JP2016089060A - Polyolefin resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin resin composition having sufficient adhesiveness to any substrate of polar and non-polar materials even when adhered at low temperature in consideration for designability, especially excellent heat resistance even at high temperature about 100°C in manufacturing for automobile interior, housing interior and consumer electronics body.SOLUTION: There is provided a polyolefin resin composition containing at least a modified polyolefin resin composition graft modified by using a monomer component containing an ethylenic double bond and an epoxy group in same molecule as one component and having storage elastic modulus at 100°C G'(100) of 1.0 MPa or more and storage elastic modulus at 130°C G'(130) of less than 0.15 MPa for solving problems.SELECTED DRAWING: None

Description

  The present invention relates to a polyolefin resin composition.

  Thermoplastic resins such as olefin polymers, thermoplastic elastomers, vinyl polymers, and engineering plastics are excellent in physical properties, moldability, surface properties, etc., and are therefore used in fields such as automobiles, home appliances, electronics, architecture, and miscellaneous goods. Is used a lot. In order to make these molded products into products having a desired shape, or to improve performance and diversify functions, a plurality of molded products are bonded and combined. In particular, it is widely used to laminate a surface material, weather resistance, and decorative sheet with excellent surface properties, weather resistance, and decorativeness on the outer layer of a resin molded product with rich mechanical properties. Is widely used in automobile interiors, house interiors, and housings for home appliances. However, such a laminated body generally has poor adhesion between the layers, and there are many examples in which an adhesive layer is provided and laminated. As adhesives, solvent-type adhesives and hot-melt type adhesives are used. However, solvent-type adhesives tend to have uneven coating, and the use of organic solvents has the disadvantage of adverse environmental and hygienic effects. Have Therefore, there is a demand for a hot melt adhesive that is simple and excellent in adhesive strength.

  The resin composition used as such a hot melt adhesive includes one or more base polymers selected from the group consisting of ethylene copolymers, styrene block copolymers, and olefin (co) polymers. A tackifier resin, a compound containing a crystalline polar group-containing compound (Patent Document 1), an amorphous poly α-olefin, a tackifier resin and a polypropylene-based wax (Patent Document 2), styrene-ethylenepropylene- A styrene block copolymer rubber or a styrene-butadiene-styrene block copolymer rubber added with a liquid plasticizer such as a tackifier resin component and process oil (Patent Documents 3 and 4), a modified polyolefin and a tackifier Blended (Patent Document 5), styrenic block copolymer and acid (Patent Document 6), a mixture of acid-modified polypropylene and an acid-modified styrene block copolymer (Patent Document 7), a styrene block copolymer and a tackifier, ethylene The thing (patent documents 8, 9, 10) etc. which mix | blend a polymer based are proposed.

  However, when such a resin composition is applied to an automobile interior material or the like particularly required to have a heat resistance of about 100 ° C., there may be a problem that the skin floats and peels off in a high temperature atmosphere. By applying the pressure at a relatively high heating temperature during bonding, it may be possible to improve the adhesion to the resin substrate, but the use of the laminate requires automotive design, house interior, In the case of a home appliance housing or the like, there arises a problem that the molded member is damaged and the design is impaired. For these reasons, there is a demand for a resin composition that can achieve both low-temperature adhesiveness that does not impair the design and practical heat resistance.

Japanese Patent Laid-Open No. 10-168417 JP 2004-284575 A Japanese Patent Laid-Open No. 3-160083 JP-A-8-60121 JP-A-6-293845 Japanese Patent Laid-Open No. 2007-169531 JP 2008-163121 A Japanese Patent Laid-Open No. 11-131037 JP-A-10-279774 Japanese Patent Laid-Open No. 10-265751

  The object of the present invention is to manufacture for automobile interiors, house interiors, and home appliance housings, even when they are bonded at a low temperature in consideration of design properties, and for both polar and non-polar materials. An object of the present invention is to provide a polyolefin resin composition having sufficient adhesiveness and having excellent heat resistance particularly at a high temperature of about 100 ° C.

  As a result of intensive studies, the present inventors have found that a polyolefin-based resin composition having a specific elastic modulus solves the above-mentioned problem of achieving both low-temperature adhesiveness and heat resistance, and completes the following invention. It came to.

