Block polymer and an adhesive, an aqueous dispersion, and a resin modifier containing the block polymer

Abstract

To provide a block polymer to be an adhesive that gives adhesion to a polyolefin base material at high temperatures (80-100°C) and a modification effect with excellent thermal creep resistance.SOLUTION: A block polymer (Y) contains an acid-modified polyolefin (a) block and a polyamide (b) block. The acid-modified polyolefin (a) contains a polyolefin (A) having a carbon-carbon double bond and an unsaturated (poly)carboxylic acid (anhydride) (B) as constituent monomers. The acid-modified polyolefin (a) satisfies requirements (1)-(3). The polyolefin (A) contains ethylene and α-olefin (C3-8) as constituent monomers. The weight ratio between the ethylene and α-olefin (C3-8) [ethylene / α-olefin] as constituent monomers is 5 / 95-50 / 50.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Modified polyolefins are used in a wide range of applications such as surface modifiers, dispersants, compatibilizers, adhesives, coating materials, and ink materials for resins. Recently, the use of polyolefins (especially polypropylene) has been increasing from the viewpoints of light weight, processability, chemical resistance, electrical insulation, and no generation of harmful substances during combustion. On the other hand, since polyolefins do not have polar groups and are chemically inert, they have poor compatibility and dispersibility with other inorganic fillers (inorganic fibers, fillers, etc.), and also have problems such as insufficient adhesiveness with adhesives and insufficient adhesion with coating materials and ink materials. As a method for improving the dispersibility of polyolefins and other inorganic fillers, a method using polyolefins modified with unsaturated carboxylic acids such as maleic anhydride or their derivatives has been proposed for glass fibers (see, for example, Patent Document 1) and carbon fibers (see, for example, Patent Document 2). Further, as a method for improving the adhesiveness with adhesives, a method of subjecting the surface of a thermoplastic resin, for example, a polyolefin resin molded product, to corona treatment or plasma treatment (Patent Document 3) has been proposed, and as a method for improving the adhesion with coating materials, an aqueous polyurethane resin composition using chlorinated polyol has been proposed (see, for example, Patent Document 4).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Disclosure of the Invention

Problems to be Solved by the Invention

[0004] However, in applications where workability and productivity of complex molded products and the like are required in a composite material of a polyolefin resin and other inorganic fillers, the above technology is not sufficient, and further mechanical strength and improvement in fluidity during molding of the composite material are required. Also, from the perspective of adhesiveness to a polyolefin substrate, the above post-processing technology is complicated in treatment and cannot be said to be sufficiently satisfactory in terms of adhesiveness. Further, conventional adhesives are excellent in adhesive strength at room temperature in a polyolefin substrate, but have a problem of inferior adhesive strength and heat-resistant creep properties at high temperatures (80 to 100°C) due to insufficient heat resistance. Furthermore, even the technology of Patent Document 4 above is not sufficiently satisfactory in terms of storage stability and improvement has been demanded. An object of the present invention is to provide a block polymer capable of obtaining (1) an adhesive excellent in adhesive strength and heat-resistant creep properties at high temperatures (80 to 100°C) to a polyolefin substrate, (2) a water dispersion having high storage stability and high substrate adhesion of the obtained coating film, and (3) a resin composition capable of imparting mechanical strength such as impact resistance characteristics to a molded product formed by molding a resin modifier that imparts excellent dispersibility of other inorganic fillers to a polyolefin resin and a resin composition containing the resin modifier.

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 block polymer having an acid-modified polyolefin (a) block and a polyamide (b) block, wherein the acid-modified polyolefin (a) is an acid-modified polyolefin containing a polyolefin (A) having a carbon-carbon double bond and an unsaturated (poly) carboxylic acid (anhydride) (B) as constituent monomers, the acid-modified polyolefin (a) satisfies all of the following requirements (1) to (3), the polyolefin (A) is a polyolefin containing ethylene and an α-olefin (having 3 to 8 carbon atoms) as 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 50 / 50, which is a block polymer (Y). (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 moiety is 1 to 50% [Advantages of the Invention]

[0006] The present invention has the following effects. (1) The adhesive containing the block polymer of the present invention is excellent in adhesion at high temperature (80 to 100°C) to a polyolefin substrate and heat-resistant creep properties. (2) The aqueous dispersion containing the block polymer of the present invention is excellent in storage stability and excellent in adhesion of the coating film to the substrate. (3) The resin modifier containing the block polymer of the present invention imparts dispersibility of an inorganic filler to a polyolefin resin, and a molded article formed by molding a resin composition containing the resin modifier is excellent in mechanical strength (such as impact resistance). [Embodiments for Carrying Out the Invention]

[0007] The present invention relates to a block polymer having an acid-modified polyolefin (a) block and a polyamide (b) block, wherein the acid-modified polyolefin (a) is an acid-modified polyolefin containing a polyolefin (A) having a carbon-carbon double bond and an unsaturated (poly) carboxylic acid (anhydride) (B) as constituent monomers, the acid-modified polyolefin (a) satisfies all of the following requirements (1) to (3), the polyolefin (A) is a polyolefin containing ethylene and an α-olefin (having 3 to 8 carbon atoms) as constituent monomers, and the weight ratio [ethylene / α-olefin] of ethylene to the α-olefin (having 3 to 8 carbon atoms) as constituent monomers is 5 / 95 to 50 / 50, which is a block polymer (Y). (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 moiety 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 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, and 1-octene. 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 base material, the adhesion of the coating film obtained by the aqueous dispersion to the base material, the impact resistance characteristics of the molded article containing the resin modifier, and the industrial viewpoint, 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, which is a constituent monomer of the polyolefin (A) having a carbon-carbon double bond, and an α-olefin (having 3 to 8 carbon atoms) is 5 / 95 to 50 / 50. Regarding the lower limit, it is preferably 8 / 92, more preferably 10 / 90, and particularly preferably 15 / 85. Regarding the upper limit, it is preferably 40 / 60, more preferably 30 / 70. When the weight ratio [ethylene / α-olefin] is less than 5 / 95, the adhesiveness of the adhesive to the polyolefin 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 50 / 50, the heat creep resistance of the adhesive of the polyolefin (A), the storage stability of the aqueous dispersion, and the bending physical properties of the molded article containing the resin modifier are inferior. The above weight ratio [ethylene / α-olefin] can be calculated, for example, 1 by 1H-NMR.

[0010] The polyolefin (A) may contain other monomers as constituent monomers in addition to ethylene and α-olefins (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 other monomers include unsaturated monomers having 4 to 30 carbon atoms other than α-olefins (for example, 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 (1-decene, 1-dodecene, etc.).

[0011] From the viewpoints of the adhesiveness of the adhesive to the polyolefin substrate, the adhesion of the coating film obtained by the aqueous dispersion to the substrate, the impact resistance characteristics 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] For the measurement conditions of the number-average molecular weight (Mn) and weight-average molecular weight (Mw) of polyolefin (A) having a carbon-carbon double bond, high molecular weight polyolefin (A0), acid-modified polyolefin (a), and block polymer (Y) by GPC (gel permeation chromatography) in the present invention, they are as follows. Apparatus: High-temperature gel permeation chromatograph [「Alliance GPC V2000」, manufactured by Waters Corporation] Detector: 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, Ltd.] Column temperature: 135 °C

[0013] The measurement conditions of Mn and Mw of polyamide (b) by GPC are the same as the above measurement conditions except that the solvent is changed to hexafluoroisopropanol and the column temperature is changed to 25 °C.

[0014] As the polyolefin (A) having a carbon-carbon double bond, the number of carbon-carbon double bonds per 1000 carbon atoms [(the number of carbon-carbon double bonds at the molecular terminals and in the molecular chains of (A))] is preferably 1 to 20, more preferably 1.5 to 18, and particularly preferably 2 to 15 from the viewpoints of reactivity and productivity with the following (poly)carboxylic acid (anhydride) (B). Here, the number of double bonds is that of (A) 1It can be determined from the spectrum of H-NMR (nuclear magnetic resonance) spectroscopy. That is, the peaks in the spectrum are assigned, and from the integral value derived from the double bond at 4.5 to 6 ppm of (A) and the integral value derived from (A), the relative values of the number of carbon-carbon double bonds and the number of carbons in (A) are determined, and the number of carbon-carbon double bonds at the molecular terminal and in the molecular chain per 1,000 carbons in (A) is calculated. The number of carbon-carbon double bonds in the examples described later was in accordance with this method.

[0015] The isotacticity of the α-olefin moiety of the polyolefin (A) having a carbon-carbon double bond is 1 to 50%, preferably 5% for the lower limit, more preferably 10%, particularly preferably 15%, preferably 45% for the upper limit, more preferably 40%, and particularly preferably 35%. When the isotacticity of the α-olefin moiety of the polyolefin (A) is less than 1%, the adhesiveness of the adhesive to the polyolefin substrate, the adhesion of the coating film obtained by the aqueous dispersion to the substrate, 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 later.

