Modified polyolefin, and adhesive, aqueous dispersion, and resin modifier containing the modified polyolefin

Abstract

To provide a molding obtained by molding a resin composition containing a resin modifier containing modified polyolefin which has excellent wettability to water and excellent persistence of the wettability.SOLUTION: Modified polyolefin (Y) contains acid-modified polyolefin (a) and a compound (b0) having at least one amino group as essential constituent raw materials. The acid-modified polyolefin (a) is acid-modified polyolefin containing polyolefin (A) containing a carbon-carbon double bond and an unsaturated (poly)carboxylic acid (anhydride) (B) as essential constituent raw materials. The acid-modified polyolefin (a) satisfies all of the requirements (1) to (3), the polyolefin (A) having the carbon-carbon double bond is polyolefin containing ethylene and α-olefin (3 to 8 carbon atoms) as essential constituent monomers, and a weight ratio [ethylene / α-olefin] of the ethylene to the α-olefin (3 to 8 carbon atoms) as the constituent monomers is 5 / 95 to 65 / 35.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a modified polyolefin and an adhesive, an aqueous dispersion, and a resin modifier containing the modified polyolefin.

Background Art

[0002] Modified polyolefins are used in a wide range of applications such as resin surface modifiers, dispersants, compatibilizers, adhesives, coating materials, and ink materials. Recently, the use of polyolefins (especially polypropylene) has increased from the viewpoints of light weight, processability, chemical resistance, electrical insulation, and no generation of harmful substances during combustion. On the other hand, polyolefins have no polar groups, are chemically inert, have high crystallinity, and have extremely low solubility in solvents. Therefore, they have insufficient adhesion to coating materials and ink materials, poor wettability with water, and problems such as inability to apply aqueous coatings due to water repellency. Conventionally, as a method for improving the wettability of a polyolefin substrate, a method of performing corona treatment or plasma treatment on the surface of a thermoplastic resin substrate, for example, a polyolefin resin molded article (see, for example, Patent Document 1) has been proposed. As a method for improving adhesion to a coating, an aqueous polyurethane resin composition using chlorinated polyol has been proposed (for example, Patent Document 2). In recent years, with the increase in the speed of transmission signals in printed wiring boards, the frequency of signals has been increasing. Printed wiring boards have an increasing requirement for low dielectric characteristics (low dielectric constant, low dielectric tangent) in the high-frequency region. In response to this requirement, low-polarity films such as liquid crystal polymers, syndiotactic polystyrene, and polyphenylene sulfide having low dielectric characteristics have been proposed in place of polyimide and polyethylene terephthalate films. However, since the above films are low in polarity, conventional epoxy adhesives and acrylic adhesives have poor adhesiveness and also have poor low dielectric characteristics, resulting in problems such as impairing the dielectric characteristics of printed wiring boards. On the other hand, polyolefin resins are known to have low polarity and low dielectric characteristics, and adhesive compositions using polyolefin resins have been proposed. (For example, Patent Document 3)

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Disclosure of the Invention

Problems to be Solved by the Invention

[0004] However, in the method of subjecting the surface of a molded product to corona treatment or plasma treatment, there is a problem that the wettability decreases with the passage of time after the treatment. Further, in the method of adding a surfactant to a polyolefin resin composition and using this as a molded product, when an addition amount that sufficiently exhibits the modification effect is added, the mechanical strength (tensile elastic modulus, impact resistance, etc. The same shall apply hereinafter.) originally possessed by the molded product of the original polyolefin resin base material is impaired, or there are problems such as the surfactant bleeding out from the molded product. Also, from the viewpoint of adhesiveness to a polyolefin base material, the above post-processing technology is complicated in processing and cannot be said to be sufficiently satisfactory in terms of adhesiveness. Also, even the technology of the above Patent Document 2 is not sufficiently satisfactory in terms of storage stability, and improvement has been demanded. Further, in the technology of the above Patent Document 3, since the solvent solubility is poor, the coatability when using an adhesive is poor, and coating at a high temperature is required, and improvement has been demanded. An object of the present invention is to provide a resin modifier containing a modified polyolefin that imparts excellent wettability to water to a polyolefin resin substrate without impairing mechanical strength, a resin composition obtained by molding a resin composition containing the resin modifier, which imparts mechanical strength such as impact resistance characteristics, excellent processability, an adhesive containing a modified polyolefin that imparts low dielectric characteristics, a modified polyolefin having an effect of imparting excellent storage stability to an aqueous dispersion, and an aqueous dispersion containing the modified polyolefin.

Means for Solving the Problems

[0005] As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention is a modified polyolefin having an acid-modified polyolefin (a), a polyamine compound having two or more amino groups and at least one group selected from the group consisting of a primary amino group and a secondary amino group, and a compound (b0) having at least one amino group selected from the group consisting of a hydroxyl group and a tertiary amino group as essential constituent raw materials, wherein the acid-modified polyolefin (a) is an acid-modified polyolefin having a polyolefin (A) having a carbon-carbon double bond and an unsaturated (poly) carboxylic acid (anhydride) (B) as essential constituent raw materials, the acid-modified polyolefin (a) satisfies all of the following requirements (1) to (3), the polyolefin (A) having a carbon-carbon double bond is a polyolefin having ethylene and an α-olefin (carbon number 3 to 8) as essential constituent monomers, and the weight ratio [ethylene / α-olefin] of ethylene and the α-olefin (carbon number 3 to 8) as constituent monomers is 5 / 95 to 65 / 35. Modified polyolefin (Y). (1) Acid value is 1 to 100 mgKOH / g (2) Number average molecular weight (Mn) is 1,000 to 60,000 (3) Isotacticity of the α-olefin unit chain part is 1 to 50%

Effects of the Invention

[0006] The present invention has the following effects. (1) The resin modifier containing the modified polyolefin of the present invention imparts excellent water wettability to the polyolefin resin substrate without impairing the original mechanical strength. The molded article formed by molding the resin composition containing the resin modifier has excellent water wettability and excellent persistence thereof. (2) The adhesive containing the modified polyolefin of the present invention is excellent in adhesiveness to a substrate and low dielectric characteristics of the adhesive. (3) The aqueous dispersion containing the modified polyolefin of the present invention is excellent in storage stability and excellent in adhesion of the coating film to the substrate.

Mode for Carrying Out the Invention

[0007] The present invention relates to a modified polyolefin having an acid-modified polyolefin (a), a polyamine compound having two or more amino groups and at least one group selected from the group consisting of a primary amino group and a secondary amino group, and a compound having a hydroxyl group and a tertiary amino group as essential constituent raw materials. The acid-modified polyolefin (a) is an acid-modified polyolefin having a polyolefin (A) having a carbon-carbon double bond and an unsaturated (poly) carboxylic acid (anhydride) (B) as essential constituent raw materials. The acid-modified polyolefin (a) satisfies all of the following requirements (1) to (3). The polyolefin (A) having a carbon-carbon double bond is a polyolefin having ethylene and an α-olefin (having 3 to 8 carbon atoms) as essential constituent monomers, and the weight ratio [ethylene / α-olefin] of ethylene and the α-olefin (having 3 to 8 carbon atoms) as constituent monomers is 5 / 95 to 65 / 35. It is a modified polyolefin (Y). (1) Acid value is 1 to 100 mgKOH / g (2) Number average molecular weight (Mn) is 1,000 to 60,000 (3) Isotacticity of the α-olefin unit chain part is 1 to 50%

[0008] <Polyolefin (A) having a carbon-carbon double bond> The polyolefin (A) having a carbon-carbon double bond in the present invention contains ethylene and an α-olefin (having 3 to 8 carbon atoms) as essential constituent monomers. The α-olefin (having 3 to 8 carbon atoms) is an α-olefin having 3 to 8 carbon atoms, and examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and the like. Note that the α-olefin may be used alone or in combination of two or more, but one kind is preferred. Among the above α-olefins (having 3 to 8 carbon atoms), from the viewpoints of the adhesiveness of the adhesive to the polyolefin substrate, the adhesion of the aqueous dispersion, the impact resistance characteristics of the molded article containing the resin modifier, and industrial viewpoints, it is preferably a linear α-olefin (having 3 to 8 carbon atoms), more preferably a linear α-olefin (having 3 to 6 carbon atoms), and particularly preferably propylene.

[0009] The weight ratio [ethylene / α-olefin] of ethylene and an α-olefin (having 3 to 8 carbon atoms) which are constituent monomers of the polyolefin (A) having a carbon-carbon double bond is 5 / 95 to 65 / 35, preferably 8 / 92 for the lower limit, more preferably 10 / 90, particularly preferably 15 / 85, and preferably 60 / 40 for the upper limit, more preferably 40 / 60, particularly preferably 30 / 70. When the weight ratio [ethylene / α-olefin] is less than 5 / 95, the adhesiveness of the adhesive to the substrate, the adhesion of the coating film obtained by the aqueous dispersion to the substrate, and the impact resistance characteristics of the molded article containing the resin modifier are inferior. When it exceeds 65 / 35, the low dielectric characteristics of the adhesive, the storage stability of the aqueous dispersion, and the bending physical properties of the molded article containing the resin modifier are inferior.

[0010] The polyolefin (A) may contain other monomers as constituent monomers in addition to ethylene and an α-olefin (having 3 to 8 carbon atoms). In that case, based on the weight of all the monomers constituting (A), the weight of the other monomers is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less. Examples of the above-mentioned other monomers include unsaturated monomers having 4 to 30 carbon atoms other than α-olefins (e.g., olefins such as 2-butene and vinyl monomers such as styrene, acrylonitrile, acrylamide, and vinyl acetate), and α-olefins having 9 to 30 carbon atoms (abbreviated as [C] sometimes) (1-decene, 1-dodecene, etc.).

[0011] From the viewpoints of the adhesiveness of the adhesive to the substrate, the adhesiveness of the aqueous dispersion, the water wettability of the molded article containing the resin modifier, the coatability of the adhesive, the leveling property of the aqueous dispersion, and the moldability of the molded article containing the resin modifier, the number average molecular weight (Mn) of the polyolefin (A) having a carbon-carbon double bond is preferably 800 to 50,000, more preferably 1,500 to 40,000, and particularly preferably 2,000 to 30,000.

[0012] The measurement conditions of Mn and weight average molecular weight (Mw) of the polyolefin (A) having a carbon-carbon double bond, the high molecular weight polyolefin (A0) described below, the acid-modified polyolefin (a), and the modified polyolefin (Y) by GPC (gel permeation chromatography) in the present invention are as follows. Apparatus: High-temperature gel permeation chromatograph [「Alliance GPC V2000」, manufactured by Waters Corporation] Detection device: Refractive index detector Solvent: Orthodichlorobenzene Standard substance: Polystyrene Sample concentration: 3 mg / ml Column stationary phase: PLgel 10 μm, two MIXED-B columns in series [Manufactured by Polymer Laboratories Co., Ltd.] Column temperature: 135 °C

[0013] The polyolefin (A) having a carbon-carbon double bond preferably has 1 to 20 carbon-carbon double bonds per 1,000 carbon atoms [(the number of carbon-carbon double bonds at the molecular terminals and in the molecular chains of (A))], more preferably 1.5 to 18, and particularly preferably 2 to 15, from the viewpoints of reactivity and productivity with the unsaturated (poly)carboxylic acid (anhydride) (B) described below. Here, the number of double bonds can be determined from the 1 spectrum of 1H-NMR (nuclear magnetic resonance) spectroscopy. That is, the peaks in the spectrum are assigned, and the relative values of the number of carbon-carbon double bonds of (A) and the number of carbon atoms of (A) are determined from the integral value derived from the double bond at 4.5 to 6 ppm of (A) and the integral value derived from (A), and the number of carbon-carbon double bonds at the molecular terminals and in the molecular chains per 1,000 carbon atoms of (A) is calculated. The number of carbon-carbon double bonds in the examples described below was determined according to this method.

