Composite molding, and method for manufacturing the same

Abstract

To provide a composite molding which comprises a polyolefin molding, and an adherend adhered directly to the polyolefin molding, and in which the components are adhered at excellent adhesive strength.SOLUTION: A composite molding comprises a polyolefin molding and an adherend A adhered directly to the polyolefin molding, where the polyolefin molding contains polyolefin and unsaturated carboxylic acid metal salt, the unsaturated carboxylic acid metal salt contains unsaturated carboxylic acid and a metal element with a valence of 2 or higher, the adherend A has an inorganic material surface formed of an inorganic material, the inorganic material surface contacts the polyolefin molding, and in an infrared absorption spectrum on an interface between the polyolefin molding and the adherend A, a ratio of C=O peak intensity to CH3 peak intensity is 0.30 or more.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a composite molded body and a method for producing the same. [Background technology]

[0002] A molded article containing an ethylene-α-olefin copolymer rubber such as an ethylene-α-olefin-non-conjugated polyene copolymer rubber may be used to form a composite molded article by combining it with a metal member (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2018 / 212180 Summary of the Invention [Problem to be solved by the invention]

[0004] Polyolefin molded articles containing polyolefins often have poor adhesion to other materials. Therefore, polyolefin molded articles are usually bonded to molded articles of other materials using adhesives. However, from the viewpoint of reducing the number of processes and preventing defective products caused by uneven application of adhesive, it is desirable to be able to bond two types of molded articles directly without using adhesives.

[0005] Therefore, one aspect of the present invention provides a composite molded article comprising a polyolefin molded article and an adherend directly adhered to the polyolefin molded article, the two being bonded together with excellent adhesive strength. [Means for solving the problem]

[0006] In some aspects of the present invention, the following [1] to

[10] are provided. [1] A method for manufacturing a polyolefin molded article, comprising: a polyolefin molded article; and an adherend A directly bonded to the polyolefin molded article; the polyolefin molded article is a molded article containing a polyolefin and an unsaturated carboxylic acid metal salt, the unsaturated carboxylic acid metal salt is a salt containing an unsaturated carboxylic acid and a divalent or higher metal element, The adherend A has an inorganic material surface formed of an inorganic material, the inorganic material surface is in contact with the polyolefin molded body, A composite molded article in which the ratio of the C=O peak intensity to the CH3 peak intensity in the infrared absorption spectrum of the interface between the polyolefin molded article and adherend A is 0.30 or more. [2] The composite molded article according to [1], wherein the polyolefin contains a propylene polymer. [3] The composite molding according to [1] or [2], wherein the polyolefin contains ethylene propylene diene rubber. [4] The composite molded article according to any one of [1] to [3], wherein the polyolefin includes a crosslinked polyolefin. [5] The composite molded body according to any one of [1] to [4], wherein the unsaturated carboxylic acid is acrylic acid or methacrylic acid. [6] The composite molding according to any one of [1] to [5], wherein the metal element is zinc or magnesium. [7] The composite molded product according to any one of [1] to [6], wherein the content of the unsaturated carboxylic acid metal salt is 1 to 30 parts by mass based on 100 parts by mass of the polyolefin. [8] The composite molded body according to any one of [1] to [7], wherein the inorganic material comprises at least one selected from the group consisting of iron, aluminum, silicon, and glass. [9] The composite molded product according to any one of [1] to [8], wherein the inorganic material surface has a water contact angle of 85° or less.

[10] The composite molding according to any one of [1] to [9], wherein in the polyolefin molding, an adherend B is directly bonded to the surface opposite to the surface to which the adherend A is bonded.

[11] A method for producing a composite molded article comprising a polyolefin molded article and an adherend A directly bonded to the polyolefin molded article, The polyolefin, the unsaturated carboxylic acid metal salt, and the crosslinking agent are heated to a temperature T k Step 1: kneading the mixture at (°C) to obtain a polyolefin composition; Step 2: forming the polyolefin composition obtained in step 1 to obtain a polyolefin molded article; and step 3 of directly adhering the adherend A, which has an inorganic material surface formed from an inorganic material, to the polyolefin molded article obtained in step 2 so that the inorganic material surface is in contact with the polyolefin molded article, the unsaturated carboxylic acid metal salt is a salt containing an unsaturated carboxylic acid and a divalent or higher metal element, The 1-minute half-life temperature of the crosslinker is T 1min (℃) as T 1min -20≧T k That's the method.

[12] The step 3 is performed at a temperature T a (°C), and 1min ≦T a The method for producing a composite molding according to

[11] , [Effects of the Invention]

[0007] According to one aspect of the present invention, there is provided a composite molded article comprising a polyolefin molded article and an adherend directly bonded to the polyolefin molded article, the adherends being bonded together with excellent adhesive strength. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a cross-sectional view showing one embodiment of a composite molded body. [Figure 2] FIG. 1 is a cross-sectional view showing one embodiment of a composite molded body. [Figure 3] 1 is an example of an infrared absorption spectrum of the interface between a polyolefin molded article and an adherend. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, several embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0010] Fig. 1 is a cross-sectional view showing one embodiment of a composite molded body. The composite molded body 1A shown in Fig. 1 comprises a sheet-like polyolefin molded body 10 and one sheet-like adherend 20. The polyolefin molded body 10 is directly bonded to the adherend 20. The polyolefin molded body 10 is in direct contact with the adherend 20 without an adhesive.

