Hot-melt adhesive resin laminate, laminate, and method for manufacturing hot-melt adhesive resin laminate

Abstract

To provide a hot-melt adhesive resin laminate which has strong adhesive force to an adherend, and can maintain the adhesive force after a severe durable condition, and a laminate using the same.SOLUTION: A hot-melt adhesive resin laminate has a base material layer containing a resin as a formation material and an adhesive layer, and has the adhesive layer on at least one surface of the base material layer, wherein the base material layer has an acidic group exposed to the base material surface by corona treatment or oxygen plasma treatment, on a surface in contact with the adhesive layer, the adhesive composition constituting the adhesive layer contains an adhesive polyolefin-based resin, the adhesive polyolefin-based resin is imine-modified polyolefin or modified polyolefin having a carbodiimide group, and a melt flow rate of the imine-modified polyolefin or the modified polyolefin having the carbodiimide group is 2 g / 10 min or more and 25 g / 10 min or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a hot melt adhesive resin laminate and a laminate. [Background technology]

[0002] Conventionally, as an adhesive film that adheres to an adherend, a laminate film having a three-layer structure in which a thermosetting epoxy-based adhesive layer is formed on both sides of a substrate made of a heat-resistant resin film, as described in Patent Document 1, has been known. Such laminated films are sometimes used to bond on-board parts, which are exposed to high temperatures and humidity. Therefore, laminated films used for on-board parts must have not only improved adhesive strength but also durability under harsh conditions. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-28738 Summary of the Invention [Problem to be solved by the invention]

[0004] The laminated film described in Patent Document 1 had room for improvement from the viewpoint of strengthening the adhesive strength to the adherend, particularly when bonding to a metal as the adherend, and from the viewpoint of maintaining sufficient adhesive strength after being subjected to severe durability conditions. The laminated film described in Patent Document 1 had the problem that when it was made into a laminate, it was unable to ensure the strength of the laminate, causing peeling between the layers of the laminate, and therefore not being able to maintain sufficient strength as an adhesive. The present invention has been made in consideration of the above circumstances, Reduced delamination The present invention addresses the problem of providing a hot-melt adhesive resin laminate that has strong adhesive strength to an adherend and can maintain adhesive strength even after being subjected to severe durability conditions, and a laminate using the same. [Means for solving the problem]

[0005] That is, the present invention employs the following configuration. [1] A hot melt adhesive resin laminate having a base layer made of a resin and an adhesive layer, the base layer having an adhesive layer on at least one side thereof, the base layer having acidic groups on the side in contact with the adhesive layer, the adhesive composition constituting the adhesive layer containing an adhesive polyolefin resin, the adhesive polyolefin resin being an imine-modified polyolefin, and the melt flow rate of the imine-modified polyolefin being 2 g / 10 min or more and 25 g / 10 min or less. [2] The hot melt adhesive resin laminate according to [1], wherein the imine-modified polyolefin is an imine-modified polypropylene. [3] A hot melt adhesive resin laminate having a base layer made of a resin and an adhesive layer, the base layer having an adhesive layer on at least one side thereof, the base layer having acidic groups on the side in contact with the adhesive layer, the adhesive composition constituting the adhesive layer containing an adhesive polyolefin resin, the adhesive polyolefin resin being a modified polyolefin having carbodiimide groups, and the melt flow rate of the modified polyolefin having carbodiimide groups being 2 g / 10 min or more and 25 g / 10 min or less. [4] The hot melt adhesive resin laminate according to any one of [1] to [3], wherein the acidic group is a carboxyl group, a carbonyl group, a phosphoric acid group, a hydroxyl group, or a sulfo group. [5] The hot melt adhesive resin laminate according to any one of [1] to [4], wherein the resin is at least one selected from the group consisting of fluororesin, polyether ether ketone, polyphenylene sulfide resin, polyphenylene ether, syndiotactic polystyrene resin, polyethylene naphthalate, polyethylene terephthalate, polyimide resin, phenolic resin, epoxy resin, acrylic resin, polyketone, cyclic olefin resin, polymethylpentene, polypropylene, and polyethylene. [6] The hot melt adhesive resin laminate according to any one of [1] to [5], wherein the thickness of the base layer is 10 μm or more and 200 μm or less. [7] The hot melt adhesive resin laminate according to any one of [1] to [6], wherein the base layer is a film formed from the resin, or a composite of the resin and one selected from a nonwoven fabric or a woven fabric. [8] The hot melt adhesive resin laminate according to any one of [1] to [7], wherein the adhesive composition contains an olefin-based elastomer. [9] The hot melt adhesive resin laminate according to any one of [1] to [8], wherein the adhesive composition contains an unmodified polyolefin having a melt flow rate of 2 g / 10 min or more and 25 g / 10 min or less.

