufactured by Farrel Co., Ltd.], LCM [trade name, Co., Ltd. manufactured by Kobe Steel Co., Ltd.], CIM [trade name, manufactured by Nippon Steel Works Co., Ltd.], etc.], single screw extruder, twin screw extruder, and the like.

The masterbatch resin composition is also one aspect of the present invention.
The ratio of (A) based on the total weight of (A) and (B) in the masterbatch resin composition of the present invention is 1 to 95% from the viewpoints of paintability, mechanical property maintenance and workability of (B), Preferably it is 10 to 80%.

The molded product of the present invention is formed by molding the polyolefin resin composition. Examples of the molding method include extrusion molding, injection molding, compression molding, slush molding, rotational molding, transfer molding, stampable molding, blow molding, stretched film molding, laminate molding, calendar molding, and foam molding. Examples of foaming agents used in foam molding include inorganic foaming agents (eg, nitrogen, carbon dioxide, air, argon, water, ammonia carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, sodium nitrite, ammonium chloride, nitrourea, etc.) And organic blowing agents [nitroso-based blowing agents (for example, dinitrosopentamethylenetetramine, N, N′dimethylN, N′dinitrosotephthalamide), sulfohydrazide-based blowing agents (for example, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide) , Pp′-oxybisbenzenesulfonyl hydrazide, 3-3 ′ disulfone hydrazide diphenyl sulfone, toluene disulfonyl hydrazide, etc.), sulfohydrazone-based blowing agents (p-toluenesulfonyl hydrazone, etc.), azide-based blowing agents (for example, -Toluenesulfonyl azide, etc.), azo foaming agents (for example, azobisisobutyronitrile, azodicarbonamide, barium azodicarboxylate, diethylazodicarboxylate, etc.)] It is usually 20% or less, preferably 1 to 15%, based on the total weight of the product.

The molded article of the present invention can be obtained by molding the polyolefin resin composition. The molded article has excellent mechanical properties and good paintability, and can be coated and / or printed to form a molded article.
Examples of the method for coating the molded product include spray coating (air spray, airless spray, electrostatic spray coating, etc.), dip coating, roller coating, brush coating, and the like.
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, and acrylic urethane resin paint. The coating film thickness (film thickness after drying) can be appropriately selected according to the purpose, but is usually 5 to 100 μm, and preferably 10 to 50 μm from the viewpoint of coating properties and economy.
In addition, as a method for printing on the molded article, any printing method generally used for plastic printing can be used. For example, gravure printing, flexographic printing, screen printing, pad printing, dry offset printing, Examples include offset printing.
As the printing ink, those usually used for printing plastics, for example, gravure ink, flexo ink, screen ink, pad ink, dry offset ink, offset ink and the like can be used.

The coating property improving agent comprising the modified polyolefin of the present invention is excellent in the effect of improving the coating property of the polyolefin resin, so that the coating property can be improved with a small amount of addition without impairing the mechanical properties of the polyolefin resin. There is an effect.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In addition, performance evaluation was performed by the below-mentioned test method, and the molded article test piece used what was cut out from the injection molded molded article.
The Mn of the modified polyolefin is a value measured by a GPC method using a high temperature GPC {manufactured by Waters Co., Ltd., column: PLgel MIX ED-B, manufactured by Polymer Laboratories Co., Ltd.}.