[0011] Fig. 2 is a cross-sectional view showing another embodiment of a composite molded body. The composite molded body 1B shown in Fig. 2 comprises a sheet-like polyolefin molded body 10 and two sheet-like adherends 21 and 22. The sheet-like polyolefin molded body 10 is sandwiched between the two sheet-like adherends 21 and 22 arranged opposite each other.

[0012] The polyolefin molded article 10 is a molded article containing a polyolefin and a metal salt of an unsaturated carboxylic acid.

[0013] Polyolefin is, for example, a polymer containing 50% by mass or more of structural units derived from olefins having from 2 to 10 carbon atoms (where the total amount of polyolefins is taken as 100% by mass). Examples of olefins having from 2 to 10 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene.

[0014] The polyolefin may contain a structural unit derived from a monomer other than an olefin having from 2 to 10 carbon atoms. Examples of the monomer other than an olefin having from 2 to 10 carbon atoms include aromatic vinyl monomers such as styrene; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate; vinyl ester compounds such as vinyl acetate; conjugated dienes such as 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene); and non-conjugated dienes such as dicyclopentadiene and 5-ethylidene-2-norbornene.

[0015] The polyolefin may be at least one selected from the group consisting of ethylene polymers, propylene polymers, butene polymers, and diene rubbers, or may be a combination of two or more of these. The polyolefin may also be a crosslinked product of the above-mentioned polyolefins.

[0016] Examples of the ethylene polymer include an ethylene homopolymer, an ethylene random copolymer, and an ethylene block copolymer. The ethylene polymer may be a combination of two or more kinds of ethylene polymers.

[0017] Examples of propylene polymers include propylene homopolymers, heterophasic polymer materials, and propylene random copolymers. The propylene polymers may be used alone or in combination of two or more.

[0018] The propylene random copolymer may be, for example, a propylene random copolymer having monomer units derived from propylene and monomer units derived from ethylene and / or monomer units derived from an α-olefin having 4 to 10 carbon atoms. Examples of the α-olefin having 4 to 10 carbon atoms include linear α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene; and branched α-olefins such as 3-methyl-1-butene and 3-methyl-1-pentene. The α-olefins having 4 to 10 carbon atoms may be used alone or in combination of two or more.

[0019] Examples of the propylene random copolymer include the following propylene random copolymers (1) to (3). (1) A propylene-ethylene random copolymer in which the content of monomer units derived from propylene is 90 to 99.5 mass% and the content of monomer units derived from ethylene is 0.5 to 10 mass%, relative to 100 mass% of the total amount of monomer units derived from propylene and monomer units derived from ethylene. (2) A propylene-ethylene-α-olefin random copolymer, in which the content of monomer units derived from propylene is 81 to 99 mass%, the content of monomer units derived from ethylene is 0.5 to 9.5 mass%, and the content of monomer units derived from α-olefin having 4 to 10 carbon atoms is 0.5 to 9.5 mass%, relative to 100 mass% of the total amount of monomer units derived from propylene, monomer units derived from ethylene, and monomer units derived from α-olefin having 4 to 10 carbon atoms. (3) A propylene-α-olefin random copolymer in which the content of monomer units derived from propylene is 90 to 99.5 mass% and the content of monomer units derived from α-olefins having 4 to 10 carbon atoms is 0.5 to 10 mass%, relative to 100 mass% of the total amount of monomer units derived from propylene and monomer units derived from α-olefins having 4 to 10 carbon atoms.

[0020] The heterophasic polymeric material is a polymeric material comprising a propylene homopolymer component (I) and an ethylene copolymer component (II) having monomer units derived from at least one selected from the group consisting of propylene and α-olefins having 4 or more carbon atoms and monomer units derived from ethylene. The content of the propylene homopolymer component (I) in the heterophasic polymeric material may be 70 to 90 mass% relative to 100 mass% of the total amount of the heterophasic polymeric material. The content of the ethylene copolymer component (II) in the heterophasic polymeric material may be 10 to 30 mass% relative to 100 mass% of the total amount of the heterophasic polymeric material. The content of the propylene homopolymer component (I) may be 75 to 90 mass% relative to 100 mass% of the total amount of the heterophasic polymeric material. The content of the ethylene copolymer component (II) may be 10 to 25 mass% relative to 100 mass% of the total amount of the heterophasic polymeric material.