[10] A laminate comprising the hot melt adhesive resin laminate according to any one of [1] to [9] and an adherend. [Effects of the Invention]

[0006] According to the present invention, Reduced delamination It is possible to provide a hot-melt adhesive resin laminate that has strong adhesive strength with an adherend and can maintain adhesive strength even after being subjected to severe endurance conditions, and a laminate using the same. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a diagram showing an example of a hot-melt adhesive resin laminate of the present invention. [Figure 2] 1 is a diagram showing an example of a hot-melt adhesive resin laminate of the present invention. [Figure 3] 1 is a diagram showing an example of a hot-melt adhesive resin laminate of the present invention. [Figure 4] 1 is a diagram showing an example of a hot melt laminate of the present invention. [Figure 5] 1 is a diagram showing an example of a hot melt laminate of the present invention. [Figure 6] 1 is a diagram showing an example of a hot melt laminate of the present invention. [Figure 7] FIG. 2 is a schematic diagram illustrating the stacking state of a test piece used in a peel test. [Figure 8] FIG. 1 is a schematic diagram of an apparatus used in a peel test. DETAILED DESCRIPTION OF THE INVENTION

[0008] Preferred embodiments of the present invention will be described below. Note that the following embodiments are examples of the present invention and are not intended to limit the present invention.

[0009] <Hot melt adhesive resin laminate 1> A hot melt adhesive resin laminate 1 according to a first embodiment of the present invention has a base layer and an adhesive layer. A hot melt adhesive resin laminate 10 of this embodiment is shown in Fig. 1. The hot melt adhesive resin laminate of this embodiment has an adhesive layer 1 on at least one surface 3 of a base layer 2. The base layer 2 has acidic groups on the surface 3 in contact with the adhesive layer 1. The adhesive layer 1 is composed of an adhesive composition. In the hot-melt adhesive resin laminate 1, the adhesive composition contains an adhesive polyolefin-based resin, and the adhesive polyolefin-based resin is an imine-modified polyolefin. The melt flow rate of the imine-modified polyolefin is 2 g / 10 min or more and 25 g / 10 min or less.

[0010] <Hot melt adhesive resin laminate 2> A hot melt adhesive resin laminate 2 according to a second embodiment of the present invention has a base layer and an adhesive layer. A hot melt adhesive resin laminate 10 of this embodiment is shown in Fig. 1. The hot melt adhesive resin laminate of this embodiment has an adhesive layer 1 on at least one surface 3 of the base layer 2. The base layer 2 has acidic groups on the surface 3 in contact with the adhesive layer 1. The adhesive layer 1 is composed of an adhesive composition. In the hot melt adhesive resin laminate 2, the adhesive composition contains an adhesive polyolefin resin, which is a modified polyolefin having a carbodiimide group. The melt flow rate of the modified polyolefin is 2 g / 10 min or more and 25 g / 10 min or less.

[0011] The hot-melt adhesive resin laminate of this embodiment has acidic groups on the surface of the substrate layer. These acidic groups react with the imine-modified polyolefin in the adhesive composition that constitutes the adhesive layer, forming a strong bond. This not only ensures strong adhesion between the adhesive layer and the substrate layer, but also ensures the strength of the hot-melt adhesive resin laminate. As a result, even under harsh conditions such as high temperature or high humidity, the occurrence of interlayer delamination between the substrate layer and the adhesive layer is suppressed, and high adhesive strength can be maintained. Each material constituting the present invention will be described below.

[0012] [Base material layer] The resin constituting the base layer 2 is not particularly limited as long as it has sufficient heat resistance. In this embodiment, examples thereof include one or more selected from the group consisting of fluororesin, polyether ether ketone, polyphenylene sulfide resin (SPS), polyphenylene ether, syndiotactic polystyrene resin, polyethylene naphthalate, polyethylene terephthalate (PET), polyimide resin, phenolic resin, epoxy resin, acrylic resin, polyketone, cyclic olefin resin, polymethylpentene, polypropylene, and polyethylene. In this embodiment, of the above, fluororesin, PET, or SPS is preferred.

[0013] The thickness of the base layer 2 is preferably 10 μm or more, more preferably 50 μm or more, and particularly preferably 100 μm or more, and is preferably 220 μm or less, more preferably 200 μm or less, and particularly preferably 190 μm or less. The upper and lower limits can be combined arbitrarily. In this embodiment, the range is preferably 10 μm or more and 200 μm or less.