[0016] The isotacticity of the present invention 13 is calculated using C-NMR (nuclear magnetic resonance spectroscopy). Generally, it is known that the side-chain methyl group is affected by the steric configuration (meso or racemo) with methyl groups up to about both adjacent (triplet, triad), both adjacent to that triad (pentad, pentad), and further both adjacent to that pentad (heptad), and peaks are observed at different chemical shifts. The evaluation of stereoregularity is generally 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 13Regarding 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 by meso structures of the pentad 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 by meso structures of the pentad), H is the peak height of each pentad, and Σ(H) is the sum of the peak heights of each pentad. Note that the isotacticity of the α-olefin moiety in (a) described later can also be measured in the same manner as above.

[0017] Examples of the method for producing the polyolefin (A) in the present invention include a method of thermally decomposing a high molecular weight polyolefin (A0) having a Mn exceeding 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.

[0018] The thermal decomposition method includes a method of thermally decomposing the high molecular weight polyolefin (A0) (1) in the absence of an organic peroxide, for example, at 300 to 450°C for 0.5 to 10 hours, and (2) in the presence of an organic peroxide [for example, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane], at 180 to 300°C for 0.5 to 10 hours, and the like. Among these, from the industrial viewpoint and the viewpoint of the productivity of the acid-modified polyolefin (a) described later, preferably, the method (1) in which more double bonds in the molecular terminal and / or the molecular chain are easily obtained is used.

[0019] The weight ratio [ethylene / α-olefin] of ethylene and α-olefin (having 3 to 8 carbon atoms) which are monomers constituting the above (A) tends to be maintained as it is for the weight ratio [ethylene / α-olefin] of the high molecular weight polyolefin (A0). Moreover, the higher the thermal decomposition temperature and the longer the thermal decomposition time, the greater the tendency for the number of double bonds per 1000 carbon atoms to be large. Furthermore, the smaller the Mn of (A0), the higher the thermal decomposition temperature, and the longer the thermal decomposition time, the greater the tendency for the Mn of (A) to be small. Also, the greater the isotacticity of (A0), the greater the tendency for the isotacticity of (A) to be large. The isotacticity of (A0) can be adjusted by selecting (A) having a predetermined isotacticity.

[0020] <Unsaturated (poly)carboxylic acid (anhydride) (B)> The unsaturated (poly)carboxylic acid (anhydride) (B) in the present invention is a (poly)carboxylic acid (anhydride) having 1 polymerizable unsaturated group and 3 to 30 carbon atoms [hereinafter sometimes abbreviated as C]. 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.]. (B) may be used alone or in combination of two or more. Among the above (B), from the viewpoints of reactivity with polyolefin (A) and reactivity with polyamide (b) described later, unsaturated dicarboxylic acid anhydride is preferable, and maleic anhydride is more preferable.

[0021] <Acid-modified polyolefin (a)> The acid-modified polyolefin (a) in the present invention is an acid-modified polyolefin containing the polyolefin (A) having the carbon-carbon double bond and the unsaturated (poly)carboxylic acid (anhydride) (B) as constituent monomers, and is an acid-modified polyolefin obtained by reacting the polyolefin (A) having the carbon-carbon double bond and the unsaturated (poly)carboxylic acid (anhydride) (B). The modification by reaction with the unsaturated (poly)carboxylic acid (anhydride) (B) includes, for example, adding the unsaturated (poly)carboxylic acid (anhydride) (B) to the double bond of the polyolefin (A) by either a solution method or a melt method, or reacting the polyolefin (A) and / or the unsaturated (poly)carboxylic acid (anhydride) (B). 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 of (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 polyolefin substrate, the adhesion of the aqueous dispersion to the polyolefin substrate, the compatibility between the resin modifier and the polyolefin resin, the heat resistance creep property of the adhesive, the dispersion stability of the aqueous dispersion, and the effect of imparting the dispersibility of the inorganic filler to the polyolefin resin by 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. Incidentally, the radical initiator (D) is a known one, for example, an azo initiator (such as azobisisobutyronitrile), a peroxide initiator (such as dicumyl peroxide). Among the above (D), a peroxide initiator is preferred.

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

[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, more preferably 5 to 50. The acid value here is a value measured according to JIS K0070:1992. When the acid value is less than 1, the heat resistance creep property of the adhesive, the dispersion stability of the aqueous dispersion, and the effect of imparting the dispersibility of the inorganic filler to the polyolefin resin of the resin modifier are inferior. When it exceeds 100, the adhesiveness of the adhesive of (a) to the polyolefin substrate, the adhesion of the coating film obtained by the aqueous dispersion to the polyolefin substrate, and the impact resistance characteristics of the molded product containing the resin modifier are inferior. In addition, the above acid value can be appropriately adjusted according to the number of double bonds of (A), the weights of (A) and (B) in the reaction between (A) and (B), the type and weight of (B). In the present invention, when the acid value of (a) is within the above range, the proportion of the polyamide (b) block having a highly polar amide bond added becomes appropriate, and the acid value in the block polymer becomes appropriate, so that the handleability of the block polymer and the optimization of various performances can be achieved.

[0027] Requirement (2): The Mn of (a) is from 1,000 to 60,000, preferably from 2,000 to 50,000, and more preferably from 3,000 to 40,000. When Mn is less than 1,000, the adhesiveness of the adhesive to the polyolefin substrate, the adhesion of the coating film obtained from 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. Also, the Mn of the above (a) can be appropriately adjusted by the Mn of (A), the type and amount of (B), and the control of the reaction between (A) and (B). In the present invention, when the Mn of (a) is within the above range, the block polymer (Y) can have a portion with high softness and mechanical strength. Furthermore, the acid-modified polyolefin (a) block and the polyamide (b) block tend to be easily microphase-separated, and the resin modification effect, the adhesion performance of the adhesive, and the balance of the coating film physical properties of the paint tend to be good.

[0028] Requirement (3): The isotacticity of the α-olefin unit chain portion of (a) is from 1% to 50%, preferably from 5% to 45%, and more preferably from 10% to 40%. When the isotacticity is less than 1%, the adhesiveness of the adhesive to the polyolefin substrate, the adhesion of the coating film obtained from the aqueous dispersion to the polyolefin substrate, and the bending 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 of (a) can be appropriately adjusted by the isotacticity of (A) and (A0) as described above. In the present invention, the weight ratio [ethylene / α-olefin] of the polyolefin (A) before acid modification is 5 / 95 to 50 / 50, so that the ethylene unit appropriately disrupts the regularity of the three-dimensional structure of the polyolefin. Further, the isotacticity of the α-olefin unit chain portion of the acid-modified polyolefin (a) is 1 to 50%, so that the three-dimensional regularity of the α-olefin portion is appropriately disrupted. The block polymer of the present invention having an acid-modified polyolefin (a) block can have appropriate softness and mechanical strength, and it is presumed that the adhesiveness of the adhesive to the polyolefin substrate, the adhesion of the coating film obtained by the aqueous dispersion to the polyolefin substrate, the bending physical properties of the molded article containing the resin modifier, and the impact resistance characteristics will be improved.

[0029] <Polyamide (b)> The polyamide (b) in the present invention is a polyamide having an amino group. (b) includes a polymer having an amide bond formed from (1) an aminocarboxylic acid (c1) and / or a lactam (c2), a polymer having an amide bond formed from (2) a diamine (c3) and a dicarboxylic acid (c4), and a polymer having an amide bond formed from (1) and (2).

[0030] Examples of the aminocarboxylic acid (c1) include C2-20 aminocarboxylic acids (including the carbon of the carboxyl group, the same hereinafter) having a primary amino group or a secondary amino group and a carboxyl group, such as glycine, alanine, 4-aminobutanoic acid, 6-aminohexanoic acid, 12-aminododecanoic acid, etc. Examples of the lactam (c2) include C3-12 lactams, such as β-lactam, γ-lactam, δ-lactam, ε-caprolactam, laurolactam, etc. As the diamine (c3), there are C2-20 alkylenediamines having a total of 2 primary amino groups and / or secondary amino groups (for example, ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, etc.), aromatic aliphatic diamines (for example, metaxylylenediamine, paraxylylenediamine, etc.), alicyclic skeleton-containing diamines (for example, 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, etc.), bis(aminopropyl)piperazine, aminoethylpiperazine, etc.; As the dicarboxylic acid (c4), there are C4-20 aliphatic dicarboxylic acids (for example, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, etc.), aromatic dicarboxylic acids (for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, etc.), alicyclic skeleton-containing dicarboxylic acids (for example, hexahydroterephthalic acid, hexahydroisophthalic acid, etc.), diglycolic acid, dimer acid, etc. and / or its derivatives (for example, dimethyl ester derivatives, etc.).

[0031] Among these (c1), (c2), (c3) and (c4), those having 6 to 13 carbon atoms are preferable from the viewpoints of coatability and heat-resistant creep property, and 12-aminododecanoic acid, 6-aminohexanoic acid, decamethylenediamine, bis(4-aminocyclohexyl)methane and dodecanedioic acid are more preferable. When these are used, the length between amide groups becomes appropriate, and it is presumed that the adhesiveness of the adhesive to the polyolefin base material, the adhesion of the coating film obtained by the aqueous dispersion to the polyolefin base material, the flexural physical properties of the molded article containing the resin modifier, and the flexural physical properties of the molded article containing the resin modifier tend to be good.

