JP2011148156A - Laminated body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method regarding the bonding of polyimide and a dissimilar material for bonding with a simple device, an easy method, free from VOC, with a less heat amount, in a short period of time, and with low pressure, and obtain a laminated body having polyimide and the dissimilar material bonded. <P>SOLUTION: The modified polyolefin resin composition obtained by graft-modification of a polyolefin resin with a monomer containing an ethylenic double bond and a polar group in the same molecule has an excellent adhesiveness with polyimide, and it is found that the modified polyolefin resin composition exerts excellent adhesiveness with respect to polyimide and the dissimilar material, free from VOC, with a less heat amount, in a short period of time, and with low pressure. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a laminate comprising a thermoplastic polyolefin adhesive layer having heat-fusibility and polyimide, and relates to a laminate capable of adhering to dissimilar materials with a small amount of heat, in a short time and at low pressure. An electronics member, an automobile member, a building material, etc. can be used suitably.

Polyimide is widely used for applications such as a base film for a flexible circuit board laminated with a metal foil such as a copper foil because of its excellent insulation and heat resistance.
Under such circumstances, attempts have been made to further improve the long-term reliability required for long-term use of a laminate of a polyimide film and a metal. As this method, the surface of the polyimide film is improved by an electrical plasma treatment to improve the adhesive force (Patent Document 1), the thermoplastic polyimide having heat-fusibility, or the base polyimide and the metal foil are bonded together via an adhesive. (Patent Documents 2 and 3) have been proposed.
The method of performing plasma treatment on the polyimide film surface requires a step of performing plasma treatment before bonding. The method of using thermoplastic polyimide having heat-fusible properties is to apply to the base polyimide as a thermoplastic polyimide solution, so it is necessary to dry at a high temperature of 250 ° C. for 3 hours, the tact time is long, and there is a problem in productivity. In addition, since a solvent is used, it is not preferable from the recent demand for VOC reduction. Further, the method using an adhesive for acrylic polyamide as an adhesive also has a problem in productivity because it needs to be thermocompression-bonded at 180 ° C. under a high pressure of 44 MPa for 1 hour.

JP-A-8-41227 Japanese Patent Laid-Open No. 5-112768 JP 2004-263170 A

The present invention relates to bonding of polyimide and dissimilar materials by providing a method of bonding VOC-free, with a small amount of heat, in a short time, and with low pressure, using a simple apparatus and using a simple device. The object is to obtain a bonded laminate.

As a result of intensive studies in view of the above-described present situation, the present inventors have found that a modified polyolefin resin composition obtained by graft-modifying a polyolefin resin with a monomer containing an ethylenic double bond and a polar group in the same molecule has adhesiveness to polyimide. It has been found that it exhibits excellent adhesion to polyimides and dissimilar materials in a VOC-free manner, with a small amount of heat, for a short time, and at low pressure, and has completed the present invention.

  That is, the present invention is as follows.

  1) (B) A laminate in which an adhesive layer containing (A) a modified polyolefin resin composition is laminated in contact with at least one surface of polyimide.

  2) (B) An adhesive layer containing the modified polyolefin resin composition is laminated on at least one surface of the polyimide, and (C) an adherend is laminated on the surface of the adhesive layer not in contact with the polyimide. Laminated body.

  3) (C) The laminate according to 2), wherein the adherend is a metal material.

  4) The metal material is iron, copper, silver, gold, aluminum, zinc, lead, tin, magnesium, an alloy mainly composed of iron, an alloy mainly composed of copper, an alloy mainly composed of silver, gold A group consisting of an alloy mainly containing aluminum, an alloy mainly containing aluminum, an alloy mainly containing zinc, an alloy mainly containing lead, an alloy mainly containing tin, and an alloy mainly containing magnesium The laminate according to 3), which is at least one selected from the above.

  5) (C) The laminate according to 2), wherein the adherend is a polymer material.