[0014] In this embodiment, the base layer 2 has an acidic group on the surface 3 in contact with the adhesive layer 1. Examples of the acidic group include a carboxyl group, a carbonyl group, a phosphate group, a hydroxyl group, and a sulfo group. When the acidic group is a hydroxyl group, a phenolic hydroxyl group is preferred. In this embodiment, methods for introducing acidic groups onto the surface of the substrate layer include a method of using a resin material whose surface has been acid-modified in advance, and a method of exposing acidic groups on the substrate surface by corona treatment or oxygen plasma treatment.

[0015] The plasma treatment in this embodiment is atmospheric pressure glow plasma treatment in a rare gas atmosphere such as helium or argon, or nitrogen gas, and nitrogen gas, oxygen gas, carbon dioxide gas, or the like can be used as the reactive gas. Atmospheric pressure plasma treatment using oxygen gas as the reactive gas can generate oxygen functional groups such as carbonyl groups (>CO) and carboxyl groups (-COOH) in the main chains and side chains of polymers on the surface of the substrate. CH4, CO2, etc. may also be added to the reactive gas. When CO2 is added as the reactive gas, weak oxidation occurs on the surface of the substrate, primarily generating oxygen functional groups.

[0016] In this embodiment, the substrate layer may be a film formed from the resin, or a composite of the resin and one material selected from a nonwoven fabric or a woven fabric.

[0017] [Adhesive layer] In this embodiment, the adhesive layer 1 is composed of an adhesive composition. The adhesive composition used in this embodiment contains an adhesive polyolefin resin, which is an imine-modified polyolefin. The imine-modified polyolefin has a melt flow rate of 2 g / 10 min or more and 25 g / 10 min or less. In another aspect, the adhesive polyolefin resin is a modified polyolefin having a carbodiimide group. The modified polyolefin having a carbodiimide group has a melt flow rate of 2 g / 10 min or more and 25 g / 10 min or less.

[0018] The thickness of the adhesive layer 1 is not particularly limited, and may be, for example, 10 μm or more and 50 μm or less, or 15 μm or more and 45 μm or less.

[0019] Adhesive composition The adhesive composition used in this embodiment contains an imine-modified polyolefin or a modified polyolefin having a carbodiimide group as an essential component, and may also contain any unmodified polyolefin and any olefin-based elastomer.

[0020] ··Imine-modified polyolefin In this embodiment, the imine-modified polyolefin is preferably obtained by grafting a polyimine compound having a plurality of imino groups onto an adhesive polyolefin in the presence of a radical generator. In this embodiment, the imine-modified polypropylene is preferably an imine-modified polypropylene grafted with polypropyleneimine.

[0021] In the present embodiment, the melt flow rate measured in accordance with ASTM D1238 under conditions of a temperature of 190°C or 230°C and a load of 2.16 kg is preferably 2 g / 10 min or more and 25 g / 10 min or less, more preferably 2.5 g / 10 min or more and 20 g / 10 min or less, and even more preferably 2.8 g / 10 min or more and 18 g / 10 min or less.

[0022] Examples of adhesive polyolefins include polyethylene, polypropylene, poly-1-butene, polyisobutylene, copolymers of propylene and ethylene, and copolymers of propylene and olefinic monomers. Examples of the olefinic monomer to be copolymerized include 1-butene, isobutylene, and 1-hexene. The copolymer may be a block copolymer or a random copolymer.

[0023] Among these, preferred adhesive polyolefins are polypropylene-based resins polymerized using propylene as a raw material, such as homopolypropylene (propylene homopolymer), copolymers of propylene and ethylene, and copolymers of propylene and butene; in particular, propylene-1-butene copolymers, i.e., polyolefin resins having methyl and ethyl groups in the side chains, are preferred.

[0024] Polyimine compounds In this embodiment, the polyimine compound is preferably, for example, a compound represented by the following formula (1).

[0025] [ka] [R in the formula 1 , R 2 , R 3 may be the same or different and represent a non-reactive atom or organic group; R 1 and R 2 may be bonded to each other to form a ring. n is a natural number, and n 1 represents an integer between 20 and 2000.

[0026] R in the formula 1 , R 2 , R 3 may be the same or different, and are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or an alkoxy group. R 1 , R 2 , R 3 The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, including a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, an isopropyl group, an isobutyl group, etc., more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms.

[0027] The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms, still more preferably an alkenyl group having 2 to 5 carbon atoms, and particularly preferably an alkenyl group having 2 to 4 carbon atoms.