[0021] The α-olefin having 4 or more carbon atoms in the ethylene copolymer component (II) may be an α-olefin having 4 to 20 carbon atoms. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, and 2,2,4-trimethyl-1-pentene. The α-olefin having 4 or more carbon atoms in the ethylene copolymer component (II) may be an α-olefin having 4 to 10 carbon atoms, such as 1-butene, 1-hexene, or 1-octene. The α-olefin having 4 or more carbon atoms in the ethylene copolymer component (II) may be one type alone or two or more types.

[0022] The content of the monomer units derived from ethylene in the ethylene copolymer component (II) may be 22 to 90 mass%, 25 to 80 mass%, or 27 to 70 mass%, relative to 100 mass% of the total amount of the monomer units derived from ethylene and at least one selected from the group consisting of propylene and an α-olefin having 4 or more carbon atoms. The content of the monomer units derived from at least one selected from the group consisting of propylene and an α-olefin having 4 or more carbon atoms in the ethylene copolymer component (II) may be 20 to 78 mass%, 30 to 75 mass%, or 40 to 73 mass%, relative to 100 mass% of the total amount of the monomer units derived from ethylene and at least one selected from the group consisting of propylene and an α-olefin having 4 or more carbon atoms. The content of the ethylene-derived monomer units and the content of the at least one monomer unit selected from the group consisting of propylene and α-olefins having 4 or more carbon atoms in the ethylene copolymer component (II) can be determined, for example, by measurement by infrared spectroscopy. Specifically, the infrared absorption spectrum of the ethylene copolymer component (II) is measured using an infrared spectrophotometer, and the content of the ethylene-derived units and the content of the at least one monomer unit selected from the group consisting of propylene and α-olefins having 4 or more carbon atoms are calculated according to the method described in "Characterization of Polyethylene by Infrared Absorption Spectroscopy (Takayama, Usami et al.)" or "Die Makromolekulare Chemie, 177, 461 (1976) (McRae, MA, Madam S, WF et al.)."

[0023] Examples of the ethylene copolymer component (II) include propylene-ethylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-ethylene-1-octene copolymer. The ethylene copolymer component (II) may be a propylene-ethylene copolymer or a propylene-ethylene-1-butene copolymer. The ethylene copolymer component (II) may be a random copolymer or a block copolymer.

[0024] The melt flow rate (MFR) of the propylene polymer, measured in accordance with JIS K7210 at a temperature of 230°C and a load of 21.18 N, may be 60 g / 10 min or less, 30 g / 10 min or less, or 10 g / 10 min or less. The MFR of the propylene polymer may be 0.05 g / 10 min or more, or 0.1 g / 10 min or more. The MFR of the propylene polymer may be 0.05 to 60 g / 10 min, 0.1 to 30 g / 10 min, or 0.1 to 10 g / 10 min.

[0025] The content of the propylene polymer in the polyolefin molded article may be 0 parts by mass or more, 1 part by mass or more, 5 parts by mass or more, or 10 parts by mass or more, based on 100 parts by mass of the polyolefin. The content of the propylene polymer in the polyolefin molded article may be 100 parts by mass or less, 99 parts by mass or less, 95 parts by mass or less, or 90 parts by mass or less, based on 100 parts by mass of the polyolefin. The content of the propylene polymer in the polyolefin molded article may be 0 to 100 parts by mass, or 5 to 95 parts by mass, based on 100 parts by mass of the polyolefin.

[0026] The diene rubber, which is a type of polyolefin, may be, for example, an ethylene-α-olefin copolymer rubber containing a non-conjugated polyene as a monomer unit. The ethylene-α-olefin copolymer rubber is a copolymer containing ethylene and an α-olefin as a monomer unit. An example of the diene rubber is ethylene propylene diene rubber.

[0027] The non-conjugated polyene may be a non-conjugated polyene having 3 to 20 carbon atoms. Examples of the non-conjugated polyene having 3 to 20 carbon atoms include linear non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene; 5-ethylidene-2-norbornene, cyclohexadiene, dicyclopentadiene, methyltetraindene, 5-vinylnorbornene, 5- (2-propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene, 5-(4-pentenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene, 5-(5-heptenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene, 5-methylene-2-norbornene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9,13-trimethyl- Examples of suitable non-conjugated diolefins include cyclic non-conjugated dienes such as methyl-1,4,8,12-tetradecadiene, 4-ethylidene-12-methyl-1,11-pentadecadiene, and 6-chloromethyl-5-isopropenyl-2-norbornene; trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 1,3,7-octatriene, 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 13-ethyl-9-methyl-1,9,12-pentadecatriene, 5,9,8,14,16-trimethyl-1,7,14-hexadecatriene, and 1,4,9-decatriene; and combinations of two or more compounds selected from the above. The non-conjugated polyene may be 5-ethylidene-2-norbornene, dicyclopentadiene, or a combination thereof.

[0028] The α-olefin may be an α-olefin having 3 to 20 carbon atoms. Examples of α-olefins having 3 to 20 carbon atoms include linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene; branched olefins such as 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl-1-pentene; vinylcyclohexane; and combinations of two or more compounds selected from these. From the viewpoint of easy availability, the α-olefin may be propylene or 1-butene, or may be propylene.