  6) The polymer material is polyolefin, polystyrene, polyester, styrene / acrylonitrile / conjugated diene copolymer, polyamide, polyimide, unsaturated polyester, polyurethane, urea resin, melamine resin, phenol resin, epoxy resin, (meth) acrylic Resin, styrene / acrylonitrile copolymer, styrene / acrylonitrile / conjugated diene copolymer, polyolefin-based thermoplastic elastomer, polystyrene-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, and polyurethane-based thermoplastic elastomer and The laminate according to 5), which is at least one selected from the group consisting of these foamed molded products.

  7) (A) Modified polyolefin resin is a polyolefin obtained by graft-modifying (a-1) polyolefin resin with a monomer containing an ethylenic double bond and a polar group in the same molecule, 1) to 6) The laminated body in any one of.

  8) At least one monomer characterized in that the polar group of the monomer containing the ethylenic double bond and the polar group in the same molecule is a carboxylic acid, an anhydride thereof, or a derivative thereof. The laminated body as described in 7).

  9) The monomer according to 8), wherein the monomer containing the ethylenic double bond and the polar group in the same molecule is at least one selected from (meth) acrylic acid, maleic anhydride, and glycidyl (meth) acrylate. Laminated body.

  10) (A) A modified polyolefin resin is a polyolefin graft-modified with an aromatic vinyl monomer or a conjugated diene monomer in addition to a compound containing an ethylenic double bond and a polar group in the same molecule. The laminated body in any one of 7) -9).

  11) (a-1) The laminate according to any one of 7) to 10), wherein the polyolefin resin is a majority of ethylene units or propylene units.

  12) The laminate according to any one of 1) to 11), wherein (A) a modified polyolefin resin composition is mixed with a polyolefin resin.

  13) The laminate according to any one of 1) to 12), wherein the adhesive layer containing (A) the modified polyolefin resin composition is in the form of a sheet or film.

  14) The laminate according to any one of 1) to 13), wherein (B) the polyimide is in the form of a sheet or film.

  15) (B) Any one of 1) to 14), wherein an adhesive layer containing (A) a modified polyolefin resin composition is laminated by heating lamination in contact with at least one surface of polyimide. The manufacturing method of the laminated body as described in any one of.

  16) (B) An adhesive layer containing (A) a modified polyolefin resin composition is disposed in contact with at least one surface of the polyimide, and further in contact with a surface of the adhesive layer not in contact with the polyimide (C) Is disposed, and the adhesive layer is adhered by being melted, and the method for producing a laminate according to any one of 2) to 14).

In the present invention, a modified polyolefin resin composition is laminated on polyimide to ensure excellent adhesion with polyimide on an adherend such as a metal member, and is VOC-free and has a small amount of heat and a short time. It is possible to provide high productivity that enables processing at a low pressure.

Details of the present invention will be described below.
(Polyolefin resin)
Polyolefin resins for obtaining modified polyolefin resins include, for example, polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymers or block copolymers in any ratio of propylene and ethylene and / or 1-butene, Cyclic polyolefins such as ethylene-propylene-diene terpolymers having a diene component of 50% by weight or less in any ratio of ethylene and propylene, polymethylpentene, a copolymer of cyclopentadiene and ethylene and / or propylene, Examples thereof include random copolymers or block copolymers of ethylene or propylene and 50% by weight or less of a vinyl compound.

  Among these, polypropylene, polyethylene, and polyisobutylene are preferable, and polypropylene is particularly preferable.