Example 1
In a four-necked flask equipped with a nitrogen introduction tube, an exhaust gas distillation tube, a stirrer, and a cooling tube, 100 parts of a commercially available polypropylene (pellet-shaped) [Noblen H501, manufactured by Sumitomo Chemical Co., Ltd., Mn 120,000] was added to a nitrogen atmosphere. The melt was heated and melted with a mantle heater while bubbling nitrogen through the gas phase portion, and subjected to thermal degradation at 360 ° C. for 70 minutes while stirring. The amount of double bonds per 1,000 carbon atoms of the obtained thermal degradation product was 2.7.
90 parts of the thermal degradation product, 10 parts of maleic anhydride and 100 parts of xylene were added and, after purging with nitrogen, heated to 130 ° C. under nitrogen flow to dissolve uniformly. A solution prepared by dissolving 0.5 part of dicumyl peroxide in 10 parts of xylene was added dropwise thereto, and then the temperature was raised to xylene reflux temperature and 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 product (1).
90 parts of the obtained product (1), 150 parts of xylene, and 80 parts of decahydronaphthalene were added, heated to 130 ° C. and dissolved uniformly. A mixed solution of 80 parts of N-methyl-1,3-propanediamine and 150 parts of xylene was added dropwise thereto, and stirring was continued for 10 hours at the reflux temperature. Thereafter, unreacted N-methyl-1,3-propanediamine, xylene and decahydronaphthalene were distilled off under reduced pressure to obtain a modified polyolefin (P1). (P1) had an amine value of 51, Mn of 5,000, and a thermal softening point of 143 ° C. (P1) was used as a coating property improving agent (A1) in Example 3 described later.

Example 2
In Example 1, it replaced with polypropylene (pellet shape) and carried out similarly to Example 1 except having used the propylene alpha olefin copolymer (pellet shape) [Tafmer XR107L, Mitsui Chemicals, Mn90,000]. Further, a heat-degraded product and a modified polyolefin (P2) were obtained. The heat-degraded product had an amount of double bonds per 1,000 carbon atoms of 2.8, and (P2) had an amine value of 49, Mn of 5,100, and a heat softening point of 111 ° C. (P2) was used as a paintability improver (A2) in Example 4 described later.

Comparative Example 1
In the same four-necked flask as in Example 1, 95 parts of polypropylene (pellet-like) [Noblen H501, manufactured by Sumitomo Chemical Co., Ltd., Mn 120,000, double bond amount per 1,000 carbons], anhydrous male 5 parts of acid and 1,000 parts of xylene were added, and after substitution with nitrogen, the mixture was heated to 135 ° C. under nitrogen flow to dissolve uniformly. A solution prepared by dissolving 0.3 part of dicumyl peroxide in 5 parts of xylene was added dropwise thereto, and then the temperature was raised to xylene reflux temperature and stirring was continued for 3 hours. Thereafter, 300 parts of xylene and unreacted maleic anhydride were distilled off under normal pressure, cooled to 130 ° C., and taken out into a tray with release paper. The remaining xylene and unreacted maleic anhydride were distilled off in a vacuum dryer at 150 ° C.
97 parts of the obtained product, 500 parts of xylene, and 800 parts of decahydronaphthalene were placed in another four-necked flask equipped with a nitrogen introduction tube, a stirrer, and a cooling tube, and heated to 140 ° C. and heated uniformly. Dissolved. A mixed solution of 30 parts of N-methyl-1,3-propanediamine and 150 parts of xylene was added dropwise thereto, and stirring was continued for 10 hours at the reflux temperature. Thereafter, unreacted N-methyl-1,3-propanediamine, xylene and decahydronaphthalene were distilled off under normal pressure, and then cooled to 150 ° C. and taken out to a tray on which release paper was laid. The remaining xylene, decahydronaphthalene and unreacted N-methyl-1,3-propanediamine were distilled off in a vacuum dryer at 190 ° C. to obtain a modified polyolefin (ratio P1). (Ratio P1) had an amine value of 8, Mn 120,000, and a thermal softening point of 200 ° C. or higher. (Ratio P1) was used as a paintability improver (Ratio A1) in Comparative Example 3 described later.

Comparative Example 2
In a four-necked flask similar to that in Example 1, 80 parts of the product (1) obtained in the same manner as in Example 1 and 20 parts of monoethanolamine were added, and stirring was continued at 180 ° C. for 2 hours. Thereafter, unreacted monoethanolamine was distilled off under reduced pressure to obtain a modified polyolefin (ratio P2). (Ratio P2) was an amine value of 0, a hydroxyl value (unit: mgKOH / g) 52, Mn of 4,900, and a thermal softening point of 145 ° C. (Ratio P2) was used as a paintability improver (Ratio A2) in Comparative Example 4 described later.