[0014] The isotacticity of the α-olefin moiety of the polyolefin (A) having a carbon-carbon double bond is 1 to 50%, more preferably 5 to 45%, and particularly preferably 10 to 40%. When the isotacticity of the α-olefin moiety of the polyolefin (A) is less than 1%, the adhesiveness to the substrate of the adhesive, the adhesion to the polyolefin substrate of the aqueous dispersion, and the bending physical properties of the molded article containing the resin modifier are insufficient. When it exceeds 50%, the coatability of the adhesive, the leveling property of the aqueous dispersion, and the impact resistance characteristics of the molded article containing the resin modifier deteriorate. The isotacticity of the α-olefin moiety of the above polyolefin (A) tends to be directly reflected in the isotacticity of the α-olefin moiety of the acid-modified polyolefin (a) described below.

[0015] The isotacticity of the present invention is 13It is calculated using 13C-NMR (nuclear magnetic resonance spectroscopy). Generally, the side-chain methyl group is affected by the configuration (meso or racemo) with methyl groups up to about both adjacent (triad), both adjacent to that triad (pentad), and further both adjacent to that pentad (heptad), and peaks are observed at different chemical shifts. It is generally known that the evaluation of stereoregularity is performed for the pentad, and the isotacticity in the present invention is also calculated based on the evaluation of the pentad. For example, when the α-olefin is propylene, 13 Regarding the carbon peak derived from the side-chain methyl group in propylene obtained by 13C-NMR, when each peak (H) of the pentad and the peak (Ha) derived from the methyl group in isotactic propylene formed only of meso structures are used, the isotacticity is calculated by the following formula. Isotacticity (%) = [(Ha) / Σ(H)] × 100 (1) However, in formula (1), Ha is the peak height of the signal of isotactic (formed only of meso structures in the pentad), H is the peak height of each peak of the pentad, and Σ(H) is the sum of the peak heights of each peak of the pentad. Note that the isotacticity of the α-olefin moiety in (a) described later can also be measured in the same manner as above.

[0016] Examples of the method for producing the polyolefin (A) having a carbon-carbon double bond in the present invention include a method of thermally reducing a high molecular weight polyolefin (A0) having a Mn of more than 60,000. From the viewpoint of the productivity of the polyolefin (A), the Mn of the high molecular weight polyolefin (A0) is preferably more than 60,000 and 400,000 or less, and more preferably 80,000 to 250,000.

[0017] In the thermal degradation method, there are included methods such as (1) a method of thermally degrading the high molecular weight polyolefin (A0) at 300 to 450°C for 0.5 to 10 hours in the absence of an organic peroxide, and (2) a method of thermally degrading at 180 to 300°C for 0.5 to 10 hours in the presence of an organic peroxide [for example, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane]. Among these, from the viewpoints of industrial aspects and the productivity of the acid-modified polyolefin (a) described later, preferably, the method (1) is used, which is likely to obtain a higher number of double bonds at the molecular terminals and / or in the molecular chain.

[0018] The weight ratio of ethylene to α-olefin (having 3 to 8 carbon atoms) [ethylene / α-olefin], which is the monomer constituting the above (A), tends to be maintained as it is in the weight ratio [ethylene / α-olefin] of the high molecular weight polyolefin (A0). Also, the higher the thermal degradation temperature and the longer the thermal degradation time, the greater the tendency for the number of double bonds per 1000 carbon atoms to be larger. Furthermore, the smaller the Mn of (A0), the higher the thermal degradation temperature, and the longer the thermal degradation time, the greater the tendency for the Mn of (A) to be smaller. Also, the greater the isotacticity of (A0), the greater the tendency for the isotacticity of (A) to be larger. The isotacticity of (A0) can be adjusted by selecting (A) having a predetermined isotacticity.

[0019] <Unsaturated (poly)carboxylic acid (anhydride) (B)> The unsaturated (poly)carboxylic acid (anhydride) (B) in the present invention is a (poly)carboxylic acid (anhydride) having 3 to 30 carbon atoms [hereinafter, may be abbreviated as C] having one polymerizable unsaturated group. In the present invention, the unsaturated (poly)carboxylic acid (anhydride) means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid, and / or an unsaturated polycarboxylic acid anhydride. Among these (B), examples of the unsaturated monocarboxylic acid include aliphatic (C3 to 24, such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid), alicyclic-containing (C6 to 24, such as cyclohexenecarboxylic acid); examples of the unsaturated poly(2 to 3 or more) carboxylic acid (anhydride) include unsaturated dicarboxylic acid (anhydride) [aliphatic dicarboxylic acid (anhydride) (C4 to 24, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and their anhydrides), alicyclic-containing dicarboxylic acid (anhydride) (C8 to 24, such as cyclohexenedicarboxylic acid, cycloheptenedicarboxylic acid, bicycloheptenedicarboxylic acid, methyltetrahydrophthalic acid, and their anhydrides), etc.]. Note that (B) may be used alone or in combination of two or more.

[0020] Among the above (B), from the viewpoint of reactivity with the polyolefin (A) having a carbon-carbon double bond, an unsaturated dicarboxylic anhydride is preferred, and maleic anhydride is more preferred.

[0021] <Acid-modified polyolefin (a)> The acid-modified polyolefin (a) in the present invention is an acid-modified polyolefin having a polyolefin (A) having a carbon-carbon double bond and an unsaturated (poly)carboxylic acid (anhydride) (B) as essential constituent raw materials, and is an acid-modified polyolefin obtained by subjecting the polyolefin (A) having a carbon-carbon double bond and the unsaturated (poly)carboxylic acid (anhydride) (B) to an addition reaction. The modification by the reaction with the unsaturated (poly)carboxylic acid (anhydride) (B) is, for example, an addition reaction between the polyolefin (A) and the unsaturated (poly)carboxylic acid (anhydride) (B) by any of a solution method or a melt method to the double bond of the polyolefin (A). Preferably, it is a modification obtained by reacting the polyolefin (A) and the unsaturated (poly)carboxylic acid (anhydride) (B) in the absence or presence of a radical initiator.

[0022] The weight ratio [(A) / (B)] of (A) to (B) in the reaction between (A) and (B) is preferably 80 / 20 to 99.5 / 0.5, more preferably 90 / 10 to 99 / 1, from the viewpoints of the adhesiveness of the adhesive to the base material, the adhesion of the aqueous dispersion to the polyolefin base material, the compatibility between the resin modifier and the polyolefin resin, and the low dielectric properties of the adhesive, the dispersion stability of the aqueous dispersion, and the water wettability imparting effect of the resin modifier.

[0023] The acid-modified polyolefin (a) can preferably be produced by reacting the polyolefin (A) and the unsaturated (poly)carboxylic acid (anhydride) (B) in the presence of a radical initiator (D) in an appropriate organic solvent [C3-18, such as hydrocarbons (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbons (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.)] if necessary. The radical initiator (D) is a known one, such as an azo initiator (azobisisobutyronitrile, etc.) and a peroxide initiator (dicumyl peroxide, etc.). Among the above (D), a peroxide initiator is preferred.

[0024] The reaction temperature is preferably 100 to 270°C, more preferably 120 to 250°C, and particularly preferably 130 to 240°C from the viewpoints of the reactivity and productivity of (A) and (B).

[0025] The acid-modified polyolefin (a) satisfies all of the following requirements (1) to (3). (1) The acid value is 1 to 100 mgKOH / g (2) The number average molecular weight (Mn) is 1,000 to 60,000 (3) The isotacticity of the α-olefin unit chain portion is 1 to 50%

[0026] Requirement (1): The acid value of (a) is 1 to 100 mgKOH / g (only the following numerical values are shown), preferably 3 to 75, and more preferably 5 to 50. The acid value herein is a value measured in accordance with JIS K0070:1992 and is a value measured by the following procedures (i) to (iii). (i) Dissolve 1 g of (X) in 100 g of xylene adjusted to a temperature of 100 °C. (ii) Using phenolphthalein as an indicator at the same temperature, titrate 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.]. (iii) Convert the amount of potassium hydroxide required for titration to mg and calculate the acid value (unit: mgKOH / g).

[0027] In the above measurement, it is possible to obtain a result in which one acid anhydride group is equivalent to one carboxyl group. When the acid value is less than 1, the adhesiveness of the adhesive to a metal substrate (such as a copper foil), the dispersion stability of the aqueous dispersion, and the effect of imparting water wettability to the resin modifier are inferior. When it exceeds 100, the productivity of (a) is inferior. In addition, the above acid value can be appropriately adjusted according to the number of double bonds of (A), the weight of (A), the type and weight of (B).

[0028] Requirement (2): The Mn of (a) is 1,000 to 60,000, preferably 2,000 to 50,000, and more preferably 3,000 to 40,000. When Mn is less than 1,000, the adhesiveness of the adhesive to the substrate, the adhesion of the coating film obtained by the aqueous dispersion to the polyolefin substrate, and the impact resistance characteristics of the molded article containing the resin modifier are inferior. When it exceeds 60,000, the coatability of the adhesive, the leveling property of the aqueous dispersion, and the productivity of the molded article containing the resin modifier deteriorate. In addition, the Mn of (a) above can be appropriately adjusted by controlling the Mn of (A), the type and amount of (B), and the reaction between (A) and (B).

[0029] Requirement (3): The isotacticity of the α-olefin unit chain portion in (a) is 1 to 50%, preferably 5 to 45%, more preferably 10 to 40%. When the isotacticity is less than 1%, the adhesiveness of the adhesive to the substrate, the adhesion of the coating film obtained from the aqueous dispersion to the polyolefin substrate, and the flexural physical properties of the molded article containing the resin modifier tend to be inferior. When it exceeds 50%, the coatability of the adhesive, the leveling property of the aqueous dispersion, and the impact resistance characteristics of the molded article containing the resin modifier tend to be inferior. Also, the isotacticity of the α-olefin unit chain portion in (a) can be appropriately adjusted by the isotacticity of (A) and (A0) as described above.

[0030] The acid-modified polyolefin (a) in the present invention may be further secondarily modified after reacting a polyolefin (A) having a carbon-carbon double bond with an unsaturated (poly)carboxylic acid (anhydride) (B). Specifically, (poly)aminocarboxylic acids and (poly)hydroxycarboxylic acids (m20) reactive with (B), lactams and lactones (m21) which are precursors of (m20) [compounds capable of forming (m20)], combinations (m22) of carboxy-reactive coupling agents and polycarboxylic acids (meaning an acid or its ester-forming derivative. The same applies hereinafter), and combinations of two or more of these can be used for modification. Also, this secondary modification can be carried out by (co)condensation of (m20), ring-opening addition (polymerization) of (m21), or coupling reaction of (m22).

[0031] Examples of the (poly)aminocarboxylic acid of (m20) include those having 2 to 12 carbon atoms, such as amino acids [glycine, alanine, valine, (iso)leucine, phenylalanine, etc.], ω-aminoalkanoic acids (e.g., ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc.), and aromatic aminocarboxylic acids (e.g., o-, m-, or p-aminobenzoic acid, etc.).

[0032] Examples of the (poly)hydroxycarboxylic acid of (m20) include ω-hydroxycaproic acid, salicylic acid, p- or m-hydroxybenzoic acid, glycolic acid, glyceric acid, tartronic acid, malic acid, tartaric acid, and benzoic acid. Examples of the lactam of (m21) include those having 4 to 15 (preferably 6 to 12) carbon atoms, such as ε-caprolactam, enanthlactam, laurolactam, and undecanolactam. Examples of the lactone of (m21) include ε-caprolactone, γ-butyrolactone, and γ-valerolactone.

[0033] Among these, ε-caprolactam and 12-aminododecanoic acid are preferred. The usage amounts of (m21) and (m20) are 1 to 10 moles or more, preferably 1 to 2 moles, per mole of the carboxylic acid group (anhydride group in the case of carboxylic acid anhydride) possessed by the acid-modified polyolefin (a).