[0032] The amine value of the polyamide (b) is preferably 1 to 250 mgKOH / g (only the numerical values are shown below) from the viewpoints of the coatability of the adhesive and its adhesiveness to the polyolefin base material, the leveling property of the aqueous dispersion and the adhesion of the coating film obtained by the aqueous dispersion to the polyolefin base material, and the effect of imparting dispersibility of the inorganic filler to the polyolefin resin of the resin modifier and the impact resistance characteristics of the molded article containing the resin modifier. More preferably, it is 3 to 150, and particularly preferably 5 to 100. The amine value herein is a value measured in accordance with JIS K7237:1995.

[0033] The number average molecular weight (Mn) of the polyamide (b) is preferably 400 to 60,000 from the viewpoints of the coatability of the adhesive, the adhesiveness of the adhesive to the polyolefin base material, the leveling property of the aqueous dispersion, the adhesion of the coating film obtained by the aqueous dispersion to the polyolefin base material, the effect of imparting dispersibility of the inorganic filler to the polyolefin resin of the resin modifier and the impact resistance characteristics of the molded article containing the resin modifier. More preferably, it is 1,000 to 40,000, and particularly preferably 1,500 to 25,000. In the present invention, when the Mn of (b) is within the above range, it can be made to have a highly polar hard structure in a certain unit, and furthermore, the acid-modified polyolefin (a) block and the polyamide (b) block tend to be easily microphase-separated, and the resin modification effect, the adhesion performance of the adhesive, and the balance of the coating film physical properties of the paint tend to be good.

[0034] <Block polymer (Y)> The block polymer (Y) of the present invention is a block polymer having an acid-modified polyolefin (a) block and a polyamide (b) block. When producing a block polymer having an acid-modified polyolefin (a) block and a polyamide (b) block by reacting the carboxylic acid group of the acid-modified polyolefin (a) with the amino group of the polyamide (b) block, the molar ratio of the carboxylic acid group of the acid-modified polyolefin (a) to the amino group of the polyamide (b) (carboxylic acid group / amino group) is preferably 1.01 / 1 to 5 / 1, more preferably 1.2 / 1 to 4 / 1, and particularly preferably 1.5 / 1 to 3 / 1 from the viewpoints of the adhesiveness of the adhesive to the polyolefin substrate, the adhesion of the aqueous dispersion to the polyolefin substrate, and the impact resistance characteristics of the molded article containing the resin modifier.

[0035] The weight ratio [(a) / (b)] of (a) and (b) constituting the block polymer (Y) of the present invention is preferably 25 / 75 to 90 / 10, more preferably 50 / 50 to 85 / 15 from the viewpoints of the adhesiveness of the adhesive to the polyolefin substrate, the adhesion of the coating film obtained by the aqueous dispersion to the polyolefin substrate, the compatibility with the polyolefin resin of the resin modifier, and the heat creep resistance of the adhesive, the dispersion stability of the aqueous dispersion, and the effect of imparting the dispersibility of the inorganic filler to the polyolefin resin of the resin modifier. When within the above range, the acid-modified polyolefin (a) block and the polyamide (b) block tend to be easily microphase-separated, and the balance of the resin modification effect, the adhesive performance of the adhesive, and the coating film physical properties of the paint tends to be good. The Mn of (Y) is preferably 1,500 to 120,000, more preferably 2,000 to 100,000 from the viewpoints of the adhesiveness of the adhesive to the polyolefin substrate, the adhesion of the aqueous dispersion to the polyolefin substrate, the impact resistance characteristics of the molded article containing the resin modifier, and the productivity of the block polymer (Y). The molecular weight ratio (a / b) of the number average molecular weight of the acid-modified polyolefin (a) block to the number average molecular weight of the polyamide (b) block in (Y) is preferably from 0.8 to 15.0, more preferably from 1.0 to 14.0, from the viewpoints of the adhesiveness of the adhesive to the polyolefin substrate, the adhesion of the coating film obtained from the aqueous dispersion to the polyolefin substrate, the flexural physical properties of the molded article containing the resin modifier, and the impact resistance. When it is within the above range, the blocks of the acid-modified polyolefin (a) and the polyamide (b) block tend to be easily microphase-separated, and the balance of the resin modification effect, the adhesive performance of the adhesive, and the coating film physical properties of the paint tends to be good. The number average molecular weight (Mn a ) of each acid-modified polyolefin (a) block in the block polymer (Y) and the number average molecular weight (Mn b ) of each polyamide (b) block, the ratio of the number average molecular weight (Mn Y ) of the block polymer (Y) to the total {Mn Y / (Mn a +Mn b )} is preferably from 1.0 to 10.0, more preferably from 1.0 to 9.0, from the viewpoints of the adhesiveness of the adhesive to the polyolefin substrate, the adhesion of the coating film obtained from the aqueous dispersion to the polyolefin substrate, the flexural physical properties of the molded article containing the resin modifier, and the impact resistance.

[0036] The content of the amide group in (Y) is preferably from 0.3 to 5.0 mmol / g, more preferably from 0.5 to 4.0 mmol / g, based on the weight of (Y), from the viewpoints of the adhesiveness of the adhesive to the polyolefin substrate, the adhesion of the coating film obtained from the aqueous dispersion to the polyolefin substrate, the flexural physical properties of the molded article containing the resin modifier, and the impact resistance. In addition, when the reaction is carried out so that the carboxyl group is in excess, the content of the amide group can be calculated from the acid value and the charged amount of the block polymer, and when the reaction is carried out so that the amino group is in excess, it can be calculated from the amine value and the charged amount of the block polymer. For example, when the reaction is carried out so that the carboxyl group is in excess, it is as follows. Content of amide group (mmol / g) = { (number of moles of carboxyl groups in the charged compound) - (number of moles of carboxyl groups calculated from the acid value of block polymer (Y))} / (total amount of the charged compound) When lactam (c2) or the like is contained in the charged compound, lactam (c2) is counted and calculated as a compound having one carboxyl group and one amino group.

[0037] (Y) preferably has a carboxyl group. The acid value (mgKOH / g) of block polymer (Y) is preferably 100 or less, more preferably 0.2 to 80, from the viewpoints of the heat creep resistance of the adhesive, the dispersion stability of the aqueous dispersion, the effect of imparting the dispersibility of the inorganic filler to the polyolefin resin by the resin modifier, the adhesiveness of the adhesive to the polyolefin 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. The acid value here is a value measured in accordance with JIS K0070:1992. The amine value (mgKOH / g) of block polymer (Y) is preferably 5 or less, more preferably 3 or less, from the viewpoints of the heat creep resistance of the adhesive, the dispersion stability of the aqueous dispersion, the effect of imparting the dispersibility of the inorganic filler to the polyolefin resin by the resin modifier, the adhesiveness of the adhesive to the polyolefin 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. The amine value here is a value measured in accordance with JIS K7237:1995.

[0038] The production method of block polymer (Y) is not particularly limited, (1) A method of reacting acid-modified polyolefin (a) and polyamide (b) having an amino group under a nitrogen atmosphere at a high temperature (for example, 140 to 280 ° C), normal pressure or reduced pressure (for example, 0.1 to 50 kPa), (2) In the presence of the acid-modified polyolefin (a), the raw materials of the aminocarboxylic acid (c1), lactam (c2), diamine (c3) and dicarboxylic acid (c4) which are the constituent raw materials of the polyamide (b) are reacted at a high temperature (for example, 140 to 280 ° C), normal pressure or pressure (for example, 1.1 to 3 MPa) in a nitrogen atmosphere to produce a polyamide (b) having an amino group, and the reaction between the carboxylic acid group of the acid-modified polyolefin (a) and the amino group of the polyamide (b) is carried out in one step. In addition, in the case of the production method of (2), the Mn and amine value of the polyamide (b) can be obtained by calculation from the number of moles and molecular weights of the aminocarboxylic acid (c1), lactam (c2), diamine (c3) and dicarboxylic acid (c4) which are the constituent raw materials of the polyamide (b), and the number of moles of the carboxyl groups of the acid-modified polyolefin (a). The specific calculation formula used will be described in the examples below.

[0039] The amidation reaction temperature in the reaction between the acid-modified polyolefin (a) and the polyamide (b) having an amino group is preferably 140 to 280 ° C from the viewpoints of reactivity and prevention of side reactions. The reaction is preferably carried out without a solvent, but if necessary, it is carried out in a solvent [for example, aromatic hydrocarbons (such as toluene and xylene), aliphatic hydrocarbons (such as hexane and cyclohexane), ethers (such as diethyl ether and tetrahydrofuran) and mixtures of two or more of these], and these solvents may be removed by distillation later.

[0040] Since the block polymer of the present invention is excellent in adhesion to a polyolefin substrate, heat creep resistance, dispersibility of an inorganic filler, and mechanical strength, the block polymer of the present invention is useful as a binder resin in adhesives, paints (including coating agents), etc., a resin modifier for polyolefins, an inorganic filler dispersant for polyolefins, etc.