[0029] The content of the ethylene-α-olefin copolymer rubber containing a non-conjugated polyene as a monomer unit in the polyolefin molded product may be 0 part by mass or more, 1 part by mass or more, 5 parts by mass or more, or 10 parts by mass or more, based on 100 parts by mass of the polyolefin. The content of the propylene polymer in the polyolefin molded product may be 90 parts by mass or less, or 85 parts by mass or less, based on 100 parts by mass of the polyolefin. The content of the propylene polymer in the polyolefin molded product may be 0 to 90 parts by mass, or 5 to 85 parts by mass, based on 100 parts by mass of the polyolefin.

[0030] The polyolefin molded product may contain a diene rubber that does not contain a structural unit derived from an olefin having from 2 to 10 carbon atoms. Examples of diene rubber that does not contain a structural unit derived from an olefin having from 2 to 10 carbon atoms include styrene-butadiene rubber, chloroprene rubber, natural rubber, acrylonitrile-butadiene rubber, isoprene rubber, and butadiene rubber.

[0031] The unsaturated carboxylic acid metal salt is a salt containing an unsaturated carboxylic acid and a divalent or higher metal element. The unsaturated carboxylic acid metal salt may be, for example, a compound represented by the following formula (1). In formula (1), R 1 and R 2each independently represents a hydrogen atom or a hydrocarbon group, M represents a metal element, and n represents an integer of 2 or more. The unsaturated carboxylic acid metal salt represented by formula (1) is a metal salt of n carboxylate ions and an n-valent metal cation M n+ and a salt formed from the above, in which some of the n carboxylate ions may be replaced by hydroxide ions. [ka]

[0032] R in formula (1) 1 or R 2 The hydrocarbon group as R may be, for example, an alkyl group, and may have 1 to 10 carbon atoms. 1 and R 2 may be a hydrogen atom. n may be 2 to 3, or may be 2. M may be, for example, zinc, magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel, copper, or aluminum, and may be zinc or magnesium from the viewpoint of easily obtaining a composite molded article in which a polyolefin molded article and an adherend are bonded with excellent adhesive strength. The unsaturated carboxylic acid of the unsaturated carboxylic acid metal salt may be acrylic acid or methacrylic acid from the viewpoint of easily obtaining a composite molded article in which a polyolefin molded article and an adherend are bonded with excellent adhesive strength.

[0033] Examples of the unsaturated carboxylic acid metal salt include zinc acrylate, zinc methacrylate, magnesium acrylate, magnesium methacrylate, aluminum acrylate, and aluminum methacrylate.

[0034] The content of the unsaturated carboxylic acid metal salt in the polyolefin molded product may be 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more, based on 100 parts by mass of the polyolefin, from the viewpoint of easily obtaining a composite molded product in which the polyolefin molded product and an adherend are bonded with excellent adhesive strength. The content of the unsaturated carboxylic acid metal salt in the polyolefin molded product may be 30 parts by mass or less, 25 parts by mass or less, or 20 parts by mass or less, based on 100 parts by mass of the polyolefin. From these viewpoints, the content of the unsaturated carboxylic acid metal salt in the polyolefin molded product may be 1 to 30 parts by mass, or 5 to 25 parts by mass, based on 100 parts by mass of the polyolefin.

[0035] The polyolefin molded article may further contain other components in addition to the polyolefin and the metal salt of an unsaturated carboxylic acid. Examples of the other components include a crosslinking agent, a crosslinking aid, a softener, a processing aid, and a filler.

[0036] Examples of crosslinking agents include organic peroxides, sulfur, sulfur compounds, oxime compounds, nitroso compounds, polyamine compounds, and alkylphenol-formaldehyde condensates. These may be used alone or in combination.

[0037] Examples of organic peroxides include ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, peroxydicarbonates, and peroxyesters. More specific examples include dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, 1,3-bis(t-butylperoxyisopropyl)benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,2,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzohydroperoxide, cumene peroxide, t-butyl peroxide, 1,1-di(t-butylperoxy)3,5,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, and p-chlorobenzoyl peroxide. These may be used alone or in combination of two or more.

[0038] The crosslinking aid may be, for example, a compound having two or more double bonds in the molecule. Examples of crosslinking aids include N,N'-m-phenylene bismaleimide, toluylene bismaleimide, triallyl isocyanurate, triallyl cyanurate, p-quinone dioxime, nitrobenzene, diphenyl guanidine, divinylbenzene, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and allyl methacrylate. These may be used alone or in combination of two or more. The content of the crosslinking aid in the polyolefin molded article may be 0.05 parts by mass or more, or 0.1 parts by mass or more, or 20 parts by mass or less, or 8 parts by mass or less, based on 100 parts by mass of the polyolefin.