[0034] Examples of the carboxy-reactive coupling agent of (m22) include compounds having two or more groups reactive with the carboxy group of polycarboxylic acids, such as polyols, organic polyisocyanates, polyepoxides, and epoxy alcohols. Examples of these polycarboxylic acids, polyols, organic polyisocyanates, and polyepoxides are those described later, and examples of the epoxy alcohol include glycidol.

[0035] Examples of the above polyol of (m22) include dihydric to octahydric or higher polyols, low molecular weight polyols (having a hydroxyl equivalent of less than 250), and mixtures of two or more of these. The above hydroxyl equivalent means the molecular weight per hydroxyl group based on the hydroxyl value. Examples of the low molecular weight polyol include polyhydric alcohols and low molecular weight hydroxyl-terminated polymers (such as polyether polyols and polyester polyols).

[0036] Examples of polyhydric alcohols include dihydric alcohols (C2 to 20 or more), such as aliphatic dihydric alcohols having 2 to 12 carbon atoms [(di)alkylene glycols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,3-, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentanediol (hereinafter abbreviated as EG, DEG, PG, DPG, BD, HD, NPG and MPD, respectively) and dodecanediol, etc.], alicyclic dihydric alcohols having 6 to 10 carbon atoms [1,4-cyclohexanediol and cyclohexanedimethanol, etc.], and araliphatic dihydric alcohols having 8 to 20 carbon atoms [xylylene glycol and bis(hydroxyethyl)benzene, etc.];Trivalent to octavalent or higher polyhydric alcohols, such as (cyclo)alkanepolyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol, dipentaerythritol, 1,2,6 - hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, and diglycerin and other polyglycerins, etc.], saccharides and their derivatives [e.g., sucrose, glucose, fructose, mannose, lactose, and glucosides (such as methyl glucoside, etc.)], nitrogen - containing polyols (tertiary amino group - containing polyols and quaternary ammonium group - containing polyols): for example, nitrogen - containing diols, such as bis - hydroxyalkyl (C2 - 4) compounds of aliphatic, alicyclic, and aromatic primary monoamines having 1 to 12 carbon atoms [methylamine, ethylamine, 1 - or 2 - propylamine, (iso)amylamine, hexylamine, 1,3 - dimethylbutylamine, 3,3 - dimethylbutylamine, 1 -, 2 - or 3 - aminoheptane, nonylamine, decylamine, undecylamine, dodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, aniline, benzylamine, etc.] [bis(2 - hydroxyethyl) compounds, bis(hydroxypropyl) compounds, etc., such as the tertiary nitrogen atom - containing polyols described in U.S. Patent No. 4,271,217] and their quaternized products [quaternized products with the quaternizing agents or dialkyl carbonates (such as dimethyl carbonate, etc.) described in the above - mentioned U.S. Patent Specification], for example, the quaternary nitrogen atom - containing polyols described in the above - mentioned U.S. Patent Specification; trivalent to octavalent or higher nitrogen - containing polyols, such as trialkanol (C2 - 4) amines (such as triethanolamine, etc.) and their quaternized products similar to the above.;

[0037] Examples of the low molecular weight hydroxyl-terminated polymers include those having a hydroxyl equivalent of less than 250 among the polyether polyols, polyester polyols, and polyurethane polyols described below. Examples thereof include low-degree-of-polymerization alkylene oxide (hereinafter abbreviated as AO) ring-opening polymers and low-molar AO adducts of active hydrogen atom-containing polyfunctional compounds [for example, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc., bis(hydroxyethoxy)benzene, and ethylene oxide 2 to 4 mol adducts of bisphenol A described below], low-condensation-degree condensation polyester polyols, and low-molar lactone adducts of polyols [condensates of polycarboxylic acids and excess (1 mol per carboxy group) polyhydric alcohols (for example, dihydroxyethyl adipate) and 1 mol caprolactone adduct of EG], and low-degree-of-polymerization polyurethane polyols (for example, reaction products of 1 mol of tolylene diisocyanate and 2 mol of EG).

[0038] Examples of the polyether polyols include AO ring-opening polymers, polyether polyols (AO adducts) having a structure in which one or more types of AOs are added to initiators having at least two (two to eight or more) active hydrogen atoms [the above polyhydric alcohols, hydroxylamines, aminocarboxylic acids, and hydroxycarboxylic acids; polyvalent phenols; and polycarboxylic acids (described below, etc.)], and polyether polyols obtained by coupling two molecules or more thereof (identical or different) with a coupling agent (polyhalide, epihalohydrin, polyepoxide, etc.).

[0039] Examples of the above AOs include C2 to 12 or more (preferably 2 to 4) AOs, such as ethylene oxide, 1,2-propylene oxide, tetrahydrofuran, and 3-methyl-tetrahydrofuran (hereinafter abbreviated as EO, PO, THF, and MTHF, respectively), 1,3-propylene oxide, 1,2-, 2,3-, 1,3- or isobutylene oxide, C5 to 12 α-olefin oxides, substituted AOs, such as styrene oxide and epihalohydrin (epichlorohydrin, etc.), and those using two or more of these in combination (random addition and / or block addition).

[0040] Examples of polyether polyols include polyether diols such as polyalkylene glycols [e.g., polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol (hereinafter abbreviated as PEG, PPG, and PTMG, respectively), poly-3-methyltetramethylene ether glycol], copolymerized polyoxyalkylene diols [EO / PO copolymerized diols, THF / EO copolymerized diols, THF / MTHF copolymerized diols, etc. (weight ratio, e.g., 1 / 9 to 9 / 1)], polyoxyalkylene diols containing an aromatic ring [polyoxyalkylene bisphenol A (EO and / or PO adducts of bisphenol A, etc.)]; and polyether polyols having three or more functional groups, such as polyoxypropylene triol (PO adduct of glycerin, etc.); and those obtained by coupling one or more of these with methylene dichloride.

[0041] Examples of polyester polyols include condensation polyester polyols, polylactone polyols, castor oil-based polyols [castor oil (triglyceride of ricinoleic acid) and its polyol-modified products], and polycarbonate polyols.

[0042] Condensation polyester polyols are produced by polycondensation of polyols and polycarboxylic acids (and, if necessary, hydroxycarboxylic acids) or reaction of polyols with polycarboxylic acid anhydrides and AO. Polylactone polyols are produced by ring-opening addition of lactones using polyols as initiators (or polycondensation of polyols and hydroxycarboxylic acids). Castor oil-based polyol-modified products are produced by transesterification of castor oil and polyols. And polycarbonate polyols can be produced by (1) ring-opening addition / polycondensation of alkylene carbonates using polyols as initiators, (2) polycondensation (transesterification) of polyols and diphenyl or dialkyl carbonates, or (3) phosgenation of polyols or dihydric phenols (such as bisphenol A).

[0043] The polyol used in the production of the polyester polyol has a hydroxyl equivalent weight of less than 250. Examples thereof include the above polyhydric alcohols [diols (e.g., EG, 1,4-BD, NPG, HD, and DEG), polyols having three or more hydroxyl groups (such as glycerin, trimethylolpropane, and pentaerythritol, etc.)], the above polyether polyols (PEG, PPG, PTMG, etc.), and mixtures of two or more of these. Preferred for the production of the condensation polyester polyol is the combined use of a diol and a polyol having three or more hydroxyl groups in a small proportion (e.g., 10 equivalent % or less) thereof.

[0044] Examples of the polycarboxylic acids include dicarboxylic acids and polycarboxylic acids having three to four or more carboxyl groups. Examples thereof include saturated and unsaturated aliphatic polycarboxylic acids having 2 to 30 or more carbon atoms (preferably 2 to 12 carbon atoms), such as C2-15 dicarboxylic acids (e.g., 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 acids (e.g., tricarballylic acid, hexanetricarboxylic acid, etc.); aromatic polycarboxylic acids having 8 to 15 carbon atoms, such as dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, phthalic acid, etc.), tri- or tetra-carboxylic acids (e.g., trimellitic acid, pyromellitic acid, etc.); alicyclic polycarboxylic acids having 6 to 40 carbon atoms (dimer acid, etc.); sulfonic group-containing polycarboxylic acids [those obtained by introducing a sulfonic group into the above polycarboxylic acids, such as sulfosuccinic acid, sulfomalonic acid, sulfoglutaric acid, sulfoadipic acid, sulfoisophthalic acid, and salts thereof [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; as well as amine salts and quaternary ammonium salts, etc.]]; and polymers having a carboxyl terminal.

[0045] Examples of the carboxy-terminated polymers include polyether polycarboxylic acids such as carboxymethyl ethers of polyols (such as the above-mentioned polyhydric alcohols and polyether polyols) obtained by reacting monochloroacetic acid in the presence of an alkali; polyamide polycarboxylic acids, polyester polycarboxylic acids, and polyurethane polycarboxylic acids, such as polylactam polycarboxylic acids and polylactone polycarboxylic acids obtained by ring-opening polymerization of lactams or lactones using the above-mentioned polycarboxylic acids as initiators, condensation polyester polycarboxylic acids and condensation polyamide polycarboxylic acids obtained by coupling (esterifying or amidating) two or more molecules of the above-mentioned polycarboxylic acids with a polyol or polyamine, and polyurethane polycarboxylic acids obtained by reacting the above-mentioned polycarboxylic acids, polyols, and organic polyisocyanates.

[0046] Examples of the ester-forming derivatives of polycarboxylic acids include acid anhydrides, lower alkyl (C1 - 4) esters, and acid halides, such as anhydrides of succinic acid, maleic acid, itaconic acid, and phthalic acid, dimethyl terephthalate, and malonyl dichloride.

[0047] For the production of the condensation polyester polyol, it is preferable to use a combination of dicarboxylic acids and a small proportion (for example, 10 equivalent% or less) of trivalent to tetravalent or higher polycarboxylic acids. Examples of the lactones and hydroxycarboxylic acids are those described above. Examples of the alkylene carbonates include those having a C2 - 6 alkylene group, such as ethylene carbonate and propylene carbonate. Examples of the dialkyl carbonates include those having a C1 - 4 alkyl group, such as dimethyl, diethyl, or di - i - propyl carbonate.

[0048] Specific examples of the polyester polyol include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene / propylene adipate, polyethylene / butylene adipate, polybutylene / hexamethylene adipate, polydiethylene adipate, poly(polytetramethylene ether) adipate, polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol, polyhexamethylene carbonate diol, and the like.

[0049] Examples of the organic polyisocyanate include the following organic polyisocyanates having 2 to 6 or more (preferably 2 to 3, particularly preferably 2) isocyanate groups and mixtures of two or more thereof. Aliphatic polyisocyanates having C (excluding carbon in the NCO group, the same applies hereinafter) of 2 to 18: diisocyanates, such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, 2,6-diisocyanatoethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, etc.; polyisocyanates having 3 or more functional groups (triisocyanates, etc.), such as 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatemethyloctane, 1,3,6-hexamethylene triisocyanate, lysine ester triisocyanate (phosgenated product of the reaction product of lysine and alkanolamine), 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- or 3-isocyanatopropyl-2,6-diisocyanatohexanoate, etc.;

[0050] C4 - 15 alicyclic polyisocyanates: diisocyanates such as isophorone diisocyanate (IPDI), dicyclohexylmethane - 4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2 - isocyanatoethyl)-4 - cyclohexylene - 1,2 - dicarboxylate, 2,5 - or 2,6 - norbornane diisocyanate; polyisocyanates with three or more functional groups (triisocyanates, etc.), such as bicycloheptane triisocyanate; C8 - 15 araliphatic polyisocyanates: m - or p - xylylene diisocyanate (XDI), diethylbenzene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI);

[0051] C6 - 20 aromatic polyisocyanates: diisocyanates such as 1,3 - or 1,4 - phenylene diisocyanate, 2,4 - or 2,6 - tolylene diisocyanate (TDI), 4,4'- or 2,4'-diphenylmethane diisocyanate (MDI), m - or p - isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl - 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl - 4,4'-diisocyanatodiphenylmethane, 1,5 - naphthylene diisocyanate, etc.; polyisocyanates with three or more functional groups (triisocyanates, etc.), such as crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate);

[0052] And modified products of organic polyisocyanates: modified products of these organic polyisocyanates [such as modified products having carbodiimide, urethane, urea, isocyanurate, uretoimine, allophanate, biuret, oxazolidone and / or uretdione groups], for example, urethane - modified products of MDI, TDI, HDI, IPDI, etc. (NCO - terminal urethane prepolymers obtained by reacting a polyol with an excess of organic polyisocyanate), biuret - modified products, isocyanurate - modified products, trihydrocarbyl phosphate - modified products, and mixtures thereof.