  In addition, a polyolefin resin into which a polar group is introduced can be used because it is easily compatible with an unsaturated carboxylic acid monomer having a polar group. Specific examples of polyolefin resins having polar groups introduced include acid-modified polypropylene such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, and acrylic acid-modified polypropylene; ethylene / vinyl chloride copolymer, ethylene / vinylidene chloride copolymer , Ethylene / acrylonitrile copolymer, ethylene / methacrylonitrile copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylamide copolymer, ethylene / methacrylamide copolymer, ethylene / acrylic acid copolymer, ethylene / Methacrylic acid copolymer, ethylene / maleic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / isopropyl acrylate copolymer, ethylene / butyl acrylate copolymer, Ethylene / A Isobutyl acrylate copolymer, ethylene / 2-ethylhexyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / isopropyl methacrylate copolymer, ethylene / butyl methacrylate Copolymer, ethylene / isobutyl methacrylate copolymer, ethylene / 2-ethylhexyl methacrylate copolymer, ethylene / maleic anhydride copolymer, ethylene / ethyl acrylate / maleic anhydride copolymer, ethylene / acrylic acid Metal salt copolymer, ethylene / methacrylic acid metal salt copolymer, ethylene / vinyl acetate copolymer or saponified product thereof, ethylene / vinyl propionate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / acrylic Ethylate / Glycidyl methacrylate copolymer Body, ethylene / ethylene or α- olefin / vinyl monomer copolymers such as vinyl acetate / glycidyl methacrylate copolymer; chlorinated polypropylene, chlorinated polyolefins such as chlorinated polyethylene. These polar group-introduced polyolefins can be used even if mixed. As the polyolefin into which the polar group has been introduced, a polypropylene type is preferable because it can be produced on an industrial scale at a low cost.

  If necessary, another resin or rubber may be added to the raw material polyolefin resin as long as the effects of the present invention are not impaired.

  Examples of the other resin or rubber include poly α-olefins such as polypentene-1 and polymethylpentene-1, α-olefin copolymers such as propylene / butene-1 copolymers, and ethylene / propylene / 5- Ethylene such as ethylidene-2-norbornene copolymer or α-olefin / α-olefin / diene monomer copolymer; polydiene copolymer such as polybutadiene and polyisoprene; vinyl styrene such as styrene / butadiene random copolymer Monomer / diene monomer random copolymer; vinyl monomer / diene monomer / vinyl monomer block copolymer such as styrene / butadiene / styrene block copolymer; hydrogenation (styrene / butadiene random copolymer) Hydrogenation (polymer)) (vinyl monomer / diene monomer random copolymer); hydrogenation Hydrogenation such as styrene / butadiene / styrene block copolymer) (vinyl monomer / diene monomer / vinyl monomer block copolymer); acrylonitrile / butadiene / styrene graft copolymer, methyl methacrylate / butadiene / Vinyl monomer such as styrene graft copolymer / Diene monomer / Vinyl monomer graft copolymer; Polyvinyl chloride, Polyvinylidene chloride, Polyacrylonitrile, Polyvinyl acetate, Polyethyl acrylate, Polyacrylic acid Vinyl polymers such as butyl, polymethyl methacrylate and polystyrene; vinyl copolymers such as vinyl chloride / acrylonitrile copolymer, vinyl chloride / vinyl acetate copolymer, acrylonitrile / styrene copolymer, methyl methacrylate / styrene copolymer Examples thereof include polymers.

  The amount of the other resin or rubber added to the polyolefin resin varies depending on the type of the resin or the rubber and may be within the range not impairing the effects of the present invention as described above. It is preferable that it is about wt% or less.

  These polyolefin resins (which may contain various additive materials) may be in the form of particles or pellets, and the size and shape are not particularly limited.

  In addition, when using the above-mentioned additive materials (other resins and rubbers), even if this additive material is added to the polyolefin resin in advance, it is added when the polyolefin resin is melted. Alternatively, after the modified polyolefin resin is produced, it may be added to the modified polyolefin resin by an appropriate method.

  Regarding the propylene component in the polyolefin resin, it is preferable that the propylene unit is a majority amount in that radicals are easily generated in the polyolefin resin. The majority amount here means that the propylene component with respect to the polyolefin resin is 50% by weight or more.

(Monomer containing ethylenic double bond and polar group in the same molecule)
As the monomer containing an ethylenic double bond and a polar group for graft modification of the polyolefin resin in the same molecule, various monomers can be used without any particular limitation. As the polar group, a carboxylic acid, an acid anhydride, or a derivative thereof can be preferably used.