[0039] Examples of softeners include process oil, lubricating oil, paraffinic oils such as paraffin and liquid paraffin, naphthenic oil, petroleum asphalt, petrolatum, coal tar pitch, castor oil, linseed oil, sap, beeswax, and ricinoleic acid. These may be used alone or in combination of two or more. The content of the softener in the polyolefin molded article may be 10 parts by mass or more, 150 parts by mass or less, or 100 parts by mass or less, based on 100 parts by mass of polyolefin.

[0040] Examples of processing aids include fatty acids such as oleic acid, palmitic acid, and stearic acid; fatty acid metal salts such as zinc laurate, zinc stearate, barium stearate, and calcium stearate; fatty acid esters; and glycols such as ethylene glycol and polyethylene glycol. These may be used alone or in combination. The content of the processing aid in the polyolefin molded article may be 0.2 parts by mass or more, or 0.3 parts by mass or more, or 10 parts by mass or less, or 8 parts by mass or less, based on 100 parts by mass of the polyolefin.

[0041] The filler may be, for example, an inorganic filler. Inorganic fillers are usually added to polyolefin molded articles as reinforcing agents. Examples of inorganic fillers include carbon black, silica, calcium carbonate, mica, magnesium silicate, aluminum silicate, lignin, aluminum hydroxide, and magnesium hydroxide. These fillers may be used alone or in combination. Examples of carbon black include SRF, GPF, FEF, MAF, ISAF, SAF, FT, and MT. Examples of silica include dry-process silica, wet-process silica, synthetic silicate silica, and colloidal silica. The content of the filler in the polyolefin molded article may be 10 parts by mass or more, 200 parts by mass or less, or 150 parts by mass or less, based on 100 parts by mass of polyolefin.

[0042] The polyolefin molded article may further contain a rubber component other than polyolefin. Examples of the rubber component that may be contained in the polyolefin molded article include butyl rubber, silicone rubber, fluororubber, urethane rubber, acrylic rubber, and ethylene propylene rubber. The content of the rubber component other than polyolefin in the polyolefin molded article may be 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, based on 100 parts by mass of polyolefin.

[0043] The total content of the polyolefin and the unsaturated carboxylic acid metal salt in the polyolefin molded article may be 50 to 100 mass %, 60 to 100 mass %, or 70 to 100 mass % based on the total mass of the polyolefin molded article.

[0044] The polyolefin molded article can be obtained, for example, by a step of kneading a mixture containing a polyolefin, an unsaturated carboxylic acid metal salt, and other components added as necessary to obtain a polyolefin composition, and a step of shaping the polyolefin composition. The kneading can be performed using an internal kneader such as a mixer, a kneader, or a twin-screw extruder. The kneading time may be 1 minute or more and 60 minutes or less. The kneading temperature may be 40°C or more and 200°C or less.

[0045] In one embodiment of the method for producing a polyolefin molded article, a polyolefin, an unsaturated carboxylic acid metal salt, and a crosslinking agent are heated at a temperature T k (°C) to obtain a polyolefin composition, and step 2 to mold the polyolefin composition obtained in step 1 to obtain a polyolefin molded article, wherein the unsaturated carboxylic acid metal salt is a salt containing an unsaturated carboxylic acid and a divalent or higher metal element, and the one-minute half-life temperature of the crosslinking agent is T 1min (℃) as T 1min -20≧T k There is a method in which:

[0046] The adherends 20 and 22 have an inorganic surface formed from an inorganic material. Examples of inorganic materials include metals such as iron, aluminum, copper, silver, gold, nickel, and chromium, or metal materials containing alloys, oxides, nitrides, etc. of these metals; silicon; and glass. The adherend may have an inorganic surface formed from an inorganic material containing at least one selected from the group consisting of iron, aluminum, silicon, and glass. The adherend may consist solely of an inorganic material, or may consist of a composite material of an inorganic material and an organic material.

[0047] The inorganic material surface of the adherend may have a water contact angle of 85° or less. When a polyolefin molded article is directly bonded to the inorganic material surface of an adherend, a water contact angle of 85° or less on the inorganic material surface improves the adhesive strength between the polyolefin molded article and the adherend. The water contact angle on the inorganic material surface may be 80° or less, 60° or less, 50° or less, or 35° or less, from the viewpoint of easily obtaining a composite molded article in which the polyolefin molded article and the adherend are bonded with excellent adhesive strength. The water contact angle can be measured with a contact angle meter as the contact angle with pure water in the atmosphere (about 25°C).

[0048] The adherend 21 is directly adhered to the surface of the polyolefin molded body 10 opposite to the surface to which the adherend 22 is adhered. The adherend 21 may contain a polyolefin. Examples of the polyolefin contained in the adherend 21 include the polyolefins exemplified as the polyolefins in the polyolefin molded body. The adherend 21 may also contain an inorganic material.