That is, this invention consists of the following structures.
(1) A polyolefin resin composition comprising a modified polyolefin resin graft-modified with a monomer having an ethylenic double bond and an epoxy group in the same molecule, at a frequency of 10 Hz at a shear mode A polyolefin system characterized by having a measured storage modulus G ′ (100) of 1.0 MPa or more, a frequency of 10 Hz at 130 ° C., and a storage modulus G ′ (130) measured in a shear mode of less than 0.15 MPa. Resin composition.
(2) A polyolefin-based resin composition in which the modified polyolefin-based resin (A) is graft-modified using a monomer having an ethylenic double bond and an epoxy group in the same molecule and an aromatic vinyl monomer object.
(3) The polyolefin resin composition according to (1) or (2), wherein the monomer having an ethylenic double bond and an epoxy group in the same molecule is glycidyl methacrylate.
(4) The polyolefin resin composition according to (2), wherein the aromatic vinyl monomer is styrene.
(5) A hot-melt adhesive resin film comprising the polyolefin resin composition according to any one of (1) to (4).
(6) A laminated molded article, wherein the hot melt adhesive film according to (5) is laminated in the order of a skin material layer, a layer comprising a hot melt adhesive film, and a base material layer.
(7) The laminated molded product according to (6), wherein the skin material layer is made of a thermoplastic resin or a thermosetting resin.
(8) The laminated molded body according to (6), wherein the base material layer is a base material selected from the group consisting of a thermoplastic resin, a thermosetting resin, and a metal material.

  The polyolefin resin composition of the present invention can ensure excellent adhesion to any nonpolar resin such as polyolefin resin and polar resin such as polyester resin, which has been difficult in the past. In particular, since it can be bonded at low temperatures, it can be used for stacking complex three-dimensional molded products and skin materials using vacuum forming, vacuum pressure forming, pressure forming, hot stamping, etc. It can be suitably used for interior decoration, house interior, and molded product decoration of home appliance housings.

Details of the present invention will be described below.
<Modified polyolefin resin composition>
The modified polyolefin resin composition of the present invention is a modified polyolefin resin composition containing the modified polyolefin resin (A).

<Modified polyolefin resin (A)>
The modified polyolefin resin (A) of the present invention is obtained by graft-modifying a polyolefin resin using a monomer having an ethylenic double bond and an epoxy group in the same molecule.

<Polyolefin resin>
Examples of polyolefin resins include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymers or block copolymers in any ratio of propylene and ethylene and / or 1-butene, and any of ethylene and propylene. Cyclic polyolefins such as ethylene-propylene-diene terpolymers having a diene content of 50% by weight or less, polymethylpentene, a copolymer of cyclopentadiene and ethylene and / or propylene, and 50% by weight of ethylene or propylene %, A random copolymer with a vinyl compound or the like, or a block copolymer.

  Of these, propylene homopolymers and olefin elastomers are preferred. Specifically, homopolypropylene, ethylene / propylene copolymer, random polypropylene, block polypropylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methylpentene-1 copolymer , Ethylene / 1-octene copolymer, propylene / ethylene copolymer, propylene / ethylene / 1-ten / propylene copolymer, 4-methylpentene-1 / propylene copolymer, 4-methylpentene-1 / 1 -Butene copolymer, 4-methylpentene-1, propylene / 1-butene copolymer, propylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid copolymer, ethylene / methacrylic acid Examples thereof include an acid methyl copolymer. A propylene homopolymer and an ethylene / propylene copolymer are particularly preferable from the viewpoint of easy procurement of raw materials, easy generation of radicals on the polyolefin, and heat resistance.

  The propylene weight ratio in the ethylene / propylene copolymer is preferably 80 to 97% by weight and more preferably 85 to 95% by weight from the viewpoints of adhesiveness and heat resistance, low temperature adhesiveness, and film appearance.

  The melting point of the polyolefin resin is preferably 80 ° C. or higher and 140 ° C. or lower from the viewpoints of low-temperature adhesiveness and heat resistance. Here, the melting point is the melting obtained when the temperature is raised again at 10 ° C./min after passing through the temperature lowering process after raising the temperature at 10 ° C./min in a nitrogen atmosphere with a differential scanning calorimeter. The temperature defined as the peak top of the peak observed from the endothermic curve is defined as the melting point.