[0028] The alkynyl group is preferably an alkynyl group having 2 to 18 carbon atoms, such as an ethynyl group, a 1-propynyl group, or a 1-heptynyl group, more preferably an alkynyl group having 2 to 10 carbon atoms, still more preferably an alkynyl group having 2 to 6 carbon atoms, and particularly preferably an alkynyl group having 2 to 4 carbon atoms.

[0029] The cycloalkyl group is preferably a cycloalkyl group having 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, more preferably a cycloalkyl group having 3 to 6 carbon atoms, and particularly preferably a cycloalkyl group having 5 to 6 carbon atoms.

[0030] The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a tolyl group, or a naphthyl group.

[0031] Examples of the heterocyclic group include heterocyclic rings containing an oxygen atom as a heteroatom, such as 5-membered rings like a furan ring, an oxazole ring, an isoxazole ring, and a tetrahydrofuran ring; 6-membered rings like a pyran ring; fused rings like a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a xanthone ring, a xanthene ring, a chroman ring, an isochroman ring, and a chromene ring; heterocyclic rings containing a sulfur atom as a heteroatom, such as a thiophene ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, and a benzothiophene ring; and further, examples of the heterocyclic group include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, and a pyrrolidine ring. and heterocycles containing a nitrogen atom as a heteroatom, typified by 5-membered rings such as those mentioned above, 6-membered rings such as a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, and a morpholine ring, and fused rings such as an indole ring, an indole ring, an isoindole ring, an indazole ring, an indoline ring, an isoindoline ring, a quinoline ring, an isoquinoline ring, a quinolinequinoline ring, a quinoxaline ring, a quinazoline ring, a phthalazine ring, a purine ring, a carbazole ring, an acridine ring, a naphthoquinoline ring, a phenanthridine ring, a phenanthroline ring, a naphthyridine ring, a benzoquinoline ring, a phenoxazine ring, a phthalocyanine ring, and an anthracyanine ring.

[0032] Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

[0033] A specific example of a suitable polyimine compound is polypropyleneimine.

[0034] The polyimine compound preferably has a molecular weight of 1,000 or more, but from the viewpoint of reactivity with olefin after activation treatment, a higher molecular weight is preferred. Specifically, the molecular weight is preferably 1,000 to 200,000, more preferably 3,000 to 200,000, and particularly preferably 15,000 to 200,000.

[0035] The radical generator used in the grafting treatment includes organic peroxides and organic peresters. Benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxidebenzoate)hexyne-3, 1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate, and tert-butyl perdiethyl acetate, as well as other azo compounds such as azobisisobutyronitrile and dimethyl azoisobutyrate, may be used. Among these, dialkyl peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferred.

[0036] Among these, organic peroxides are preferred as radical generators. Suitable organic peroxides have a decomposition temperature of 100°C or higher and a half-life of 1 minute. Specifically, the organic peroxide is preferably at least one selected from the group consisting of dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-di-(t-butylperoxy)hexane, 2,5-dimethyl-2,5-(t-butylperoxy)hexane-3, lauroyl peroxide, and t-butyl peroxybenzoate.

[0037] The radical generator is usually used in an amount of 0.001 to 1 part by mass per 100 parts by mass of polyolefin.

[0038] The imine-modified olefin can be produced by uniformly mixing a polyolefin, a polyimine compound, and a radical generator and processing the mixture. Specific examples include a melt-kneading method using an extruder, Banbury mixer, kneader, or the like; a solution method in which the polyolefin is dissolved in an appropriate solvent; a slurry method in which the polyolefin is suspended in an appropriate solvent; and a so-called vapor-phase grafting method. The temperature for the treatment is appropriately selected taking into consideration factors such as deterioration of the polyolefin, decomposition of the polyimine compound, and the decomposition temperature of the radical generator used. For example, the melt-kneading method is typically carried out at a temperature of 60 to 350°C. The temperature for the treatment is preferably 190 to 350°C, more preferably 200 to 300°C.

[0039] Modified polyolefin with carbodiimide groups The modified polyolefin having a carbodiimide group is preferably obtained by reacting a polyolefin having a group reactive with a carbodiimide group with a carbodiimide group-containing compound in the presence of an unmodified polyolefin. The reaction can be carried out by melt-kneading at a temperature of 230°C or higher.

[0040] Examples of polyolefins include homopolymers and copolymers of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 1-octene, tetracyclododecene, and norbornene.

[0041] Examples of compounds having a group reactive with a carbodiimide group include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid, as well as their acid anhydrides and derivatives (e.g., acid halides, amides, imides, esters, etc.). Among these, maleic anhydride, (meth)acrylic acid, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid anhydride, hydroxyethyl (meth)acrylate, glycidyl methacrylate, and aminopropyl methacrylate are preferred.