[0049] The composite molded body can be produced by a method including step 3 of directly adhering the adherend to the polyolefin molded body so that the inorganic material surface of the adherend is in contact with the polyolefin molded body. That is, the composite molded body can be produced by adhering the polyolefin, the unsaturated carboxylic acid metal salt, and the crosslinking agent at a temperature T k(°C) to obtain a polyolefin composition; step 2 to mold the polyolefin composition obtained in step 1 to obtain a polyolefin molded article; and step 3 to adhere an adherend having an inorganic material surface formed from an inorganic material to the polyolefin molded article obtained in step 2 so that the inorganic material surface is in contact with the polyolefin molded article, wherein the unsaturated carboxylic acid metal salt is a salt containing an unsaturated carboxylic acid and a divalent or higher metal element, and the one-minute half-life temperature of the crosslinking agent is T 1min (℃) as T 1min -20≧T k It can be produced by a method in which

[0050] For example, composite molded body 1A can be produced by directly bonding polyolefin molded body 10 to the inorganic material surface of adherend 20, and then heating the precomposite having polyolefin molded body 10 and adherend 20 using a molding machine such as an injection molding machine, compression molding machine, or hot air vulcanizer. For example, composite molded body 1B can be produced by directly bonding polyolefin molded body 10 to the inorganic material surface of adherend 22 or adherend 21, and then heating the precomposite having adherend 21, polyolefin molded body 10, and adherend 22 using a molding machine such as an injection molding machine, compression molding machine, or hot air vulcanizer. The pressure used to form the composite molded body from the precomposite is adjusted to ensure sufficient adhesive strength, etc. The heating temperature used to form the composite molded body from the precomposite is T a (℃) is T 1min ≦T a The heating time may be 0.5 minutes or more and 60 minutes or less.

[0051] In the infrared absorption spectrum of the interface between the polyolefin molded article and the adherend, the composite molded article has a ratio of C=O peak intensity to CH3 peak intensity of 0.30 or more. Hereinafter, the ratio of C=O peak intensity to CH3 peak intensity may be referred to as parameter X.

[0052] The parameter X may be 0.40 or more, 0.50 or more, 0.60 or more, or 0.65 or more, from the viewpoint of facilitating the production of a composite molded article in which the polyolefin molded article and the adherend are bonded with excellent adhesive strength.

[0053] The ratio of the C=O peak intensity to the CH3 peak intensity in the infrared absorption spectrum of the interface between the polyolefin molded article and the adherend is measured by the following method. A 180-degree peel test is carried out in which the polyolefin molded body of the composite molded body is peeled away from the adherend in a direction of 180 degrees at a speed of 50 mm / min. After the peel test, the adherend was cut into 1cm x 1cm pieces and extracted with THF solvent at 66°C for 5 hours under reflux to clean the adhesive surface. After cleaning, the adhesive surface was vacuum dried for 4 hours, and then the infrared absorption spectrum of the adhesive surface was measured using a Fourier transform infrared spectrophotometer with the attenuated total reflection (ATR) method. From the obtained infrared absorption spectrum, the CH3 peak intensity and C=O peak intensity were calculated. In the absorption band derived from the carbonyl group, a baseline is set as shown in Figure 3, and the C=O peak intensity is determined by subtracting the absorbance on the baseline (white circle in the figure) from the maximum absorbance (black circle in the figure). The C=O peak intensity is the intensity at 1574±30 cm in the infrared absorption spectrum. ―1 Absorbance at 1500±50cm ―1 The CH3 intensity is the value obtained by subtracting the absorbance at 2950±30 cm in the infrared absorption spectrum. ―1 From the absorbance at 2783±50cm ―1 The absorbance on the baseline should be a point where no other peaks overlap, and is not limited to the above value. Then, the parameter X=(C=O peak intensity) / (CH3 peak intensity) is calculated.

[0054] Examples of methods for adjusting the parameter X include a method for adjusting the type and content of an unsaturated carboxylic acid metal salt in the polyolefin composition, a method for adjusting the type and content of a propylene polymer in the polyolefin composition, and a method for adjusting the temperature during molding of a polyolefin molded article. The parameter X may be adjusted by using a single of these methods, or by combining a plurality of methods.

[0055] The form of the composite molded article composed of a polyolefin molded article and an adherend is not limited to the forms exemplified in Figures 1 and 2. The composite molded article may have two or more polyolefin molded articles. The composite molded article may be a tubular article composed of a tubular polyolefin molded article and a tubular adherend. The tubular composite molded article is used, for example, as a hose.

[0056] The size and thickness of the polyolefin molded article and the adherend can be appropriately determined depending on the application of the composite molded article, etc. The maximum thickness of the polyolefin molded article may be, for example, 0.1 to 50 mm. [Example]

[0057] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to these examples.