  The reason why the range of the melting point is preferable is, for example, a part that is required to maintain excellent adhesiveness even at a high temperature of 100 ° C. or higher in an automobile interior application in which a decorative sheet is laminated on the surface. In addition, the product for the application is bonded and laminated on the base material by, for example, vacuum molding or vacuum / pressure forming. At this time, the adhesive layer is 100 ° C. to 140 ° C. in order not to damage the skin material. Often molded in the temperature range of ° C. Under such circumstances, by using the raw material polyolefin resin having the melting point, it becomes possible to achieve both the adhesiveness and the heat resistance. The raw material polyolefin-based resin (which may contain various additive materials) may be in the form of particles or pellets, and the size and shape are not particularly limited.

<Monomer having an ethylenic double bond and an epoxy group in the same molecule>
Monomers having an ethylenic double bond and an epoxy group in the same molecule include glycidyl (meth) acrylate, diglycidyl maleate, diglycidyl itaconate, diglycidyl allyl succinate, glycidyl p-styrenecarboxylate, allyl glycidyl ether, Examples include methallyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, vinylcyclohexene monoxide, and the like. it can. Among these, glycidyl (meth) acrylate is more preferable, and glycidyl methacrylate is particularly preferable from the viewpoints of adhesiveness and heat resistance.

  The amount of the monomer having an ethylenic double bond and an epoxy group in the same molecule is preferably 0.1 to 10 parts by weight, and 0.1 to 7 parts by weight with respect to 100 parts by weight of the polyolefin resin. More preferred is 0.1 to 5 parts by weight. If it is less than 0.1 part by weight, the adhesion may not be sufficient. On the other hand, when the amount is more than 10 parts by weight, a large amount of residual monomer is generated, which may adversely affect physical properties.

<Other monomers>
When the polyolefin resin is graft-modified, other monomers may be used in combination. Other monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, conjugated diene compounds, vinyl ester compounds, vinyl chloride, oxazoline group-containing unsaturated monomers. Etc. Among these, when grafting onto a molecular chain-breaking polyolefin such as polypropylene, the molecular chain breakage is suppressed, and a single amount containing an ethylenic double bond and an epoxy group in the same molecule while maintaining a high molecular weight. An aromatic vinyl monomer is preferable from the viewpoint that the body can be introduced at a high ratio.

<Aromatic vinyl monomer>
Examples of aromatic vinyl monomers include styrene; methyl styrene such as o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, β-methyl styrene, dimethyl styrene, and trimethyl styrene; o-chlorostyrene. , M-chlorostyrene, p-chlorostyrene, α-chlorostyrene, β-chlorostyrene, dichlorostyrene, trichlorostyrene and the like; o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, tri Bromostyrene such as bromostyrene; fluorostyrene such as o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, trifluorostyrene; o-nitrostyrene, m-nitrostyrene, p-nitrostyrene, dinit Nitrostyrenes such as styrene and trinitrostyrene; vinylphenols such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene; o-divinylbenzene, m-divinylbenzene, p-divinylbenzene 1 type, or 2 or more types, such as divinyl benzene, such as; diisopropenyl benzene, such as o-diisopropenyl benzene, m-diisopropenyl benzene, p-diisopropenyl benzene; Of these, styrene; methyl styrene such as α-methyl styrene and p-methyl styrene; divinylbenzene monomer or divinylbenzene isomer mixture is preferable in that it is inexpensive. Of these, styrene is particularly preferable.

  The amount of the aromatic vinyl monomer used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the polyolefin resin. More preferably, it is 1 to 5 parts by weight. If the amount used is too small, the graft ratio of the monomer containing an ethylenic double bond and an epoxy group in the same molecule tends to be poor. On the other hand, when the amount used exceeds 10 parts by weight, the graft efficiency of the monomer containing an ethylenic double bond and an epoxy group in the same molecule may reach the saturation range.

<Radical polymerization initiator>
When modifying a polyolefin resin, the modified polyolefin resin can be obtained by heating and reacting in the presence of a radical polymerization initiator.