[0053] Among organic polyisocyanates, from the viewpoint of light resistance, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates and combinations thereof are preferred, and aliphatic polyisocyanates, alicyclic polyisocyanates and combinations thereof are particularly preferred.

[0054] Examples of the polyepoxide in (m22) include the following. (1) Aliphatic polyepoxides: polyglycidyl ethers of aliphatic polyols [the above divalent to octavalent or higher polyhydric alcohols and polyether polyols]: diglycidyl ethers [for example, diglycidyl ethers of EG, PG, 1,4-BD, HD, MPD, DEG, NPG, PEG (Mn 150 to 200,000) or PPG (Mn 134 to 200,000)], triglycidyl ethers [for example, triglycidyl ethers of glycerin or trimethylolpropane, etc.] and tetravalent or higher glycidyl ethers [for example, pentaerythritol tetraglycidyl ether and sorbitol hexaglycidyl ether]; polyglycidyl esters of aliphatic polycarboxylic acids (the above divalent to trivalent or higher aliphatic polycarboxylic acids mentioned for the production of polyester polyols) [for example, diglycidyl esters of oxalic acid and adipic acid and tricarballyl triglycidyl ester, etc.],

[0055] (2) Alicyclic polyepoxides: those having 8 to 20 carbon atoms, such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl) ether, EG bisepoxy dicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate and hydrogenated products of the nuclei of the aromatic ring-containing polyepoxides described below; (3) Heterocyclic ring-containing polyepoxides: having 5 to 20 carbon atoms, such as trisglycidyl melamine, etc.;

[0056] (4) Aromatic ring-containing polyepoxide: Polyglycidyl ether of polyhydric phenol (the above-mentioned dihydric to trihydric or higher polyhydric phenol) or its AO adduct: Diglycidyl ether of dihydric phenol (diglycidyl ether of bisphenol F, A, B, AD or S, catechol diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, and diglycidyl ether obtained by reacting 2 moles of bisphenol A with 3 moles of epichlorohydrin, etc.); Triglycidyl ether of trihydric phenol (pyrogallol triglycidyl ether, etc.), and the like.

[0057] Among the polyepoxides in (m22), from the viewpoint of reactivity with (a), aliphatic polyepoxides and aromatic ring-containing polyepoxides are preferred, and trimethylolpropane triglycidyl ether and bisphenol A diglycidyl ether are more preferred. Moreover, among the above polyepoxides, those having an epoxy equivalent of 50 to 500 g / eq, particularly 60 to 200 g / eq, are more preferred.

[0058] The secondary modified product of the reaction product of the polyolefin (A) having a carbon-carbon double bond and the unsaturated (poly)carboxylic acid (anhydride) (B) of the present invention has a structure in which at least a part of the carboxy group or carboxylic anhydride group of the reaction product of the polyolefin (A) having a carbon-carbon double bond and the unsaturated (poly)carboxylic acid (anhydride) (B) is converted into a carboxy-containing group represented by, for example, the following three general formulas. -E-(G-L-E) n -G-L-E-OH (-E-) p G-L 3 [-G-(E-L 1 -E-G-L 2 -G) n -E-L 1 -E-OH] f (-E-) p G-L 3[-G-E-(L-G-E) n -L 1 -(E-G-L) n -E-OH] f

[0059] 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 (excluding amino group or hydroxyl group and carboxy group) or a residue of lactam or lactone (excluding amide or ester bond); L 1 is a residue of dicarboxylic acid (excluding two carboxy groups); L 2 is a residue of diol (excluding hydroxyl group); f is an integer of 0 or 1 or more; L 3 is a residue of (1 + f)-valent polyol or organic polyisocyanate (excluding hydroxyl group or isocyanate group) or an epoxy ring-opening group (a group formed by ring-opening of epoxide); p is 1 or 2; G is -O- (when L is a residue of hydroxycarboxylic acid or lactone, L 2 is a residue of diol, L 3 is a residue of polyol or epoxy ring-opening group) or -NH- (when L is a residue of aminocarboxylic acid or lactam, L 3 is a residue of organic polyisocyanate) [that is, (-E-) p G- represents an ester bond, an amide bond or an imide bond]. In the above and below, the groups of each symbol in the case of multiple existence may be the same or different. Examples of the epoxy ring-opening group include -CH 2 -CH(OH)-CH 2 -, and polyepoxy ring-opening groups, for example, a group represented by the formula -CR 4 -CR 5 -J-(CR 5 -CR 4 -) f [In the formula, J is a residue of polyepoxide (excluding epoxy group); R 4 and R 5 One of them (for example, R 5 ) is OH, and the other (for example, R 4) is H, or they (e.g., two Rs 4 ) may be bonded to each other or to J to form a ring (when J is a residue of an alicyclic polyepoxide).

[0060] <Compound (b0) having an amino group> The compound (b0) having an amino group in the present invention is at least one amino group-containing compound selected from the group consisting of a polyamine compound having two or more amino groups and at least one group selected from the group consisting of a primary amino group and a secondary amino group, and a compound having a hydroxyl group and a tertiary amino group.

[0061] Examples of the polyamine compound having two or more amino groups and at least one group selected from the group consisting of a primary amino group and a secondary amino group include those having 2 to 69 carbon atoms, such as ethylenediamine, N-methyl or N-ethylethylenediamine, 1,3-propanediamine, N-methyl-, N-ethyl- or N-butyl-1,3-propanediamine, p-phenylenediamine, N-methyl- or N-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- or -dibutyl-1,3-propanediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N,N,N'-trimethyl-1,3-propanediamine, tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, isophoronediamine, 3,8-bis(aminomethyl)tricyclodecane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, aminoethylpiperazine and the like. Examples of the compound having a hydroxyl group and a tertiary amino group include those having 4 to 69 carbon atoms, such as 2-dimethylaminoethanol, 2-diethylaminoethanol, m-dimethylaminophenol and N-methyldiethanolamine.

[0062] Among the above (b0), from the viewpoint of the reactivity between the acid-modified polyolefin (a) and (b0), preferred are polyamine compounds having two or more amino groups and at least one group selected from the group consisting of primary amino groups and secondary amino groups, more preferably polyamine compounds having at least one group selected from the group consisting of primary amino groups and secondary amino groups and at least one tertiary amino group, polyamine compounds having at least one primary amino group and at least one secondary amino group, and polyamine compounds having two or more primary amino groups only as amino groups.

[0063] The compound (b0) having an amino group in the present invention is preferably a compound represented by the following general formula (1) from the viewpoints of adhesion to the base material of the adhesive described later, adhesion to the polyolefin base material of the aqueous dispersion, and water wettability of the molded article containing the resin modifier.

[0064]

Chemical formula

[0065] R in the general formula (1) 1 、R 2 、R 3 and R 4 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and an aralkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group.

[0066] R 1 、R 2 、R 3 and R 4 are preferably those having 1 to 15 carbon atoms and a hydrogen atom from the viewpoints of adhesion to the base material of the adhesive, dispersion stability of the aqueous dispersion, and water wettability of the resin modifier, and more preferably those having 1 to 4 carbon atoms and a hydrogen atom.

[0067] R in the general formula (1) 5and R 6 is each independently a divalent hydrocarbon group having 2 to 20 carbon atoms. Examples of the divalent hydrocarbon group having 2 to 20 carbon atoms include an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, and an aralkylene group, such as an ethylene group, a propylene group, a butylene group, a cyclohexylene group, and a phenylene group. R 5 and R 6 is preferably a group having 2 to 15 carbon atoms, more preferably 3 to 13 carbon atoms, from the viewpoints of adhesiveness to the base material of the adhesive, dispersibility stability of the aqueous dispersion, and water wettability characteristics of the resin modifier. n in the general formula (1) is preferably an integer of 0 to 9, more preferably an integer of 0 to 6, and particularly preferably 0 to 3, from the viewpoints of low dielectric characteristics of the adhesive, adhesion of the coating film obtained from the aqueous dispersion to the polyolefin base material, and mechanical strength of the molded article containing the resin modifier.

[0068] (b0) is preferably hexamethylenediamine, isophoronediamine, 3,3'-diaminodipropylamine, 1,2-diaminobutane, bis(4-aminocyclohexyl)methane, N,N-dimethyl-1,3-propanediamine, more preferably hexamethylenediamine, isophoronediamine, bis(4-aminocyclohexyl)methane, N,N-dimethyl-1,3-propanediamine, from the viewpoints of adhesiveness to the base material of the adhesive, dispersibility stability of the aqueous dispersion, and water wettability characteristics of the resin modifier.

[0069] <Modified polyolefin (Y)> The modified polyolefin (Y) of the present invention comprises the acid-modified polyolefin (a), a polyamine compound having two or more amino groups and at least one group selected from the group consisting of primary amino groups and secondary amino groups, and at least one compound (b0) having an amino group selected from the group consisting of a compound having a hydroxyl group and a tertiary amino group as essential constituent monomers.

[0070] The modified polyolefin (Y) is obtained by reacting a carboxy group or a carboxylic anhydride group in the modified polyolefin (a) with at least one selected from the group consisting of (poly)aminocarboxylic acid and (poly)hydroxycarboxylic acid (m20), lactam and lactone (m21) which are precursors of (m20), and a combination of a carboxy-reactive coupling agent and a polycarboxylic acid (m22), and at least one group selected from the group consisting of a hydroxyl group, a primary amino group, and a secondary amino group in the compound (b0) having an amino group.

[0071] The molar ratio (carboxylic acid group / amino group) of the carboxylic acid group of the acid-modified polyolefin (a) to the amino group of (b0) is preferably 1 / 1.01 to 1 / 5, more preferably 1 / 1.2 to 1 / 4, and particularly preferably 1 / 1.5 to 1 / 3 from the viewpoints of the adhesiveness of the adhesive to the base material, the adhesion of the aqueous dispersion to the polyolefin base material, and the impact resistance characteristics of the molded article containing the resin modifier.

[0072] The melt viscosity of the modified polyolefin (Y) at 220°C is preferably 0.1 to 20 Pa·s, more preferably 0.3 to 15 Pa·s, and particularly preferably 0.5 to 10 Pa·s. The above melt viscosity can be adjusted, for example, by the number average molecular weight (Mn), isotacticity, and type of the polyolefin (A) of the acid-modified polyolefin (a).

[0073] The amine value of the obtained modified polyolefin (Y) is preferably 0.5 to 100 mgKOH / g, more preferably 0.9 to 80 mgKOH / g, and particularly preferably 10 to 30 mgKOH / g from the viewpoints of the adhesiveness of the adhesive to the base material, the dispersion stability of the aqueous dispersion, the water wettability characteristics of the molded article containing the resin modifier and the low dielectric characteristics of the adhesive, the adhesion of the aqueous dispersion to the polyolefin base material, and the compatibility between the resin modifier and the polyolefin resin. The amine value herein is a value measured in accordance with JIS K7237:1995.

[0074] The method for producing the modified polyolefin (Y) in the present invention is not particularly limited, but examples include a method in which an acid-modified polyolefin (a) and a compound (b0) having an amino group are reacted at a high temperature (for example, 140 to 280 ° C), normal pressure or reduced pressure (for example, 0.1 to 760 mmHg) in a nitrogen atmosphere.