  Specific examples of such monomers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2, 1] Unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid, or acid anhydrides or derivatives thereof (for example, acid halides, amides, imides, esters, etc.). Specific examples of the compound include maleenyl chloride, maleenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid. Anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid Dimethyl acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, monoglycidyl maleate, diglycidyl maleate, monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl allyl succinate, allyl succinate Diglycidyl succinate, glycidyl p-styrenecarboxylate, allyl glycidyl ether, methallyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, 3,4-epoxy-1-butene, 3,4-epoxy-3- Mention may be made of methyl-1-butene, vinylcyclohexene monoxide, aminoethyl methacrylate and aminopropyl methacrylate. Among these, (meth) acrylic acid, maleic anhydride, and glycidyl (meth) acrylate are preferable.

 The amount of the monomer containing an ethylenic double bond and a polar group in the same molecule is not particularly limited, but is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of polyolefin as a main chain. . If the amount is less than 0.1 parts by weight, the adhesion to the substrate is not sufficient, and if it is more than 20 parts by weight, a large amount of residual monomer is generated, which adversely affects physical properties.

 When the ethylenically unsaturated carboxylic acid or its derivative is graft-polymerized to the polyolefin resin, other monomers may be used as long as the object of the present invention is not impaired. Other monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, conjugated diene compounds, vinyl ester compounds, vinyl chloride. And oxazoline group-containing unsaturated monomers.

 When an aromatic vinyl compound or a conjugated diene compound is used, the molecular chain scission is suppressed during grafting to a molecular chain scission-type polyolefin such as polypropylene, and the ethylenically unsaturated carboxylic acid or The derivative is preferable because it can be introduced at a high ratio.

  Examples of aromatic vinyl compounds 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-chloro. Chlorostyrenes such as styrene, m-chlorostyrene, p-chlorostyrene, α-chlorostyrene, β-chlorostyrene, dichlorostyrene, trichlorostyrene; o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, Bromostyrene such as tribromostyrene; fluorostyrene such as o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, trifluorostyrene; o-nitrostyrene, m-nitrostyrene, p-nitrostyrene Nitrostyrenes such as dinitrostyrene and trinitrostyrene; vinylphenols such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene and trihydroxystyrene; o-divinylbenzene, m-divinylbenzene and p-divinyl 1 type, or 2 or more types, such as divinylbenzene, such as benzene; diisopropenylbenzene, such as o-diisopropenylbenzene, m-diisopropenylbenzene, and p-diisopropenylbenzene; Of these, methylstyrene such as styrene, α-methylstyrene, p-methylstyrene, divinylbenzene monomer or divinylbenzene isomer mixture is preferable in that it is inexpensive.

  Examples of the conjugated diene monomer include isoprene and 1,3-butadiene.

  The addition amount of the aromatic vinyl monomer or conjugated diene monomer is preferably 0.01 to 10 parts by weight, and 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin. More preferably. If the amount added is too small, the graft ratio of the monomer containing an ethylenic double bond and a polar group in the same molecule tends to be poor. On the other hand, when the addition amount exceeds 10 parts by weight, the graft efficiency of the monomer containing an ethylenic double bond and a polar group in the same molecule reaches a saturation range.

  A monomer containing an ethylenically unsaturated group and a polar functional group in the same molecule, and optionally a vinyl aromatic monomer or a conjugated diene monomer in the presence of a radical polymerization initiator. Alternatively, the modified polyolefin can be obtained by reacting by heating in the absence.

(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.

 Of these, those having a particularly high hydrogen abstraction ability are preferred. Examples of such radical polymerization initiators include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1. Peroxyketals such as bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; dicumyl Peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di Dialkyl peroxides such as t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; Diacyl peroxides such as nzoyl peroxide; t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butylperoxy-3,5,5-trimethylhexano Ate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxyiso 1 type, or 2 or more types, such as peroxyesters, such as a phthalate, is mention | raise | lifted.

 The addition amount of the radical polymerization initiator is preferably in the range of 0.01 to 10 parts by weight and in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin. Further preferred. 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.

  The graft polymerization reaction used in the present invention 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.