[0041] <Adhesive> The adhesive of the present invention contains a block polymer (Y). The softening point of the adhesive is preferably 60 to 200°C, more preferably 70 to 180°C, from the viewpoints of the heat creep resistance of the adhesive and the coatability of the adhesive.

[0042] In the adhesive, the content of the block polymer (Y) is preferably 10 to 80% by weight, more preferably 15 to 70% by weight, particularly preferably 20 to 60% by weight, based on the weight of the adhesive, from the viewpoints of the heat creep resistance of the adhesive and the coatability of the adhesive.

[0043] 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 release agent (F10), a light stabilizer (F11), a fragrance (F12), and an ultraviolet absorber (F13).

[0044] Examples of the tackifier (F1) include polyolefins (e.g., the aforementioned (A), polyolefins other than (A) (e.g., ethylene-propylene copolymer, etc.)), acid-modified polyolefins (a), terpene resins, terpene-phenol resins, phenol resins, aromatic hydrocarbon-modified terpene resins, rosin resins, modified rosin resins, synthetic petroleum resins (aliphatic, aromatic, or alicyclic synthetic petroleum resins, etc.), coumarone-indene resins, xylene resins, styrene resins, dicyclopentadiene resins, and hydrogenated products of those having an unsaturated double bond capable of hydrogenation among these.

[0045] As the plasticizer (F2), various plasticizers [such as those described in Adhesion Technology Vol. 20, (2), 21 (2000), etc.] can be used, including 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, etc.

[0046] Examples of the adsorbent (F3) include alumina, silica gel, molecular sieve, etc.

[0047] Examples of the colorant (F4) include inorganic pigments [white pigments, cobalt compounds, iron compounds, sulfides, etc.], organic pigments [azo pigments, polycyclic pigments, etc.], dyes [azo-based, indigoid-based, sulfur-based, alizarin-based, acridine-based, thiazole-based, nitro-based, aniline-based, etc.], etc.

[0048] 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.

[0049] Examples of the filler (F6) include, for example, inorganic fillers (calcium carbonate, talc, clay, etc.).

[0050] Examples of the lubricant (F7) include, for example, calcium stearate, butyl stearate, oleic acid amide, etc.

[0051] Examples of the nucleating agent (F8) include sorbitol, metal phosphate salts, metal benzoate salts, metal phosphate salts, etc.

[0052] Examples of the antioxidant (F9) include phenolic compounds [monocyclic phenols (such as 2,6-di-t-butyl-p-cresol), bisphenols (such as 2,2'-methylenebis(4-methyl-6-t-butylphenol)), 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), phosphorus compounds (such as triphenyl phosphite), etc.

[0053] Examples of the release agent (F10) include carboxyl-modified silicone oil, hydroxyl-modified silicone oil, etc.

[0054] Examples of the light stabilizer (F11) include hindered amine compounds [such as bis-2,2,6,6-tetramethyl-4-piperidyl sebacate, etc.].

[0055] Examples of the fragrance (F12) include diterpenes, limonene, etc.

[0056] 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.], etc.

[0057] From the perspective of the adhesiveness of the adhesive to the polyolefin substrate, the content of the tackifier (F1) is preferably 20 to 80% by weight, more preferably 25 to 75% by weight, based on the total weight of the adhesive. From the perspectives of the additive effect and adhesiveness, the total content of the additives (F) other than (F1) 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 total weight of the adhesive.

[0058] When additives are the same and overlap among (F1) to (F13) above, instead of directly using the amount of each additive that exhibits the corresponding additive effect, the usage amount shall be adjusted according to the purpose of use, taking into account that the effects as other additives can also be obtained simultaneously.

[0059] The adhesive of the present invention can be used as a hot-melt adhesive. The adhesive of the present invention can be appropriately formed into a desired shape such as a block, pellet, powder, sheet or film. For forming, a pelletizer, crusher, extruder, etc. are used. The usage method of the adhesive of the present invention is not particularly limited. For example, when the adhesive is in the form of a block or pellet, after melting the adhesive, it is applied to the adherend to be bonded and then used.

[0060] <Adherend> The adhesive of the present invention can obtain an adherent by adhering an adherend. Examples of the adherend include plastic molded articles [polyolefins (such as polyethylene and polypropylene), polystyrene, ABS, polyvinyl chloride, polycarbonate, polyacetal, polyester, polyamide, polyurethane, modified PPO, polymethyl methacrylate, epoxy resin, phenolic resin, 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 iron, tinplate, galvanized steel, aluminum, and zinc steel plates, etc.), glass, tile slate, and ceramics, etc.]. Among these, from the viewpoint of adhesiveness, a polyolefin substrate is preferably used. It is preferable that at least one of the adherends is a polyolefin substrate.

[0061] As a method of adhering the adherend, for example, the adhesive of the present invention can be applied to the adherend using an applicator for hot melt adhesives [for example, a roll coater (gravure roll, reverse roll, etc.) having a heatable melting tank, a curtain coater, a bead, a spiral, a spray, a slot] and an extruder [for example, a single screw extruder, a twin screw extruder, a kneader extruder, etc.] and adhered. In the case of the former applicator, the adhesive can be applied to one or both of the adherends and laminated before cooling and solidifying, or after cooling and solidifying, the adherends can be brought together and reheated and laminated. It is better to apply pressure during lamination, and the pressure can be released after cooling and solidifying. In the case of the latter extruder, it is extruded onto one or both of the adherends, and after cooling and solidifying, the adherends are brought together and reheated and laminated. It is better to apply pressure during lamination, and the pressure can be released after cooling and solidifying. Also, coextrusion can be performed between the adherends to perform lamination simultaneously.

[0062] When the adhesive is in powder form, it is used by spraying it on the adherend and then heating and laminating. The heating temperature is not particularly restricted, but it is preferably 10 to 20 °C or higher than the melting point (or softening point). It is better to apply pressure during lamination, and the pressure can be released after cooling and solidifying. The pressure applied is not particularly restricted as long as sufficient adhesion can be obtained, and is preferably 10 kPa to 5 MPa. The basis weight of the powder is not particularly restricted as long as the desired adhesive force can be obtained, but is preferably 10 to 500 g / m 2 is. When the adhesive is in the form of a sheet or film, it can be sandwiched between the substrates to be bonded, heated and melted for bonding, or placed on one or both of them, heated and melted, and bonded before cooling and solidifying, or after cooling and solidifying, the adherends are brought together and heated again for bonding. There are no particular restrictions on the heating temperature during heating and melting, but it is preferably 10 to 20 °C or more higher than the melting point (or softening point). There are no particular restrictions on the heating temperature when reheating, but it is preferably 10 to 20 °C or more higher than the melting point (or softening point). Also, it is better to apply pressure during bonding, and the pressure can be released after cooling and solidifying. The pressure applied has no particular restrictions as long as the desired adhesive strength can be obtained, and is preferably 10 kPa to 5 MPa. The size of the sheet or film is not particularly limited as long as it has the desired area. The thickness of the sheet or film is not particularly limited, but is preferably 10 to 500 μm, more preferably 30 to 300 μm.

[0063] <Aqueous dispersion> The aqueous dispersion of the present invention contains water and the block polymer (Y). The above aqueous dispersion can be produced, for example, by the following method.

[0064] (1) Prepare a solvent solution containing the block polymer (Y) and, if necessary, a solvent described below. Next, charge water and, if necessary, a solvent, carry out phase inversion emulsification, and further, if necessary, distill off the solvent to obtain an aqueous dispersion. (2) Prepare a solvent solution containing the block polymer (Y) and, if necessary, a solvent described below. Next, add water and disperse, for example, with a disperser, and if necessary, distill off the solvent to obtain an aqueous dispersion. The production apparatus is not particularly limited, and any apparatus with mixing and dispersing capabilities can be used. However, from the viewpoints of temperature adjustment and mixing and dispersing capabilities, etc., it is preferable to use a rotary mixing and dispersing apparatus. Examples of the rotary mixing and dispersing device include mixing devices having general stirring blades such as Max Blend and helical blades, TK Homomixer [manufactured by Primix Corporation], Clear Mix [manufactured by M Technique Co., Ltd.], Filmix [manufactured by Primix Corporation], Ultra Turrax [manufactured by IKA Japan Co., Ltd.], Ebara Mildar [manufactured by Ebara Corporation], Cavitron [manufactured by Eurotech], and Biomixer [manufactured by Nippon Seiki Co., Ltd.].

[0065] 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.

[0066] 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.

[0067] From the viewpoint of the ease of handling of the aqueous dispersion, the solid content concentration (content of components other than volatile components) of 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 remaining weight after heating to the weight before heating.

[0068] Also, 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.

[0069] 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 with a pH Meter M-12 [manufactured by Horiba, Ltd.].

[0070] From the viewpoint of dispersion stability, the volume average particle diameter (Dv) of the block polymer (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.