[0075] <Adhesive> The adhesive of the present invention contains a modified polyolefin (Y). In the adhesive of the present invention, various curing agents that react with the amino groups of the modified polyolefin (Y) can be contained as necessary within a range that does not inhibit the effects of the present invention. The curing agent is not particularly limited, and examples include naphthalene-type epoxy compounds, glycidyl ether-type epoxy compounds, glycidyl ester-type epoxy compounds, alicyclic epoxy compounds, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, dicyclopentadiene-type epoxy compounds, novolac phenol-type epoxy compounds, biphenyl-type epoxy compounds, etc., and mixtures of two or more of these. Preferably, glycidyl ether-type epoxy compounds and alicyclic epoxy compounds are mentioned. The content of the curing agent is preferably 30% by weight or less, more preferably 0.002 to 25% by weight, and particularly preferably 1 to 20% by weight, from the viewpoints of the addition effect and adhesiveness, based on the weight of the modified polyolefin (Y).

[0076] When the additives are the same and overlapping between the curing agent and the additives (F1) to (F13) described later, the amounts of the curing agent and each additive that exhibit the corresponding additive effects are not used as they are. Instead, the effects as the curing agent and other additives are also considered, and the usage amounts are adjusted according to the purpose of use.

[0077] In the adhesive of the present invention, various additives (F) can be further contained as necessary within a range that does not inhibit the effects of the present invention. Examples of the additive (F) include one or more selected from the group consisting of a tackifier (F1), a plasticizer (F2), an adsorbent (F3), a colorant (F4), a flame retardant (F5), a filler (F6), a lubricant (F7), a nucleating agent (F8), an antioxidant (F9), a mold release agent (F10), a light stabilizer (F11), a fragrance (F12), and an ultraviolet absorber (F13).

[0078] Examples of the tackifier (F1) include terpene resins, terpene phenol resins, phenol resins, aromatic hydrocarbon-modified terpene resins, rosin resins, modified rosin resins, synthetic petroleum resins (such as aliphatic, aromatic, or alicyclic synthetic petroleum resins), coumarone-indene resins, xylene resins, styrene resins, dicyclopentadiene resins, and hydrogenated products of those having hydrogenatable unsaturated double bonds among these.

[0079] As the plasticizer (F2), various plasticizers [for example, those described in Adhesion Technology Vol. 20, (2), 21 (2000), etc.] can be used, such as process oils (paraffin, naphthene, or aromatic compound type); liquid resins (Mn 300 to 6,000, such as liquid polybutene, liquid polybutadiene, liquid polyisoprene); hydrogenated products of the liquid resins; low molecular weight (Mn 300 to 10,000) polyisobutylene; and mixtures of two or more of these.

[0080] Examples of the adsorbent (F3) include alumina, silica gel, molecular sieves, etc.

[0081] Examples of the colorant (F4) include inorganic pigments [such as white pigments, cobalt compounds, iron compounds, sulfides, etc.], organic pigments [such as azo pigments, polycyclic pigments, etc.], dyes [such as azo-based, indigoid-based, sulfur-based, alizarin-based, acridine-based, thiazole-based, nitro-based, aniline-based, etc.].[[]END]]

[0082] Examples of the flame retardant (F5) include halogen-containing flame retardants, sulfur-containing flame retardants, phosphorus-containing flame retardants, metal hydroxide-containing flame retardants, etc.

[0083] Examples of the filler (F6) include inorganic fillers (such as calcium carbonate, talc, clay, etc.).

[0084] Examples of the lubricant (F7) include calcium stearate, butyl stearate, oleic acid amide, etc.

[0085] Examples of the nucleating agent (F8) include sorbitol, metal phosphate salts, metal benzoate salts, metal phosphate salts, etc.

[0086] Examples of the antioxidant (F9) include phenolic compounds [monocyclic phenols (such as 2,6-di-t-butyl-p-cresol, etc.), bisphenols (such as 2,2'-methylenebis(4-methyl-6-t-butylphenol), etc.), polycyclic phenols (such as 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, etc.)], sulfur compounds (such as dilauryl 3,3'-thiodipropionate, etc.), phosphorus compounds (such as triphenyl phosphite, etc.).

[0087] Examples of the mold release agent (F10) include carboxy-modified silicone oil, hydroxyl-modified silicone oil, etc.

[0088] Examples of the light stabilizer (F11) include hindered amine compounds [such as bis-2,2,6,6-tetramethyl-4-piperidyl sebacate, etc.].

[0089] Examples of the fragrance (F12) include diterpenes, limonene, etc.

[0090] Examples of the ultraviolet absorber (F13) include benzotriazoles [such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, etc.], benzophenones [such as 2-hydroxy-4-methoxybenzophenone, etc.], salicylates [such as phenyl salicylate, etc.].

[0091] The total content of the additive (F) is preferably 50% by weight or less, more preferably 0.002 to 40% by weight, and particularly preferably 1 to 30% by weight based on the weight of the modified polyolefin (Y) from the viewpoints of the additive effect and adhesiveness.

[0092] When the additives are the same and overlap among the above (F1) to (F13), instead of using the amount of each additive that exhibits the corresponding additive effect as it is, the amount used shall be adjusted according to the purpose of use, taking into account that the effects as other additives can also be obtained simultaneously.

[0093] The adhesive of the present invention may be used in a form dissolved in an organic solvent described below if necessary, or may be appropriately formed into a desired shape such as a block, pellet, powder, sheet, or film and then used. A pelletizer, crusher, extruder, etc. are used for forming. The method of using the adhesive of the present invention is not particularly limited. For example, when the adhesive is dissolved in an organic solvent, it is directly applied to the adherend, and the organic solvent is volatilized if necessary. When the adhesive is in the form of a block or pellet, it is melted and then applied to the adherend for use.

[0094] <Adherend> The adhesive of the present invention can adhere an adherend to obtain an adhesive body. Examples of the adherend include various plastics [polyolefins (such as polyethylene and polypropylene), polystyrene, syndiotactic polystyrene, ABS, polyvinyl chloride, polycarbonate, polyacetal, polyester, polyamide, polyimide, polyurethane, modified PPO, polymethyl methacrylate, liquid crystal polymer, epoxy resin, phenolic resin, and melamine resin, etc.], rubbers [natural rubber, synthetic rubbers (such as chloroprene rubber, isoprene rubber, SBR, NBR, butyl rubber, and EP rubber, etc.)], porous materials [wood, paper, cloth (woven or non-woven fabric of natural fibers and synthetic fibers, etc.), and plastic foams (such as polyolefin foam and polyurethane foam, etc.)], and inorganic materials [metals (such as copper, iron, tinplate, galvanized steel, aluminum, and zinc steel plate, etc.), glass, tile slate, and ceramics, etc.]. Among these, from the viewpoints of low dielectric properties and heat resistance, polyolefin, polyimide, syndiotactic polystyrene, and liquid crystal polymer base materials are preferable. Moreover, it is preferable that at least one of the adherends is a polyolefin base material.

[0095] The method for applying the adhesive of the present invention to an adherend is not particularly limited, and for example, known coating methods such as spiral coating, roll coating, slot coating, control seam coating, and bead coating can be used. Examples of coating apparatuses include a gravure coater, a roll coater (such as a gravure roll and a reverse roll), a reverse coater, a doctor blade, a bar coater, a comma coater, a fountain die coater, a lip coater, a knife coater, a curtain coater, a bead, a spiral, a spray, a slot, and an extruder (single-screw, twin-screw extruder, and kneader extruder).

[0096] <aqueous dispersion> The aqueous dispersion of the present invention contains water and the modified polyolefin (Y). The above aqueous dispersion can be produced, for example, by the following method.

[0097] (1) A solvent solution containing the modified polyolefin (Y) and, if necessary, a solvent described later is prepared. Next, water and, if necessary, a solvent are charged, phase inversion emulsification is carried out, and if necessary, the solvent is distilled off to obtain an aqueous dispersion. (2) A solvent solution containing the modified polyolefin (Y) and, if necessary, a solvent described later is prepared. Next, water is added and dispersed, for example, by a disperser, and if necessary, the solvent is distilled off to obtain an aqueous dispersion. The production apparatus is not particularly limited, and any apparatus having mixing and dispersing capabilities can be used. However, from the viewpoints of temperature adjustment and mixing and dispersing capabilities, it is preferable to use a rotary mixing and dispersing apparatus. Examples of the rotary mixing and dispersing device include a mixing device having a general stirring blade such as a Max Blend or a helical blade, a TK homomixer [manufactured by Primix Corporation], a Clear Mix [manufactured by M Technique Co., Ltd.], a Filmix [manufactured by Primix Corporation], an Ultra Turrax [manufactured by IKA Japan Co., Ltd.], an Ebara milder [manufactured by Ebara Corporation], a Cavitron [manufactured by Eurotech Co., Ltd.], and a Biomixer [manufactured by Nippon Seiki Co., Ltd.].

[0098] In the step of obtaining the aqueous dispersion, in addition to (Y) and the solvent and water, if necessary, known anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants may be used.

[0099] Examples of the solvent include organic solvents such as ketone solvents (e.g., acetone and methyl ethyl ketone), ester solvents [e.g., ethyl acetate and dibasic acid ester (DBE)], ether solvents (e.g., tetrahydrofuran), amide solvents (e.g., N,N-dimethylformamide and N-methylpyrrolidone), alcohol solvents (e.g., isopropyl alcohol), and aromatic hydrocarbon solvents (e.g., toluene). The above solvent may also be contained in the aqueous dispersion.

[0100] From the viewpoint of ease of handling of the aqueous dispersion, the content of the modified polyolefin (Y) in the aqueous dispersion is preferably 20 to 65% by weight, more preferably 25 to 55% by weight. The solid content concentration can be obtained by thinly spreading about 1 g of the aqueous dispersion on a Petri dish, precisely weighing it, then precisely weighing the weight after heating at 130°C for 45 minutes using a circulating constant temperature dryer, and calculating the ratio (percentage) of the residual weight after heating to the weight before heating.

[0101] The viscosity of the aqueous dispersion is preferably 10 to 100,000 mPa·s, more preferably 10 to 5,000 mPa·s. The viscosity can be measured at a constant temperature of 25°C using a BL type viscometer.

[0102] The pH of the aqueous dispersion is preferably from 2 to 12, more preferably from 4 to 10. The pH can be measured at 25 °C using a pH Meter M-12 (manufactured by Horiba, Ltd.).

[0103] From the viewpoint of dispersion stability, the volume average particle diameter (Dv) of the modified polyolefin (Y) in the aqueous dispersion of the present invention is preferably from 0.01 to 1 μm, more preferably from 0.02 to 0.7 μm, and particularly preferably from 0.03 to 0.4 μm. When (Dv) is 0.01 μm or more, the viscosity is appropriate and the handleability is good, and when it is 1 μm or less, the dispersion stability is good.

[0104] The above volume average particle diameter (Dv) can be controlled by the ionic polar groups in the modified polyolefin (Y) and the type and operating conditions of the disperser used in the dispersion step.

[0105] The aqueous dispersion of the present invention can be used in aqueous paint compositions, aqueous adhesive compositions, aqueous fiber processing treatment agent compositions (such as pigment printing binder compositions, non-woven fabric binder compositions, reinforcing fiber sizing agent compositions, antibacterial agent binder compositions, and artificial leather and synthetic leather raw material compositions), aqueous coating compositions (such as waterproof coating compositions, water repellent coating compositions, and antifouling coating compositions), aqueous paper treatment agent compositions, and aqueous ink compositions, etc., and is particularly suitable as a coating agent. The coating film can be obtained, for example, by coating a substrate (such as a plastic film) and, if necessary, heating and / or curing.

[0106] When used for these applications, one or more other resins and additives (such as catalysts, pigments, pigment dispersants, viscosity modifiers, defoamers, leveling agents, preservatives, anti-degradants, stabilizers, and anti-freezing agents) can be added if necessary.

[0107] Examples of other resins include water-dispersible or water-soluble polyurethane resins, polyacrylic resins, and polyester resins other than the modified polyolefin (Y) in the present invention.