  Regarding the order and method of addition during melt kneading, an aromatic vinyl monomer is added to a mixture obtained by melt kneading a polyolefin resin, a radical polymerization initiator, a monomer containing an ethylenic double bond and a polar group in the same molecule. In addition, the addition order of melt kneading is good, and by carrying out in this addition order, monomers containing ethylenic double bonds and polar groups in the same molecule are efficiently grafted to the polyolefin, and the mechanical properties during modification are reduced. Can be suppressed. In addition, the order and method of mixing and melt-kneading the materials added as necessary are not particularly limited.

  The heating temperature at the time of melt kneading is preferably 100 to 250 ° C. from the viewpoint that the polyolefin resin is sufficiently melted and is not thermally decomposed. The time for melt kneading (the time after mixing the radical polymerization initiator) is usually 30 seconds to 60 minutes.

  Further, as the melt kneading apparatus, an extruder, a Banbury mixer, a mill, a kneader, a heating roll, or 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, the melt kneading may be repeated a plurality of times.

  If necessary, the modified polyolefin resin composition may be stabilized with antioxidants, metal deactivators, phosphorus processing stabilizers, UV absorbers, UV stabilizers, fluorescent brighteners, metal soaps, antacid adsorbents, etc. Additives or additives such as crosslinking agents, chain transfer agents, nucleating agents, lubricants, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants, antistatic agents, etc. within the range that does not impair the effects of the present invention May be. When these stabilizers and additives are used, they may be added in advance to the polyolefin resin, may be added when the polyolefin resin is graft-modified, After the production, it may be added to the modified polyolefin resin by an appropriate method.

  The modified polyolefin resin composition can be used by mixing with a polyolefin resin.

  Examples of the polyolefin resin mixed with the modified polyolefin resin composition include polypropylene homopolymer, high density polyethylene, low density polyethylene, linear low density polyethylene, poly-1-butene, polyisobutylene, propylene and ethylene and / or 1 A random copolymer or block copolymer in any ratio with butene, an ethylene-propylene-diene terpolymer having a diene component of 50% by weight or less in any ratio of ethylene and propylene, polymethylpentene, Cyclic polyolefin such as a copolymer of cyclopentadiene and ethylene and / or propylene, ethylene or propylene and 50% by weight or less such as vinyl acetate, methacrylic acid alkyl ester, acrylic acid alkyl ester, aromatic vinyl Random copolymers with vinyl compounds, polyolefin-based thermoplastic elastomer block copolymers, olefin-based thermoplastic elastomers (simple mixtures of polypropylene and ethylene / propylene copolymer or ethylene-propylene-diene terpolymer, The partially crosslinked product or the completely crosslinked product) can be used, and these can be used alone or in admixture of two or more.

  A polypropylene homopolymer is preferable from the viewpoint of high rigidity and low cost, and a block copolymer of propylene and another monomer is preferable from the viewpoint of high rigidity and impact resistance. When flexibility is required, a polyolefin-based thermoplastic elastomer is preferable.

  The mixing amount of the modified polyolefin resin composition and the polyolefin resin is not particularly limited. However, the adhesive property may be 0.1 to 100 parts by weight of the polyolefin resin with respect to 100 parts by weight of the modified polyolefin resin composition. It is preferable at this point, Furthermore, it is preferable to contain 0.1-70 weight part. More preferably, it is 0.3-50 weight part, More preferably, it is 0.5-30 weight part.

(About sheet or film-shaped molded product)
The modified polyolefin resin composition can be made into a sheet or film-like molded product having heat-welding properties. Further, a polyolefin resin composition obtained by adding a modified polyolefin resin composition to a polyolefin resin can also be formed into a sheet or film-like molded article having heat-welding properties. The heat-weldability referred to in the present invention refers to the property of melting with heat and joining to the adherend. The sheet or film-like molded product of the present invention can be exemplified by a thickness of 3 μm to 3 mm, preferably 10 μm to 1 mm, and can be used as a sheet or film.