[0071] The above volume average particle diameter (Dv) can be controlled by the carboxy groups in the block polymer (Y) and the type and operating conditions of the disperser used in the dispersion step.

[0072] 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 binders, non-woven fabric binders, reinforcing fiber sizing agents, antibacterial agent binders, and artificial leather / 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.

[0073] 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.

[0074] Examples of other resins include water-dispersible or water-soluble polyurethane resins, polyacrylic resins, and polyester resins other than the block polymer (Y) in the present invention.

[0075] Examples of the viscosity modifier include thickeners such as inorganic viscosity modifiers (e.g., sodium silicate and bentonite), cellulose-based viscosity modifiers (e.g., methyl cellulose, carboxymethyl cellulose, and hydroxymethyl cellulose with Mn of 20,000 or more), protein-based viscosity modifiers (e.g., casein, sodium caseinate, and ammonium caseinate), acrylic-based (e.g., sodium polyacrylate and ammonium polyacrylate with Mn of 20,000 or more), and vinyl-based viscosity modifiers (e.g., polyvinyl alcohol with Mn of 20,000 or more). Examples of the antifoaming agent include long-chain alcohols (e.g., octyl alcohol), sorbitan derivatives (e.g., sorbitan monooleate), silicone oils (e.g., polymethylsiloxane and polyether-modified silicone), and the like.

[0076] Examples of the preservative include organic nitrogen-sulfur compound-based preservatives and organic sulfur halide-based preservatives, and the like. Examples of the anti-degradant and stabilizer (e.g., ultraviolet absorber and antioxidant) include hindered phenol-based, hindered amine-based, hydrazine-based, phosphorus-based, benzophenone-based, or benzotriazole-based anti-degradants and stabilizers, and the like. Examples of the antifreeze include ethylene glycol and propylene glycol, and the like. The contents of the viscosity modifier, antifoaming agent, preservative, anti-degradant, stabilizer, and antifreeze 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.

[0077] <Resin modifier> The resin modifier of the present invention contains the block polymer (Y). The resin modifier is suitably used as a modifier for polyolefin resins, particularly as a resin modifier that imparts dispersibility of inorganic fillers to polyolefin resins. From the viewpoint of the dispersibility of inorganic fillers in polyolefin resins, the content of the block polymer (Y) in the resin modifier is preferably 90 to 100% by weight, more preferably 95 to 100% by weight.

[0078] <Polyolefin resin> The polyolefin resin in the present invention includes a high molecular weight polyolefin or a product obtained by a reduction method (thermal, chemical, and mechanical reduction) of a high molecular weight polyolefin (preferably Mn 80,000 to 400,000), and examples thereof include an ethylene unit-containing (propylene unit-free) (co)polymer, a propylene unit-containing (ethylene unit-free) (co)polymer, an ethylene / propylene copolymer, and a (co)polymer of an olefin having 4 or more carbon atoms.

[0079] <Inorganic filler (G)> Examples of the inorganic filler (G) in the present invention include oxides (e.g., silica, alumina, titanium oxide, wollastonite, calcined kaolin, quartz); hydroxides (e.g., magnesium hydroxide, calcium hydroxide, aluminum hydroxide); silicates (e.g., talc, mica, clay, dolomite, bentonite, silica, calcium silicate, zeolite); carbonates (e.g., calcium carbonate, magnesium carbonate); metal salts (e.g., barite, fluorite, calcium sulfate); metal sulfides (e.g., molybdenum disulfide); inorganic microballoons (e.g., glass, shirasu); metal powders (e.g., aluminum powder, copper powder); inorganic fibers (e.g., glass fiber, carbon fiber, alumina fiber, ceramic fiber, rock fiber, slag fiber), etc. Among these inorganic fillers (G), oxides, hydroxides, silicates, carbonates, and inorganic fibers are preferable from the viewpoints of the mechanical strength and industrial aspects of the molded product. More preferably, hydroxides, silicates, carbonates, and inorganic fibers are preferred, and particularly preferably, talc, calcium carbonate, magnesium hydroxide, and glass fiber are preferred.

[0080] The particle diameter of the inorganic filler (G) (in the case of a fibrous shape, the fiber diameter) is not particularly limited, but the volume average particle diameter (fiber diameter in the case of fibers) of the inorganic filler (G) is preferably 0.1 to 1,000 μm, more preferably 0.5 to 500 μm, and particularly preferably 1 to 100 μm from the viewpoints of the mechanical strength and moldability of the molded product.

[0081] <Polyolefin resin composition> The polyolefin resin composition of the present invention contains the resin modifier, a polyolefin resin, and an inorganic filler (G). In the resin composition, the proportion of each component based on the total weight of the resin modifier, the polyolefin resin, and the inorganic filler is as follows: the resin modifier is preferably 0.1 to 15% by weight, more preferably 0.3 to 12% by weight, and particularly preferably 0.5 to 10% by weight from the viewpoints of the impact resistance characteristics and the bending characteristics of the molded article; the polyolefin resin is preferably 30 to 98% by weight, more preferably 40 to 85% by weight, and particularly preferably 50 to 80% by weight from the viewpoints of the productivity and the mechanical strength of the molded article; the inorganic filler is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, and particularly preferably 10 to 50% by weight from the viewpoints of the mechanical strength and the productivity of the molded article. In the resin composition, the weight ratio of the block polymer (Y) is preferably 0.1 to 15% by weight, more preferably 0.3 to 12% by weight, and particularly preferably 0.5 to 10% by weight based on the total weight of the resin modifier, the polyolefin resin, and the inorganic filler from the viewpoints of the impact resistance characteristics and the bending characteristics of the molded article.

[0082] The polyolefin resin composition of the present invention can further contain various additives (H) as necessary within a range that does not inhibit the effects of the present invention. Examples of the additive (H) include one or more selected from the group consisting of a colorant (H1), a flame retardant (H2), a filler (H3), a lubricant (H4), an antistatic agent (H5), a dispersant (H6) other than the resin modifier of the present invention, an antioxidant (H7), and an ultraviolet absorber (H8).

[0083] Examples of the colorant (H1) 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.

[0084] Examples of the flame retardant (H2) include organic flame retardants [nitrogen-containing compounds [salts of urea compounds, 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.

[0085] Examples of the filler (H3) 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.

[0086] Examples of the lubricant (H4) 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.

[0087] Examples of the antistatic agent (H5) include nonionic, cationic, anionic, and amphoteric surfactants described in the following, U.S. Patent No. 3,929,678, and U.S. Patent No. 4,331,447. (1) Nonionic surfactants Alkylene oxide (hereinafter abbreviated as AO) - added non - ionic surfactants, 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 non - ionic surfactants, etc.); (poly)oxyalkylene derivatives of (alkanol)amides of higher fatty acids (the above); (poly)oxyalkylene derivatives of alkyl (C3 - 60) ethers of polyhydric alcohols (the above); and polyoxypropylene polyols [polyoxypropylene derivatives of polyhydric alcohols and polyamines (C2 - 10) (Pluronic (registered trademark) - type and Tetronic - type non - ionic surfactants)]; polyhydric alcohol (the above) - type non - ionic surfactants (for example, fatty acid esters of polyhydric alcohols, alkyl (C3 - 60) ethers of polyhydric alcohols, and fatty acid alkanol amides); and amine oxide - type non - ionic surfactants [for example, (hydroxy)alkyl (C10 - 18) di(hydroxy)alkyl (C1 - 3) amine oxides].

[0088] (2) Cationic surfactants Quaternary ammonium salt - type cationics [tetraalkylammonium salts (C11 - 100), alkyl (C8 - 18) trimethylammonium salts, and dialkyl (C8 - 18) dimethylammonium salts, etc.]; trialkylbenzylammonium salts (C17 - 80) (lauryldimethylbenzylammonium salts, etc.); alkyl (C8 - 60) pyridinium salts (cetylpyridinium salts, etc.); (poly)oxyalkylene (C2 - 4) trialkylammonium salts (C12 - 100) (polyoxyethylene lauryldimethylammonium salts, 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 It contains salts of quaternary ammonium salts (such as benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, etc.), alkyl sulfates (such as methyl sulfate, etc.), and organic acids (described below); and amine salt type cationics: inorganic acid (such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, etc.) salts and organic acid (C2-22) salts of primary to tertiary amines [such as higher aliphatic amines (C12-60), polyoxyalkylene derivatives of aliphatic amines (such as methylamine, diethylamine, etc.) (ethylene oxide (hereinafter abbreviated as EO) adducts, etc.), and acylaminoalkyl or acyloxyalkyl (described above) di(hydroxy)alkyl (described above) amines (such as stearoyloxyethyldihydroxyethylamine, stearamidoethyldiethylamine, etc.)].

[0089] (3) Anionic surfactants Salts of higher fatty acids (described above) (such as sodium laurate, etc.), ether carboxylic acids [such as carboxymethylated products of EO (1-10 moles) adducts, etc.], and their salts; sulfate ester salts (such as alkyl and alkyl ether sulfates, etc.), sulfated oils, sulfated fatty acid esters, and sulfated olefins; sulfonate salts [such as alkylbenzene sulfonate salts, alkylnaphthalene sulfonate salts, dialkyl succinate sulfonate type, α-olefin (C12-18) sulfonate salts, N-acyl-N-methyltaurine (Igepon T type, etc.), etc.]; and phosphate ester salts, etc. (such as alkyl, alkyl ether, and alkyl phenyl ether phosphates, etc.).