Examples 3 and 4 and Comparative Examples 3 and 4
Henschel mixer each of 100 parts of commercially available polypropylene [trade name: Chisso Polypro K1011, manufactured by Chisso Corporation] and 6 parts each of the coating property improvers (A1), (A2), (Ratio A1) and (Ratio A2) Were blended for 3 minutes and then melt-kneaded in a twin-screw extruder with a vent at 240 ° C., 100 rpm, and a residence time of 20 minutes to obtain four types of polyolefin resin compositions. Each composition was molded at a cylinder temperature of 230 ° C. and a mold temperature of 40 ° C. using an injection molding machine [PS40E5ASE, manufactured by Nissei Plastic Industry Co., Ltd.], and a predetermined test piece was prepared. The mechanical properties and paintability of the were evaluated. The results are shown in Table 1.

<Test method>
(1) Impact strength A molded article test piece (thickness: 3.2 mm) was measured by Method A based on ASTM D256 (notched, thickness: 3.2 mm) (unit: kgf · cm / cm ² ).
(2) The flexural modulus molded product test piece (100 × 10 × 4 mm) was measured based on ASTM D790 at a fulcrum distance of 60 mm (unit: kgf / cm ² ).
(3) Paintability test On the surface of a molded product test piece (150 × 70 × 2 mm), a commercially available melamine alkyd-based top coat [trade name: Flexen # 101, manufactured by Nippon Bee Chemical Co., Ltd.] is thinner [trade name: # 101-10, manufactured by Nihon Bee Chemical Co., Ltd.] (paint / thinner weight ratio = 2/1) was spray-coated with a sprayer, then allowed to stand at room temperature for 15 minutes and circulated. Baking was performed at 120 ° C. for 20 minutes with a wind dryer (film thickness after drying: about 40 μm). The obtained coated surface was subjected to an adhesion test by a cross-cut tape method based on JIS K5400. The number of the part which the coating film did not peel among the grids 100 was represented by 0-100.

The coating property improving agent (A) of the present invention can improve its coating properties (coating film adhesion, etc.) by adding a small amount to the polyolefin resin (B) without impairing the mechanical properties of the polyolefin resin (B). Therefore, a molded article formed by molding the polyolefin resin composition containing the (A) is widely and suitably used in various industrial fields, particularly in the interior / exterior materials and home appliance fields in the automobile field.

Claims (10)

It has a hydrophobic group comprising a polyolefin (a) having a number average molecular weight of 1,500 to 100,000, a hydrophilic group containing at least one amino group (b), and (b) a number average molecular weight per one is 400 A coating property improving agent (A) comprising a modified polyolefin having a viscosity of ˜50,000. The paintability improving agent (A) according to claim 1, wherein (a) is a polyolefin having 0.2 to 10 double bonds per 1,000 carbon atoms in the molecular terminals and / or molecules. The paintability improving agent (A) according to claim 1 or 2, wherein (a) is a thermal degradation product of polyolefin. The paintability improving agent (A) according to any one of claims 1 to 3, wherein the hydrophilic group is represented by the following general formula (1).

[In the formula, R ¹ and R ² may be the same or different, and each may have a substituent selected from the group consisting of H or a hydroxyl group and an amino group; A group; X represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent selected from the group consisting of a hydroxyl group and an amino group; Z represents N constituting an amide group or an imide group. ] A polyolefin resin composition comprising the polyolefin resin (B) containing the paintability improving agent (A) according to any one of claims 1 to 4. The composition according to claim 5, wherein the proportion of (A) based on the weight of (B) is 0.01 to 30%. Further, one or two selected from the group consisting of plasticizers, lubricants, adhesion, dispersibility and / or compatibility imparting agents, antioxidants, ultraviolet absorbers, colorants, fillers, flame retardants and antistatic agents. The composition according to claim 5 or 6, comprising at least one kind of additive (C). The paintability improving agent (A) according to any one of claims 1 to 4 and the polyolefin resin (B), wherein the proportion of (A) based on the total weight of (A) and (B) is 1 to 95%. A masterbatch resin composition. A molded article formed by molding the composition according to any one of claims 5 to 7. A molded article obtained by coating and / or printing the molded article according to claim 9.