Stacked structure and use thereof

Abstract

The present invention relates to a laminated structure in which a resin cured layer (ii) containing a curable resin (E) having a urethane bond is directly laminated on a molded body (i) made of a polypropylene resin composition, said polypropylene resin composition containing 5 to 47 parts by mass of a propylene-based polymer (A) having an MFR of 50 to 150 g / 10 min and a content of a decane-soluble component of 6 to 15 mass%; 20 to 30 parts by mass of a propylene homopolymer (B) having an MFR of 10 to 500 g / 10 min; 23 to 30 parts by mass of an ethylene / α-olefin copolymer (C) having an MFR of 0.5 to 30 g / 10 min and a melting point peak of 110°C or higher; and 30 to 40 parts by mass of an inorganic filler (D). 3 , having a density of 0.850 to 0.880 g / cm3 as a random copolymer of ethylene and an α-olefin having 4 to 8 carbon atoms.

Description

Technical Field

[0001] The present invention relates to a laminated structure having a polypropylene resin composition molded into a shape, for example, automotive exterior parts. Background Technology

[0002] In the automotive parts industry, to meet the demands for lightweight vehicles, manufacturers are actively promoting the resin-based production of exterior panels. Within this trend, the outer panel of the rear door is also undergoing a transition from metal to resin. From a design perspective, the resin-based production of this exterior panel requires dimensional accuracy comparable to metal and a material with a low coefficient of linear expansion. Furthermore, the rear door panel needs to be bonded to other components, thus requiring high bonding performance.

[0003] On the other hand, molded articles obtained from resin compositions such as polypropylene are increasingly used in various fields, including automotive parts and home appliance parts, due to their excellent mechanical and molding properties and relatively favorable cost-effectiveness compared to other materials. However, polypropylene typically exhibits a large dimensional change (coefficient of linear expansion) with respect to temperature. In this context, various technical solutions have been developed to improve the dimensional stability of polypropylene-based resin compositions by incorporating inorganic fillers such as talc and elastomer components (see Patent Documents 1-8). However, no technical means have been taught to improve the bonding performance of these polypropylene-based resin compositions when bonded to other components.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2010-077396

[0007] Patent Document 2: Japanese Patent Application Publication No. 5-051498

[0008] Patent Document 3: Japanese Patent Application Publication No. 2000-095919

[0009] Patent Document 4: Japanese Patent Application Publication No. 2007-91789

[0010] Patent Document 5: Japanese Patent Application Publication No. 2013-159709

[0011] Patent Document 6: Japanese Patent Application Publication No. 2014-58614

[0012] Patent Document 7: Japanese Patent Application Publication No. 2016-84386

[0013] Patent document 8: WO2017 / 082358 Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] To achieve a low coefficient of linear expansion in polypropylene molded bodies, it is necessary to increase the amount of auxiliary materials with low coefficients of linear expansion, as mentioned above. Furthermore, to further impart coating properties, the rubber content needs to be increased. For these reasons, the filler and rubber ratios in polypropylene composites for resin-bonded exterior panels are very high. However, during adhesion testing with other components, interfacial delamination easily occurs at the interface between these auxiliary materials and the polypropylene composite, leading to a reduction in strength. In addition, since polypropylene itself lacks polar functional groups, flame treatment and plasma treatment are required to achieve a strong chemical bond with the adhesive. These treatments can easily cause damage to the substrate surface and a reduction in adhesive strength. To ensure this adhesive strength, a primer is typically used, but the use of a primer increases cost and adds to the manufacturing process. Therefore, to achieve both high dimensional stability and high bonding performance while maintaining the low coefficient of linear expansion required for exterior panels, a composite material that possesses sufficient adhesive strength without the need for a primer is needed.

[0016] The objective of this invention is to provide a laminated structure of a polypropylene resin composition molded from a resin curing layer and a resin curing layer, which has a low coefficient of linear expansion and high bonding strength with the resin curing layer such as an adhesive layer without the need for a primer.

[0017] Technical solutions for solving the problem

[0018] In view of the above, the inventors, after in-depth research, discovered that a polypropylene resin composition containing a polypropylene resin composition with a very high melting point ethylene / α-olefin copolymer as an elastomer component, forming a laminated structure with a specific resin curing layer, not only has good dimensional stability, but also exhibits high adhesive strength between the specific molded body and the specific curing resin, even at high temperatures where bonding performance is easily weakened, thus completing the present invention.

[0019] The present invention relates to, for example, the following matters.

[0020] [1] A laminated structure, characterized in that a resin-cured layer (ii) comprising a curable resin (E) having urethane bonds is directly laminated onto a molded body (i) made of a polypropylene resin composition.

[0021] The above polypropylene resin composition contains 5 to 47 parts by mass of a propylene polymer (A) with a melt flow rate (230°C, 2.16 kg load) of 50 to 150 g / 10 min and a decane-soluble component content of 6 to 15% by mass.

[0022] 20-30 parts by mass of propylene homopolymer (B) with a melt flow rate (230℃, 2.16kg load) of 10-500g / 10min;

[0023] The density of the random copolymer of ethylene and α-olefins with 4 to 8 carbon atoms is 0.850 to 0.880 g / cm³. 3 23-30 parts by mass of ethylene / α-olefin copolymer (C) with a melt flow rate (230℃, 2.16kg load) of 0.5-30 g / 10min and a peak melting point of 110℃ or higher; and

[0024] Inorganic filler (D) 30-40 parts by weight,

[0025] The total amount of components (A) to (D) is 100 parts by mass.

[0026] [2] According to the laminated structure described in [1], the characteristic is that the thermal shear strength at 90°C exceeds 1.5 MPa in the primerless adhesion test.

[0027] [3] According to the laminated structure described in [1] or [2], wherein the propylene polymer (A) is a block copolymer of propylene and ethylene, and the limiting viscosity [η] of the decane-soluble component of the block copolymer is 2 to 9 dl / g.

[0028] [4] The laminated structure according to any one of [1] to [3], wherein the inorganic filler (D) is talc, and the aspect ratio of the talc is 3 or more and less than 15.

[0029] [5] The laminated structure according to any one of [1] to [4], wherein the resin curing layer containing the curable resin (E) having urethane bonds is a layer formed after curing a polyurethane adhesive containing a polyether backbone and an aliphatic isocyanate derivative.

[0030] [6] The laminated structure according to any one of [1] to [5], wherein the molded body (i) is an injection molded body or a compression molded body.

[0031] [7] The stacked structure according to any one of [1] to [6], wherein the stacked structure is used for automotive exterior parts.

[0032] [8] An automotive exterior trim component, comprising any one of [1] to [7] a laminated structure.

[0033] [9] A method for manufacturing a laminated structure, characterized in that it includes a step of manufacturing a molded body (i) by molding a polypropylene resin composition by injection molding or compression molding, and a step of contacting or coating a curable resin (E) having urethane bonds or its raw material onto the molded body (i) and then curing it to form a resin cured layer (ii), wherein,

[0034] The above polypropylene resin composition contains 5 to 47 parts by mass of a propylene polymer (A) with a melt flow rate (230°C, 2.16 kg load) of 50 to 150 g / 10 min and a decane-soluble component content of 6 to 15% by mass.

[0035] 20-30 parts by mass of propylene homopolymer (B) with a melt flow rate (230℃, 2.16kg load) of 10-500g / 10min;

[0036] The density of the random copolymer of ethylene and α-olefins with 4 to 8 carbon atoms is 0.850 to 0.880 g / cm³. 3 23-30 parts by mass of ethylene / α-olefin copolymer (C) with a melt flow rate (230℃, 2.16kg load) of 0.5-30 g / 10min and a peak melting point of 110℃ or higher; and

[0037] Inorganic filler (D) 30-40 parts by weight,

[0038] The total amount of components (A) to (D) is 100 parts by mass.

[0039]

[10] A curable resin composition, wherein the curable resin composition is used to form an adhesive layer by direct lamination on a molded body comprising a polypropylene resin composition, the curable resin composition comprising a polyurethane prepolymer with a polyether backbone and an aliphatic isocyanate derivative.

[0040] The above-mentioned polypropylene resin composition contains

[0041] 5-47 parts by mass of propylene polymer (A) with a melt flow rate (230℃, 2.16kg load) of 50-150g / 10min and a decane soluble component content of 6-15% by mass;

[0042] 20-30 parts by mass of propylene homopolymer (B) with a melt flow rate (230℃, 2.16kg load) of 10-500g / 10min;

[0043] The density of the random copolymer of ethylene and α-olefins with 4 to 8 carbon atoms is 0.850 to 0.880 g / cm³. 323-30 parts by mass of ethylene / α-olefin copolymer (C) with a melt flow rate (230℃, 2.16kg load) of 0.5-30 g / 10min and a peak melting point of 110℃ or higher; and

[0044] Inorganic filler (D) 30-40 parts by weight,

[0045] The total amount of components (A) to (D) is 100 parts by mass.

[0046]

[11] The curable resin composition according to

[10] further comprises an adduct of a compound represented by formula (X) and a phenolic compound.

[0047]

[0048] In the above formula (X), R 37 and R 38 Each is independent and represents a hydrocarbon group.

[0049]

[12] The curable resin composition according to

[10] or

[11] , wherein the aliphatic isocyanate derivative of the curable resin composition comprises an isocyanurate body of pentamethylene diisocyanate.

[0050] Invention Effects

[0051] According to the present invention, a molded body made of a polypropylene resin composition and a resin cured layer can be directly laminated without the aid of a primer. This not only provides good dimensional stability, but also provides a laminated structure with high adhesive strength between the molded body and the cured resin, even at high temperatures where bonding performance is easily weakened, in a primerless environment. Attached Figure Description

[0052] Figure 1 This is a schematic diagram for testing the thermal shear strength of a laminated structure. Detailed Implementation

[0053] The present invention will be described in detail below.

[0054] The laminated structure of the present invention has a resin curing layer (ii) containing a curable resin having urethane bonds directly laminated on a polypropylene resin composition mold (i). Specifically, it is a laminated structure in which a curable resin layer (ii) formed by a polypropylene resin composition mold (i) and a polyurethane adhesive is directly laminated without the aid of a primer.

[0055] [Molded body(i)]

[0056] The molded body (i) of the present invention is a molded body made of a polypropylene resin composition.

[0057] Polypropylene resin composition

[0058] The polypropylene resin composition of the present invention contains a propylene polymer (A), a propylene homopolymer (B), an ethylene / α-olefin copolymer (C), an inorganic filler (D), and may also contain other components as needed.

[0059] <Propylene Polymer (A)>

[0060] The propylene polymer (A) used in this invention is a propylene polymer with a melt flow rate (230°C, 2.16 kg load) of 50-150 g / 10 min and a decane-soluble component content of 6-15% by mass.

[0061] The propylene polymer (A) substantially comprises 6–15% by mass of a decane-soluble component (a1) and 85–94% by mass of a decane-insoluble component (a2). The decane-insoluble component (a2) refers to the component that is generally insoluble in n-decane at room temperature (23°C), and typically corresponds to the portion of the propylene homopolymer (propylene homopolymer component) in the propylene polymer (A). The decane-soluble component (a1) corresponds to the portion other than the propylene homopolymer portion, and is preferably the copolymer portion of propylene and ethylene (ethylene / propylene copolymer component).

[0062] The propylene polymer (A) typically contains 6-15% by mass of a decane-soluble component (a1) and 85-94% by mass of a decane-insoluble component (a2), preferably containing 7-12% by mass of a decane-soluble component (a1) and 88-93% by mass of a decane-insoluble component (a2), wherein the total content of (a1) and (a2) is 100% by mass.

[0063] The propylene polymer (A) is preferably a propylene block copolymer obtained from propylene and ethylene. The limiting viscosity [η] of the decane-soluble component (a1) of the propylene block copolymer is preferably 2 to 9 dl / g, more preferably 3 to 8 dl / g.

[0064] The melt flow rate (230°C, 2.16 kg load) of the propylene polymer (A) is 50-150 g / 10 min, preferably 50-130 g / 10 min, more preferably 60-120 g / 10 min, and particularly preferably 70-110 g / 10 min.

[0065] Propylene-based polymers (A) can be manufactured by known methods. For example, propylene is polymerized using a catalyst for olefin polymerization comprising a solid titanium catalyst component (I) and an organometallic compound catalyst component (II) as described below, and then propylene and ethylene are copolymerized to obtain a propylene-based block copolymer.

[0066] [Solid titanium catalyst component (I)]

[0067] The solid titanium catalyst component (I) constituting the catalyst for olefin polymerization includes, for example, titanium, magnesium, halogens, and an electron donor as needed. This solid titanium catalyst component (I) can be made from known components without limitation.