[0090] (4) Amphoteric surfactants: Carboxylic acid (salt) type amphoterics [amino acid type amphoterics (such as lauryl aminopropionic acid (salt), etc.), and betaine type amphoterics (such as alkyldimethylbetaine, alkyldihydroxyethylbetaine, etc.), etc.]; sulfate ester (salt) type amphoterics [such as sulfate ester (salt) of laurylamine, sulfate ester (salt) of hydroxyethylimidazoline, etc.]; sulfonic acid (salt) type amphoterics [such as pentadecyl sulfotaurine, imidazoline sulfonic acid (salt), etc.]; and phosphate ester (salt) type amphoterics, etc. [such as phosphate ester (salt) of glycerol laurate, etc.].

[0091] The salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and Group IIB metals (zinc, etc.); ammonium salts; and amine salts and quaternary ammonium salts. are included.

[0092] As the dispersant (H6), polymers with Mn of 1,000 to 20,000 are used, such as vinyl resins [polyolefins (polyethylene, polypropylene, etc.), modified polyolefins [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 [polyvinyl halides (polyvinyl chloride, polyvinyl bromide, etc.), polyvinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly(meth)acrylic acid, poly(meth)acrylate [poly(meth)acrylate methyl, etc.] and styrene resins [polystyrene, acrylonitrile / styrene (AS) resins, etc.]]; polyester resins [polyethylene terephthalate, etc.], polyamide resins [6,6-nylon, 12-nylon, etc.], polyether resins [polyethersulfone, etc.], polycarbonate resins [condensation polymers of bisphenol A and phosgene, etc.], and their block copolymers, etc.

[0093] As the antioxidant (H7), 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-butylbenzyl phosphonate, etc.] and the like can be mentioned.

[0094] Examples of the ultraviolet absorber (H8) include salicylate compounds [such as phenyl salicylate]; benzophenone compounds [such as 2,4-dihydroxybenzophenone]; benzotriazole compounds [such as 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole], and the like.

[0095] The total content of the additives (H) in the polyolefin resin composition is 20% by weight or less, preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, from the viewpoints of the functional expression of each additive (H) and industrial applications. The usage amount of each additive based on the total weight of the composition is as follows: (H1) is 5% by weight or less, preferably 0.1 to 3% by weight; (H2) is 8% by weight or less, preferably 1 to 3% by weight; (H3) is 5% by weight or less, preferably 0.1 to 1% by weight; (H4) is 8% by weight or less, preferably 1 to 5% by weight; (H5) is 8% by weight or less, preferably 1 to 3% by weight; (H6) is 1% by weight or less, preferably 0.1 to 0.5% by weight; (H7) is 2% by weight or less, preferably 0.05 to 0.5% by weight; (H8) is 2% by weight or less, preferably 0.05 to 0.5% by weight.

[0096] When the additives are the same and overlapping among the above (H1) to (H8), the amounts of the respective additives that exhibit the corresponding additive effects are not used as they are. Instead, the usage amounts are adjusted according to the usage purpose, taking into account that the effects as other additives can also be obtained simultaneously.

[0097] As a method for producing the polyolefin resin composition of the present invention, there are: (1) a method of batch-mixing the resin modifier, polyolefin resin, inorganic filler (G), and optionally (H) of the present invention 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 (H) to once prepare a masterbatch polyolefin resin composition containing a high concentration of the resin modifier, and then adding and mixing the remaining polyolefin resin, inorganic filler, and optionally the remaining amount of (H) to obtain a polyolefin resin composition (masterbatch method). From the viewpoint of the mixing efficiency of the resin modifier, the method (2) is preferred.

[0098] As a specific mixing method in the above method for producing the polyolefin resin composition, (i) Each component to be mixed is, for example, mixed with a powder mixer [such as "Henschel Mixer" (trade name "Henschel Mixer FM150L / B", manufactured by Mitsui Mining Co., Ltd., changed to 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 of directly kneading each component to be mixed under the same conditions using the same melt-kneading device without previously mixing the powders can be mentioned. Among these methods, the method (i) is preferred from the viewpoint of mixing efficiency.

[0099] The polyolefin composition of the present invention is excellent in the dispersibility of the inorganic filler, and the molded article described below is excellent in mechanical strength (impact resistance). The mechanical strength of the molded article can be evaluated by the impact resistance and flexural modulus described below.

[0100] <Formed body, molded article> The molded article of the present invention is formed by molding the above polyolefin resin composition. As the molding method, injection molding, compression molding, calendering, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.) and the like can be mentioned, and single-layer molding, multi-layer molding, foam molding and other means can also be incorporated by any method according to the purpose. As the form of the molded product, plate shape, sheet shape, film, fabric, fiber (including non-woven fabric, etc.) and the like can be mentioned.

[0101] The molded product of the present invention has excellent mechanical strength, good paintability and printability, and a molded article can be obtained by applying paint and / or printing to the molded product. Examples of the method for painting the molded product include air spray painting, airless spray painting, electrostatic spray painting, dip painting, roller painting, brush painting, etc., but are not limited thereto. Examples of the paint include paints generally used for painting plastics, 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 to 50 μm.

[0102] In addition, as the method of further printing on the molded product or the molded product coated with paint, any printing method generally used for printing plastics 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 printing plastics, such as gravure ink, flexographic ink, screen ink, pad ink, dry offset ink and offset ink, can be used.

Examples

[0103] The present invention will be further described by the following examples, but the present invention is not limited thereto.

[0104] <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, Mn 76,000] 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 degradation 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 8,500, the number of double bonds in the molecular chain per 1000 carbons was 2.5, and the isotacticity was 20%.

[0105] <Production Examples 2 to 4> Except that the heat degradation conditions in Production Example 1 were in accordance with Table 1, the same procedure as in Production Example 1 was carried out to obtain polyolefins (A-2) to (A-4) having a carbon-carbon double bond.

[0106] <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, Mn 113,000] containing 91% by weight of propylene and 9% by weight of ethylene as constituent monomers. Except that the heat degradation conditions were in accordance with Table 1, the same procedure as in Production Example 1 was carried out to obtain a polyolefin (A-5) having a carbon-carbon double bond.

[0107] <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 carried out in the same manner as in Production Example 1 except that the thermal reduction conditions were according to Table 1, to obtain a polyolefin (A-6) having a carbon-carbon double bond.

[0108] <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 carried out in the same manner as in Production Example 1 except that the thermal reduction conditions were according to Table 1, to obtain polyolefin (Ratio A-1).

[0109] <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.

[0110] <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 carried out in the same manner as in Production Example 1 except that the thermal reduction conditions were according to Table 1, to obtain polyolefin (Ratio A-3).

[0111] Table 1 shows the measurement results of Mn, the number of double bonds per 1000 carbons, and isotacticity of polyolefins (A-1) to (A-6) and polyolefins (Ratio A-1) to (Ratio A-3) having a carbon-carbon double bond.

[0112]

Table 1

[0113] <Production Example 7> Into a reaction vessel, 100 parts by weight of a polyolefin (A-1) having a carbon-carbon double bond and 2.4 parts by weight of maleic anhydride (B-1) were charged. After purging with nitrogen, the temperature was raised to 180 °C under nitrogen flow and uniformly dissolved. A solution prepared by dissolving 0.5 part 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, 0.1 part by weight of unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin resin (a-1). Note that the blending amount of maleic anhydride described in Table 2 is the amount obtained by subtracting the amount distilled off from the charged amount. Also, the acid value of (a-1) was 12, Mn was 10,000, and the isotacticity was 20%.

[0114] <Production Example 8> Into a reaction vessel, 100 parts by weight of a polyolefin (A-1) having a carbon-carbon double bond and 3.5 parts by weight of maleic anhydride (B-1) were charged. 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 an acid-modified polyolefin resin (a-2). Note that the blending amount of maleic anhydride described in Table 2 is the amount obtained by subtracting the amount distilled off from the charged amount. Also, the acid value of (a-2) was 10, Mn was 8,700, and the isotacticity was 20%.

[0115] <Production Examples 9 to 14 and Comparative Production Examples 4 to 5> Except that the number of parts of the raw materials used was in accordance with Table 2, the procedure was the same as in Production Example 7 to obtain acid-modified polyolefin resins (a-3) to (a-8) and acid-modified polyolefin resins (ratio a-1) to (ratio a-2).

[0116] <Production Examples 15 to 17 and Comparative Production Example 6> Except for following Table 2 regarding the compounding parts of the raw materials used, it was carried out in the same manner as in Production Example 8 to obtain acid-modified polyolefin resins (a-9) to (a-11) and acid-modified polyolefin resin (ratio a-3).