  The method for producing a polyolefin sheet or film-like molded article having heat-welding properties is not particularly limited. For example, after a dry blending or melt-kneading a modified polyolefin resin composition and a polyolefin resin as necessary, It can be formed into a sheet-like molded body using various types of extrusion molding machines, injection molding machines, calendar molding machines, inflation molding machines, roll molding machines, or hot press molding machines.

(About polyimide)
The polyimide used in the present invention is not particularly limited, and examples thereof include non-thermoplastic polyimide, thermoplastic polyimide, polyamideimide, and polyetherimide. As the non-thermoplastic polyimide, a polyimide obtained from pyromellitic anhydride and 4,4-diaminodiphenyl ether is general-purpose and preferable.

  Moreover, it is preferable that the polyimide used by this invention is a sheet form or a film form, and 1 micrometer-3 mm can illustrate the thickness of a polyimide of a sheet | seat and a film form, Preferably it is 5 micrometers-0.5 mm.

(Laminated body of polyimide and modified polyolefin resin composition)
The production method of the laminate of the polyimide and the modified polyolefin resin composition of the present invention is not particularly limited, but the modified polyolefin resin composition sheet or film-shaped product, and the polyimide sheet or film are laminated. Then, it can be processed into a sheet-like laminate using various thermal laminator machines, roll molding machines, hot press molding machines, and the like.

(About adherend)
Examples of the material of the adherend used in the present invention include iron, copper, silver, gold, aluminum, zinc, lead, tin, magnesium, an alloy mainly containing iron, an alloy mainly containing copper, and silver. Alloy containing gold as a main component, alloy containing gold as a main component, alloy containing aluminum as a main component, alloy containing zinc as a main component, alloy containing lead as a main component, alloy containing tin as a main component, magnesium as a main component Examples include metal materials such as alloys as components. In addition, inorganic materials such as glass and ceramics; cellulosic polymer materials such as paper and cloth; polyolefin resins, polystyrene resins, polyester resins, polyamide resins, polyimide resins, unsaturated polyester resins, polyurethane Resin, urea resin, melamine resin, phenol resin, epoxy resin, acrylic / urethane resin, (meth) acrylic resin, styrene / acrylonitrile copolymer, styrene / acrylonitrile / conjugated diene copolymer, polycarbonate resin, silicone resin, polyolefin Examples thereof include synthetic polymer materials such as thermoplastic elastomers, polystyrene-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers. Foam molded bodies based on these polymer materials can also be used as adherends.

(Laminated body of polyimide, modified polyolefin resin composition and adherend)
The production method of the laminate of the polyimide, the modified polyolefin resin composition and the adherend of the present invention is not particularly limited, but (B) is in contact with at least one surface of the polyimide, and (A) the modified polyolefin resin composition. An adhesive layer containing the adhesive layer, and (C) an adherend is placed in contact with the surface of the adhesive layer that is not in contact with polyimide, and the adhesive layer is bonded by melting to obtain a laminate. it can. To melt the adhesive layer, use various heat laminator machines, hot press molding machines, etc., or use an injection molding machine for the laminate of polyimide and modified polyolefin resin composition. Can be used.

  Specific examples are shown below, 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.

(How to create a test piece)
The example which obtained the test piece for adhesion | attachment evaluation laminated | stacked in order of the polyimide film / adhesion layer / adherence body is shown. A press machine is laminated with one end aligned in the order of polyimide film (manufactured by Kaneka: Apical AH thickness 50 μm, 25 mm × 150 mm), adhesive film (thickness 100 μm, 25 mm × 70 mm), copper plate (thickness 1.5 mm, 25 mm × 100 mm). The test piece was bonded under the processing conditions of a pressing temperature of 220 ° C., a pressing time of 1 minute, and a pressing force of 0.5 MPa.

(Adhesion evaluation)
Adhesion evaluation was performed using the test piece. Using a Shimadzu AG-2000A, a polyimide sheet and a copper plate at one end where the adhesive layer of the test piece is not laminated are sandwiched between chucks at 23 ° C. and a take-off speed of 100 mm / min, and evaluated by a 180 ° peel test. did.