[0068] There are many examples of the use of magnesium compounds and titanium compounds in the preparation of solid titanium catalyst component (I).

[0069] Specific examples of magnesium compounds include magnesium halides such as magnesium chloride and magnesium bromide; alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, and phenoxy magnesium chloride; alkoxy magnesiums such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, and 2-ethylhexyloxy magnesium; aryloxy magnesiums such as phenoxy magnesium; and magnesium carboxylates such as magnesium stearate. Magnesium compounds can be used alone or in combination of two or more. Furthermore, magnesium compounds can also be complexes, compounds, or mixtures with other metals.

[0070] Preferably, the magnesium compound contains a halogen, more preferably magnesium halide, and particularly preferably magnesium chloride. Furthermore, alkoxymagnesium compounds such as magnesium ethoxylate are also preferred. The magnesium compound can also be a derivative derived from other substances, such as an organomagnesium compound obtained by contacting titanium halide, silicon halide, or haloalcohol with Grignard reagents.

[0071] Examples of titanium compounds include tetravalent titanium compounds represented by the following formula.

[0072] Ti(OR) g X 4－g

[0073] In the formula, R is a hydrocarbon group, X is a halogen atom, and g is 0 ≤ g ≤ 4.

[0074] Specific examples of titanium compounds include titanium tetrahalides such as TiCl4 and TiBr4; titanium trihalides such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(O-n-C4H9)Cl3, Ti(OC2H5)Br3, and Ti(O-i-C4H9)Br3; titanium dihalides such as Ti(OCH3)2Cl2 and Ti(OC2H5)2Cl2; titanium monohalides such as Ti(OCH3)3Cl, Ti(O-n-C4H9)3Cl, and Ti(OC2H5)3Br; and titanium tetraalkoxy compounds such as Ti(OCH3)4, Ti(OC2H5)4, Ti(OC4H9)4, and Ti(O-2-ethylhexyl)4. A single titanium compound can be used alone, or in combination of two or more. Titanium tetrahalides are preferred, and titanium tetrachloride is more preferred.

[0075] As magnesium and titanium compounds, compounds detailed in publications such as Japanese Patent Application Publication No. 57-63310 and Japanese Patent Application Publication No. 5-170843 may also be used.

[0076] Specific examples of preferred preparation methods for the solid titanium catalyst component (I) used in this invention include the following methods (P-1) to (P-4).

[0077] (P-1) A method for contacting a solid adduct made of a magnesium compound and an electron donor component (1) such as an alcohol, an electron donor component (2) described later, and a liquid titanium compound in a suspension state in the presence of an inert hydrocarbon solvent.

[0078] (P-2) A method for contacting a solid adduct made of a magnesium compound and an electron donor component (1), an electron donor component (2), and a liquid titanium compound in multiple steps.

[0079] (P-3) A method for contacting a magnesium compound and an electron donor component (1) in a solid adduct, an electron donor component (2), and a liquid titanium compound in a suspension in the presence of an inert hydrocarbon solvent, and for contacting them in multiple stages.

[0080] (P-4) A method for contacting a magnesium compound with a liquid magnesium compound, a liquid titanium compound, and an electron donor component (2) made from an electron donor component (1).

[0081] The preferred reaction temperature for preparing solid titanium catalyst component (I) is -30 to 150°C, more preferably -25 to 130°C, and particularly preferably -25 to 120°C.

[0082] Depending on the requirements, the preparation of the solid titanium catalyst component (I) can also be carried out in the presence of a known medium. Specific examples of such media include aromatic hydrocarbons such as toluene with slight polarity, and known aliphatic or alicyclic hydrocarbons such as heptane, octane, decane, and cyclohexane. Among these, aliphatic hydrocarbons are preferred.

[0083] The electron donor component (1) used in the formation of solid adducts and liquid magnesium compounds is preferably a known compound that can dissolve magnesium compounds in a temperature range of room temperature to 300°C, such as alcohols, aldehydes, amines, carboxylic acids and mixtures thereof. Examples of such compounds include those described in Japanese Patent Application Publication Nos. 57-63310 and 5-170843.

[0084] Specific examples of alcohols that can dissolve magnesium compounds include fatty alcohols such as methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, and dodecanol; alicyclic alcohols such as cyclohexanol and methylcyclohexanol; aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol; and fatty alcohols with alkoxy groups such as n-butyl cellosolve.

[0085] Specific examples of carboxylic acids include organic carboxylic acids with 7 or more carbon atoms, such as octanoic acid and 2-ethylhexanoic acid. Specific examples of aldehydes include aldehydes with 7 or more carbon atoms, such as decanal and 2-ethylhexanal. Specific examples of amines include amines with 6 or more carbon atoms, such as heptamine, octamine, nonylamine, laurylamine, and 2-ethylhexylamine.

[0086] As the electron donor component (1), the above-mentioned alcohols are preferred, and ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, and decanol are particularly preferred.

[0087] Although the ratio of magnesium to electron donor component (1) in the resulting solid adduct and liquid magnesium compound varies depending on the type of compound used, it cannot be specified in general terms. However, the electron donor component (1) is preferably 2 moles or more, more preferably 2.3 moles or more, particularly preferably 2.7 moles or more, and less than 5 moles, relative to 1 mole of magnesium in the magnesium compound.

[0088] As a particularly preferred example of the electron donor to be used in solid titanium catalyst component (I), examples include aromatic carboxylic acid esters and / or compounds having two or more ether bonds by means of multiple carbon atoms (hereinafter also referred to as "electron donor component (2)").

[0089] As the electron donor component (2), known aromatic carboxylic acid esters and polyether compounds that are conventionally preferred for catalysts for olefin polymerization can be used without limitation, such as compounds described in Japanese Patent Application Publication No. 5-170843 and Japanese Patent Application Publication No. 2001-354714.

[0090] As aromatic carboxylic acid esters, specifically, in addition to aromatic carboxylic acid monoesters such as benzoate and tolueneate, aromatic polycarboxylic acid esters such as phthalate esters can also be mentioned. Among them, aromatic polycarboxylic acid esters are preferred, and phthalate esters are more preferred. As such phthalate esters, alkyl phthalates such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate, and heptyl phthalate are preferred, and diisobutyl phthalate is particularly preferred.

[0091] As polyether compounds, examples include compounds represented by the following chemical structural formula (1).

[0092]

[0093] In the above equation (1), m is an integer of 1 ≤ m ≤ 10, more preferably an integer of 3 ≤ m ≤ 10, and R 11 ~R 36 Each is independent and is either a hydrogen atom or has a substituent selected from at least one element chosen from carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron, and silicon. When m is 2 or more, multiple R atoms exist. 11 and R 12 They can be the same or different. Any R 11 ~R 36 R is preferred. 11 and R 12 Together they form rings other than the benzene ring.

[0094] Specific examples of such compounds include monosubstituted diekoxypropanes such as 2-isopropyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, and 2-cumyl-1,3-dimethoxypropane; and compounds such as 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, and 2-methyl-2-cyclohexyl- 1,3-Dimethoxypropane, 2-Methyl-2-isobutyl-1,3-dimethoxypropane, 2,2-Diisobutyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2,2-disec-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane Propane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane and other disubstituted diekoxypropanes, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-di Dialkoxyalkanes include methoxyhexane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, and 2,4-diisopentane-1,5-dimethoxypentane; trialkoxyalkanes include 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, and 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane. Polyether compounds can be used alone or in combination of two or more. Preferably, 1,3-diethers are preferred, and particularly preferred are 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane.

[0095] In the solid titanium catalyst component (I), the halogen / titanium (atomic ratio) (i.e., the number of moles of halogen atoms / the number of moles of titanium atoms) is 2–100, preferably 4–90; the electron donor component (1) / titanium (molar ratio) is 0–100, preferably 0–10; and the electron donor component (2) / titanium (molar ratio) is 0–100, preferably 0–10. The magnesium / titanium (atomic ratio) (i.e., the number of moles of magnesium atoms / the number of moles of titanium atoms) is 2–100, preferably 4–50.

[0096] For more detailed preparation conditions of the solid titanium catalyst component (I), in addition to using the electron donor component (2), the conditions described in, for example, EP585869A1 and Japanese Patent Application Publication No. 5-170843 may be used.

[0097] [Organometallic catalyst component (II)]

[0098] The organometallic catalyst component (II) is a component containing a metal element selected from Group I, Group II, and Group III of the periodic table. For example, compounds containing Group III metals (organoaluminum compounds, etc.), complex alkylates containing Group I metals and aluminum, and organometallic compounds containing Group II metals can be used. Among these, organoaluminum compounds are preferred.

[0099] As an organometallic catalyst component (II), the organometallic catalyst components described in known literature such as EP585869A1 can be used appropriately.

[0100] Known electron donor components (3) may be used in combination with the electron donor components (1) and (2) described above, provided that the purpose of the invention is not impaired.

[0101] As the electron donor component (3), an organosilicon compound is preferred. The organosilicon compound is, for example, a compound represented by the following formula.

[0102] R n Si(OR') 4－n

[0103] In the formula, R and R′ are hydrocarbon groups, and n is an integer of 0 < n < 4.

[0104] Specific examples of organosilicon compounds represented by the above formulas include diisopropyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylmethyldiethoxysilane, tert-pentylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, tert-butyltriethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, and cyclopentyldimethylethoxysilane. Preferably, vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, or dicyclopentadimethoxysilane are used.

[0105] Furthermore, silane compounds represented by the following formulas as described in International Publication No. 2004 / 016662 are also preferred examples of organosilicon compounds.

[0106] Si(OR a )3(NR b R c )

[0107] In the above formula, R a It is a hydrocarbon group having 1 to 6 carbon atoms. For example, it is an unsaturated or saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and is particularly preferred to be a hydrocarbon group having 2 to 6 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, etc. Among them, ethyl is particularly preferred.

[0108] R b It is a hydrocarbon group or hydrogen with 1 to 12 carbon atoms. For example, it is an unsaturated or saturated aliphatic hydrocarbon group or hydrogen with 1 to 12 carbon atoms. Specific examples include hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, octyl, etc. Among them, ethyl is particularly preferred.

[0109] R c It is a hydrocarbon group having 1 to 12 carbon atoms. For example, it is an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, octyl, etc. Among them, ethyl is particularly preferred.

[0110] Specific examples of organosilicon compounds represented by the above formulas include dimethylaminotriethoxysilane, diethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotri-n-propoxysilane, di-n-propylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, tert-butylaminotriethoxysilane, ethyl-n-propylaminotriethoxysilane, ethyl isopropylaminotriethoxysilane, and methyl ethylaminotriethoxysilane.

[0111] In addition, other examples of organosilicon compounds include compounds represented by the following formulas.

[0112] RNSi(OR a )3

[0113] In the above formula, RN represents a cyclic amino group. Specific examples include perhydroquinolinyl, perhydroisoquinolinyl, 1,2,3,4-tetrahydroquinolinyl, 1,2,3,4-tetrahydroisoquinolinyl, and octamethyleneimine. Ra Same as above.

[0114] Specific examples of organosilicon compounds represented by the above formulas include (perhydroquinolinyl)triethoxysilane, (perhydroisoquinolinyl)triethoxysilane, (1,2,3,4-tetrahydroquinolinyl)triethoxysilane, (1,2,3,4-tetrahydroisoquinolinyl)triethoxysilane, and octamethyleneiminotriethoxysilane.

[0115] The organosilicon compounds described above can also be used in combination of two or more.

[0116] [polymerization]

[0117] The propylene / ethylene block copolymer, as a preferred embodiment of the propylene-based polymer (A), can be manufactured by methods such as polymerizing propylene in the presence of the above-mentioned olefin polymerization catalyst and then copolymerizing propylene with ethylene, or polymerizing propylene in the presence of a prepolymer catalyst obtained by prepolymerization and then copolymerizing propylene with ethylene.

[0118] Prepolymerization is typically carried out by prepolymerizing 0.1 to 1000 g of olefin per 1 g of catalyst used for olefin polymerization, preferably 0.3 to 500 g of olefin, and particularly preferably 1 to 200 g of olefin. In prepolymerization, a catalyst with a concentration higher than that in the main polymerization system can be used.

[0119] The concentration of the solid titanium catalyst component (I) in the prepolymer, calculated in terms of titanium atoms, is typically 0.001–200 mmol per liter of liquid medium, preferably 0.01–50 mmol, and more preferably 0.1–20 mmol.

[0120] The amount of organometallic catalyst component (II) in the prepolymer is sufficient to generate 0.1 to 1000 g, preferably 0.3 to 500 g of polymer per 1 g of solid titanium catalyst component (I), and is typically 0.1 to 300 mol, preferably 0.5 to 100 mol, and more preferably 1 to 50 mol of titanium atoms per 1 mol of solid titanium catalyst component (I).