[0058] <Ingredients> [Diene rubber] Ethylene propylene diene rubber (EPDM-1): Esprene E670F, manufactured by Sumitomo Chemical Co., Ltd., ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber [Propylene polymer] Ethylene-propylene copolymer (PP-1): Noblen S131, manufactured by Sumitomo Chemical Co., Ltd. (MFR = 1.5 g / 10 min, content of ethylene-derived monomer units = 5.9 wt%) Ethylene-propylene copolymer (PP-2): VERSIFY 4200, manufactured by Dow Inc. (MFR = 25 g / 10 min) [Unsaturated carboxylic acid metal salts] Zinc acrylate (ZDA): ZDA-90, manufactured by Asada Chemical Industry Co., Ltd. [Crosslinking agent] PO-1: A composition containing 10% by mass of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (crosslinking agent) and 90% by mass of paraffinic mineral oil (manufactured by Idemitsu Kosan Co., Ltd., trade name "PW-100") (APO-10DL, manufactured by Kayaku Akzo Co., Ltd., 1-minute half-life temperature = 179.8°C) PO-2: Niper BW (NOF Corporation, 1-minute half-life temperature = 130.0) [Mineral oil] Paraffinic mineral oil (oil 1): Idemitsu Kosan Co., Ltd., product name "PW-100"

[0059] Example 1 <Preparation of polyolefin molded body> 80 parts by mass of EPDM-1, 20 parts by mass of PP-1, 18 parts by mass of ZDA, and 1 part by mass of PO-1 were kneaded in a bench mixer (Labo Plastomill, manufactured by Toyo Seiki Seisaku-sho) at 80°C for 6 minutes at 80 rpm. The resulting polyolefin composition was heat-molded in a press molding machine (trade name: F37, manufactured by Shinto Metal Industries Co., Ltd.) at 160°C for 6 minutes at 9.5 MPa to obtain a 2.2 mm thick pressed sheet (polyolefin molded product).

[0060] <Production of composite molding (two layers)> An aluminum plate (A1050, 250 x 250 x 0.5 mm thick, manufactured by Engineering Test Services Co., Ltd.) was prepared as the adherend, and the aluminum plate was placed on a polyolefin molded body (150 mm x 150 mm x 2.2 mm thick) to form a laminate.The laminate was then heated and pressed using a press molding machine at 200°C for 6 minutes at 9.5 MPa to produce a composite molded body (2 layers) in which the aluminum plate and polyolefin molded body were directly bonded to each other.

[0061] Example 2 A composite molded article (two layers) was produced in the same manner as in Example 1, except that the polyolefin molded article contained 50 parts by mass of EPDM-1 and 50 parts by mass of PP-1.

[0062] Example 3 A composite molded article (two layers) was produced in the same manner as in Example 1, except that the polyolefin molded article contained 20 parts by mass of EPDM-1 and 80 parts by mass of PP-1.

[0063] Example 4 A composite molded article (two layers) was produced in the same manner as in Example 1, except that the polyolefin molded article contained 0 parts by mass of EPDM-1 and 100 parts by mass of PP-1.

[0064] Example 5 <Preparation of polyolefin molded body> 100 parts by mass of PP-2, 18 parts by mass of ZDA, 0.6 parts by mass of PO-2, and 6 parts by mass of Oil 1 were kneaded in a bench mixer (Labo Plastomill, manufactured by Toyo Seiki Seisaku-sho) at 80°C for 6 minutes at a rotation speed of 80 rpm. The resulting polyolefin composition was heat-molded in a press molding machine (trade name: F37, manufactured by Shinto Metal Industries Co., Ltd.) at 100°C for 6 minutes at 9.5 MPa to obtain a 2.2 mm thick pressed sheet (polyolefin molded product).

[0065] <Production of composite molding (two layers)> An aluminum plate (A1050, 250 x 250 x 0.5 mm thick, manufactured by Engineering Test Services Co., Ltd.) was prepared as the adherend, and the aluminum plate was placed on a polyolefin molded body (150 mm x 150 mm x 2.2 mm thick) to form a laminate.The laminate was then heated and pressed using a press molding machine at 140°C for 6 minutes at 9.5 MPa to produce a composite molded body (2 layers) in which the polyolefin molded body and the aluminum plate were directly bonded to each other.

[0066] Example 6 A composite molding (two layers) was produced in the same manner as in Example 5, except that 50 parts by mass of EPDM-1 and 50 parts by mass of PP-2 were used instead of the 100 parts by mass of PP-2 contained in the polyolefin molding.

[0067] (Comparative Examples 1 to 4) A composite molded body (two layers) was produced in the same manner as in Examples 1 to 4, except that the temperature during heat molding was 200°C instead of 160°C.

[0068] (Comparative Example 5) A composite molded body (two layers) was produced in the same manner as in Example 2, except that ZDA was not added.

[0069] (Comparative Example 6) A composite molded article (two layers) was produced in the same manner as in Example 5, except that the temperature when the polyolefin composition was hot molded using a press molding machine was 140°C.