(Production Example 1)
100 parts of homopolypropylene (Prime Polymer J105G, MFR = 10), 1,3-di (t-butylperoxyisopropyl) benzene (Nippon Yushi Co., Ltd .: Perbutyl P, 1 minute half-life 175 ° C.) 0.5 part After supplying from a mouth to a twin screw extruder (Nippon Steel Works, product name LABOTEX30; φ30 mm, L / D = 28) set at a cylinder temperature of 200 ° C. and a screw rotation speed of 250 rpm, melt and knead, then styrene from the middle of the cylinder 5 parts and 5 parts of glycidyl methacrylate were added and melt-kneaded to obtain modified polyolefin resin pellets (A-1). The obtained resin pellet (A-1) is a hopper of a single screw extruder (product name: Labo plast mill; φ20 mm, L / D = 20) manufactured by a cylinder and a die temperature of 200 ° C. and a screw rotation speed of 100 rpm. The film (A-1T) having a width of about 13 cm and a thickness of 100 μm was obtained from a T-shaped die attached to the tip of the die.

(Production Example 2)
Hopper 100 parts of block polypropylene (M142E made of prime polymer, MFR = 10), 0.5 parts of 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF: perbutyl P, half-life 175 ° C. for 1 minute) After supplying from a mouth to a twin screw extruder (Nippon Steel Works, product name LABOTEX30; φ30 mm, L / D = 28) set at a cylinder temperature of 200 ° C. and a screw rotation speed of 250 rpm, melt and knead, then styrene from the middle of the cylinder 5 parts and 5 parts of glycidyl methacrylate were added and melt-kneaded to obtain modified polyolefin resin pellets (A-2). The obtained resin pellet (A-2) is a hopper of a single screw extruder (product name: Labo plast mill; φ20 mm, L / D = 20) manufactured by a cylinder and a die temperature of 200 ° C. and a screw rotation speed of 100 rpm. The film (A-2T) having a width of about 13 cm and a thickness of 100 μm was obtained from a T-type die attached to the tip of the die.

(Production Example 3)
100 parts of polypropylene ethylene rubber (D340 Chemical V3401, MFR = 8), 1,3-di (t-butylperoxyisopropyl) benzene (Nippon Yushi: Perbutyl P, 1 minute half-life 175 ° C.) 0.5 part After supplying from a hopper port to a twin screw extruder (manufactured by Nippon Steel Works, product name LABOTEX30; φ30 mm, L / D = 28) set to a cylinder temperature of 200 ° C. and a screw rotation speed of 250 rpm, then from the middle of the cylinder 5 parts of styrene and 5 parts of glycidyl methacrylate were added and melt kneaded to obtain modified polyolefin resin pellets (A-3). The obtained resin pellet (A-3) is a hopper of a single-screw extruder (product name: Laboplast Mill; φ20 mm, L / D = 20) manufactured by a cylinder and a die temperature of 200 ° C. and a screw rotation speed of 100 rpm. The film (A-3T) having a width of about 13 cm and a thickness of 100 μm was obtained from a T-type die attached to the tip of the die.

(Production Example 4)
80 parts of the resin pellet (A-1) obtained in Example 1 and 20 parts of polypropylene ethylene rubber (D340 Chemical V3401, MFR = 8) were mixed, and the cylinder and die temperature were set to 200 ° C. and the screw rotation speed was set to 100 rpm. A film (A-4T) having a width of about 13 cm and a thickness of 100 μm from a T-type die attached to the hopper of a single-screw extruder (manufactured by Toyo Seiki, product name: Laboplast Mill; φ20 mm, L / D = 20). )

(Reference Example 1)
A single screw extruder (manufactured by Toyo Seiki, product name Lab Plast Mill; φ20 mm, L / D = 20) in which polypropylene ethylene rubber (D340 Chemical V3401, MFR = 8) is set to a cylinder and a die temperature of 200 ° C. and a screw speed of 100 rpm. The film (A-5T) having a width of about 13 cm and a thickness of 100 μm was obtained from a T-type die that was placed in the hopper of the die and attached to the tip of the die.