[0117] Table 2 shows the results of the properties of acid-modified polyolefin resins (a-1) to (a-11) and acid-modified polyolefin resins (ratio a-1) to (ratio a-3).

[0118]

Table 2

[0119] <Example 1> Into a reaction vessel, 20 parts by weight of 6-aminohexanoic acid (c1-1) as aminocarboxylic acid (c1) and 0.5 part by weight of hexamethylenediamine (c3-1) as diamine (c3) were charged under a nitrogen atmosphere, and after reacting at 220 ° C, normal pressure for 8 hours, the water generated by the reaction was distilled off under reduced pressure (1.0 kPa) over 3 hours to obtain polyamide (b-1) (Mn: 1,300, amine value: 86). Next, 100 parts by weight of acid-modified polyolefin (a-1) was charged into the reaction vessel of the polyamide (b-1) synthesized above under a nitrogen atmosphere, and after reacting at 220 ° C, normal pressure for 1 hour, the water generated by the reaction was distilled off under reduced pressure (1.0 kPa) over 3 hours to obtain block polymer (Y-1) (acid value: 6, Mn: 21,000, melt viscosity at 220 ° C: 5 Pa·s). Block polymer (Y-1) is a block polymer having an acid-modified polyolefin (a-1) block and a polyamide (b-1) block composed of 6-aminohexanoic acid (c1-1) and hexamethylenediamine (c3-1). In addition, in Table 3, the amide group content was calculated based on the following formula. Amide group content (mmol / g) ={(number of moles of carboxyl groups in the charged compounds)-(number of moles of carboxyl groups calculated from the acid value of block polymer (Y))} / (total amount of charged compounds) Number of moles of carboxyl groups calculated from the acid value of block polymer (Y)=(total amount of charged compounds)×acid value / 56100

[0120] <Example 2> Into a reaction vessel, 33 parts by weight of laurolactam (c2-2) as lactam (c2) and 0.8 part by weight of isophoronediamine (c3-2) were charged under a nitrogen atmosphere, and reacted at 220 °C under pressure (2.0 MPa) for 8 hours. Then, unreacted laurolactam (c2-2) and unreacted isophoronediamine (c3-2) were distilled off under reduced pressure (1.0 kPa) over 3 hours to obtain polyamide (b-2) (Mn: 6,500, amine value: 17). Next, 100 parts by weight of acid-modified polyolefin (a-2) was charged into the reaction vessel of the polyamide (b-2) synthesized above under a nitrogen atmosphere, and reacted at 220 °C, normal pressure for 1 hour. Then, water generated by the reaction was distilled off under reduced pressure (1.0 kPa) over 3 hours to obtain block polymer (Y-2) (acid value: 4, melt viscosity at 220 °C: 6 Pa·s). Block polymer (Y-2) is a block polymer having an acid-modified polyolefin (a-2) block and a polyamide (b-2) block composed of laurolactam (c2-2) and isophoronediamine (c3-2). The blending amounts of laurolactam (c2-2) and isophoronediamine (c3-2) shown in Table 3 are the amounts after subtracting the amounts distilled off from the charge. Also, the same applies to the blending amounts shown in Table 3 for the following examples.

[0121] <Example 3> Into a reaction vessel, 100 parts by weight of acid-modified polyolefin (a-3) and 50 parts by weight of 12-aminododecanoic acid (c1-2) as aminocarboxylic acid (c1) were charged under a nitrogen atmosphere, and reacted at 220 °C, normal pressure for 8 hours. Then, water generated by the reaction was distilled off under reduced pressure (1.0 kPa) over 3 hours to obtain block polymer (Y-3) (acid value: 36, Mn: 7,500, melt viscosity at 220 °C: 1.5 Pa·s). Block polymer (Y-3) is a block polymer having an acid-modified polyolefin (a-3) block and a polyamide (b-3) (Mn: 560, amine value: 200) block composed of 12-aminododecanoic acid (c1-2). The Mn and amine value of polyamide (b-3) were calculated by the following calculation formulas. Calculation formula: {Mn of polyamide (b)} = {number of moles of aminocarboxylic acid (c1)} ÷ {number of moles of carboxyl groups of acid-modified polyolefin (a)} × [{molecular weight of aminocarboxylic acid (c1)} - 18] Calculation formula: (amine value of polyamide (b)) = 56100 × 2 ÷ (Mn of polyamide (b))

[0122] <Example 4> 100 parts by weight of acid-modified polyolefin (a-4) and 85 parts by weight of ε-caprolactam (c2-1) as lactam (c2) were charged into a reaction vessel under a nitrogen atmosphere, and reacted at 220 °C under pressure (2.0 MPa) for 8 hours. Then, unreacted ε-caprolactam (c2-1) was distilled off under reduced pressure (1.0 kPa) over 3 hours to obtain a block polymer (Y-4) (acid value: 68, melt viscosity at 220 °C: 3 Pa·s) having a polyamide (b-4) block (Mn: 480, amine value: 234). The block polymer (Y-4) is a block polymer having an acid-modified polyolefin (a-4) block and a polyamide (b-4) block composed of ε-caprolactam (c2-1). The amount of ε-caprolactam (c2-1) charged as described in Table 3 is the amount after subtracting the amount distilled off. The Mn and amine value of polyamide (b-4) were calculated by the following calculation formulas. Calculation formula: {Mn of polyamide (b)} = {number of moles of lactam (c2)} ÷ {number of moles of carboxyl groups of acid-modified polyolefin (a)} × {molecular weight of lactam (c2)} Calculation formula: {amine value of polyamide (b)} = 56100 × 2 ÷ {Mn of polyamide (b)}

[0123] <Examples 5, 6, 8 to 10, 12, 15, 16, Comparative Examples 2, 3> Except for following Table 3 regarding the number of parts by weight of the raw materials used, the same procedure as in Example 1 was carried out to obtain each block polymer, (Y-5), (Y-6), (Y-8) to (Y-10), (Y-12), (Y-15), (Y-16) and (Comp. Y-2), (Comp. Y-3).

[0124] <Examples 7, 11, 13, 14, 17> Except for following Table 3 regarding the blending parts of the raw materials used, the procedure was the same as in Example 3, and block polymers (Y-7), (Y-11), (Y-13), (Y-14) and (Y-17) were obtained.

[0125] <Comparative Example 1> In Comparative Example 1, except for following Table 3 regarding the blending parts of the raw materials used, the procedure was the same as in Example 4, and block polymer (Ratio Y-1) was obtained.

[0126] Table 3 shows the results of the properties of block polymers (Y-1) to (Y-17) and block polymers (Ratio Y-1) to (Ratio Y-3).

[0127]

Table 3

[0128] <Example 18> 100 parts of block polymer (Y-1), 65 parts by weight of tackifier (F1-1) [ethylene-propylene copolymer, trade name "RT2330", manufactured by REXtac], and 120 parts by weight of tackifier (F1-2) [hydrogenated petroleum resin, trade name "Alcon P-140", manufactured by Arakawa Chemical Industries, Ltd.] were charged into a reaction vessel and melt-mixed at 220°C to obtain an adhesive containing block polymer (Y-1). The softening point of the adhesives in Table 4 was measured according to JIS K6863.

[0129] <Examples 19 to 43, Comparative Examples 4 to 6> Except for following Table 4 regarding the blending parts of the raw materials used, the procedure was the same as in Example 18, and adhesives containing each block polymer (Y) or comparative block polymer (Ratio Y) were obtained.

[0130] <Evaluation Method> <1> Adhesion strength at room temperature after curing (unit: kg / 25 mm) Each adhesive to be evaluated was formed into a film with a thickness of 100 μm using a press molding machine (at a temperature of 150°C). The obtained film-shaped adhesives were sandwiched between two OPP sheets (biaxially stretched polypropylene film, thickness 30 μm) and adhered under the conditions of a temperature of 150°C, a press pressure of 98 kPa, and a time of 30 seconds to obtain an adherend. After leaving it standing for 1 week in an atmosphere of 23°C and 50% RH, the T-peel strength was measured in an atmosphere of 23°C, and it was taken as the normal temperature adhesive strength after curing. The above initial adhesive strength was measured using an autograph in accordance with JIS K6854-1999 under the condition of a tensile strength of 50 mm / min. <2> High-temperature adhesive strength after curing (unit: kg / 25 mm) In the same manner as <1>, they were laminated, left standing for 1 week in an atmosphere of 23°C and 50% RH, and then the T-peel strength was measured in an atmosphere of 80°C in the same manner as <1>. <3> Heat-resistant creep property after curing (unit: mm / h) An adhesive film with a length of 10 mm × width of 25 mm × thickness of 50 μm was placed on an aluminum plate with a length of 100 mm × width of 25 mm × thickness of 1 mm, and then an OPP film with a length of 100 mm × width of 25 mm × thickness of 50 μm was placed thereon. After that, they were pressure-bonded and laminated under the conditions of 100°C and 0.1 MPa for 10 seconds. After leaving it standing for 1 week in an atmosphere of 23°C and 50% RH, it was left standing for 1 hour in an atmosphere of 90°C with a shear load of 1 kg applied in a direction perpendicular to the OPP film, and the creep amount was measured. In Table 4, "unmeasurable" means that during the 1-hour standing with a shear load of 1 kg applied in a direction perpendicular to the OPP film in an atmosphere of 90°C, the aluminum plate and the OPP film were completely peeled off, and the creep amount could not be determined.