[0042] As a method for introducing a compound having a group reactive with a carbodiimide group into a polyolefin, well-known methods can be adopted. Examples of such methods include a method of graft copolymerizing a compound having a group reactive with a carbodiimide group onto the polyolefin main chain, and a method of radical copolymerizing an olefin with a compound having a group reactive with a carbodiimide group.

[0043] As the polyolefin having a group reactive with a carbodiimide group, maleic anhydride graft copolymers of crystalline polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and their α-olefin copolymers are preferred, and maleic anhydride graft copolymers of polyethylene are more preferred. 3 The above polyethylene maleic anhydride graft copolymers are preferred.

[0044] The carbodiimide group-containing compound is preferably a polycarbodiimide having a repeating unit represented by the following formula (2). -N=C=NR 4 - (2) (In the formula, R 4 represents a divalent organic group having 2 to 40 carbon atoms.

[0045] Polycarbodiimides can be produced by carrying out a decarboxylation condensation reaction of an organic diisocyanate such as an aliphatic diisocyanate, an aromatic diisocyanate, or an alicyclic diisocyanate in the presence of a condensation catalyst, either without a solvent or in an inert solvent. Examples of the organic diisocyanate that can be used include hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, xylylene diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and isophorone diisocyanate.

[0046] Examples of unmodified polyolefins include low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polybutene-1, poly-4-methyl-1-pentene, poly-3-methyl-1-butene, and cyclic polyolefins such as ethylene-tetracyclododecene copolymer.

[0047] Unmodified polyolefin In this embodiment, the adhesive composition may contain an unmodified polyolefin. Examples of the unmodified polyolefin include the unmodified polyolefins described above in the description of the modified polyolefin having a carbodiimide group, and among these, polypropylene is preferred.

[0048] In the present embodiment, the unmodified polyolefin preferably has a melt flow rate of 2 g / 10 min or more and 25 g / 10 min or less, more preferably 2.5 g / 10 min or more and 20 g / 10 min or less, and even more preferably 2.8 g / 10 min or more and 18 g / 10 min or less, as measured in accordance with ASTM D1238 under conditions of a temperature of 190°C or 230°C and a load of 2.16 kg.

[0049] In this embodiment, when the adhesive composition contains an unmodified polyolefin, the amount of the unmodified polyolefin is preferably 1 part by mass or more and 40 parts by mass or less, and more preferably 5 parts by mass or more and 35 parts by mass or less, relative to 100 parts by mass of the total amount of the adhesive composition.

[0050] Olefin elastomer In this embodiment, the adhesive composition may contain an olefin-based elastomer. Examples of the olefin-based elastomer include block copolymers having a hard segment made of polystyrene or the like and a soft segment made of polyethylene, polybutadiene, polyisoprene, or the like. Examples of olefin-based polymers that can be used for the olefin-based elastomer include aromatic olefin-aliphatic olefin copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, and styrene-ethylene copolymer.

[0051] In this embodiment, when the adhesive composition contains an olefin-based elastomer, the amount of the olefin-based elastomer is preferably 1 part by mass or more and 40 parts by mass or less, and more preferably 5 parts by mass or more and 35 parts by mass or less, relative to 100 parts by mass of the total amount of the adhesive composition.

[0052] The hot melt adhesive resin laminate of this embodiment may be a hot melt adhesive resin laminate 10 having a two-layer structure including an adhesive layer 1 and a base layer 2 in this order as shown in FIG. As shown in FIG. 2, the hot melt adhesive resin laminate 20 may have a three-layer structure including a first adhesive layer 21, a base layer 22, and a second adhesive layer 23 in this order. Also, as shown in FIG. 3, the hot melt adhesive resin laminate 40 may have a five-layer structure including a first adhesive layer 41, a first base material layer 42, a second adhesive layer 43, a second base material layer 44, and a third adhesive layer 45 in this order.

[0053] [Method for producing hot melt adhesive resin laminate] As a method for producing the hot melt adhesive resin laminate according to one embodiment of the present invention, for example, a co-extrusion method can be mentioned. When producing a two-layer hot-melt adhesive resin laminate using the co-extrusion method, the resin that makes up the base layer and the resin that makes up the adhesive layer are extruded separately from different extruders. These separately molten resins are laminated in a die in the order of adhesive layer / base layer to form a composite film. This composite film is then stretched to obtain a hot-melt adhesive resin laminate of the desired thickness.

[0054] In the case of a three-layer structure, the two-layer hot-melt adhesive resin laminate and the second adhesive layer may be laminated by extruding the resin constituting the second adhesive layer from an extruder in the order of adhesive layer / substrate layer / second adhesive layer. Alternatively, the resin constituting the second adhesive layer may be thermally laminated in the order of adhesive layer / substrate layer / second adhesive layer.