[0121] In the prepolymerization process, the above-mentioned electron donor components may also be used as needed. In this case, the amount of these components is typically 0.1 to 50 mol, preferably 0.5 to 30 mol, and more preferably 1 to 10 mol per mol of titanium atoms in the solid titanium catalyst component (I).

[0122] Prepolymerization can be carried out under mild conditions with the addition of olefins and the aforementioned catalyst components in an inert hydrocarbon medium. When using an inert hydrocarbon medium, prepolymerization is preferably carried out in a batch manner.

[0123] Specific examples of inert hydrocarbon media include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, cycloheptane, methylcycloheptane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroethane and chlorobenzene; or mixtures of these compounds. Among these, aliphatic hydrocarbons are preferred.

[0124] Prepolymerization can also be carried out using the olefin itself as a solvent. Furthermore, prepolymerization can be carried out in a substantially solvent-free state. In this case, continuous prepolymerization is preferred.

[0125] The olefin used in the prepolymerization can be the same as or different from the olefin used in the main polymerization, which will be described later. Propylene is particularly preferred as the olefin.

[0126] The temperature during prepolymerization is typically -20 to 100°C, preferably -20 to 80°C, and more preferably 0 to 40°C.

[0127] Next, the main polymerization process will be explained, either after prepolymerization or without prepolymerization.

[0128] The main polymerization process is divided into the process of manufacturing propylene homopolymer components and the process of manufacturing propylene / ethylene copolymer components.

[0129] The primary polymerization (and prepolymerization) can be carried out by any of the following methods: bulk polymerization, solution polymerization, suspension polymerization, or gas-phase polymerization. As a process for manufacturing propylene homopolymer components, bulk polymerization, suspension polymerization, or gas-phase polymerization are preferred. As a process for manufacturing propylene / ethylene copolymer components, bulk polymerization, suspension polymerization, or gas-phase polymerization are preferred, and gas-phase polymerization is more preferably preferred.

[0130] When the main polymerization adopts the reaction mode of slurry polymerization, either the inert hydrocarbons used in the prepolymerization process or olefins that are liquid at the reaction temperature and pressure can be used as the reaction solvent.

[0131] In the main polymerization, the solid titanium catalyst component (I) is typically used in an amount of 0.0001 to 0.5 mmol, preferably 0.005 to 0.1 mmol, based on titanium atoms per liter of polymerization volume. Additionally, the organometallic catalyst component (II) is typically used in an amount of 1 to 2000 mol, preferably 5 to 500 mol, relative to 1 mole of titanium atoms in the prepolymer catalyst component of the polymerization system. When an electron donor component is used, it is typically used in an amount of 0.001 to 50 mol, preferably 0.01 to 30 mol, and more preferably 0.05 to 20 mol, relative to 1 mol of the organometallic catalyst component (II).

[0132] If the primary polymerization is carried out in the presence of hydrogen, the molecular weight of the resulting polymer can be adjusted (reduced), resulting in a polymer with a high melt flow rate (MFR). The amount of hydrogen required to adjust the molecular weight varies depending on the type of manufacturing process, polymerization temperature, and pressure used; appropriate adjustments are necessary.

[0133] In the process of manufacturing propylene homopolymer components, the molecular weight ratio (MFR) can be adjusted by regulating the polymerization temperature and the amount of hydrogen. Furthermore, in the process of manufacturing propylene / ethylene copolymer components, the limiting viscosity can also be adjusted by regulating the polymerization temperature, pressure, and the amount of hydrogen.

[0134] In the primary polymerization, the polymerization temperature of olefins is typically 0–200°C, preferably 30–100°C, and more preferably 50–90°C. The pressure (gauge pressure) is typically atmospheric pressure to 100 kgf / cm². 2 (9.8MPa), preferably 2~50kgf / cm 2 (0.20~4.9MPa).

[0135] In the manufacture of the propylene / ethylene block copolymer, which is a preferred embodiment of the propylene-based polymer (A), polymerization can be carried out by any batch, semi-continuous, or continuous method. The shape of the reaction apparatus can be either tubular or tank-like. Furthermore, polymerization can be carried out in two or more stages by changing the reaction conditions. In this case, tubular and tank-like apparatuses can be used in combination.

[0136] In order to obtain the propylene / ethylene copolymer portion in the propylene / ethylene block copolymer of the preferred embodiment of the propylene-based polymer (A), the gas ratio of ethylene / (ethylene + propylene) was controlled in polymerization step 2 described later. The gas ratio of ethylene / (ethylene + propylene) is typically 5 to 80 mol%, preferably 10 to 70 mol%, and more preferably 15 to 60 mol%.

[0137] As described above, the decane-insoluble component (a2) of the propylene / ethylene block copolymer is mainly composed of the propylene homopolymer component. On the other hand, the decane-soluble component (a1) is mainly composed of the ethylene / propylene copolymer component as a rubber-like component. By, for example, continuously performing the following two polymerization steps 1 and 2, a propylene / ethylene block copolymer as a preferred embodiment of the propylene-based polymer (A) can be obtained.

[0138] (Polymerization process 1)

[0139] The process of polymerizing propylene in the presence of a solid titanium catalyst component to produce a propylene homopolymer component (propylene homopolymer manufacturing process).

[0140] (Polymerization process 2)

[0141] The process of manufacturing ethylene / propylene copolymer components by copolymerizing propylene and ethylene in the presence of a solid titanium catalyst component (copolymer rubber manufacturing process).

[0142] More preferably, polymerization step 1 is performed in the preceding stage, and polymerization step 2 is performed in the following stage. Both polymerization steps 1 and 2 can be carried out using two or more polymerization tanks. The content of the decane-soluble component (a1) can be adjusted by the polymerization time (residence time) of polymerization steps 1 and 2. Furthermore, polymerization step 1 in the preceding stage can also be carried out using two or more polymerization units connected in series. In this case, the ratio of propylene to hydrogen in each stage can vary depending on the specific polymerization unit.

[0143] The propylene polymer (A) used in this invention may also contain more than one type of biomass-derived monomer. The same type of monomer constituting the polymer may contain only biomass-derived monomers, or it may contain both biomass-derived monomers and fossil fuel-derived monomers. Biomass-derived monomers refer to monomers made from all renewable natural raw materials and their residues, including fungi, yeast, algae, and bacteria, derived from plants or animals, and containing 10% carbon. ﹣12 orders of magnitude 14 The carbon isotope concentration (pMC) of the biomass, as measured according to ASTM D 6866, is 100 pMC. Monomers derived from biomass can be obtained by methods already known. From the perspective of reducing environmental impact, the propylene polymer (A) used in this invention preferably contains monomers derived from biomass. As long as the polymer manufacturing conditions, such as the polymerization catalyst and polymerization temperature, are the same, even if the raw material olefin contains olefins derived from biomass, containing 10 pMC... ﹣12 orders of magnitude 14 The molecular structure, excluding C isotopes, is also equivalent to that of propylene polymers formed from monomers derived from fossil fuels. Therefore, the properties remain unchanged.

[0144] Furthermore, the propylene-based polymer (A) of the present invention may also include propylene derived from chemical recycling. The propylene constituting the polymer may be solely derived from chemical recycling, or it may include propylene derived from chemical recycling, propylene derived from fossil fuels, and / or propylene derived from biomass. Propylene derived from chemical recycling is obtained by methods already known. From the perspective of reducing environmental impact (primarily reducing waste), the propylene-based polymer (A) of the present invention preferably contains propylene derived from chemical recycling. Even if the raw material monomers contain monomers derived from chemical recycling, since these monomers are monomers obtained by depolymerizing polymers such as waste plastics into monomer units such as propylene through depolymerization, thermal cracking, etc., and monomers manufactured using these monomers as raw materials, the molecular structure is identical to that of propylene homopolymers formed from monomers derived from fossil fuels, provided that the polymerization catalyst, polymerization process, polymerization temperature, and other polymer manufacturing conditions are the same. Therefore, the properties remain unchanged.

[0145] <Propylene Homopolymer (B)>

[0146] The propylene homopolymer (B) used in this invention is a propylene homopolymer with a melt flow rate (230°C, 2.16 kg load) of 10–500 g / 10 min.

[0147] The propylene homopolymer (B) can be a polymer that is essentially polymerized from propylene alone. For example, a homopolymer polymerized from propylene alone or a crystalline polymer copolymerized from propylene with 6 mol% or less, preferably 3 mol% or less, of other α-olefins can be used. Among these, a homopolymer polymerized from propylene alone is preferred.

[0148] Propylene homopolymer (B) can be manufactured by polymerizing propylene-based monomers using known methods. For example, it can be obtained by polymerizing propylene-based monomers in the presence of a catalyst for olefin polymerization containing a previously described solid titanium catalyst component (I) and an organometallic compound catalyst component (II), or a combined catalyst of titanium trichloride, commonly known as a Ziegler-Natta type catalyst, and an alkylaluminum compound. The polymerization reaction can be carried out continuously or batch-wise. It can be readily manufactured, for example, by performing only the previously described polymerization step 1.

[0149] In polymerization reactions, the polymerization temperature is typically 0–200°C, preferably 30–100°C, and more preferably 50–90°C. The pressure (gauge pressure) is typically atmospheric pressure to 100 kgf / cm². 2 (9.8MPa), preferably 2~50kgf / cm 2 (0.20~4.9MPa).

[0150] The melt flow rate (230°C, 2.16 kg load) of propylene homopolymer (B) is 10-500 g / 10 min, preferably 10-300 g / 10 min, and more preferably 20-250 g / 10 min.

[0151] The propylene homopolymer (B) can be a single polymer or any combination of two or more propylene homopolymers that, as a whole, satisfy the above-mentioned melt flow rate range.

[0152] The propylene homopolymer (B) used in this invention may also contain propylene derived from biomass. The propylene constituting the polymer may contain only propylene derived from biomass, or it may contain both propylene derived from biomass and propylene derived from fossil fuels. Propylene derived from biomass refers to monomers made from all renewable natural raw materials and their residues, including fungi, yeast, algae, and bacteria, derived from plants or animals, containing 10% carbon. ﹣12 orders of magnitude 14 The carbon isotope concentration (pMC) of the biomass, as measured according to ASTM D 6866, is 100 (pMC). Propylene derived from biomass can be obtained by conventionally known methods. From the perspective of reducing environmental impact, the propylene homopolymer (B) used in this invention preferably contains monomers derived from biomass. As long as the polymer manufacturing conditions, such as the polymerization catalyst and polymerization temperature, are the same, even if the raw propylene contains propylene derived from biomass, containing 10... ﹣12 orders of magnitude 14 The molecular structure, excluding C isotopes, is also identical to that of propylene homopolymers derived from fossil fuels. Therefore, the properties remain unchanged.

[0153] Furthermore, the propylene homopolymer (B) used in this invention, like the propylene-based polymer (A) described above, may also include propylene derived from chemical recycling as a monomer. That is, the propylene constituting the polymer may be solely derived from chemical recycling, or may include propylene derived from chemical recycling, propylene derived from fossil fuels, and / or propylene derived from biomass.

[0154] <Ethylene / α-olefin copolymer (C)>

[0155] The ethylene / α-olefin copolymer (C) used in this invention is a random copolymer of ethylene and an α-olefin with 4 to 8 carbon atoms, with a density of 0.850 to 0.880 g / cm³. 3The ethylene / α-olefin copolymer has a melt flow rate (230°C, 2.16 kg load) of 0.5–30 g / 10 min and a peak melting point of 110°C or higher. This ethylene / α-olefin copolymer (C) is expected to not only improve the dimensional stability (reduced coefficient of linear expansion) of the molded body (i) and the laminated structure having the molded body through synergistic effects with other components, but also help improve other physical properties, resulting in a high degree of property balance in the molded product.

[0156] The α-olefins with 4 to 8 carbon atoms constituting the ethylene / α-olefin copolymer (C) are preferably 1-butene, 1-hexene, or 1-octene. One type of α-olefin may be used alone, or two or more may be used in combination. Ethylene-octene copolymers and ethylene-butene copolymers are particularly preferred as the ethylene / α-olefin copolymer (C).

[0157] The melt flow rate (230°C, 2.16 kg load) of the ethylene / α-olefin copolymer (C) is 0.5 to 30 g / 10 min, preferably 1 to 25 g / 10 min, and more preferably 2 to 20 g / 10 min.