  Examples of radical polymerization initiators include organic peroxides and azo compounds. Illustrative examples include ketone peroxides such as methyl ethyl ketone peroxide and methyl acetoacetate peroxide; 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t- Peroxyketals such as butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; permethane hydroperoxide, 1 , 1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, etc .; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl Peroxy) hexane, α, α′-bis ( -Butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, dialkyl such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 Peroxides; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as di (3-methyl-3-methoxybutyl) peroxydicarbonate and di-2-methoxybutylperoxydicarbonate; t-butylperoxy Octate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyisopropyl carbonate, 2,5-dimethyl -2,5-di (benzoylperoxy) hexa , T- butyl peroxy acetate, t- butyl peroxybenzoate, one or more organic peroxides such as peroxy esters such as di -t- butyl peroxy isophthalate and the like.

  The addition amount of the radical polymerization initiator is preferably in the range of 0.01 to 10 parts by weight and more preferably in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin. preferable. If it is less than 0.01 part by weight, the modification does not proceed sufficiently, and if it exceeds 10 parts by weight, fluidity and mechanical properties may be lowered.

<Production method of (A)>
The polymerization reaction for graft modification is not particularly limited, and solution polymerization, impregnation polymerization, melt polymerization and the like can be used. In particular, melt polymerization is simple and preferable.

<Melt polymerization of (A)>
Melt polymerization is a method in which a polyolefin resin and a radical polymerization initiator, an ethylenic double bond, and a monomer having an epoxy group in the same molecule are melt-kneaded.

  The temperature at the time of melt polymerization is preferably 60 to 300 ° C. from the viewpoint that the raw polyolefin resin is sufficiently melted and is not thermally decomposed. The melt kneading time is usually 30 seconds to 60 minutes.

  As an apparatus for melt polymerization, an extruder, a Banbury mixer, a mill, a kneader, a heating roll, and the like can be used. From the viewpoint of productivity, a method using a single-screw or twin-screw extruder is preferred. Moreover, in order to mix each material sufficiently uniformly, melt-kneading may be repeated a plurality of times.

  For modified polyolefin resins, stabilizers such as antioxidants, metal deactivators, dehydrating agents, antacid adsorbents, crosslinking agents, chain transfer agents, nucleating agents, lubricants, plasticizers, fillers as necessary Additives such as reinforcing materials, pigments, dyes, and flame retardants may be added within a range that does not impair the effects of the present invention. When these stabilizers and additives are used, they may be added to the raw polyolefin resin in advance, or may be added when the raw polyolefin resin is graft-modified, After the modified polyolefin resin is produced, it may be added to the modified polyolefin resin by an appropriate method.

<Thermoplastic resin (B)>
The modified polyolefin resin composition of the present invention may contain a thermoplastic resin (B). Examples of the thermoplastic resin (B) include propylene homopolymer, high density polyethylene, low density polyethylene, linear low density polyethylene, poly-1-butene, polyisobutylene, polypentene-1, polymethylpentene-1, and other poly-α -Olefin; Ethylene such as an ethylene / propylene copolymer having a propylene content of 50% by weight or more or an α-olefin / α-olefin copolymer; Ethylene / propylene / 5-ethylidene having a propylene content of 50% by weight or more Ethylene such as 2-norbornene copolymer or α-olefin / α-olefin / diene monomer copolymer; olefin elastomer such as styrene-isobutylene-styrene and styrene-ethylene / propylene-styrene; polybutadiene, polyisoprene, etc. A polydiene copolymer of Vinyl monomer / diene monomer random copolymer such as styrene / butadiene random copolymer, styrene / isoprene random copolymer; styrene / butadiene / styrene block copolymer, styrene / isoprene / styrene block copolymer Hydrogenation (vinyl) such as vinyl monomer / diene monomer / vinyl monomer block copolymer; hydrogenation (styrene / butadiene random copolymer), hydrogenation (styrene / isoprene random copolymer), etc. Monomer / diene monomer random copolymer); Hydrogenation (vinyl monomer) such as hydrogenation (styrene / butadiene / styrene block copolymer), hydrogenation (styrene / isoprene / styrene block copolymer) / Diene monomer / vinyl monomer block copolymer); acrylonitrile / butadiene / styrene Copolymer, vinyl methacrylate / diene monomer / vinyl monomer graft copolymer such as methyl methacrylate / butadiene / styrene graft copolymer; polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyacetic acid Vinyl polymers such as vinyl, polyethyl acrylate, polybutyl butyl, polymethyl methacrylate, and polystyrene; vinyl chloride / acrylonitrile copolymers, vinyl chloride / vinyl acetate copolymers, acrylonitrile / styrene copolymers, methacrylic acid Examples thereof include vinyl copolymers such as methyl / styrene copolymers, and these can be used alone or in admixture of two or more.