(Examples 1-9, Comparative Examples 1-2)
Using the modified polyolefin resin composition film obtained in Production Examples 1 to 4 or Reference Example 1, a test piece composed of polyimide / modified polyolefin resin composition adhesive layer / adhered body by the above-described test piece preparation method was used. Obtained. Table 1 shows the results of evaluating the obtained test pieces by the above-described adhesion evaluation method.

Examples 1 to 9 are examples in which the modified polyolefin resin composition of the present invention was used for adhesion processing, and showed very good adhesion performance for any adherend. On the other hand, Comparative Examples 1 and 2 indicate that the adhesiveness is not exhibited.

Claims (16)

(B) A laminate in which an adhesive layer containing (A) a modified polyolefin resin composition is laminated in contact with at least one surface of polyimide. (B) An adhesive layer containing the modified polyolefin resin composition is laminated in contact with at least one surface of the polyimide, and (C) an adherend is laminated on the surface of the adhesive layer not in contact with the polyimide. Laminated body. (C) The laminate according to claim 2, wherein the adherend is a metal material. The metal material is mainly composed of iron, copper, silver, gold, aluminum, zinc, lead, tin, magnesium, iron-based alloys, copper-based alloys, silver-based alloys, and gold. Selected from the group consisting of alloys containing components, alloys based on aluminum, alloys based on zinc, alloys based on lead, alloys based on tin, and alloys based on magnesium The laminate according to claim 3, wherein the laminate is at least one kind. (C) The laminate according to claim 2, wherein the adherend is a polymer material. The polymer material is polyolefin, polystyrene, polyester, styrene / acrylonitrile / conjugated diene copolymer, polyamide, polyimide, unsaturated polyester, polyurethane, urea resin, melamine resin, phenol resin, epoxy resin, (meth) acrylic resin, Styrene / acrylonitrile copolymer, styrene / acrylonitrile / conjugated diene copolymer, polyolefin-based thermoplastic elastomer, polystyrene-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, and these The laminate according to claim 5, wherein the laminate is at least one selected from the group consisting of foamed molded products. The (A) modified polyolefin resin is a polyolefin obtained by graft-modifying (a-1) a polyolefin resin with a monomer containing an ethylenic double bond and a polar group in the same molecule. The laminate according to claim 1. The polar group of the monomer containing the ethylenic double bond and the polar group in the same molecule is at least one monomer characterized in that it is a carboxylic acid, an anhydride thereof, or a derivative thereof. Item 8. A laminate according to Item 7. The laminate according to claim 8, wherein the monomer containing the ethylenic double bond and the polar group in the same molecule is at least one selected from (meth) acrylic acid, maleic anhydride, and glycidyl (meth) acrylate. body. (A) The modified polyolefin resin is a polyolefin graft-modified with an aromatic vinyl monomer or a conjugated diene monomer in addition to a compound containing an ethylenic double bond and a polar group in the same molecule. Item 10. The laminate according to any one of Items 7 to 9. (A-1) The laminate according to any one of claims 7 to 10, wherein the polyolefin resin has a majority of ethylene units or propylene units. (A) The laminated body as described in any one of Claims 1-11 with which polyolefin resin is mixed with the modified polyolefin resin composition. (A) The contact bonding layer containing a modified polyolefin resin composition is a sheet | seat or a film form, The laminated body as described in any one of Claims 1-12. (B) A polyimide is a sheet | seat or a film form, The laminated body as described in any one of Claims 1-13. (B) The adhesive layer containing the modified polyolefin resin composition (A) in contact with at least one surface of the polyimide is laminated by lamination processing by heating. The manufacturing method of the laminated body as described in any one of. (B) An adhesive layer containing (A) a modified polyolefin resin composition is disposed in contact with at least one surface of the polyimide, and (C) an adherend is disposed in contact with the surface of the adhesive layer not in contact with polyimide. The method for producing a laminate according to any one of claims 2 to 14, wherein the adhesive layer is bonded by being melted.