[0158] As long as the melt flow rate (230°C, 2.16 kg load) of the ethylene / α-olefin copolymer (C) is above 0.5 g / 10 min, it is less likely to cause a decrease in the fluidity of the polypropylene resin composition or poor dispersion during the mixing process, nor is it likely to cause a decrease in physical properties such as impact resistance or a deterioration in the surface appearance of the molded product. In addition, as long as the melt flow rate (230°C, 2.16 kg load) is below 30 g / 10 min, the molded body (i) and the laminated structure having the molded body tend to have sufficient impact resistance.

[0159] The density of the ethylene / α-olefin copolymer (C) is 0.850–0.880 g / cm³. 3 The preferred value is 0.855–0.875 g / cm³. 3 .

[0160] The melting point peak of the ethylene / α-olefin copolymer (C) is 110°C or higher, preferably 110–130°C. The melting point peak refers to the value obtained by differential scanning calorimetry (DSC). Specifically, the melting point peak (Tm) can be obtained by taking the temperature of the maximum peak position when obtaining the DSC endothermic curve. By ensuring that the melting point peak of the ethylene / α-olefin copolymer (C) meets the above-mentioned high-temperature range, the laminated structure of the present invention, consisting of a molded body (i) made of a polypropylene resin composition containing this component and a resin cured layer (ii), will form an article with excellent adhesive strength.

[0161] <Inorganic filler (D)>

[0162] As the inorganic filler (D) used in this invention, known inorganic fillers can be used, such as, but not particularly limited to, talc, calcium carbonate, natural mica, synthetic mica, wollastonite, montmorillonite, etc. The inorganic filler (D) can be used alone or in combination of two or more. Talc is preferred. By using such an inorganic filler (D), the mechanical properties of the molded body (i) and the laminated structure having the molded body are improved.

[0163] The inorganic filler (D) is not particularly limited, as long as it can be dispersed in the resin composition. Its average particle size is, for example, 1 μm to 20 μm, preferably greater than 3.0 μm and less than 10.0 μm, more preferably 3.0 μm to 8.0 μm, and even more preferably 3.0 μm to 7.0 μm. This average particle size is a measured value obtained by laser diffraction. Specifically, it refers to the particle size at 50% of the particle size distribution integral value obtained by a particle size analyzer such as a laser diffraction scattering particle size analyzer. Examples of measuring devices include, for example, the Microtrac MT3300EXII and the Horiba LA-920.

[0164] The aspect ratio of the inorganic filler (D) is not particularly limited, but is generally 3 or more and less than 15, preferably 4 to 13, and more preferably 5 to 11. Generally, the aspect ratio is a value representing the ratio of the filler's long axis diameter to its thickness or the ratio of its long side to its short side. As long as the aspect ratio is 3 or more, the rigidity and dimensional stability of the molded body are less likely to decrease; as long as it is less than 15, the uniformity of mechanical properties is less likely to decrease, and the impact strength is also less likely to decrease. Specifically, this aspect ratio is obtained by taking photographs using an electron microscope, measuring the long axis diameter and thickness of the powder, calculating the average value, and then determining the value based on the ratio of average particle size to average thickness.

[0165] Inorganic fillers (D) not only contribute to the improvement of dimensional stability (reduction of the coefficient of linear expansion) of the molded body (i) and the laminated structure having the molded body, but also contribute to the improvement of mechanical properties such as rigidity and impact strength. When the inorganic filler (D) has the above-mentioned average particle size (and aspect ratio), it is particularly easy to exhibit a high balance of physical properties, which not only has excellent dimensional stability but also excellent rigidity and impact strength, due to the synergistic effect with other components, and is therefore suitable.

[0166] As the inorganic filler (D), inorganic fillers of any shape, such as granules, plates, rods, fibers, and whiskers, can be used. Furthermore, commercially available inorganic fillers used as polymer fillers can also be used. Moreover, in addition to the usual powder and roving forms, products in the form of chopped fibers, compressed blocks, pellets, and granules, which improve processing convenience, can also be used. Powder, compressed blocks, and granules are preferred.

[0167] Inorganic filler (D) can also be a mixture of two or more inorganic fillers.

[0168] There are no particular limitations on the manufacturing method of inorganic filler (D), and it can be manufactured by various known methods. When talc is used as an inorganic filler (D), for example, it can be manufactured by crushing or granulating talc with a specific average particle size and aspect ratio. Specifically, methods include crushing raw talc using an impact crusher or a micro-grinding mill, further crushing it using a jet mill, and classifying it using a cyclone separator or a micro-separator. The aspect ratio and average particle size of the talc can be appropriately adjusted according to the crushing device and crushing time to obtain talc with controlled shape and graded as needed.

[0169] As an inorganic filler (D), products obtained directly from crushed raw stone can be used, or products that have undergone at least some surface treatment can be used. Surface treatment can utilize various surface treatment agents such as organotitanate coupling agents, organosilane coupling agents, modified polyolefins grafted with unsaturated carboxylic acids or their anhydrides, fatty acids, fatty acid metal salts, fatty acid esters, etc. Surface treatment agents can be used alone or in combination of two or more.

[0170] In the polypropylene resin composition of the present invention, without prejudice to the purpose of the present invention, nucleating agents, heat stabilizers, antistatic agents, weather stabilizers, light stabilizers, anti-aging agents, antioxidants, fatty acid metal salts, softeners, dispersants, fillers, colorants, lubricants, pigments, and other additives may be added as needed. The mixing order of the additives is arbitrary; they may be mixed simultaneously or in a multi-step mixing method where some components are mixed before the others are mixed.

[0171] <Polypropylene Resin Compositions>

[0172] The polypropylene resin composition of the present invention contains 5 to 47 parts by weight of propylene polymer (A), 20 to 30 parts by weight of propylene homopolymer (B), 23 to 30 parts by weight of ethylene / α-olefin copolymer (C), and 30 to 40 parts by weight of inorganic filler (D), wherein the total amount of components (A) to (D) is 100 parts by weight.

[0173] The polypropylene resin composition of the present invention preferably contains 7 to 35 parts by weight of propylene polymer (A), 20 to 30 parts by weight of propylene homopolymer (B), 23 to 28 parts by weight of ethylene / α-olefin copolymer (C), and 32 to 40 parts by weight of inorganic filler (D), wherein the total amount of components (A) to (D) is 100 parts by weight.

[0174] The polypropylene resin composition of the present invention more preferably contains 8 to 28 parts by weight of propylene polymer (A), 23 to 30 parts by weight of propylene homopolymer (B), 24 to 28 parts by weight of ethylene / α-olefin copolymer (C), and 33 to 38 parts by weight of inorganic filler (D), wherein the total amount of components (A) to (D) is 100 parts by weight.

[0175] The polypropylene resin composition of the present invention particularly preferably contains 10 to 22 parts by mass of propylene polymer (A), 25 to 30 parts by mass of propylene homopolymer (B), 24 to 27 parts by mass of ethylene / α-olefin copolymer (C), and 34 to 37 parts by mass of inorganic filler (D), wherein the total amount of components (A) to (D) is 100 parts by mass.

[0176] The polypropylene resin composition of the present invention can be manufactured by combining the above-described components (A) to (D) with optional components such as additives as needed. The components can be combined sequentially in any order, or they can be mixed simultaneously. Furthermore, a multi-step mixing method can be used, where some components are mixed before the others are mixed. Specifically, it can be manufactured, for example, by first combining components (A) to (C) as resin components (organic compound components) in the polypropylene resin composition, and then adding component (D) and optional components such as additives as needed.

[0177] As a method for combining the components, examples include using mixing devices such as Banbury mixers, single-screw extruders, twin-screw extruders, and high-speed twin-screw extruders to simultaneously or sequentially mix the components or to melt-mix the components.

[0178] The melt flow rate (230°C, 2.16 kg load) of the polypropylene resin composition of the present invention is typically 23 g / 10 min or more, preferably greater than 23 g / 10 min, and less than 50 g / 10 min. By setting the melt flow rate within such a range, articles with good moldability can be formed, and the deterioration of the coating appearance after injection molding can be suppressed.

[0179] <Molded Body (i)>

[0180] The molded body (i) of the present invention is a molded body obtained from the polypropylene resin composition of the present invention described above. The molded body (i) can be obtained by appropriately molding the polypropylene resin composition of the present invention. The molding method for the polypropylene resin composition is not particularly limited, and various known methods for molding resin compositions can be used. Injection molding and compression molding are particularly preferred methods for molding the molded body (i). The molded body (i) obtained from the polypropylene resin composition of the present invention not only exhibits small dimensional changes due to temperature variations and good dimensional stability, but also, the laminated structure of this molded body results in an article with small dimensional changes due to temperature variations and good dimensional stability.

[0181] [Resin Curing Layer (ii)]

[0182] The resin curing layer (ii) of the present invention is a layer of resin curing material containing a curable resin (E) having urethane bonds.

[0183] The curable resin (E) used in this invention is a curable resin having urethane bonds. Known curable resins having urethane bonds can be used as such a curable resin (E) without limitation, and examples include polyurethane resins. In addition to urethane bonds, the curable resin (E) may also contain urea bonds, biuret bonds, etc. When manufacturing a resin curing layer (ii) containing the curable resin (E) having urethane bonds, a curing agent can be used as needed.

[0184] As a curable resin (E) having urethane bonds, known polyurethane resins can be used. For example, polymers obtained by reacting polyfunctional isocyanates or their derivatives with polyols or their derivatives and / or polyesters or their derivatives can be used.

[0185] Examples of polyfunctional isocyanates or their derivatives used as raw materials for polyurethane resins include toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), isophorone diisocyanate, and norbornene diisocyanate, as well as end-capped derivatives or isocyanurate derivatives. These compounds can be used alone or in combination of two or more.

[0186] Examples of polyols or their derivatives used as raw materials for polyurethane resins include polypropylene glycol with a molecular weight of 500 to 100,000, polyethylene glycol / polypropylene glycol block copolymers, and polypropylene glycol with acylated end groups. These compounds can be used alone or in combination of two or more.

[0187] Polyesters or their derivatives used as raw materials for polyurethane resins include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, and polybutylene isophthalate, as well as reaction products of these polyesters with polyethylene glycol or polypropylene glycol. These compounds can be used alone or in combination of two or more.

[0188] To obtain a polyurethane resin from a polyfunctional isocyanate and a polyol and / or a polyester, it can be achieved, for example, by mixing and stirring in an equimolar state or with an excess of the polyfunctional isocyanate. In this case, a polymerization accelerator, such as an amine compound, may also be incorporated.

[0189] The resin curing layer (ii) of the present invention can be manufactured by applying a composition containing the above-mentioned polyurethane resin raw material, such as an adhesive or coating, onto the molded body (i) and curing it, or by applying it onto other components bonded to the molded body (i) and curing it. Furthermore, a laminate including the molded body (i), the resin curing layer (ii), and other components can be manufactured by applying a composition containing the above-mentioned polyurethane resin raw material onto the molded body (i), bonding other components bonded to the molded body (i) before the composition cures, and then curing them, or by applying it onto components other than the molded body (i), bonding those components to the molded body (i) before the composition cures, and then curing them.

[0190] The resin curing layer (ii) of the present invention can be obtained, for example, by forming a layer of a composition comprising a curable resin (E) having urethane bonds and an auxiliary agent containing a curing agent and then curing it, or by forming a layer of a water vapor curing composition comprising a curable resin (E) having urethane bonds and then curing it, or by forming a layer comprising a curable resin (E) having urethane bonds as a thermosetting resin and then heating and curing it.

[0191] Furthermore, the resin cured layer (ii) of the present invention is preferably a cured product of an adhesive containing polyurethane resin or an adhesive forming urethane bonds. Examples of adhesives include, for instance, room-temperature two-component curing adhesives, one-component water vapor curing adhesives, and thermosetting adhesives. The resin cured layer obtained after curing these adhesives forms a curable resin layer containing urethane bonds.

[0192] As adhesives containing polyurethane resin or adhesives that form urethane bonds, known adhesives can be used, but two-component curing or one-component water-curing adhesives and water-based or water-based emulsion adhesives are preferred. Specifically, two-component curing or one-component water-curing adhesives and water-based or water-based emulsion adhesives containing polyurethane resins such as polyurethane resins, acrylic resins, polyurethane / acrylic resins, and epoxy resins can be used, as well as adhesives that form urethane bonds after coating, such as polyurethane resins, acrylic resins, polyurethane / acrylic resins, and epoxy resins.

[0193] Adhesives can be formulated by combining a base agent (a composition containing isocyanate compounds) with a curing agent (a composition containing compounds such as polyols that contain active hydrogen). Examples of such base agents include isocyanate-based and polyisocyanate-based agents, while examples of curing agents include polyol-based and polyamine-based agents. The curing agent is sometimes applied in a concealed finish before being combined with the adhesive, but it is usually mixed with the adhesive in a specific ratio just before application. Isocyanate-based and polyisocyanate-based base agents are preferred. Commercially available polyurethane adhesives can also be used as adhesives.