[0131] The evaluation results of the adhesives containing each block polymer (Y) are shown in Table 4.

[0132]

Table 4

[0133] As is clear from Table 4, it can be seen that the adhesive of the present invention is excellent in adhesion at high temperature and heat creep resistance to a polyolefin substrate as compared with the comparative adhesives.

[0134] <Example 44> Into a simple pressure reactor equipped with a stirrer and a heating device, 100 parts of a block polymer (Y-3) and 125 parts of an organic solvent [THF, tetrahydrofuran] were charged under a nitrogen atmosphere, and stirred at 60 ° C for 1 hour to dissolve the block polymer (Y-3) in the organic solvent. Then, 233 parts of ion-exchanged water was gradually added with stirring to emulsify it. Thereafter, THF was distilled off at 65 ° C for 12 hours under reduced pressure (10 kPa) to obtain an aqueous dispersion.

[0135] <Examples 45, 46, Comparative Example 7> Except that the raw materials used were according to Table 5, each aqueous dispersion was obtained in the same manner as in Example 44.

[0136] Each of the obtained aqueous dispersions was evaluated by the following procedure. The results are shown in Table 5.

[0137] The volume average particle diameter (Dv) was measured using a laser diffraction particle size distribution analyzer "LA-750" [manufactured by Horiba, Ltd.].

[0138] <1> Adhesion A resin aqueous dispersion was applied (coated) to a surface-treated polypropylene film (OPP) ["Pyren P-2161" manufactured by Toyobo Co., Ltd. (thickness 30 μm)], a surface-treated polyester film (PET) ["Espert E-5102" manufactured by Toyobo Co., Ltd. (thickness 12 μm)], and a surface-treated nylon film ["Harden N-1130" manufactured by Toyobo Co., Ltd. (thickness 15 μm)] so that the film thickness after drying was 50 μm, and dried in an atmosphere of 25 ° C and 50% RH for 7 days. 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. Conditions other than temperature and humidity shall comply with JIS K5600-5-6, and cellophane tape (registered trademark) (manufactured by Nichiban Co., Ltd.) shall be used for evaluation according to the following criteria. <Evaluation Criteria> ◎: 100 meshes without peeling ○: 90 - 99 meshes without peeling ×: Less than 90 meshes without peeling

[0139] <2> Storage Stability of Aqueous Dispersion (40°C, High Temperature) 30 g of the aqueous dispersion was placed in a screw tube bottle [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 criteria. (Storage stability at 40°C) (%) = (Volume average particle diameter after storage) × 100 / (Volume average particle diameter before storage)

[0140] <Evaluation Criteria> ○: Less than 150% ×: 150% or more

[0141] <2> Storage Stability of Aqueous Dispersion (10°C, Low Temperature) 30 g of the aqueous dispersion was placed in a screw tube bottle [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 criteria. (Storage stability at 10°C) (%) = (Volume average particle diameter after storage) × 100 / (Volume average particle diameter before storage)

[0142] <Evaluation Criteria> ○: Less than 150% ×: 150% or more

[0143]

Table 5

[0144] From the results in Table 5, it can be seen that the aqueous dispersion of the present invention is excellent in substrate adhesion and further in storage stability (high temperature, low temperature) compared with the comparative aqueous dispersion.

[0145] [Resin modifier, polyolefin resin composition and molded article] Examples 47 to 58 and Comparative Examples 8 to 10 Using the resin modifiers containing the block polymers (Y-1) to (Y-6), (Y-8) to (Y-11) of the examples and the block polymers (Ratio Y-1) to (Ratio Y-3) of the comparative examples together with the following raw materials used [polyolefin resin (E) and inorganic filler (G)], according to the compounding composition in Table 6 (the unit of the numerical value is part), a twin-screw extruder equipped with a side feeder was used to melt-knead at 220 °C, 100 rpm, and a residence time of 5 minutes to obtain a polyolefin resin composition. For each resin composition, an injection molding machine [trade name "PS40E5ASE", manufactured by Nissei Plastic Industrial Co., Ltd.] was used to mold at a cylinder temperature of 220 °C and a mold temperature of 50 °C. After producing a predetermined test piece, the impact resistance, flexural modulus, and flexural strength were measured by the following test methods. The results are shown in Table 6.

[0146] [Raw materials used] [Polyolefin resin (E)] (E-1): Commercially available polypropylene [trade name "Sun Allomer VMD81M", manufactured by Sun Allomer Co., Ltd., Mn 300,000] (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] [Inorganic filler (G)] (G-1): Glass fiber [trade name "FT157C", manufactured by Asahi Fiber Glass Co., Ltd., fineness 2,200 tex, fiber diameter 16 μm] cut to a fiber length of 5 mm (G-2): Glass fiber [trade name "230QR-483AS", manufactured by Nitto Boseki Co., Ltd., fiber diameter 13 μm] cut to a fiber length of 5 mm.

[0147] <Test Method> (1) Impact Resistance (unit: kJ / m 2 ) Measured in accordance with ASTM D6110. The higher the numerical value of impact resistance, the more uniformly the inorganic filler is dispersed in the polyolefin resin, which means that the modification effect by the resin modifier is good. (2) Flexural Modulus (unit: GPa) Measured in accordance with ASTM D790. (3) Flexural Strength (unit: MPa) Measured in accordance with ASTM D790.

[0148]

Table 6

[0149] From the results in Table 6, it can be seen that the resin modifier of the present invention imparts dispersibility of the inorganic filler to the polyolefin resin as compared with the comparative ones, and the molded article formed by molding the resin composition containing the resin modifier has excellent mechanical strength (such as impact resistance).

Industrial Applicability

[0150] The adhesive containing the block polymer of the present invention is excellent in adhesiveness at high temperature (80 - 100 °C) to the polyolefin substrate and heat-resistant creep property, and thus can be suitably used for polyolefin substrates such as polyethylene films, polypropylene plates, and polypropylene films. The obtained adhesive body can be used as a food film, a plastic molded article material, a building material, and an automotive interior material. The aqueous dispersion containing the block polymer of the present invention is excellent in storage stability and film adhesion, and thus can be suitably used for coating agents, paint compositions, adhesive compositions, fiber processing treatment agent compositions, etc. The resin modifier containing the block polymer of the present invention imparts excellent dispersibility with an inorganic filler to a polyolefin resin, and a molded article formed by molding a resin composition containing the modifier is excellent in excellent mechanical strength (such as impact resistance), so it can be suitably applied to a wide range of fields such as for electric and electronic equipment, transport materials, household materials, and building materials.

Claims

1. A block polymer having an acid-modified polyolefin (a) block and a polyamide (b) block, wherein the acid-modified polyolefin (a) is an acid-modified polyolefin containing a polyolefin (A) having a carbon-carbon double bond and an unsaturated (poly) carboxylic acid (anhydride) (B) as constituent monomers, the acid-modified polyolefin (a) satisfies all of the following requirements (1) to (3), the polyolefin (A) is a polyolefin containing ethylene and an α-olefin (having 3 to 8 carbon atoms) as constituent monomers, and the weight ratio [ethylene / α-olefin] of ethylene to the α-olefin (having 3 to 8 carbon atoms) as constituent monomers is 5 / 95 to 50 / 50, a block polymer (Y). (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 moiety is 1 to 50%

2. The block polymer according to Claim 1, wherein the number average molecular weight of the polyolefin (A) is 800 to 50,000.

3. The block polymer according to Claim 1 or 2, wherein the polyolefin (A) has 1 to 20 carbon-carbon double bonds per 1,000 carbon atoms.

4. The block polymer according to any one of Claims 1 to 3, having a number average molecular weight of 2,000 to 100,000.

5. The number-average molecular weight (Mn ａ ) of the acid-modified polyolefin (a) block and the number-average molecular weight (Mn ｂ ) of the polyamide (b) block, and the number-average molecular weight (Mn Ｙ ) of the block polymer with respect to the total thereof {Mn Ｙ / (Mn ａ + Mn ｂ )} is from 1.0 to 9.

0. The block polymer according to any one of claims 1 to 4.

6. An adhesive comprising the block polymer according to any one of Claims 1 to 5.

7. An adherend obtained by adhering an adherend with the adhesive according to Claim 6.

8. The adherend according to Claim 7, wherein at least one of the adherends is a polyolefin substrate.

9. An aqueous dispersion comprising the block polymer according to any one of Claims 1 to 5.

10. A coating agent comprising the aqueous dispersion according to Claim 9.

11. A resin modifier comprising the block polymer according to any one of Claims 1 to 5.

12. A polyolefin resin composition comprising the resin modifier according to Claim 11 and an inorganic filler (G).

13. A molded article obtained by molding the polyolefin resin composition according to Claim 12.

14. A molded article obtained by coating and / or printing the molded article according to Claim 13.

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