[0055] Examples of the layer structure of the hot melt adhesive resin laminate of the present invention include Lamination Examples 1 to 6 having the following layer structures. Lamination example 1 A laminate in which an adhesive layer and a base material layer are laminated in this order. Lamination example 2 A laminate in which an adhesive layer / base layer / adhesive layer are laminated in this order. Lamination example 3 A laminate in which an adhesive layer, an intermediate layer, and a base material layer are laminated in this order. Lamination example 4 A laminate in which adhesive layer / intermediate layer / base material layer / intermediate layer / adhesive layer are laminated in this order. Lamination example 5 A laminate in which adhesive layer / first base material layer / adhesive layer / second base material layer / adhesive layer are laminated in this order. Lamination example 6 A laminate in which adhesive layer / intermediate layer / first base material layer / adhesive layer / second base material layer / intermediate layer / adhesive layer are laminated in this order. Lamination example 7 A laminate in which an adherend adhesive layer / adhesive layer / substrate layer are laminated in this order. Lamination example 8 A laminate in which the following layers are laminated in this order: adherend adhesive layer / adhesive layer / substrate layer / adhesive layer / adherend adhesive layer.

[0056] The hot melt adhesive resin laminate of this embodiment includes an adhesive layer on at least one side as shown in Lamination Example 1. In other embodiments, as shown in Lamination Examples 2 and 4 to 6, adhesive layers may be provided on both sides of the base layer. Furthermore, as shown in Lamination Examples 3 and 4, an intermediate layer may be provided between the adhesive layer and the base material layer. By providing an intermediate layer, the adhesive strength between the layers can be improved. This intermediate layer is preferably a layer made of a resin material. The intermediate layer is preferably formed using the adhesive composition, and preferably uses an adhesive polyolefin different from the material used for the adhesive layer. An example of the "adhesive polyolefin different from the material used in the adhesive layer" is an adhesive polyolefin having a different melt flow rate. In Lamination Examples 3 and 4, when the adhesive layer has acidic groups and the intermediate layer contains an imine-modified polyolefin or a modified polyolefin having carbodiimide groups, the acidic groups in the adhesive layer react with the substituents in the intermediate layer to provide strong adhesion, improving the strength of the entire adhesive laminate.

[0057] The hot melt adhesive resin laminate of this embodiment may have a configuration including a plurality of base material layers, as in Lamination Examples 5 and 6. In this configuration, the adhesive layer that bonds the plurality of (for example, two) base material layers may be an adhesive layer different from the adhesive layer on the surface, or the same adhesive layer may be used. It is preferable to provide a plurality of base layers, as in Lamination Examples 5 and 6, because the thickness of the base layer can be adjusted as desired. Furthermore, such a configuration can improve the flexibility of the adhesive layer. The hot melt adhesive resin laminate of this embodiment may have various adhesive layers on the outer side of the adhesive layer depending on the adherend, as in Lamination Examples 7 and 8. In this case, it is preferable that the adherend adhesive layer that adheres to the adherend uses an adhesive polyolefin resin different from that of the adhesive layer on the substrate surface. An example of a different adhesive polyolefin resin is epoxy-modified polyolefin. When an adhesive layer for an adherend is provided according to the adherend, as in Lamination Examples 7 and 8, it is possible to select the most suitable adhesive polyolefin for the adherend, which is preferable because it improves the adhesive strength of the adherend surface. In addition, the substrate surface is firmly adhered by the reaction between the adhesive layer and the acidic groups, ensuring the strength of the adhesive laminate.

[0058] When an adhesive composition is used as the resin constituting the adhesive layer, the imine-modified polyolefin or the modified polyolefin having a carbodiimide group is melt-kneaded with any other resin component.

[0059] As the melt-kneading device, a single-screw extruder, a multi-screw extruder, a Banbury mixer, a plastomill, a heated roll kneader, or the like can be used.

[0060] The heating temperature during melt-kneading is preferably selected from the range of 240°C to 300°C so that the imine-modified polyolefin or the modified polyolefin having a carbodiimide group and any other resin components are sufficiently melted and do not undergo thermal decomposition. The kneading temperature can be measured by a method such as contacting a thermocouple with the adhesive resin composition in a molten state immediately after it has been extruded from the melt kneading device.