[0194] Among such adhesives, those comprising a polyurethane prepolymer and an isocyanate derivative are preferred, and those comprising a polyurethane prepolymer containing a polyether backbone and an aliphatic isocyanate derivative are more preferred. That is, the resin-cured layer comprising a curable resin (E) having urethane bonds is preferably a product cured from a polyurethane-based adhesive comprising a polyurethane prepolymer containing a polyether backbone and an aliphatic isocyanate derivative.

[0195] Polyurethane prepolymer

[0196] Polyurethane prepolymers can be obtained by reacting a polyisocyanate compound having two or more isocyanate groups in one molecule with an active hydrogen compound having two or more active hydrogens in one molecule that can react with isocyanate groups.

[0197] Examples of polyisocyanate compounds used in the preparation of polyurethane prepolymers include aliphatic polyisocyanates such as hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine methyl ester diisocyanate; and 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated toluene diisocyanate, norbornene diisocyanate, hydrogenated m-xylene diisocyanate, and hydrogenated p-xylene diisocyanate. Alicyclic polyisocyanates such as esters, aromatic polyisocyanates such as terephthalic diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, m-xylene diisocyanate, and bitoluidine diisocyanate, and modified products of the above polyisocyanates after modification with carbodiimide or isocyanurate, etc., these compounds can be used alone or in mixtures of two or more. Among them, aromatic isocyanates are preferred from the perspective of better adhesion and better curing properties.

[0198] As the active hydrogen compound used in the preparation of polyurethane prepolymers, one or more polyol compounds having two or more hydroxyl groups in one molecule can be used, such as polyether polyols, polyester polyols, or other polyols, but polyether polyols are preferred. Polyurethane prepolymers obtained by using polyether polyols as active hydrogen compounds have a polyether backbone, and the resulting adhesive exhibits excellent bonding properties with the molded body (i). Among these polyol compounds, those with a number average molecular weight of 100 to 50,000 are preferred, and particularly preferred are those with a number average molecular weight of 300 to 10,000.

[0199] As specific examples of polyether polyols that are active hydrogen compounds applicable to the preparation of polyurethane prepolymers, in addition to polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethyleneoxypropylene glycol, polyoxytetramethylene glycol, and polyoxyhexamethylene glycol, low molecular weight active hydrogen compounds with two or more active hydrogens can also be mentioned, such as diols such as bisphenol A, ethylene glycol, propylene glycol, butanediol, and 1,6-hexanediol; triols such as glycerol, trimethylolpropane, and 1,2,6-hexanetriol; and random copolymers obtained by ring-opening polymerization of propylene oxide and / or ethylene oxide in the presence of one or more amines such as ammonia, methylamine, ethylamine, propylamine, and butylamine.

[0200] Polyurethane prepolymers can be obtained by reacting a polyol compound and a polyisocyanate compound by heating, as needed, in a ratio where the stoichiometric ratio (NCO / OH) is greater than 1 mole of isocyanate groups relative to the hydroxyl groups in the polyol compound. Such polyurethane prepolymers typically have isocyanate groups at both ends of their molecules. From the perspectives of workability and the physical properties of the cured product, a polyol compound reacting with a polyisocyanate compound in a ratio of 1.5 to 20 (NCO / OH) to form a liquid product at 23°C is more preferable. Furthermore, from the perspectives of better adhesion and better curing performance, a polyurethane prepolymer obtained by reacting a polyether polyol with an aromatic polyisocyanate compound is preferred.

[0201] Isocyanate derivatives

[0202] As isocyanate derivatives, isocyanate derivatives that function as the main agent can be used without particular restriction. For example, isocyanates, diisocyanates, polyisocyanates and their derivatives can be used, specifically the aforementioned polyfunctional isocyanates or their derivatives.

[0203] As the aforementioned isocyanate derivative, compounds having an isocyanurate structure and isocyanate groups are preferred. When using compounds having an isocyanurate structure and isocyanate groups as isocyanate derivatives, especially when using compounds having an isocyanurate structure and isocyanate groups as aliphatic isocyanate derivatives, it is preferable to form an article with high adhesion strength to the molded body (i).

[0204] The isocyanurate structure is represented by the following formula (B1). Each molecule of the above-mentioned aliphatic isocyanate derivative may have at least one of the above-mentioned isocyanurate structures, and a morphology having one of the above-mentioned isocyanurate structures can be cited as one of its preferred embodiments.

[0205]

[0206] Each molecule of the above-mentioned isocyanate derivative may have at least one isocyanate group, preferably multiple isocyanate groups, and more preferably three or more isocyanate groups.

[0207] In the above-mentioned isocyanate derivatives, the above-mentioned isocyanurate structure and the above-mentioned isocyanate group can be directly bonded or bonded through a linking group. The form of bonding through a linking group can be cited as one of its preferred embodiments.

[0208] In the above-mentioned isocyanate derivatives, the above-mentioned isocyanurate structure and the above-mentioned isocyanate group can be directly bonded or bonded through a linking group. The form of bonding through a linking group can be cited as one of its preferred embodiments.

[0209] Examples of linking groups include hydrocarbon groups that may have heteroatoms. Among these hydrocarbon groups, those consisting only of carbon and hydrogen atoms are considered as one of the preferred embodiments. Specific examples of hydrocarbon groups include, but are not particularly limited to, aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. Aliphatic hydrocarbon groups are preferred.

[0210] The aforementioned aliphatic hydrocarbon group can be any form, including straight-chain, branched, cyclic, or combinations thereof. Specific examples of the aforementioned aliphatic hydrocarbon group include, for instance, straight-chain or branched aliphatic hydrocarbon groups. From the perspective of further advantages of the present invention, the aforementioned aliphatic hydrocarbon group is preferably a straight-chain aliphatic hydrocarbon group. From the perspective of further advantages of the present invention, the aforementioned aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 3 to 10, and even more preferably 4 to 5. From the perspective of further advantages of the present invention, the aforementioned aliphatic hydrocarbon group is preferably methylene, ethylene, propylene, trimethylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, or decylene, more preferably butylene or pentylene, and even more preferably pentylene.

[0211] Heteroatoms that can be present in a hydrocarbon group include, but are not specifically limited to, oxygen atoms, nitrogen atoms, sulfur atoms, and halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.). These heteroatoms can also bond with other heteroatoms, carbon atoms, or hydrogen atoms to form functional groups.

[0212] From the perspective of achieving better results in this invention, the above-mentioned isocyanate derivative is preferably a compound represented by the following formula (B2).

[0213]

[0214] In equation (B2), R 141 R 142 R 143 Each is independent, indicating that it can have a hydrocarbon group with heteroatoms. Represented as R 141 The same applies to hydrocarbon groups that have heteroatoms.

[0215] From the perspective of achieving better results in this invention, the above-mentioned isocyanate derivatives are preferably isocyanurates containing aliphatic polyisocyanates (described later), more preferably isocyanurates containing pentamethylene diisocyanate (the compound represented by formula (B2-1) below) and / or isocyanurates containing hexamethylene diisocyanate (the compound represented by formula (B2-2) below), and even more preferably isocyanurates containing pentamethylene diisocyanate.

[0216]

[0217] The aforementioned isocyanate derivatives can be formed, for example, by polyisocyanate compounds. There are no particular limitations on the polyisocyanate compounds, as long as they are compounds in which multiple isocyanate groups are bonded to the linking group. Aliphatic polyisocyanates (compounds in which multiple isocyanate groups are bonded to the aliphatic hydrocarbon group) are preferred.

[0218] Examples of the aforementioned isocyanate derivatives include aliphatic diisocyanates such as pentamethylene diisocyanate (PDI) and hexamethylene diisocyanate (HDI). The polyisocyanate compounds that can constitute the aforementioned isocyanate compound (B) can be one or a combination of two or more.

[0219] Based on the superior effects (initial adhesion and adhesion durability) of the present invention and its ease of addition to the composition due to its low viscosity, the above-mentioned isocyanate derivative is preferably a compound represented by the above formula (B2-1).

[0220] From the perspective of improving the effects of the present invention (especially the adhesive durability), the content of the above-mentioned isocyanate derivative is preferably 0.10 to 10.0% by mass, more preferably 0.50 to 5.0% by mass, relative to the total amount of the composition of the present invention.

[0221] • Adducts

[0222] Adhesives containing polyurethane resins or adhesives forming urethane bonds may contain compounds represented by the following formula (X) (in formula (X), R...). 37 and R 38 Each compound is an adduct of a hydrocarbon group and a phenolic compound. This adduct functions as an adhesive in adhesives containing polyurethane resins or adhesives that form urethane bonds.

[0223]

[0224] In equation (X), R 37 and R 38 Each is independent and represents a hydrocarbon group.

[0225] Represented as R 37 and R 38 There are no particular limitations on the hydrocarbon group. The aforementioned hydrocarbon group may have heteroatoms. Compounds consisting only of carbon atoms and hydrogen atoms can be cited as one of the preferred embodiments. The aforementioned hydrocarbon group can specifically be, but is not particularly limited to, aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. Among them, aliphatic hydrocarbon groups are preferred.

[0226] The aforementioned aliphatic hydrocarbon group can be any form, including straight-chain, branched, cyclic, or combinations thereof. Specific examples of the aforementioned aliphatic hydrocarbon group include, for instance, straight-chain or branched aliphatic hydrocarbon groups. From the perspective of further advantages of the present invention, the aforementioned aliphatic hydrocarbon group is preferably a straight-chain aliphatic hydrocarbon group. From the perspective of further advantages of the present invention, the aforementioned aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10. From the perspective of further advantages of the present invention, the aforementioned aliphatic hydrocarbon group is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, more preferably methyl.

[0227] Examples of aromatic hydrocarbon groups include aryl and naphthyl groups. Examples of aryl groups include phenyl, tolyl, and xylyl groups, which have 6 to 18 carbon atoms.

[0228] Heteroatoms that can be present in a hydrocarbon group include, but are not specifically limited to, oxygen atoms, nitrogen atoms, sulfur atoms, and halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.). These heteroatoms can also bond with other heteroatoms, carbon atoms, or hydrogen atoms to form functional groups.

[0229] From the perspective of achieving better results in this invention, the compound represented by the above formula (X) is preferably camphene. Camphene is a compound represented by the following formula (X1).

[0230]

[0231] In this invention, the other compound forming the above-mentioned adduct is a phenolic compound. There are no particular limitations on the phenolic compound; it can be any compound with a hydroxyl group bonded to the benzene ring.

[0232] Each of the above-mentioned phenolic compounds may have one or more, preferably one, phenolic hydroxyl group (a hydroxyl group directly bonded to the benzene ring). Examples of such phenolic compounds include compounds represented by the following formula (Y).

[0233]

[0234] In formula (Y), R 39 represents a substituent, and n2 represents 0 or 1 to 4.

[0235] In formula (Y), it is represented as R 39 Examples of substituents include hydrocarbon groups and hydroxyl groups.

[0236] n2 represents 0 or 1 to 4, and from the perspective of achieving better results in this invention, 0 is preferred.

[0237] From the perspective of achieving better results in this invention, the phenolic compound is preferably phenol.

[0238] From the perspective of achieving better results and a milder odor, the above-mentioned adduct is preferably the reaction product of one molecule of the compound represented by the above formula (X) and one molecule of the above-mentioned phenolic compound.

[0239] From the perspective of achieving better results in this invention, the above-mentioned adduct preferably has a phenolic hydroxyl group or phenoxy group derived from the above-mentioned phenolic compound (both of which may also have the above-mentioned substituents on the benzene ring).

[0240] It should be noted that the above adducts only need to contain at least the above reaction products. In addition to the above reaction products, the above adducts may also contain reaction byproducts and unreacted substances.

[0241] Examples of the above-mentioned adducts include compounds represented by the formulas (Z1) to (Z3) below.

[0242]

[0243] In equation (Z1), R 40 and R 41 Each is independent, representing a hydrocarbon group, R 42 The substituent is indicated by n, where n3 represents 0 or 1 to 4.

[0244] In equation (Z1), R is represented as 40 and R 41 The hydrocarbon group and the R group in formula (X) 37 and R 38 The hydrocarbon group is the same. It is represented as R. 42 The substituents are represented as R in formula (Y). 39 The substituents are the same. n3 represents 0 or 1 to 4, preferably 0.

[0245]

[0246] In equation (Z2), R 43 and R 44 Each is independent, representing a hydrocarbon group, R 45 This indicates a substituent, and n4 represents 0 or 1 to 4.