[0108] Examples of the viscosity modifier include thickeners such as inorganic viscosity modifiers (sodium silicate, bentonite, etc.), cellulose-based viscosity modifiers (methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, etc. with Mn of 20,000 or more), protein-based viscosity modifiers (casein, sodium caseinate, ammonium caseinate, etc.), acrylic-based (sodium polyacrylate, ammonium polyacrylate, etc. with Mn of 20,000 or more), and vinyl-based viscosity modifiers (polyvinyl alcohol, etc. with Mn of 20,000 or more). Examples of the defoaming agent include long-chain alcohols (octyl alcohol, etc.), sorbitan derivatives (sorbitan monooleate, etc.), silicone oils (polymethylsiloxane, polyether-modified silicone, etc.).

[0109] Examples of the preservative include organic nitrogen-sulfur compound-based preservatives and organic sulfur-halide-based preservatives. Examples of the anti-degradant and stabilizer (ultraviolet absorber, antioxidant, etc.) include hindered phenol-based, hindered amine-based, hydrazine-based, phosphorus-based, benzophenone-based, or benzotriazole-based anti-degradants and stabilizers. Examples of the anti-freezing agent include ethylene glycol and propylene glycol. The contents of the viscosity modifier, defoaming agent, preservative, anti-degradant, stabilizer, and anti-freezing agent are each preferably 5% by weight or less, more preferably 3% by weight or less, based on the weight of each of the above compositions in the intended use.

[0110] <Resin modifier> The resin modifier of the present invention contains the modified polyolefin (Y). The resin modifier is suitably used as a modifier for polyolefin resins, particularly as a water-wettability imparting agent for polyolefin resins. The content of the modified polyolefin (Y) is preferably 85 to 100% by weight, more preferably 90 to 100% by weight, and particularly preferably 95 to 100% by weight, from the viewpoints of the water wettability of the molded article and the mechanical strength of the molded article.

[0111] <Polyolefin resin> The polyolefin resin in the present invention includes the above-mentioned (A0) high molecular weight polyolefin, or those obtained by the reduction (thermal, chemical, and mechanical reduction) method of high molecular weight polyolefin (preferably Mn 80,000 to 400,000). For example, the exemplified ethylene unit-containing (propylene unit-free) (co)polymers, propylene unit-containing (ethylene unit-free) (co)polymers, ethylene / propylene copolymers, and (co)polymers of olefins having 4 or more carbon atoms are included.

[0112] <Polyolefin resin composition> The polyolefin resin composition of the present invention contains the above-mentioned resin modifier and polyolefin resin. In the resin composition, the proportion of each component based on the total weight of the resin modifier and polyolefin resin is as follows: the resin modifier is preferably 1 to 35% by weight, more preferably 3 to 30% by weight, particularly preferably 5 to 25% by weight from the viewpoints of the water wettability of the molded product and the bending properties of the molded product; the polyolefin resin is preferably 65 to 99% by weight, more preferably 70 to 97% by weight, particularly preferably 75 to 95% by weight from the viewpoints of the productivity of the molded product and the mechanical strength.

[0113] The polyolefin resin composition of the present invention can further contain various additives (G) as necessary within a range that does not inhibit the effects of the present invention. Examples of (G) include one or more selected from the group consisting of a colorant (G1), a flame retardant (G2), a filler (G3), a lubricant (G4), an antistatic agent (G5), a dispersant (G6), an antioxidant (G7), and an ultraviolet absorber (G8).

[0114] Examples of the colorant (G1) include pigments and dyes. Examples of the pigment include inorganic pigments (such as alumina white and graphite); organic pigments (such as azo lake-based pigments). Examples of the dye include azo-based dyes and anthraquinone-based dyes.

[0115] Examples of the flame retardant (G2) include organic flame retardants [nitrogen-containing compounds [salts such as urea compounds and guanidine compounds, etc.], sulfur-containing compounds [sulfuric acid esters, sulfamic acid, and their salts, esters, amides, etc.], silicon-containing compounds [polyorganosiloxanes, etc.], phosphorus-containing compounds [phosphoric acid esters, etc.], etc.]; inorganic flame retardants [antimony trioxide, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, etc.], etc.

[0116] Examples of the filler (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, silica powder, talc, silica, zeolite, wood materials (wood powder, etc.), and mixtures thereof, etc.

[0117] Examples of the lubricant (G4) include waxes (carnauba wax, etc.), higher fatty acids (stearic acid, etc.), higher alcohols (stearyl alcohol, etc.), higher fatty acid amides (stearic acid amide, etc.), etc.

[0118] Examples of the antistatic agent (G5) include nonionic, cationic, anionic, and amphoteric surfactants described below and in U.S. Patent Nos. 3,929,678 and 4,331,447.

[0119] (1) Nonionic surfactant Alkylene oxide (hereinafter abbreviated as AO) - added nonionics, for example, active hydrogen atom - containing compounds having a hydrophobic group (C8 - 24 or more), such as saturated and unsaturated, higher alcohols (C8 - 18), higher aliphatic amines (C8 - 24), and higher fatty acids (C8 - 24), etc., (poly)oxyalkylene derivatives thereof (AO adducts and higher fatty acid mono - and di - esters of polyalkylene glycols); (poly)oxyalkylene derivatives of higher fatty acid (C8 - 24) esters of polyhydric alcohols (C3 - 60) (Tween - type nonionics, etc.); (poly)oxyalkylene derivatives of (alkanol)amides of higher fatty acids (above); (poly)oxyalkylene derivatives of alkyl (C3 - 60) ethers of polyhydric alcohols (above); and polyoxypropylene polyols [polyoxypropylene derivatives of polyhydric alcohols and polyamines (C2 - 10) (Pluronic (registered trademark) - type and Tetronic - type nonionics)]; polyhydric alcohol (above) - type nonionics (for example, fatty acid esters of polyhydric alcohols, alkyl (C3 - 60) ethers of polyhydric alcohols, and fatty acid alkanolamides); and amine oxide - type nonionics [for example, (hydroxy)alkyl (C10 - 18) di(hydroxy)alkyl (C1 - 3) amine oxide].

[0120] (2) Cationic surfactants Quaternary ammonium salt type cationics [tetraalkylammonium salts (C11 - 100), alkyl (C8 - 18) trimethylammonium salts, dialkyl (C8 - 18) dimethylammonium salts, etc.]; trialkylbenzylammonium salts (C17 - 80) (lauryldimethylbenzylammonium salt, etc.); alkyl (C8 - 60) pyridinium salts (cetylpyridinium salt, etc.); (poly)oxyalkylene (C2 - 4) trialkylammonium salts (C12 - 100) (polyoxyethylene lauryldimethylammonium salt, etc.); and acyl (C8 - 18) aminoalkyl (C2 - 4) or acyl (C8 - 18) oxyalkyl (C2 - 4) tri[(hydroxy)alkyl (C1 - 4)]ammonium salts (sapamine type quaternary ammonium salts) [these salts include, for example, halides (chloride, bromide, etc.), alkyl sulfates (methosulfate, etc.), and salts of organic acids (described below)]; and amine salt type cationics: inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salts and organic acid (C2 - 22) salts of 1 - 3 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 acylaminoalkyl or acyloxyalkyl (described above) di(hydroxy)alkyl (described above) amines (stearoyloxyethyldihydroxyethylamine, stearamidoethyldiethylamine, etc.)].

[0121] (3) Anionic surfactants Salts of higher fatty acids (described above) (sodium laurate, etc.), ether carboxylic acids [carboxymethylated products of EO (1 - 10 moles) adducts, etc.], and their salts; sulfate esters (alkyl and alkyl ether sulfates, etc.), sulfated oils, sulfated fatty acid esters, and sulfated olefins; sulfonates [alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinate esters, α - olefin (C12 - 18) sulfonates, N - acyl - N - methyltaurine (Igepon T type, etc.), etc.]; and phosphate esters (alkyl, alkyl ether, and alkyl phenyl ether phosphates, etc.).

[0122] (4) Amphoteric surfactant: Carboxylic acid (salt) type amphoterics [amino acid type amphoterics (such as lauryl aminopropionic acid (salt), etc.), and betaine type amphoterics (such as alkyl dimethyl betaine, alkyl dihydroxyethyl betaine, etc.), etc.]; Sulfate ester (salt) type amphoterics [sulfate ester (salt) of lauryl amine, sulfate ester (salt) of hydroxyethyl imidazoline, etc.]; Sulfonic acid (salt) type amphoterics [pentadecyl sulfotaurine, imidazoline sulfonic acid (salt), etc.]; And phosphate ester (salt) type amphoterics, etc. [phosphate ester (salt) of glycerol laurate, etc.].

[0123] The salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (such as lithium, sodium, potassium, etc.), alkaline earth metals (such as calcium, magnesium, etc.) and Group IIB metals (such as zinc, etc.); ammonium salts; and amine salts and quaternary ammonium salts.

[0124] As the dispersant (G6), polymers with Mn of 1,000 to 20,000, such as vinyl resins [polyolefins (such as polyethylene, polypropylene, etc.), modified polyolefins [such as oxidized polyethylene (obtained by oxidizing polyethylene with ozone, etc. and introducing carboxyl groups, carbonyl groups and / or hydroxyl groups, etc.)], and vinyl resins other than the above polyolefins [such as polyvinyl halides (such as polyvinyl chloride, polyvinyl bromide, etc.), polyvinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly(meth)acrylic acid, poly(meth)acrylate [such as poly(meth)acrylate methyl, etc.] and styrene resins [such as polystyrene, acrylonitrile / styrene (AS) resin, etc.]]; polyester resins [such as polyethylene terephthalate, etc.], polyamide resins [such as 6,6-nylon, 12-nylon, etc.], polyether resins [such as polyether sulfone, etc.], polycarbonate resins [such as polycondensate of bisphenol A and phosgene, etc.], and their block copolymers, etc. can be mentioned.

[0125] Examples of the antioxidant (G7) include hindered phenol compounds [p-t-amylphenol·formaldehyde resin, nordihydroguaiaretic acid (NDGA), 2,6-di-t-butyl-4-methylphenol (BHT), 2-t-butyl-4-methoxyphenol (BHA), 6-t-butyl-2,4-dimethylphenol (24M6B), 2,6-di-t-butylphenol (26B), etc.]; sulfur-containing compounds [N,N'-diphenylthiourea, dimyristylthiodipropionate, etc.]; phosphorus-containing compounds [2-t-butyl-α-(3-t-butyl-4-hydroxyphenyl)-p-cumenyl bis(p-nonylphenyl) phosphite, dioctadecyl 4-hydroxy-3,5-di-t-butylbenzylphosphonate, etc.].

[0126] Examples of the ultraviolet absorber (G8) include salicylate compounds [phenyl salicylate, etc.]; benzophenone compounds [2,4-dihydroxybenzophenone, etc.]; benzotriazole compounds [2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, etc.].

[0127] The total content of (G) in the polyolefin resin composition is generally 20% by weight or less, preferably 0.05 to 10% by weight, and more preferably 0.1 to 5% by weight based on the total weight of the composition, from the viewpoints of the function expression of each (G) and industrial applications. The usage amount of each additive based on the total weight of the composition is as follows: (G1) is preferably 5% or less, more preferably 0.1 to 3% by weight; (G2) is preferably 8% or less, more preferably 1 to 3% by weight; (G3) is preferably 5% or less, more preferably 0.1 to 1% by weight; (G4) is preferably 8% or less, more preferably 1 to 5% by weight; (G5) is preferably 8% or less, more preferably 1 to 3% by weight; (G6) is preferably 1% or less, more preferably 0.1 to 0.5% by weight; (G7) is preferably 2% or less, more preferably 0.05 to 0.5% by weight; (G8) is preferably 2% or less, more preferably 0.05 to 0.5% by weight.

[0128] When the additives are the same and overlapping among (G1) to (G8) above, instead of directly using the amounts of each additive that exhibit the corresponding additive effects, the usage amounts shall be adjusted according to the purpose of use, taking into account that the effects as other additives can also be obtained simultaneously.