  The blending amount of the thermoplastic resin to be mixed with the modified polyolefin resin is preferably 10 to 100 parts by weight, more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the modified polyolefin resin from the viewpoint of adhesiveness when used as an adhesive film. 100 parts by weight is preferred.

<Tackifier (C)>
The modified polyolefin resin composition of the present invention may contain a tackifier (C). Examples of tackifiers include rosin resins (gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin ester, etc.), terpene phenol resin, terpene resin (α-pinene, polymers such as β-pinene and limonene), aromatic hydrocarbon-modified terpene resins, petroleum resins (aliphatic, alicyclic, aromatic, etc.), coumarone / indene resins, styrene resins, phenolic resins (alkylphenols) Phenol xylene formaldehyde, rosin-modified phenol resin, etc.), xylene resin, and the like. These can be used alone or in combination of two or more. Among these, from the viewpoint of thermal stability, rosin resin, terpene phenol resin, terpene resin, aromatic hydrocarbon modified terpene resin, petroleum resin, hydrogenated petroleum resin are preferable, and from the viewpoint of adhesiveness, rosin resin, Terpene phenol resins and terpene resins are particularly preferred.

  Although it does not restrict | limit especially as a compounding quantity of a tackifier, It is preferable that it is 5-60 weight part with respect to 100 weight part of modified polyolefin resin total.

<Combination agent>
The modified polyolefin resin composition of the present invention comprises a stabilizer such as an antioxidant, a metal deactivator, a dehydrating agent, an antacid adsorbent, a crosslinking agent, a chain transfer agent, a nucleating agent, a lubricant, a plasticizer, and a filler. Additives such as reinforcing materials, pigments, dyes, and flame retardants may be added.
The thermoplastic resin (B), tackifier (C), and compounding agent may be added when modifying the polyolefin resin, or may be blended in the modified polyolefin resin composition.

<Storage elastic modulus G ′ of modified polyolefin resin composition>
The storage elastic modulus G ′ (100 ° C.) at 100 ° C. of the modified polyolefin resin composition of the present invention is preferably 1.0 MPa or more, more preferably 2.0 MPa or more, further preferably, from the viewpoint of heat resistance. It is 3.0 MPa or more.

  Further, the storage elastic modulus G ′ (130 ° C.) at 130 ° C. of the modified polyolefin resin composition of the present invention is preferably less than 0.15 MPa, more preferably from the viewpoint of wettability to a substrate and adhesiveness. Is 0.04 or more and less than 0.12, more preferably 0.05 or more and less than 0.12 MPa.

  The storage elastic modulus G ′ is measured with a dynamic viscoelasticity measuring device under conditions of a shear mode, a measurement frequency of 10 Hz, and a temperature increase rate of 4 ° C./min.

<About sheet or film-like molded product>
The modified polyolefin resin composition can be made into a sheet or film-like molded article having thermal adhesiveness. The heat adhesive property here is a property of being melted by heat and bonded to a molded body. From the viewpoint of thermal adhesiveness, the thickness of the sheet or film-shaped molded body is preferably 3 μm to 3 mm, and more preferably 10 μm to 1 mm.

  Examples of the method for producing the film-shaped molded body include an extrusion molding machine having a T-shaped die at the tip, an injection molding machine, a calendar molding machine, an inflation molding machine, a roll molding machine, and a hot press molding machine.

  You may laminate | stack the said film-form molded object with another thermoplastic resin film. Examples of the thermoplastic resin film used at this time include films made of polyethylene resins, polypropylene resins, polyamide resins, and polyester resins. Moreover, these thermoplastic resin films can be suitably used by either a stretched film or an unstretched film. Examples of the thickness of the thermoplastic resin film include 3 μm to 3 mm, and preferably 10 μm to 1 mm.

  The method for laminating the film-shaped molded product and the other thermoplastic resin film is not particularly limited. For example, a modified polyolefin resin composition is placed in an extruder and a T-type die provided at the tip of the extruder. A method of laminating a thermoplastic resin film to a molten resin molded into a film shape, a method of thermocompression bonding a film-like molded body having thermal adhesion and a thermoplastic resin film with a roll molding machine, a modified polyolefin resin composition The method of laminating | stacking by melt | dissolving a thing and another thermoplastic resin together, and coextruding is mentioned.