[0247] In equation (Z2), R is represented as 43 and R 44 The hydrocarbon group and the R group in formula (X) 37 and R 38 The hydrocarbon group is the same. It is represented as R. 45 The substituents are represented as R in formula (Y). 39 The substituents are the same. n4 represents 0 or 1 to 4, preferably 0.

[0248]

[0249] In equation (Z3), R51 and R 52 Each is independent, representing a hydrocarbon group, R 53 The substituent is indicated by n5, which represents 0 or 1 to 4.

[0250] In equation (Z3), R is represented as 51 and R 52 The hydrocarbon group and the R group in formula (X) 37 and R 38 The same applies to hydrocarbon groups.

[0251] Represented as R 53 The substituents are represented as R in formula (Y). 39 The substituents are the same.

[0252] n5 represents 0 or 1 to 4, preferably 0.

[0253] From the perspective of achieving better results and a milder odor, it is preferable to contain at least one compound selected from the compounds represented by formula (Z1-1), formula (Z1-2), formula (Z2-1), formula (Z2-2), and formula (Z3-1).

[0254]

[0255] There are no particular limitations on the method for producing the above adduct, as long as it is a method that allows the compound represented by formula (X) to react with the phenolic compound. There are no particular limitations on the amount of the compound represented by formula (X) and the phenolic compound used in the above reaction. The molar ratio (compound represented by (X):phenolic compound) of the compound represented by formula (X) reacting with the phenolic compound can be, for example, 1:0.5 to 2, preferably 1:0.8 to 1.2, and more preferably 1:1. The compound represented by formula (X) and the phenolic compound can react in the presence of a catalyst. Examples of catalysts include boron trifluoride ether complexes. The compound represented by formula (X) and the phenolic compound can also react in a solvent. Examples of solvents include aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as cyclohexane, and halogenated hydrocarbons such as carbon tetrachloride.

[0256] The reaction temperature when the compound represented by the above formula (X) reacts with the above phenolic compound can be, for example, 0 to 100°C.

[0257] From the perspective of achieving better results from the present invention, the content of the above-mentioned adduct is preferably 0.05 to 10% by mass, more preferably 0.1 to 1.0% by mass, relative to the total amount of the composition (adhesive) forming the curable resin (E) of the present invention.

[0258] The mass ratio of the content of the above isocyanate derivative to the mass ratio of the above adduct (mass ratio of isocyanate derivative to adduct) is preferably 0.1:1 to 50:1, more preferably 10:1 to 2:1.

[0259] In the case of a two-component formulation, the above-mentioned adducts can be appropriately selected and added to either the main agent or the curing agent.

[0260] Adhesives containing polyurethane resin or forming urethane bonds may contain components other than those mentioned above. In the case of a two-component adhesive, other components may be appropriately selected and added to either the main agent or the curing agent. These other components may further include, for example, fillers (e.g., carbon black, calcium carbonate), catalysts (curing catalysts), plasticizers, anti-aging agents, antioxidants, silane coupling agents, pigments (dyes), tackifiers, terpene compounds such as terpineol, thixotropic agents, UV absorbers, flame retardants, surfactants (including leveling agents), dispersants, dehydrating agents, antistatic agents, and various other additives. It should be noted that the above-mentioned components can be surface-treated with at least one treatment agent selected from fatty acids, resin acids, urethane compounds, and fatty acid esters. Furthermore, in the case of a two-component adhesive, the aforementioned optional components may be appropriately selected and added to either the main agent or the curing agent.

[0261] The resin curing layer (ii) can be any layer containing the curable resin (E) having urethane bonds as described above, and the method of forming the layer is preferably, but not limited to, a method of curing an adhesive containing polyurethane resin or an adhesive that forms urethane bonds.

[0262] From the perspective of utilizing renewable resources and reducing CO2 emissions, the curable resin (E) having the aforementioned urethane bonds and the resin-cured layer (ii) containing the resin are preferably manufactured using at least a portion of biomass-derived raw materials. That is, in this invention, the raw materials used to form the curable resin (E) having urethane bonds or the resin-cured layer (ii) containing the resin, such as components constituting an adhesive containing polyurethane resin or an adhesive forming urethane bonds, are preferably one or more biomass-derived raw materials. Here, biomass refers to "renewable organic resources other than fossil resources derived from organisms," and biomass-derived raw materials refer to raw materials containing components derived from organic matter produced by photosynthesis of water and carbon dioxide by organisms using solar energy. It should be noted that whether the raw material is biomass-derived or not, it can be manufactured according to ASTM D6866. 14 The proportion of carbon derived from biomass obtained by the C method is used to determine this.

[0263] As a biomass-derived raw material, it can be used without any special restrictions, such as raw materials with a biomass ratio of more than 50% as measured according to ASTM D6866 Method B, raw materials with a plant ratio (the proportion of plant-derived components) of more than 50%, and commercially available raw materials labeled as derived from natural raw materials other than fossil resources.

[0264] [Layered Structure]

[0265] The laminated structure of the present invention is an article in which a resin-cured layer (ii) comprising a curable resin (E) having urethane bonds is directly laminated onto a molded body (i) made of the above-mentioned polypropylene resin composition.

[0266] The polypropylene resin composition of the present invention has good adhesion to the resin cured layer (ii) containing a curable resin (E) having urethane bonds. Although the molded body (i) and the resin cured layer (ii) are directly laminated without the aid of a primer, they can be firmly bonded. The laminated structure maintains a high degree of adhesion even at high temperatures where adhesion would normally be weakened.

[0267] In this invention, the manufacturing method and shape of the molded body (i), the resin-cured layer (ii), and the laminated structure of the present invention formed by stacking them are not limited. Furthermore, the laminated structure of the present invention can be a laminated structure formed solely of the molded body (i) and the resin-cured layer (ii), or it can be a structure further laminated with layers other than the molded body (i) and the resin-cured layer (ii). For example, it can be a laminated structure in which the molded body (i), the resin-cured layer (ii), and other components are stacked sequentially. The laminated structure formed by stacking the molded body (i), the resin-cured layer (ii), and other components can be manufactured by a method of coating a curable composition forming the resin-cured layer (ii) onto the molded body (i), attaching other components before the composition cures, curing the composition, and forming the resin-cured layer (ii) between the molded body (i) and other components; or by coating a curable composition forming the resin-cured layer (ii) onto other components, attaching the molded body (i) before the composition cures, curing the composition, and forming the resin-cured layer (ii) between the molded body (i) and other components, etc.

[0268] When the resin curing layer (ii) is a layer formed by curing an adhesive containing polyurethane resin or an adhesive that forms urethane bonds, the resin curing layer (ii) can be manufactured by applying the adhesive to the molded body (i) and curing it; or by applying the adhesive to the molded body (i) and curing the adhesive while it is bonded to other components; or by applying the adhesive to other components bonded to the molded body (i) and curing the adhesive while it is bonded to other components. In the manufacture of a laminated structure consisting of a molded body (i), a resin-cured layer (ii), and other components, an adhesive-coated article, such as a release film, can be adhered to the molded body (i), the release film can be peeled off, an adhesive layer can be formed on the molded body (i), and the adhesive layer can be cured after being adhered to other components to manufacture the resin-cured layer (ii). Alternatively, an adhesive-coated article, such as a release film, can be adhered to other components, the release film can be peeled off, an adhesive layer can be formed on the other components, and the adhesive layer can be cured after being adhered to the molded body (i) to manufacture the resin-cured layer (ii). In the manufacture of such a resin-cured layer (ii), it is preferable that the adhesive is bonded to the molded body (i) during the curing period, and more preferably that the adhesive is applied to the molded body (i) and then cured.

[0269] Preferably, the manufacturing method of the laminated structure of the present invention includes a step of molding the above-mentioned polypropylene resin composition by injection molding or compression molding to manufacture a molded body (i), and a step of contacting or coating the above-mentioned molded body (i) with a urethane bond or its raw material with a curable resin (E) or a raw material thereof with a urethane bond with the molded body (i) and then curing it to form a resin curing layer (ii).

[0270] More preferably, the process includes a step of manufacturing a molded body (i) by molding the polypropylene resin composition by injection molding or compression molding, and a step of applying a polyurethane prepolymer containing a polyether backbone and an aliphatic isocyanate derivative onto the molded body (i) and then curing it to form a resin cured layer (ii).

[0271] Specifically, one method is to directly coat the surface of a molded body (i) obtained by injection molding or compression molding of the aforementioned polypropylene resin composition with a surface treatment such as flame treatment or plasma treatment as needed, and then cure it to form a resin cured layer (ii). The curing conditions can be selected according to the type of curable resin (E) or its raw material used, the presence and type of curing agent, etc., and can be carried out at a temperature of, for example, 20°C or higher and lower than 100°C, preferably 40°C or higher and lower than 80°C.

[0272] The laminated structure of the present invention may also have other component layers besides the molded body (i) and the resin-cured layer (ii). As one preferred embodiment of the laminated structure of the present invention, a laminated structure in which the molded body (i), the resin-cured layer (ii), and other component layers are stacked sequentially can be cited. In such a laminated structure, it is preferable that the molded body (i) and other component layers are joined by means of the resin-cured layer (ii).

[0273] There are no particular restrictions on the other components that constitute the other component layers; any type of component can be used. Examples include resin components such as ABS resin, PVC sheets, polyolefin sheets, polyolefin sheets with foamed layers, glass, fabrics, textiles, metals (iron (low-carbon steel), cationic electrodeposited steel sheets, aluminum, etc.), wood, paper, and their composite materials. In the manufacture of the laminated structure having these other component layers, methods such as directly coating the surface of the molded body (i) with a curable resin (E) having urethane bonds that constitutes the resin curing layer (ii) or an adhesive as its raw material, and then bonding the coated surface with other components by methods such as room temperature curing, heating, or pressing, can be used.

[0274] Such a laminated structure of the present invention not only exhibits excellent dimensional stability, but also ensures a strong bond between the molded body (i) and the resin-cured layer (ii) even at high temperatures where bonding performance is easily weakened, without the aid of a primer. For example, it maintains high adhesive strength even at 90°C, a temperature where high strength is most difficult to achieve in conventional bonding tests, and demonstrates sufficient adhesive strength in hot shear tests at 90°C. Specifically, in hot shear strength tests at 90°C (tensile speed 50 mm / min) according to JIS K6850:1999, it shows excellent adhesive strength between the molded body (i) and the resin-cured layer (ii), typically 1.2 MPa or more, preferably greater than 1.5 MPa, more preferably greater than 2.0 MPa, and even more preferably greater than 2.5 MPa.

[0275] The laminated structure of this invention can be applied to automotive interior components such as door trim strips, dashboards, roofs, consoles, pillars, and glove boxes; automotive exterior components such as bumpers, side protection devices, spoilers, side protection strips, mudguards, door panels, and rear doors; and industrial components such as household appliance parts and building materials. It is particularly suitable for automotive exterior components such as rear doors.

[0276] Example

[0277] The present invention will be described in more detail below based on embodiments, but the present invention is not limited to these embodiments.

[0278] The measurement and evaluation of each physical property are carried out using the following methods.

[0279] [Mel flow rate (g / 10min)]

[0280] Measurements were performed according to ISO 1133, under test conditions of 2.16 kg load and 230 °C temperature.

[0281] [Cephane soluble component content (D)] sol ) and the amount of insoluble components (D) insol )]

[0282] Approximately 3g of sample [component (A)] (measured to an accuracy of 10 g) was taken. ﹣4 The mass is expressed as x²(g) in the following formula. 500 ml of n-decane and a small amount of heat-resistant stabilizer soluble in n-decane were added to a glass measuring container. Under nitrogen atmosphere and with stirring, the mixture was heated to 150°C over 2 hours to dissolve the sample. After maintaining the temperature at 150°C for 2 hours, it was naturally cooled to 23°C for 8 hours. The resulting liquid containing precipitates was filtered under reduced pressure using a 25G-4 glass filter manufactured by Iwata Glass Co., Ltd. 100 ml of the filtrate was collected and dried under reduced pressure to obtain a portion of the decane-soluble component. Its mass was measured to an accuracy of 10 g / ml. ﹣4 The unit is g (the mass is expressed as x1(g) in the following formula). Using this measurement, the amount of decane-soluble component (D) at room temperature (i.e., 23°C) is determined by the following formula. sol ) and the amount of insoluble components (D) insol ).

[0283] D sol (mass%) = 100 × (500 × x1) / (100 × x2)

[0284] D insol (mass%) = 100 - D sol

[0285] [Peak Melting Point]

[0286] Obtain the endothermic curve of the differential scanning calorimeter (DSC) and determine the temperature at the position of the maximum peak as the melting point peak (Tm).