[0061] <Laminate> The present invention is a laminate comprising the hot melt adhesive resin laminate of the present invention and an adherend. As shown in FIG. 4, the laminate of the present invention may include an adherend 5 and the hot-melt adhesive resin laminate 10 of the present invention in this order. As shown in FIG. 5, the laminate may also include a first adherend 5, the hot melt adhesive resin laminate 20 of the present invention, and a second adherend 6 in this order. As shown in FIG. 6, the laminate may also include a first adherend 5, the hot melt adhesive resin laminate 40 of the present invention, and a second adherend 6 in this order.

[0062] Since the adhesive layer is provided with an adhesive layer made of the hot melt adhesive resin laminate of the present invention as a forming material, it is possible to obtain good adhesion and durability even when adhering adherends together. The adherend to be bonded using the laminate of the present invention can be various adherends such as metal, glass, plastic, etc. Since the hot melt adhesive resin laminate of the present invention can exhibit high adhesion to metal, metal can be suitably used as the adherend. The metal may be a commonly known metal plate, flat metal plate, or metal foil. Examples of the metal used may include iron, copper, aluminum, lead, zinc, titanium, and chromium, as well as alloys such as stainless steel. Furthermore, metals or nonmetals that have been surface-treated by metal plating or coating with a metal-containing paint may also be used as the adherend. Flat metal plates or metal foils made of iron, aluminum, titanium, stainless steel, or surface-treated metals are particularly preferred, and by using these as the adherend, the hot-melt adhesive resin laminate of the present invention exhibits particularly strong adhesive strength. [Example]

[0063] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0064] <Peel strength test after hot water immersion> The peel strength test will be explained with reference to FIGS. First, the laminate shown in Figure 7 was used as a test specimen. A hot-melt adhesive resin laminate 30 from each example and comparative example, cut to 10 mm (L7) x 10 mm (L8), was laminated onto a stainless steel foil 31 having a thickness (L3) of 30 μm, a length (L1) of 150 mm, and a width (L2) of 10 mm. A stainless steel foil 32 cut to a thickness (L6) of 30 μm, a length (L4) of 150 mm, and a width (L5) of 10 mm was placed on top of the laminate. The laminate was then bonded together at 200°C for 5 seconds under a pressure of 0.4 MPa. The laminate was laminated with one edge aligned as shown in Figure 7. In the case of the hot water test, the laminate was immersed in pure water at 95° C. for 1000 hours. Thereafter, the laminate was taken out and dried at 23°C and 55% Rh for 1 hour.

[0065] Then, as shown in Figure 8, the stainless steel foils 31 and 32 were each bent at the end positions of the hot melt adhesive resin laminate 30 so that the stainless steel foil 31 was on the tensile side, and were held with a holder 33, and the stainless steel foil 32 was held and fixed with a holder 34, and the stainless steel foil 31 was pulled in the tensile direction shown by the symbol 35, and the peel strength was measured. The measurement was performed at a tensile speed of 300 mm / min.

[0066] When a two-layer hot melt adhesive resin laminate having an adhesive layer / substrate layer laminated in this order was used as the hot melt adhesive resin laminate 30, the hot melt adhesive resin laminate and the stainless steel foil were laminated so that the adhesive layer and the stainless steel foil were in contact, and a laminate having the stainless steel foil / adhesive layer / substrate layer laminated in this order was produced. For this laminate, as shown in Fig. 8, the stainless steel foil and the substrate layer were each bent at the end positions of the hot melt adhesive resin laminate so that the stainless steel foil was on the tensile side, and each was held with a holder, the stainless steel foil was held and fixed with a holder, and the substrate layer was pulled in the same tensile direction as above, and the peel strength was measured. The measurement was performed at a tensile speed of 300 mm / min.

[0067] <Peel strength test after immersion in acid solution> The same method as in the above <Peel strength test after hot water immersion> was carried out, except that this laminate was immersed in an acid solution of pH 2 containing 500 ppm of hydrogen fluoride for 1000 hours.

[0068] <Plasma treatment> Under atmospheric pressure plasma treatment conditions, the discharge rate was 1600 W·min / m 2 Atmospheric pressure plasma treatment was performed on one side of the base layer with the oxygen concentration in the discharge atmosphere gas set to 10% and the discharge time set to 1 second.

[0069] <Corona treatment> At atmospheric pressure, 600 W·min / m on one side of the substrate layer 2 The corona discharge treatment was carried out.

[0070] <Production of Adhesive Composition> The adhesive polyolefin resin, olefin-based elastomer, unmodified polyolefin, and optional additives shown in Table 1 below were melt-kneaded at 280° C. for 2 minutes to produce adhesive compositions 1 to 9.