<Laminated molding>
If the modified polyolefin resin composition of the present invention is used, a laminate A will be obtained by adhering various skin material layers (decorative sheets) and a film-shaped molded article made of a polyolefin resin composition at a relatively low processing temperature. It is possible. Examples of the material for the skin material layer of the present invention include polyolefin resins such as polypropylene and polyethylene, polystyrene, styrene-butadiene block copolymer (SBS resin), styrene-acrylonitrile copolymer (AS resin), and acrylonitrile-ethylene / propylene. -Styrene resins such as styrene copolymers (AES resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), polyamide resins such as polycarbonate resins, (meth) acrylic resins, polyester resins, nylon and polyurethane Synthetic polymer materials such as resins, phenol resins, and epoxy resins can be used. Of the materials described above, two or more different materials may be mixed and combined. The skin material layer used here is previously formed into a film, a sheet, a foam, various nonwoven fabrics, and a woven fabric.

  The laminated body A and the base material layer described above can be bonded to form a laminated molded body. In that case, strong bonding is possible at a relatively low temperature of about 130 ° C., and it can be manufactured without damaging the texture, feel, etc. of the decorative sheet and the molded article, and the molded article using the decorative sheet as a skin material. It is suitable for decorative use. Base materials used here include ABS, PC / ABS, polyolefin, glass fiber reinforced polyolefin, injection molded products of various polymer materials such as glass fiber reinforced nylon, wood chips, wood powder, etc. Examples include wood moldings and wood boards hardened with resin by hot press molding, metal materials such as gold, silver, copper, iron, tin, lead, and aluminum. In addition, strong adhesion is possible without surface treatment of the adhesive surface on the substrate side, but surface treatment such as surface modification by plasma or laser, surface oxidation, etching, etc. is performed as necessary. May be.

  In bonding the skin material layer and the base material layer using the polyolefin resin composition of the present invention, various molding methods such as thermal lamination, vacuum molding, vacuum / pressure air molding, hot press, hot roll, hot stamp molding are used. Can be adopted. Among these, vacuum forming, vacuum pressure forming, and hot stamping are preferable in that they can be applied to the adhesion of a skin material layer and a base material having a rounded shape. A base material having a round shape refers to a molded product having a plane arc-shaped surface as a surface to be bonded to a skin material among molded products of the materials exemplified above, and is a shape skeleton of an automobile interior or home appliance housing. It is the molded object which makes. As a method for producing a laminated molded body composed of a skin material layer and a base material layer, for example, a film-shaped molded body layer composed of a skin material layer and a polyolefin resin composition is heated and laminated, and this is applied to each molding. And can be laminated along the shape of the molded body. A hot press or a hot roll is not preferable because it may impair the arc shape of such a molded body.

<Application>
The laminated molded body thus obtained can be used for the following applications requiring adhesion at high temperatures. For example, it can be suitably used as interior materials for automobiles and the like (ceiling materials for automobile interiors, door members for automobile interiors, dashboard members for automobile interiors, instrument panels, etc.).

  Hereinafter, the present invention will be described in more detail by way of specific examples and comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

(Measurement of storage modulus G ')
A dynamic viscoelasticity measuring apparatus (IT measurement) using a prismatic test piece of 6 mm × 5 mm × 2 mm under conditions of a shear mode, a measurement frequency of 10 Hz, a heating rate of 4 ° C./min, and a measurement temperature range of −70 to 150 ° C. The measurement was carried out using DVA-200 manufactured by Control Co., Ltd., and the storage elastic modulus G ′ at 100 ° C. and 130 ° C. was recorded.

(Adhesion evaluation)
Using a heating oven set at 220 ° C., an adhesive film made of a polyolefin resin composition was adhered to a corona-treated PET resin film having a thickness of 50 μm (E5000 manufactured by Toyobo), and then a vacuum laminator (manufactured by NPC Corporation). , Module Laminator LM-50x50-S), and the surface of the adhesive film opposite to the PET side was bonded to the PP substrate. The vacuum laminator conditions were such that the interlayer temperature between the adhesive film layer and the PP base material layer was 130 ° C.