[0287] The measuring instrument used was a Pyris 1 manufactured by Perkin Elmer Corporation. The sample was filled into an aluminum bowl, held at 30°C for 1 minute, then heated to 160°C at a rate of 500°C / min, held at 160°C for 5 minutes, then cooled to -30°C at a rate of 10°C / min, and then heated from -30°C to 160°C at a rate of 10°C / min. The endothermic curve was then obtained, and the melting point peak (Tm) was determined from this curve.

[0288] Average particle size of inorganic fillers

[0289] According to JIS R1620 and JIS R1622, the average particle size is the particle size value of 50% by mass of the cumulative amount read from the particle size accumulation curve measured by laser diffraction.

[0290] Aspect Ratio of Inorganic Fillers

[0291] Photographs were taken using an electron microscope, and the long axis diameter (particle size) and thickness of the powder were measured. The average value was obtained, and the aspect ratio was calculated based on the ratio of average particle size to average thickness.

[0292] [Flexural modulus (MPa)]

[0293] Measurements were performed under the following conditions in accordance with ASTM D790.

[0294] Temperature: 23℃

[0295] Test piece: 127mm (length) × 12.7mm (width) × 6.35mm (thickness)

[0296] Bending speed: 30mm / min

[0297] Span: 100cm

[0298] [IZOD Impact Strength (Cantilever Beam Impact Strength) (J / m)]

[0299] IZOD impact strength was measured under the following conditions in accordance with ASTM D256.

[0300] Test piece: 63.5mm (length) × 12.7mm (width) × 3.2mm (thickness), with notch; test temperature: -30℃

[0301] [Linear expansion coefficient (10)] ﹣5 / ℃)]

[0302] The evaluation was conducted according to ASTM D 696 using the TMA method (measurement range: -30 to 80°C).

[0303] [Interlayer adhesion test without primer (90℃ hot shear test)]

[0304] According to JIS K6850:1999, a tensile testing machine such as... Figure 1 The schematic diagram shows that the resin plate and glass plate are used as the bonding shear test objects. The resin plate side is fixed and the glass side is assembled to the fixing fixture. The shear strength is measured at a temperature of 90°C and a tensile speed of 50 mm / min. The average value of four measurements is obtained as the thermal shear test strength (MPa).

[0305] [Manufacturing Example 1] Preparation of propylene / ethylene block copolymer (A-1)

[0306] (1) Preparation of solid titanium catalyst components

[0307] Anhydrous magnesium chloride 95.2g, decane 442mL and 2-ethylhexanol 390.6g were heated at 130℃ for 2 hours to form a homogeneous solution. Phthalic anhydride 21.3g was added to the solution and stirred at 130℃ for 1 hour to dissolve the phthalic anhydride.

[0308] After cooling the homogeneous solution to room temperature, 75 mL of the homogeneous solution was added dropwise to 200 mL of titanium tetrachloride, which was kept at -20 °C, over 1 hour. After dissolution, the temperature of the mixture was raised to 110 °C over 4 hours. Once 110 °C was reached, 5.22 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred and kept at this temperature for 2 hours.

[0309] After the 2-hour reaction was complete, the solid fraction was collected by hot filtration. This solid fraction was then resuspended in 275 mL of titanium tetrachloride and heated at 110 °C for another 2 hours. After the reaction was complete, the solid fraction was collected again by hot filtration and thoroughly washed with decane and hexane at 110 °C until no free titanium compounds were detectable in the solution.

[0310] The detection of the free titanium compound was confirmed by the following method: 10 mL of the supernatant of the above solid catalyst component was collected using a syringe and transferred to a 100 mL manifold pre-purified with nitrogen. The solvent hexane was then dried with a nitrogen stream, followed by vacuum drying for 30 minutes. 40 mL of ion-exchanged water and 10 mL of (1+1) sulfuric acid were added, and the mixture was stirred for 30 minutes. The aqueous solution was transferred through filter paper to a 100 mL volumetric flask, followed by the addition of 1 mL of concentrated H3PO4 solution as an iron(II) ion masking agent and 5 mL of 3% hydrogen peroxide aqueous solution as a colorimetric reagent for titanium. The volumetric flask was then filled with ion-exchanged water to a final volume of 100 mL and shaken well. After 20 minutes, the absorbance at 420 nm was observed using UV. The free titanium was then washed away until no absorption was observed.

[0311] The solid titanium catalyst component prepared as described above was stored in the form of decane slurry, and a portion of it was dried for the purpose of studying the catalyst composition. The composition of the resulting solid titanium catalyst component was 2.3% by mass of titanium, 61% by mass of chlorine, 19% by mass of magnesium, and 12.5% ​​by mass of DIBP.

[0312] (2) Manufacturing of prepolymer catalyst

[0313] 100g of the above-mentioned solid titanium catalyst component, 131mL of triethylaluminum, 37.3mL of diethylaminotriethoxysilane, and 14.3L of heptane were added to a 20L autoclave equipped with a stirrer. The internal temperature was maintained at 15-20°C. 1000g of propylene was added, and the reaction was carried out with stirring for 120 minutes. After polymerization, the solid components were allowed to settle, and the supernatant was removed twice and the catalyst was washed twice with heptane. The obtained prepolymer catalyst was resuspended in purified heptane, and the concentration was adjusted with heptane to achieve a solid catalyst component concentration of 1.0g / L, thus obtaining the prepolymer catalyst slurry.

[0314] (3) Main aggregation

[0315] Polymerization was carried out in a jacketed tubular polymerization apparatus with an internal volume of 58L, with propylene at a rate of 43kg / h, hydrogen at a rate of 256NL / h, the prepolymer catalyst slurry prepared above (2) being fed continuously at a rate of 0.49g / h (as a solid titanium catalyst component), 4.5mL / h (triethylaluminum), and 1.8mL / h (diethylaminotriethoxysilane), in a fully liquid state without the presence of a gas phase. The temperature of the tubular polymerization apparatus was 70°C, and the pressure was 3.57MPa / G.

[0316] The resulting slurry was fed into a 100L Bessel polymerization unit equipped with a stirring device, and further polymerization was carried out. Propylene and hydrogen were supplied to the polymerization unit at a rate of 45 kg / h and a hydrogen concentration of 8.8 mol% in the gas phase. The polymerization reaction was carried out at a polymerization temperature of 68°C and a pressure of 3.36 MPa / G.

[0317] Next, the resulting slurry was transferred to a 2.4L pipette and vaporized for gas-solid separation. Then, the polypropylene homopolymer powder was fed into a 480L gas-phase polymerization apparatus for ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were continuously supplied to maintain a gas composition of ethylene / (ethylene + propylene) = 0.20 (molar ratio) and hydrogen / ethylene = 0.0031 (molar ratio) within the gas-phase polymerization apparatus. Polymerization was carried out at a polymerization temperature of 70°C and a pressure of 1.40 MPa / G.

[0318] Next, the obtained propylene block copolymer was vacuum dried at 80°C. The resulting propylene / ethylene block copolymer component (A-1) had an MFR (230°C, 2.16 kg load) of 80 g / 10 min, a decane-soluble component (propylene / ethylene copolymer component) of 7% by mass, a decane-insoluble component (propylene homopolymer component) of 93% by mass, and a limiting viscosity [η] of 7.5 dl / g for the decane-soluble component.

[0319] [Manufacturing Example 2] Preparation of propylene homopolymer (B-1)

[0320] The same procedure was performed as in the preparation of the solid titanium catalyst component (1) of Manufacturing Example 1 to obtain the solid titanium catalyst component.

[0321] (2) Manufacturing of prepolymer catalyst

[0322] 100g of solid titanium catalyst component, 39.3mL of triethylaluminum, and 100L of heptane were added to a 200L autoclave equipped with a stirrer. The internal temperature was maintained at 15-20℃. 600g of propylene was added, and the reaction was carried out with stirring for 60 minutes to obtain a prepolymer catalyst slurry.

[0323] (3) Main aggregation

[0324] In a jacketed circulating tubular polymerization apparatus with an internal volume of 58L, polymerization was carried out in a fully liquid state without the presence of a gas phase. The feed consisted of 43 kg / h of propylene, 177 NL / h of hydrogen, and a prepolymer catalyst slurry prepared by (2) being continuously fed at a rate of 0.58 g / h of solid titanium catalyst, 3.1 mL / h of triethylaluminum, and 3.3 mL / h of dicyclopentyldimethoxysilane. The temperature of the tubular polymerization apparatus was 70°C and the pressure was 3.53 MPa / G.

[0325] The resulting slurry was fed into a 100L Bessel polymerization unit equipped with a stirring device, and further polymerization was carried out. Propylene and hydrogen were supplied to the polymerization unit at a rate of 45 kg / h and a hydrogen concentration of 3.2 mol% in the gas phase. The polymerization reaction was carried out at a polymerization temperature of 70°C and a pressure of 3.28 MPa / G.

[0326] Next, the obtained propylene homopolymer was vacuum dried at 80°C. The MFR (230°C, 2.16 kg load) of the propylene homopolymer component (B-1) obtained in this way was 30 g / 10 min.

[0327] [Manufacturing Example 3] Preparation of propylene homopolymer (B-2)

[0328] First, the same procedures were performed as in the preparation of (1) solid titanium catalyst components and (2) prepolymer catalyst in Manufacturing Example 1 to obtain a prepolymer catalyst slurry.

[0329] (3) Main aggregation

[0330] Polymerization was carried out in a 1000L Bessel polymerization apparatus equipped with a stirring device, with propylene continuously fed at a rate of 131 kg / h, prepolymer catalyst slurry as a transition metal catalyst component at 0.70 g / h, triethylaluminum at 19.6 mL / h, and diethylaminotriethoxysilane at 4.2 mL / h, and hydrogen was supplied to make the hydrogen concentration in the gas phase 5.3 mol%. Polymerization was carried out at a polymerization temperature of 75°C and a pressure of 3.5 MPa / G.

[0331] The resulting slurry was fed into a 500L Bessel polymerization unit equipped with a stirring device, and further polymerization was carried out. Propylene and hydrogen were supplied to the polymerization unit at a rate of 30 kg / h of propylene and a hydrogen concentration of 3.9 mol% in the gas phase. The polymerization reaction was carried out at a polymerization temperature of 74.5°C and a pressure of 3.4 MPa / G.

[0332] Next, the resulting slurry was fed into a 500L Bessel polymerization unit equipped with a stirring device, and further polymerization was carried out. Propylene and hydrogen were supplied to the polymerization unit at a rate of 20 kg / h and a hydrogen concentration of 3.4 mol% in the gas phase, and the polymerization reaction was carried out at a polymerization temperature of 73°C and a pressure of 3.4 MPa / G.

[0333] Next, the obtained slurry was passivated, vaporized, and then subjected to gas-solid separation. The resulting propylene homopolymer was vacuum dried at 80°C. The MFR (230°C, 2.16 kg load) of the propylene homopolymer component (B-2) obtained in this way was 210 g / 10 min.

[0334] [Ethylene / α-olefin copolymer]

[0335] As an ethylene / α-olefin copolymer (C-1), it was manufactured by Mitsui Chemicals Co., Ltd. A4050S (Ethylene content = 80 mol%, 1-Butene content = 20 mol%, MFR (230℃, 2.16 kg load) = 7 g / 10 min, Density = 0.862 g / cm³) 3 (Melting point peak = below 50℃).

[0336] As an ethylene / α-olefin copolymer (C-2), it was manufactured by Mitsui Chemicals Co., Ltd. A1050S (Ethylene content = 80 mol%, 1-Butene content = 20 mol%, MFR (230℃, 2.16 kg load) = 2 g / 10 min, Density = 0.862 g / cm³) 3 (Melting point peak = below 50℃).

[0337] As an ethylene / α-olefin copolymer (C-3), a polyolefin elastomer manufactured by Dow Chemical Company was used. 11547 (MFR (230℃, 2.16kg load) = 9g / 10min, density = 0.866g / cm³) 3 (Melting point peak = 120℃).

[0338] [Inorganic filler]

[0339] Talc with the following properties was used as an inorganic filler (D-1).

[0340] (D-1): Talc, average particle size (laser diffraction) = 6.0 μm, aspect ratio (SEM measurement) = 7.0

[0341] [Manufacturing Examples 4-6] Preparation of Main Agents (E1-1) to (E1-3)

[0342] The components in Table 1 below were mixed using a stirring device according to the composition (parts by mass) shown in the table to prepare the main components (E1-1) to (E1-3) of the two-component curing adhesive.

[0343] [Table 1]

[0344]

[0345] The details of each component in Table 1 above are as follows.