[0070] <Evaluation> [Peel adhesion strength measurement] Test pieces measuring 25 mm x 70 mm were cut out from the composite molded articles (two layers) produced in Examples 1 to 6 and Comparative Examples 1 to 6. A 180-degree peel test was performed using a universal testing machine (Autograph, manufactured by Shimadzu Corporation), in which the polyolefin molded article portion and the aluminum plate portion of the test piece were gripped with chucks and peeled in a 180-degree direction at a rate of 50 mm / min, to measure the peel adhesion strength (N / mm). The measurement results are shown in Tables 1 and 2.

[0071] [Measurement of infrared absorption spectrum at the interface between polyolefin molded body and adherend] After the peel test, the aluminum plate was cut into 1 cm x 1 cm pieces and extracted with THF solvent at 66°C for 5 hours under reflux to clean the adhesive surface of the aluminum plate. The adhesive surface of the aluminum plate was then vacuum dried for 4 hours, after which an infrared absorption spectrum was obtained by measuring the adhesive surface using a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, product name: FTIR470plus) using the attenuated total reflection (ATR) method. The CH3 peak intensity and C=O peak intensity were calculated from the obtained infrared absorption spectrum. Here, the C=O peak intensity was determined by setting a baseline in the absorption band derived from the carbonyl group as shown in Figure 3, and subtracting the absorbance on the baseline (white circle in the figure) from the maximum absorbance (black circle in the figure). The C=O peak intensity was determined by subtracting the absorbance on the baseline (white circle in the figure) from the maximum absorbance (black circle in the figure). The C=O peak intensity was determined by subtracting the absorbance on the baseline (white circle in the figure) from the maximum absorbance (black circle in the figure) in the infrared absorption spectrum. ―1 Absorbance at 1500±50cm ―1 The CH3 intensity is the value obtained by subtracting the absorbance at 2950±30 cm in the infrared absorption spectrum. ―1 From the absorbance at 2783±50cm ―1 The absorbance on the baseline should be a point where no other peaks overlap, and is not limited to the above value. Then, the parameter X was calculated as follows: X = (C = O peak intensity) / (CH3 peak intensity). The obtained parameter X is shown in Tables 1 and 2.

[0072] [Table 1]

[0073] [Table 2] [Explanation of symbols]

[0074] 1A, 1B... composite molded body, 10... polyolefin molded body, 20, 21, 22... adherend.

Claims

1. A polyolefin molded article and an adherend A directly bonded to the polyolefin molded article, the polyolefin molded article is a molded article containing a polyolefin and an unsaturated carboxylic acid metal salt, the unsaturated carboxylic acid metal salt is a salt containing an unsaturated carboxylic acid and a divalent or higher metal element, The adherend A has an inorganic material surface formed of an inorganic material, the inorganic material surface is in contact with the polyolefin molded body, In the infrared absorption spectrum of the interface between the polyolefin molded body and the adherend A, CH ３ A composite molding having a ratio of C═O peak intensity to C═O peak intensity of 0.30 or more.

2. The composite molding of claim 1 , wherein the polyolefin comprises a propylene polymer.

3. The composite molded article according to claim 1 or 2, wherein the polyolefin comprises ethylene propylene diene rubber.

4. The composite molded article according to claim 1 or 2, wherein the polyolefin includes a crosslinked polyolefin.

5. 3. The composite molded article according to claim 1, wherein the unsaturated carboxylic acid is acrylic acid or methacrylic acid.

6. 3. The composite molding according to claim 1, wherein the metal element is zinc or magnesium.

7. 3. The composite molded article according to claim 1, wherein the content of the unsaturated carboxylic acid metal salt is 1 to 30 parts by mass based on 100 parts by mass of the polyolefin.

8. 3. The composite molded product according to claim 1, wherein the inorganic material comprises at least one material selected from the group consisting of iron, aluminum, silicon, and glass.

9. 3. The composite molded product according to claim 1, wherein the inorganic material surface has a water contact angle of 85° or less.

10. 3. The composite molding according to claim 1, wherein an adherend B is directly adhered to the surface of said polyolefin molding opposite to the surface to which said adherend A is adhered.

11. A method for producing a composite molded article comprising a polyolefin molded article and an adherend A directly bonded to the polyolefin molded article, comprising: The polyolefin, the metal salt of an unsaturated carboxylic acid, and the crosslinking agent are heated to a temperature T ｋ Step 1: kneading the mixture at (°C) to obtain a polyolefin composition; Step 2: forming the polyolefin composition obtained in step 1 to obtain a polyolefin molded article; and step 3 of adhering the adherend A, which has an inorganic material surface formed from an inorganic material, to the polyolefin molded article obtained in step 2 so that the inorganic material surface is in contact with the polyolefin molded article, the unsaturated carboxylic acid metal salt is a salt containing an unsaturated carboxylic acid and a divalent or higher metal element, The one-minute half-life temperature of the crosslinking agent is T １ｍｉｎ (°C), T １ｍｉｎ -20≧T ｋ That's the method.

12. In step 3, the temperature T ａ (°C), and １ｍｉｎ ≦T ａ The method for producing a composite compact according to claim 11, wherein

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