  The obtained laminate was cut to a width of 25 mm, and in an atmosphere of 100 ° C., the PET resin film was peeled in the direction of 180 degrees with respect to the laminate at a tensile rate of 100 mm / min, and the measurement of the adhesive strength (N / 25 mm) The peeled state was observed. The peeled state was expressed by adhesive layer destruction (CF) and interface peeling (AF). Interfacial peeling with the PP substrate was AF (PP), and interfacial peeling with the PET film was AF (PET). The adhesive evaluation shows that the higher the adhesive strength, the better the adhesiveness. CF indicates the breaking strength of the adhesive layer resin at 100 ° C., and indicates that the adhesive strength with the substrate interface is higher than the strength. AF indicates the adhesive strength between the substrate and the adhesive layer interface at 100 ° C.

Example 1
Ethylene / propylene copolymer (Dow Chemical Japan Co., Ltd .: Versify 3000 melting point: 120 ° C.) 100 parts, 1,3-di (t-butylperoxyisopropyl) benzene (1 minute half-life 175 ° C.) 0.5 The part was supplied to a twin-screw extruder (46 mmφ, L / D = 60, manufactured by Kobe Steel, Ltd., product name HYPERKTX46) set at a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm, and then melt-kneaded, and then the cylinder In the middle, 3 parts of glycidyl methacrylate and 3 parts of styrene were added and melt-kneaded to obtain a modified ethylene-propylene copolymer. The graft amount of glycidyl methacrylate in the obtained modified ethylene / propylene copolymer was 0.8 wt%.

  The obtained modified polyolefin resin composition was subjected to storage elastic modulus measurement. The results are shown in Table 1. Further, this modified polyolefin resin composition was extruded at 180 ° C. using a 40 mmφ single screw extruder and a 450 mm wide T-die to obtain a hot melt adhesive film having a thickness of 60 μm. The obtained film was subjected to adhesion evaluation, and the results are shown in Table 1.

(Example 2)
50 parts of an ethylene-propylene copolymer (manufactured by Dow Chemical Japan Co., Ltd .: Versify 4200 melting point: 86 ° C.) is melt-kneaded with 50 parts of the modified ethylene-propylene copolymer obtained in Example 1, and a modified polyolefin type A resin composition was obtained. Storage modulus measurement was performed about the obtained polyolefin resin composition. The results are shown in Table 1. Further, this polyolefin resin composition was extruded at 180 ° C. using a 40 mmφ single-screw extruder and a 450 mm wide T-die to obtain a hot melt adhesive film having a thickness of 60 μm. The obtained film was subjected to adhesion evaluation, and the results are shown in Table 1.

(Example 3)
60 parts of ethylene-propylene copolymer (Dow Chemical Japan Co., Ltd .: Versify 3000 melting point: 120 ° C.) and 40 parts of ethylene-propylene copolymer (Dow Chemical Japan Co., Ltd .: Versify 4301 melting point: 140 ° C.) A twin screw extruder in which 0.45 part of 1,3-di (t-butylperoxyisopropyl) benzene (1 minute half-life 175 ° C.) was set to a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm with respect to 100 parts of the mixture ( 46 mmφ, L / D = 60, manufactured by Kobe Steel Co., Ltd., product name HYPERKTX46), melt-kneaded, then melted and kneaded by adding 4 parts of glycidyl methacrylate and 4 parts of styrene from the middle of the cylinder, and modified ethylene -A propylene copolymer was obtained. The graft amount of glycidyl methacrylate in the obtained modified ethylene / propylene copolymer was 1.2 wt%.

  Storage modulus measurement was performed about the obtained polyolefin resin composition. The results are shown in Table 1. Further, this polyolefin resin composition was extruded at 180 ° C. using a 40 mmφ single-screw extruder and a 450 mm wide T-die to obtain a hot melt adhesive film having a thickness of 60 μm. The obtained film was subjected to adhesion evaluation, and the results are shown in Table 1.

Example 4
60 parts of ethylene-propylene copolymer (Dow Chemical Japan Co., Ltd .: Versify 3000 melting point: 120 ° C.) and 40 parts of ethylene / propylene copolymer (Dow Chemical Japan Co., Ltd .: Versify 3401 melting point: 140 ° C.) The procedure was the same as in Example 3 except that 100 parts of the mixture was used, and the results of storage elastic modulus and adhesion evaluation are shown in Table 1.