[0346] (Details of main component)

[0347] • Polymer 1: The polyurethane prepolymer synthesized as described below:

[0348] 700g of polyoxypropylene glycol (average molecular weight 2000), 300g of polyoxypropylene triol (average molecular weight 3000), and 499g of 4,4'-diisocyanate benzene (molecular weight 250) were mixed (NCO / OH = 2.0 at this time), and then 500g of diisononyl phthalate was added. The mixture was added under a nitrogen stream and stirred at 80°C for 12 hours to synthesize a polyurethane prepolymer (polymer 1) containing 2.10% isocyanate groups.

[0349] Polymer 2: A modified silicone resin with a main chain of polyoxypropylene and hydrolyzable methyldimethoxysilyl groups at the chain ends. Kaneka MS Polymer S203 (manufactured by Kaneka Corporation).

[0350] • Epoxy Resin 1: Adeka Resin EP-4100 (manufactured by Adeka Corporation)

[0351] • Epoxy Resin 2: Adeka Resin EP-4006 (manufactured by Adeka Corporation)

[0352] Compound 1: Isocyanurate form of hexamethylene diisocyanate (Takenate D-170HN, manufactured by Mitsui Chemicals Co., Ltd.)

[0353] Compound 2: A mixture of isocyanurate and urea carbamate forms of pentamethylene diisocyanate (Stabio D-376N (low viscosity type), manufactured by Mitsui Chemicals Co., Ltd.) (Biomass-derived compound: plant ratio (ASTM D6866-04): 67%)

[0354] Compound 3: Ketoimine-type latent curing agent EPIKURE H-30 (manufactured by Mitsubishi Chemical Corporation)

[0355] Compound 4: An adduct of camphene and phenol (manufactured by Yasuhara Chemical Co., Ltd.). The adduct used as Compound 4 is a commercially available product and contains at least one compound selected from the following formulas: (Z1-1), (Z1-2), (Z2-1), (Z2-2), and (Z3-1). (Biomass-derived compounds: Biomass ratio (ASTM D6866 Method B): 55%)

[0356]

[0357] • Carbon black: #200MP (manufactured by Shin-Nippon Chemical Carbon Black Co., Ltd.)

[0358] • Calcium carbonate 1: Super S (manufactured by Maruo Calcium Co., Ltd.)

[0359] • Calcium carbonate 2: KALFAIN 200 (manufactured by Maruo Calcium Co., Ltd.)

[0360] Plasticizer 1: Diisononyl phthalate (manufactured by J-Plus)

[0361] Plasticizer 2: Shellsol™ (manufactured by Nippon Chemical Technology Co., Ltd.)

[0362] Catalyst 1: Bismorpholino diethyl ether (manufactured by San-Apro)

[0363] Catalyst 2: Tin-based catalyst NEOSTANN U-303 (manufactured by Nitto Kasei Corporation)

[0364] [Manufacturing Examples 7 and 8] Preparation of Curing Agents (E2-1) and (E2-2)

[0365] The components in Table 2 below were mixed using a stirring device according to the composition (parts by mass) shown in the table to prepare curing agents (E2-1) to (E2-2) of the two-component curing adhesive.

[0366] [Table 2]

[0367]

[0368] The details of each component in Table 2 above are as follows.

[0369] (Details of curing agent components)

[0370] Compound 5: Trifunctional polypropylene polyol (exenol 1030, manufactured by Asahi Glass Co., Ltd.)

[0371] Compound 6: Polybutadiene glycol (Poly bd R-45HT, manufactured by Idemitsu Kosan Co., Ltd., hydroxyl value: 0.8 mol / kg)

[0372] Compound 7: Terpineol (manufactured by Yasuhara Chemical Co., Ltd.) (Biomass-derived compound: Biomass ratio (ASTM D6866 Method B): 95% or higher)

[0373] Compound 8: 3-glycidoxypropyltrimethoxysilane Sila-Ace S-510 (manufactured by Chiso Corporation)

[0374] Compound 9: X-12-972F (aminosilane oligomer) (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0375] • Calcium carbonate 2: KALFAIN 200 (manufactured by Maruo Calcium Co., Ltd.)

[0376] Catalyst 1: Bismorpholino diethyl ether (manufactured by San-Apro)

[0377] Catalyst 3: Amine catalyst TEDA-L33E (manufactured by Tosoh Corporation)

[0378] [Examples 1-3, Comparative Examples 1-3]

[0379] Preparation and surface treatment of test pieces

[0380] The components of propylene polymer (A), propylene homopolymer (B), ethylene / α-olefin copolymer (C), and inorganic filler (D) were mixed according to the types and proportions shown in Table 3, and the mixture was extruded using a twin-screw extruder (manufactured by Nippon Steel Corporation). The polypropylene resin composition was obtained by extrusion at a barrel temperature of 180℃, a screw speed of 750 rpm, and an extrusion rate of 60 kg / h. The melt flow rate (230℃, 2.16 kg load) of each polypropylene resin composition is shown in Table 3.

[0381] The obtained polypropylene resin compositions were injection molded using a mold cavity with a length of 350 mm, a width of 100 mm, and a thickness of 3 mm at a resin temperature of 210 °C and a mold temperature of 40 °C to obtain a flat plate. The flat plate was then cut into a shape of 100 mm × 50 mm × 3 mm to obtain a test piece (flat plate) of the laminated structure system for use as a molded body.

[0382] In addition, test pieces of the above-described shape were obtained by injection molding and cutting at the same resin and mold temperatures. Using the obtained test pieces, the flexural modulus, IZOD impact strength, and coefficient of linear expansion were measured according to the above testing methods. The results are shown in Table 3.

[0383] Furthermore, the obtained flat plate was cut into a shape of 100mm × 25mm × 3mm to obtain a test piece. The surface of the obtained test piece was then subjected to surface treatment (flame treatment). The surface treatment was performed using a flame treatment device (FTS201 manufactured by Arcogas). The flame treatment device can adjust the flow rate of combustion gases and air.

[0384] As a surface treatment, the air flow rate was fixed at 100 L / min, the combustion gas (propane gas) flow rate was adjusted to 3.7 L / min, the distance between the plate and the flame nozzle was set to 40 mm, and the processing speed was set to 800 mm / sec, resulting in a surface with a free energy of 42 dyn / cm (mN / m) (surface treatment state: low-level treatment). Similarly, a surface with a free energy of 52 dyn / cm (mN / m) at a distance of 30 mm and a speed of 800 mm / sec (surface treatment state: medium-level treatment) and a surface with a free energy of 64 dyn / cm (mN / m) at a distance of 10 mm and a speed of 800 mm / sec (surface treatment state: high-level treatment) were also prepared.

[0385] Preparation of adhesives

[0386] Using the base agent and curing agent of the types shown in Table 3, mix 100g of base agent and 10g of curing agent just before applying the adhesive to obtain the adhesive.

[0387] It should be noted that adhesives (E-1) and (E-3) are polyurethane-based adhesives. After curing, the adhesive layer obtained using these adhesives forms a resin-cured layer containing a curable resin with urethane bonds. In contrast, (E-2) is a non-polyurethane-based adhesive. After curing, the adhesive layer obtained using these adhesives forms a resin-cured layer containing a curable resin with non-urethane bonds.

[0388] Preparation and evaluation of laminated structures

[0389] On each test piece that has undergone surface treatment as described above, an adhesive layer with a bonding area of ​​25 mm (width) × 10 mm (length) × 5 mm is formed by the adhesive obtained above. Glass (7.5 × 25 × 5 mm thick) is selected on the object-side component with the help of the adhesive layer and cured at room temperature to obtain a test piece of a laminated structure consisting of a polypropylene resin composition mold, a resin cured layer obtained by the adhesive, and a glass laminate.

[0390] After curing at room temperature for 3 days, the resin substrate sides of the obtained laminated structure test pieces were subjected to the same surface treatment as described above. A 1mm thick cationic electroplated steel sheet was then bonded using an adhesive (WS-242 manufactured by Sika Hamatite). After further curing at room temperature for 3 days, a tensile testing machine was used according to JIS K6850:1999. Figure 1 The glass was fixed as shown, and a hot shear strength test was conducted at 90°C (tensile speed 50 mm / min). The results are shown in Table 3.

[0391] [Table 3]

[0392]

[0393] As shown in Table 3, the laminated structures of Examples 1 to 3, which have a molded body made of a polypropylene resin composition containing a high melting point of ethylene / α-olefin copolymer with a melting point peak of 110°C or higher, and a resin-cured layer containing a curable resin (cured adhesive) with urethane bonds, not only have good mechanical properties, but also form a strong bond between the layers even in laminated structures without the aid of a primer (no primer), and have high adhesive strength even at high temperature conditions such as 90°C.

[0394] Industrial availability

[0395] The laminated structure of the present invention is well applicable to automotive interior components such as door trim strips, dashboards, roofs, consoles, pillars, and glove boxes; automotive exterior components such as bumpers, side protection devices, spoilers, side protection strips, mudguards, door panels, and rear doors; and industrial components such as household appliance parts and building materials.

Claims

1. A layered structure, characterized in that, A resin-cured layer (ii) comprising a curable resin (E) having urethane bonds is directly laminated onto a molded body (i) made of a polypropylene resin composition. The polypropylene resin composition contains 5-22 parts by mass of propylene polymer (A) with a melt flow rate of 50-150 g / 10 min and a decane soluble component content of 6-15% by mass, measured at 230℃ and 2.16 kg load; 20-30 parts by mass of propylene homopolymer (B) with a melt flow rate of 10-500 g / 10 min measured at 230℃ and 2.16 kg load; The density of the random copolymer of ethylene and α-olefins with 4 to 8 carbon atoms is 0.850 to 0.880 g / cm³. 3 23-30 parts by mass of an ethylene / α-olefin copolymer (C) with a melt flow rate of 0.5-30 g / 10 min measured at 230℃ and a load of 2.16 kg, and a peak melting point above 110℃; and Inorganic filler (D) 30-40 parts by weight, The total amount of components (A) to (D) is 100 parts by mass.

2. The laminated structure as described in claim 1, characterized in that, In the primerless adhesion test, the thermal shear strength at 90°C exceeded 1.5 MPa.

3. The laminated structure as described in claim 1, characterized in that, The propylene polymer (A) is a block copolymer of propylene and ethylene, and the limiting viscosity [η] of the decane-soluble component of the block copolymer is 2 to 9 dl / g.

4. The laminated structure as described in claim 1, characterized in that, The inorganic filler (D) is talc, and the aspect ratio of the talc is greater than 3 and less than 15.

5. The laminated structure as described in claim 1, characterized in that, The resin-cured layer containing the curable resin (E) having urethane bonds is a layer formed after curing of a polyurethane-based adhesive containing a polyether backbone and an aliphatic isocyanate derivative.

6. The laminated structure as described in claim 1, characterized in that, The molded body (i) is an injection molded body or a compression molded body.

7. The laminated structure as described in claim 1, characterized in that, The laminated structure is used for automotive exterior parts.

8. The laminated structure as described in claim 1, characterized in that, In the polypropylene resin composition, 5 to 13 parts by mass of the propylene polymer (A) are contained relative to 100 parts by mass of the total amount of components (A) to (D).

9. An automotive exterior trim component, characterized in that, The stacked structure comprising any one of claims 1 to 8.

10. A method for manufacturing a laminated structure, characterized in that, The process includes a step of manufacturing a molded body (i) by molding a polypropylene resin composition through injection molding or compression molding, and a step of contacting or coating a curable resin (E) having urethane bonds or its raw material onto the molded body (i) and then curing it to form a resin cured layer (ii), wherein, The polypropylene resin composition contains 5-22 parts by mass of propylene polymer (A) with a melt flow rate of 50-150 g / 10 min and a decane soluble component content of 6-15% by mass, measured at 230℃ and 2.16 kg load; 20-30 parts by mass of propylene homopolymer (B) with a melt flow rate of 10-500 g / 10 min measured at 230℃ and 2.16 kg load; The density of the random copolymer of ethylene and α-olefins with 4 to 8 carbon atoms is 0.850 to 0.880 g / cm³. 3 23-30 parts by mass of an ethylene / α-olefin copolymer (C) with a melt flow rate of 0.5-30 g / 10 min measured at 230℃ and a load of 2.16 kg, and a peak melting point above 110℃; and Inorganic filler (D) 30-40 parts by weight, The total amount of components (A) to (D) is 100 parts by mass.

11. The method for manufacturing a laminated structure as described in claim 10, characterized in that, In the polypropylene resin composition, 5 to 13 parts by mass of the propylene polymer (A) are contained relative to 100 parts by mass of the total amount of components (A) to (D).

Images