[0129] As a method for producing the polyolefin resin composition of the present invention, there are included: (1) a method of batch-mixing the resin modifier, polyolefin resin, and optionally (G) to obtain a polyolefin resin composition (batch method); (2) a method of mixing a part of the polyolefin resin, the entire amount of the resin modifier, and optionally a part or the entire amount of (G) to once prepare a masterbatch polyolefin resin composition containing a high-concentration resin modifier, and then adding and mixing the remaining polyolefin resin and optionally the remaining (G) to obtain a polyolefin resin composition (masterbatch method). From the viewpoint of the mixing efficiency of the resin modifier, the method (2) is preferred.

[0130] As a specific mixing method in the above method for producing the polyolefin resin composition, (i) A method in which each component to be mixed is first mixed, for example, using a powder mixer [such as "Henschel Mixer" (trade name "Henschel Mixer FM150L / B", manufactured by Mitsui Mining Co., Ltd., now Nippon Coke & Engineering Co., Ltd. after the company name change), "Nauta Mixer" (trade name "Nauta Mixer DBX3000RX", manufactured by Hosokawa Micron Corporation), "Banbury Mixer" (trade name "MIXTRON BB-16MIXER", manufactured by Kobe Steel, Ltd., etc.)], and then kneaded generally at 120 to 220 °C for 2 to 30 minutes using a melt-kneading device [batch kneader, continuous kneader (single-screw kneader, twin-screw kneader, etc.)]; (ii) A method in which each component to be mixed is directly kneaded under the same conditions using the same melt-kneading device without previously mixing the powders. From the viewpoint of mixing efficiency, the method (i) is preferred among these methods.

[0131] The polyolefin composition of the present invention provides molded articles with excellent mechanical strength (impact resistance). The mechanical strength of the molded articles can be evaluated by impact resistance and flexural modulus described below.

[0132] <Molded article, formed article> The molded articles of the present invention are formed by molding the above polyolefin resin composition. Examples of molding methods include injection molding, compression molding, calender molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (cast method, tenter method, inflation method, etc.). Depending on the purpose, any method can be used, including single-layer molding, multi-layer molding, or foaming molding. Forms of the molded articles include plate-like, sheet-like, film, fabric, fiber (including non-woven fabric, etc.).

[0133] The molded articles of the present invention have excellent mechanical strength, good paintability and printability. By painting and / or printing on the molded articles, formed articles can be obtained. Examples of methods for painting the molded articles include air spray painting, airless spray painting, electrostatic spray painting, dip painting, roller painting, brush painting, etc., but are not limited thereto. Examples of paints include paints generally used for plastic painting, such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, acrylic urethane resin paint, etc. Either relatively high-polarity paints or low-polarity paints (olefin-based, etc.) can be used. The paint film thickness (dry film thickness) can be appropriately selected according to the purpose, but is generally 10 - 50 μm.

[0134] Also, as a method of further printing on the molded articles or the painted molded articles, any printing method generally used for plastic printing can be used, such as gravure printing, flexographic printing, screen printing, pad printing, dry offset printing, and offset printing. As the printing ink, those generally used for plastic printing, such as gravure ink, flexo ink, screen ink, pad ink, dry offset ink and offset ink, can be used.

Example

[0135] The present invention will be further described by the following examples, but the present invention is not limited thereto.

[0136] <Production Example 1> Into a reaction vessel, 1000 parts by weight of a high molecular weight polyolefin (A0-1) [trade name "Vistamaxx6202", manufactured by Exxonmobil, Mn76,000] containing 85% by weight of propylene and 15% by weight of ethylene as constituent monomers was charged. While purging nitrogen into the liquid phase, it was heated and melted with a mantle heater, and heat reduction was carried out under the conditions of 375 °C for 40 minutes with stirring to obtain a polyolefin (A-1) having a carbon-carbon double bond. The Mn of the polyolefin (A-1) having a carbon-carbon double bond was 6,000, the number of double bonds in the molecular chain per 1000 carbon atoms was 3.0, and the isotacticity was 20%.

[0137] <Production Examples 2 to 4> The same procedure as in Production Example 1 was carried out except that the heat reduction conditions in Production Example 1 were according to Table 1, and polyolefins (A-2) to (A-4) having a carbon-carbon double bond were obtained.

[0138] <Production Example 5> In Production Example 1, 1000 parts by weight of the high molecular weight polyolefin (A0-1) was changed to 1000 parts by weight of a polyolefin (A0-2) [trade name "Vistamaxx3980", manufactured by Exxonmobil, Mn113,000] containing 94% by weight of propylene and 9% by weight of ethylene as constituent monomers. The same procedure as in Production Example 1 was carried out except that the heat reduction conditions were according to Table 1, and a polyolefin (A-5) having a carbon-carbon double bond was obtained.

[0139] <Production Example 6> In Production Example 1, 1000 parts by weight of high molecular weight polyolefin (A0-1) was changed to 1000 parts by weight of polyolefin (A0-3) [trade name "Tafmer S4030", manufactured by Mitsui Chemicals, Inc., Mn 200,000] containing 73% by weight of propylene and 27% by weight of ethylene as constituent monomers, and the procedure was the same as in Production Example 1 except that the thermal reduction conditions were in accordance with Table 1, to obtain a polyolefin (A-6) having a carbon-carbon double bond.

[0140] <Comparative Production Example 1> In Production Example 1, 1000 parts by weight of high molecular weight polyolefin (A0-1) was changed to 1000 parts by weight of polyolefin (Ratio A0-1) [trade name "Sun Allomer PMA20V", manufactured by Sun Allomer Co., Ltd., Mn 100,000] containing 98% by weight of propylene and 2% by weight of ethylene as constituent monomers, and the procedure was the same as in Production Example 1 except that the thermal reduction conditions were in accordance with Table 1, to obtain polyolefin (Ratio A-1).

[0141] <Comparative Production Example 2> As the high molecular weight polyolefin (Ratio A-2), polyolefin (Ratio A0-1) containing 98% by weight of propylene and 2% by weight of ethylene as constituent monomers was used as it was.

[0142] <Comparative Production Example 3> In Production Example 1, 1000 parts by weight of high molecular weight polyolefin (A0-1) was changed to 1000 parts by weight of high molecular weight polyolefin (Ratio A0-2) [trade name "Wintech WFX6", manufactured by Japan Polypropylene Corporation, Mn 150,000] using a metallocene catalyst containing propylene and ethylene as constituent monomers, and the procedure was the same as in Production Example 1 except that the thermal reduction conditions were in accordance with Table 1, to obtain polyolefin (Ratio A-3).

[0143] <Comparative Production Example 4> In Production Example 1, 1000 parts by weight of high molecular weight polyolefin (A0-1) was changed to 1000 parts by weight of high molecular weight polyethylene (Ratio A0-3) [trade name "Novatech LD LJ902", manufactured by Nippon Polyethylene Co., Ltd., Mn 110,000] containing ethylene 100% by weight as a constituent monomer, and the same procedure as in Production Example 1 was carried out except that the thermal reduction conditions were according to Table 1, to obtain polyolefin (Ratio A-4).

[0144] Table 1 shows the measurement results of Mn, the number of double bonds per 1000 carbons, and isotacticity of the polyolefin (A) having each carbon-carbon double bond obtained above.

[0145]

Table 1

[0146] <Production Example 7> A reaction vessel was charged with 100 parts by weight of polyolefin (A-1) having a carbon-carbon double bond and 5 parts by weight of maleic anhydride (B-1). After nitrogen substitution, the temperature was raised to 180 °C under nitrogen flow and dissolved uniformly. A solution prepared by dissolving 1.3 parts by weight of a radical initiator [dicumyl peroxide, trade name "Perkyl D", manufactured by NOF Corporation] (D-1) in 5 parts by weight of xylene was added dropwise over 5 minutes, and then stirring was continued for 1 hour under reflux of xylene. Thereafter, 0.6 part by weight of unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain acid-modified polyolefin (a-1). The amount of maleic anhydride charged as shown in Table 2 is the amount obtained by subtracting the amount distilled off from the charged amount. The acid value of (a-1) was 24, Mn was 13,000, and isotacticity was 20%.

[0147] <Production Example 8> A reaction vessel was charged with 100 parts by weight of polyolefin (A-1) having a carbon-carbon double bond and 1.8 parts by weight of maleic anhydride (B-1). Under nitrogen flow, the temperature was raised to 200 °C and stirring was continued for 10 hours. Thereafter, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain acid-modified polyolefin (a-2). Note that the amount of maleic anhydride shown in Table 2 is the amount after subtracting the amount distilled off from the charge. Also, the acid value of (a-2) was 7, Mn was 6,100, and the isotacticity was 20%.

[0148] <Production Examples 9 to 14, Comparative Production Examples 5 to 6> In Production Example 7, except that the raw materials used (parts by weight) were in accordance with Table 2, the procedure was the same as in Production Example 7 to obtain each acid-modified polyolefin (a).

[0149] <Production Examples 15 to 17, Comparative Production Examples 7 to 8> In Production Example 8, except that the raw materials used (parts by weight) were in accordance with Table 2, the procedure was the same as in Production Example 8 to obtain each acid-modified polyolefin (a).

[0150] The results of the properties of each acid-modified polyolefin (a) obtained above are shown in Table 2.

[0151]

Table 2

[0152] <Example 1> 100 parts by weight of acid-modified polyolefin (a-1), 10 parts by weight of 6-aminohexanoic acid (m20-1) as aminocarboxylic acid (m20), and 4.4 parts of N,N-dimethyl-1,3-propanediamine (b0-4) as a compound having an amino group were charged into a reaction vessel under a nitrogen atmosphere, reacted at 220 °C, normal pressure for 8 hours, and then the water generated by the reaction was distilled off under reduced pressure (1.0 kPa) over 3 hours to obtain a modified polyolefin (Y-1) (amine value: 21, melt viscosity at 220 °C: 3.1 Pa·s).

[0153] <Example 2> 100 parts by weight of an acid-modified polyolefin (a-2), 10 parts by weight of 12-aminododecanoic acid (m20-2), 18 parts of ε-caprolactam (m21-1) as a lactam, and 2.8 parts of bis(4-aminocyclohexyl)methane (b0-3) were charged into a reaction vessel under a nitrogen atmosphere, and reacted at 220 °C under pressure (2.0 MPa) for 8 hours. After the reaction, unreacted ε-caprolactam (m21-1), unreacted bis(4-aminocyclohexyl)methane (b0-3), and water generated by the reaction were distilled off under reduced pressure (1.0 kPa) over 3 hours to obtain a modified polyolefin (Y-2) (amine value: 5.4, melt viscosity at 220 °C: 1.9 Pa·s). The amounts of ε-caprolactam (m21-1) and bis(4-aminocyclohexyl)methane (b0-3) shown in Table 3 are the amounts obtained by subtracting the distilled-off amounts from the charged amounts. The same applies to the amounts shown in Table 3 for the following examples.

[0154] <Examples 3 to 5, 7 to 17, Comparative Examples 1, 2, 4> In Example 1, except that the raw materials used (parts by weight) were in accordance with Table 3, the procedure was the same as in Example 1 to obtain each modified polyolefin (Y).

[0155] <Examples 6, Comparative Example 3> In Example 2, except that the raw materials used (parts by weight) were in accordance with Table 3, the procedure was the same as in Example 2 to obtain each modified polyolefin (Y).

[0156] The results of the properties of each modified polyolefin (Y) obtained above are shown in Table 3.

[0157]

Table 3

[0158] <Example 18> 100 parts by weight of a modified polyolefin (Y-2) and 240 parts by weight of methylcyclohexane were charged into a reaction vessel under a nitrogen atmosphere. After dissolving (Y-2) at 80 °C and normal pressure for 1 hour, 1.5 parts by weight of trimethylolpropane polyglycidyl ether (epoxy resin, trade name "Denacol EX-321L", manufactured by Nagase ChemteX Corporation) was mixed at 25 °C and normal pressure to obtain an adhesive containing the modified polyolefin (Y-2).