(Example 5)
60 parts of ethylene-propylene copolymer (Dow Chemical Japan Co., Ltd .: Versify 3000 melting point: 120 ° C.) and 40 parts of ethylene / propylene copolymer (Dow Chemical Japan Co., Ltd .: Versify 3401 melting point: 140 ° C.) A twin screw extruder in which 0.5 part of 1,3-di (t-butylperoxyisopropyl) benzene (half-life of 1 minute 175 ° C.) is set to a cylinder temperature of 200 ° C. and a rotational speed of 150 rpm with respect to 100 parts of the mixture ( 46 mmφ, L / D = 60, manufactured by Kobe Steel Co., Ltd., product name HYPERKTX46), melt-kneaded, then melted and kneaded by adding 3 parts of glycidyl methacrylate and 3 parts of styrene from the middle of the cylinder, and modified ethylene -A propylene copolymer was obtained. The graft amount of glycidyl methacrylate in the obtained modified ethylene-propylene copolymer was 0.8 wt%. Storage modulus measurement was performed about the obtained polyolefin resin composition. The results are shown in Table 1. Further, this polyolefin resin composition was extruded at 180 ° C. using a 40 mmφ single-screw extruder and a 450 mm wide T-die to obtain a hot melt adhesive film having a thickness of 60 μm. The obtained film was subjected to adhesion evaluation, and the results are shown in Table 1.

(Comparative Example 1)
The same procedure as in Example 1 was conducted except that 100 parts of an ethylene-propylene copolymer (manufactured by Dow Chemical Japan Co., Ltd .: Versify 3401 melting point: 140 ° C.), and the results of storage elastic modulus and adhesion evaluation are shown in Table 1. .

(Comparative Example 2)
The same procedure as in Example 1 was performed except that a maleic anhydride-grafted polyolefin resin (QF551, melting point: 140 ° C., manufactured by Mitsui Chemicals, Inc.) was used as the polyolefin resin composition, and the results of storage elastic modulus and adhesion evaluation are shown in Table 1. Indicated.

(Comparative Example 3)
50 parts of ethylene-propylene copolymer (Dow Chemical Japan Co., Ltd .: Versify 3000 melting point: 120 ° C.) and ethylene-propylene copolymer (Dow Chemical Japan Co., Ltd .: Versify 4200 melting point: 86 ° C.) It carried out similarly to Example 2 except not having modified | denatured 100 parts of mixtures, and the result of the storage elastic modulus and adhesive evaluation was shown in Table 1.

  In Examples 1 to 5, the modified polyolefin resin composition is at least one component, the polyolefin resin having a storage elastic modulus at 100 ° C. of 1.0 MPa or more and a storage elastic modulus at 130 ° C. of 0.1 MPa or less. The composition had high peel strength, and in Comparative Examples 1 to 3, the peel strength was low.

Claims (8)

  A polyolefin-based resin composition comprising a modified polyolefin-based resin (A) graft-modified with a monomer having an ethylenic double bond and an epoxy group in the same molecule, and having a frequency of 10 ° C. and a shear mode at 100 ° C. A polyolefin system characterized by having a measured storage modulus G ′ (100) of 1.0 MPa or more, a frequency of 10 Hz at 130 ° C., and a storage modulus G ′ (130) measured in a shear mode of less than 0.15 MPa. Resin composition.   The polyolefin-based resin according to claim 1, wherein the modified polyolefin-based resin (A) is graft-modified using a monomer having an ethylenic double bond and an epoxy group in the same molecule and an aromatic vinyl monomer. Resin composition.   The polyolefin resin composition according to claim 1 or 2, wherein the monomer having an ethylenic double bond and an epoxy group in the same molecule is glycidyl methacrylate.   The polyolefin resin composition according to claim 2, wherein the aromatic vinyl monomer is styrene.   The hot-melt-type adhesive resin film which consists of a polyolefin resin composition as described in any one of Claims 1-4.   A laminated molded article, wherein the hot melt adhesive film according to claim 5 is laminated in the order of a skin material layer, a layer comprising a hot melt adhesive film, and a base material layer.   The laminated molded body according to claim 6, wherein the skin material layer is made of a thermoplastic resin or a thermosetting resin.   The laminate molded body according to claim 6, wherein the base material layer is a base material selected from the group consisting of a thermoplastic resin, a thermosetting resin, and a metal material.