[0159] <Examples 19 to 31, Comparative Examples 5 to 7> In Example 18, an adhesive containing each modified polyolefin (Y) was obtained in the same manner as in Example 18, except that the raw materials used (parts by weight) were in accordance with Table 4.

[0160] <Evaluation Method> <1>Adhesive Strength (Unit: kg / 25 mm) Each adhesive to be evaluated was applied to a polyimide film with a thickness of 25 μm so that the dried thickness became 25 μm, and dried at 130 °C for 10 minutes using a circulating air dryer. Then, an OPP sheet (biaxially stretched polypropylene, thickness 30 μm) was laminated under the conditions of a temperature of 80 °C, a pressing pressure of 98 kPa, and a time of 30 seconds using a hot press machine. . Next, heat curing treatment was performed at 140 °C for 6 hours to obtain an adherend. After leaving it standing for 24 hours in an atmosphere of 23 °C and 50% RH, the T-peel strength was measured in an atmosphere of 23 °C and used as the adhesive strength. The above adhesive strength was measured using an autograph in accordance with JIS K6854-1999 under the condition of a tensile strength of 50 mm / min. The adhesive strength was evaluated according to the following evaluation criteria.

[0161] <Evaluation Criteria> ◎: Exceeding 2.0 ○: Exceeding 1.7 and less than or equal to 2.0 △: Exceeding 1.5 and less than or equal to 1.7 ×: 1.5 or less

[0162] <2>Dielectric Constant and Dissipation Factor Each adhesive was applied to a release film with a thickness of 50 μm so that the thickness after drying would be 100 μm. After drying at 130 °C for 10 minutes, it was heat-cured at 150 °C for 3 hours, and then peeled from the release film to obtain the adhesive. The obtained heat-cured adhesive was measured using an LCR meter in accordance with JIS C2138-2007. The dielectric constant and dielectric loss tangent were evaluated according to the following evaluation criteria.

[0163] <Evaluation Criteria> · Dielectric constant ◎: 2.5 or less ○: Exceeding 2.5 and 3.0 or less △: Exceeding 3.0 and 3.5 or less ×: Exceeding 3.5 · Dielectric loss tangent ◎: 0.005 or less ○: Exceeding 0.005 and 0.01 or less △: Exceeding 0.01 and 0.03 or less ×: Exceeding 0.03

[0164]

Table 4

[0165] As is clear from Table 4, it can be seen that the adhesive of the present invention is excellent in adhesion to the polyolefin substrate and low dielectric characteristics compared to the comparative adhesives.

[0166] <Example 32> In a simple pressure reactor equipped with a stirrer and a heating device, 100 parts by weight of modified polyolefin (Y-4) and 250 parts by weight of an organic solvent [THF, tetrahydrofuran] were charged under a nitrogen atmosphere. After stirring at 80 °C for 1 hour to dissolve the modified polyolefin (Y-4) in the organic solvent, 233 parts by weight of ion-exchanged water was gradually added with stirring to emulsify it. Then, THF was distilled off at 65 °C under reduced pressure (10 kPa) over 12 hours to obtain an aqueous dispersion.

[0167] <Examples 33 to 35, Comparative Example 8> In Example 32, each aqueous dispersion was obtained in the same manner as in Example 32, except that the raw materials used (parts by weight) were as shown in Table 5.

[0168] Each of the obtained aqueous dispersions was evaluated according to the procedure described below. The results are shown in Table 5.

[0169] The volume average particle diameter (Dv) was measured using a laser diffraction particle size distribution analyzer "LA-750" [manufactured by Horiba, Ltd.].

[0170] <1>Adhesion The resin aqueous dispersion was applied (coated) to a surface-treated polypropylene film (OPP) ["Pyren P-2161" (thickness 30 μm) manufactured by Toyobo Co., Ltd.], a surface-treated polyester film (PET) ["Espert E-5102" (thickness 12 μm) manufactured by Toyobo Co., Ltd.], and a surface-treated nylon film ["Harden N-1130" (thickness 15 μm) manufactured by Toyobo Co., Ltd.] so that the film thickness after drying was 50 μm, and dried in an atmosphere of 120°C and 50% RH for 3 hours. Then, it was cured under the conditions of a temperature of 5°C (±2°C) and a relative humidity of 10% (±10%), and a cross-cut cellophane tape (registered trademark) peel test was performed under the conditions of a temperature of 5°C (±2°C) and a relative humidity of 10% (±10%) to evaluate the adhesion to the substrate. The conditions other than temperature and humidity conformed to JIS K5600-5-6, and a cellophane tape (registered trademark) (manufactured by Nichiban Co., Ltd.) was used for evaluation according to the following evaluation criteria.

[0171] <Evaluation Criteria> ◎: 100 squares where peeling did not occur ○: 90 - 99 squares where peeling did not occur ×: Less than 90 squares where peeling did not occur

[0172] <2>Storage Stability of Aqueous Dispersion (40°C, High Temperature) 30 g of the aqueous dispersion was placed in a screw vial [50 mL (body diameter 35 mm × height 78 mm)] and stored at 40 °C for 7 days. From the measurement results of the volume average particle diameter (Dv) (unit: μm) before and after storage, the (storage stability at 40 °C) was determined by the following calculation formula and evaluated according to the following evaluation criteria. (Storage stability at 40 °C) (%) = (Volume average particle diameter after storage) × 100 / (Volume average particle diameter before storage)

[0173] <Evaluation criteria> ○: Less than 150% ×: 150% or more

[0174] <2> Storage stability of the aqueous dispersion (10 °C, low temperature) 30 g of the aqueous dispersion was placed in a screw vial [50 mL (body diameter 35 mm × height 78 mm)] and stored at 10 °C for 7 days. From the measurement results of the volume average particle diameter (Dv) (unit: μm) before and after storage, the (storage stability at 5 °C) was determined by the following calculation formula and evaluated according to the following evaluation criteria. (Storage stability at 10 °C) (%) = (Volume average particle diameter after storage) × 100 / (Volume average particle diameter before storage)

[0175] <Evaluation criteria> ○: Less than 150% ×: 150% or more

[0176]

Table 5

[0177] From the results in Table 5, it can be seen that the aqueous dispersion of the present invention is superior in substrate adhesion and further in storage stability (high temperature, low temperature) compared with the comparative aqueous dispersion.

[0178] <Example 36> Using 15 parts by weight of the modified polyolefin (Y-1) obtained above as a resin modifier and 85 parts by weight of a polyolefin resin (E-1), a polyolefin resin composition was obtained by melt-kneading in a twin-screw extruder under the conditions of 220 °C, 100 rpm, and a residence time of 5 minutes. Using an injection molding machine [trade name "PS40E5ASE", manufactured by Nissei Plastic Industrial Co., Ltd.] for the resin composition, molding was carried out at a cylinder temperature of 220 °C and a mold temperature of 50 °C. After producing a predetermined test piece (molded product), the impact resistance, flexural modulus, wettability, and durability of wettability were measured by the following test methods. The results are shown in Table 6. <Examples 37 to 43, Comparative Examples 9 to 13> In Example 36, except that each modified polyolefin (Y) was used as a resin modifier and the raw materials used (parts by weight) in Table 6 were followed, a polyolefin resin composition was obtained in the same manner as in Example 36. After producing a predetermined test piece (molded product), each measurement was carried out. The results are shown in Table 6.

[0179] <Raw materials used> [Polyolefin resin (E)] (E-1): Commercially available polypropylene [trade name "Sun Allomer PL500A", manufactured by Sun Allomer Co., Ltd., Mn 100,000] (E-2): Commercially available polyethylene [trade name "Novatec HJ490", manufactured by Japan Polyethylene Corporation, Mn 300,000] (E-3): Commercially available ethylene / propylene copolymer [trade name "Sun Allomer PB222A", manufactured by Sun Allomer Co., Ltd., Mn 350,000]

[0180] <Test method> (1) Impact resistance (unit: kJ / m 2 ) Measured in accordance with JIS K7110. (2) Flexural modulus (unit: MPa) Measured in accordance with ASTM D790. (3) Wettability (unit: °) For the evaluation of wettability, the measurement of the water contact angle was carried out in accordance with JIS R2367. The smaller the water contact angle, the better the wettability. (4) Durability of wettability (unit: °) After washing the surface of the test piece with a cotton cloth soaked in water, it was dried under reduced pressure (1 kPa, 80 °C, 1 hour). This test piece was temperature-controlled (23 °C, 50% RH, 24 hours), and the water contact angle was measured in the same manner as in (3) above.

[0181]

Table 6

[0182] From the results in Table 6, it can be seen that the resin modifier of the present invention imparts excellent wettability to water to the polyolefin resin base material without impairing the original mechanical strength, and the molded article formed by molding the resin composition containing the resin modifier has excellent wettability to water and excellent persistence.

Industrial Applicability

[0183] The adhesive containing the modified polyolefin of the present invention is excellent in adhesiveness to the base material and low dielectric characteristics of the adhesive, and thus can be suitably used for polyolefin, polyimide, syndiotactic polystyrene, and liquid crystal polymer base materials. The obtained adherend can be used for electronic material applications (such as flexible printed wiring board applications). The aqueous dispersion containing the modified polyolefin of the present invention is excellent in storage stability and excellent in adhesion of the coating film, and thus can be suitably used for coating compositions, adhesive compositions, fiber processing treatment agent compositions, and the like. The resin modifier containing the modified polyolefin of the present invention imparts excellent wettability to water to the polyolefin resin base material without impairing the original mechanical strength, and the molded article formed by molding the resin composition containing the resin modifier has excellent wettability to water and excellent persistence, and can be suitably used in a wide range of fields such as for electric and electronic equipment, transport materials, household materials, and building materials.

Claims

1. A modified polyolefin comprising an acid-modified polyolefin (a), a polyamine compound having two or more amino groups and at least one group selected from the group consisting of primary amino groups and secondary amino groups, and a compound (b0) having an amino group selected from the group consisting of a hydroxyl group and a tertiary amino group as essential constituent raw materials, wherein the acid-modified polyolefin (a) is an acid-modified polyolefin having a polyolefin (A) having a carbon-carbon double bond and an unsaturated (poly) carboxylic acid (anhydride) (B) as essential constituent raw materials, the acid-modified polyolefin (a) satisfies all of the following requirements (1) to (3), the polyolefin (A) having a carbon-carbon double bond is a polyolefin having ethylene and an α-olefin (carbon number 3 to 8) as essential constituent monomers, and the weight ratio [ethylene / α-olefin] of ethylene and the α-olefin (carbon number 3 to 8) as constituent monomers is 5 / 95 to 65 / 35, and the compound (b0) having an amino group is a compound represented by the following general formula (1). A modified polyolefin (Y). (1) Acid value is 1 to 100 mgKOH / g (2) Number average molecular weight (Mn) is 1,000 to 60,000 (3) Isotacticity of the α-olefin moiety is 1 to 50% 【Chemical 1】 [In the formula, R 1, R 2, R 3 and R 4 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom; R 5 and R 6 are each independently a divalent hydrocarbon group having 2 to 20 carbon atoms; n represents an integer from 0 to 9.]

2. The modified polyolefin according to claim 1, wherein the number average molecular weight of the polyolefin (A) having a carbon-carbon double bond is 800 to 50,000.

3. The modified polyolefin according to claim 1 or 2, wherein the polyolefin (A) having a carbon-carbon double bond has 1 to 20 carbon-carbon double bonds per 1,000 carbon atoms.

4. An adhesive comprising the modified polyolefin according to any one of claims 1 to 3.

5. An adherend obtained by adhering an adherend with the adhesive according to claim 4.

6. An aqueous dispersion comprising the modified polyolefin according to any one of claims 1 to 3.

7. A coating agent comprising the aqueous dispersion according to claim 6.

8. A resin modifier comprising the modified polyolefin according to any one of claims 1 to 3.

9. A polyolefin resin composition containing the resin modifier according to Claim 8.

10. A molded article obtained by molding the polyolefin resin composition according to Claim 9.

11. A molded article obtained by coating and / or printing the molded article according to Claim 10.

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