[0071] [Table 1]

[0072] In Table 1 above, each symbol represents the following material. The numbers in brackets [ ] are the blend amounts (parts by mass). (A)-1: Imine-modified polyolefin (Mitsui Chemicals, Admer IP, melt flow rate: 3 g / 10 min). (A)-2: Imine-modified polyolefin (Mitsui Chemicals, Admer IP, melt flow rate: 15 g / 10 min). (A)-3: Modified polyolefin having carbodiimide groups (A)-4: Imine-modified polyolefin (Mitsui Chemicals, Admer IP, melt flow rate: 1 g / 10 min). (A)-5: Imine-modified polyolefin (Mitsui Chemicals, Admer IP, melt flow rate: 30 g / 10 min). (A)-6: Acid-modified polyolefin (Mitsui Chemicals, Inc., Admer) ·(B):·Olefin-based elastomer resin (MP: 120℃). (C): Polypropylene resin manufactured by SunAllomer (melt flow rate: 3 g / 10 min) (D): Special novolac epoxy resin (epoxy equivalent 200, softening point 70°C), The molecule contains a bisphenol A skeleton and an epoxy group with a novolac structure.

[0073] <Production of modified polyolefin (A-3) having carbodiimide groups> 25 parts by weight of maleic acid-modified polypropylene was blended with 25 parts by weight of Mitsui Chemicals polypropylene and 3 parts by weight of polycarbodiimide (Nisshinbo, product name Carbodilite HMV-8CA), and the mixture was melt-kneaded at 250°C (residence time = 2 minutes) in a 65 mmφ single-screw extruder (Modern Machinery) to obtain a modified polyolefin (A-3) having carbodiimide groups.

[0074] <Production of Hot Melt Adhesive Resin Laminate> Each adhesive composition shown in Table 2 below was extruded to form a 50 μm film to obtain an adhesive layer. Each substrate layer shown in Table 2 was laminated onto the obtained adhesive layer to obtain hot melt adhesive resin laminates of Examples 1 to 12 and Comparative Examples 1 to 4. Note that Comparative Example 1 had a low melt flow rate and was not suitable for drool flow, so film formation was not possible. However, the layer structure of "5-layer structure-2" was produced with a first substrate layer thickness of 90 μm and a second substrate layer thickness of 90 μm.

[0075] [Table 2]

[0076] In Table 2 above, the layer structure of each example is as follows: 2-layer structure: adhesive layer / base material layer 3-layer structure: adhesive layer / base material layer / adhesive layer 5-layer configuration-1: Adhesive layer / intermediate layer / base material layer / intermediate layer / adhesive layer Five-layer structure-2: adhesive layer / first base layer / adhesive layer / second base layer / adhesive layer

[0077] The hot-melt adhesive resin laminates obtained in Examples 1 to 11 and Comparative Examples 1 to 4 were bonded to stainless steel foil (30 μm) as the adherend to produce laminates, and the peel strength of the laminates after production was measured. The results are shown in Table 3 as "Before immersion test." The state of the peel interface was also evaluated according to the following items, and the results are shown in Table 3. The peel strength of the hot-melt adhesive resin laminates obtained in Examples 1 to 11 and Comparative Examples 1 to 4 was measured after immersion in hot water or acid solution. The results are shown in Table 3 as "after immersion in hot water" or "after immersion in acid solution." The state of the peel interface was also evaluated according to the following items, and the results are shown in Table 3.

[0078] ·State of peeling interface A: When observing the peeling interface, there are some peeled areas on the adherend side and some peeled areas on the base layer side, and the adhesion between the adherend side and the base layer side is consistent. Below It was found that the adhesive strength was above B: When the peeled interface was observed, there was a large amount of peeled off area on the base layer side. C: When the peeled interface was observed, peeling occurred on the base layer side over the entire surface.

[0079] [Table 3]

[0080] As shown in the above results, Examples 1 to 11 to which the present invention was applied maintained their peel strength even after immersion in hot water or acid solution. It was found that Examples 1 to 7 had good peel strength compared to the Comparative Examples, and the strength of the adhesive layer was also good when observing the peel interface. The adhesive resin laminates of Examples 8 and 9 were laminates in which an adhesive composition was laminated as an intermediate layer, but the selection of the adhesive prevented interlayer delamination, making them particularly resistant to interlayer delamination. The adhesive resin laminate of Example 10 was a laminate having two base layers, and therefore the flexibility of each base layer was higher than when it was a single-layer base layer, resulting in a pliable adhesive resin laminate. The adhesive resin laminate of Example 11 had a two-layer structure and only one side had adhesive, so the peel strength of only one side was measured, but it showed good adhesiveness.

[0081] The hot-melt adhesive resin laminates obtained in Examples 9 and 12 and Comparative Example 3 were bonded in the same manner as in the "Peel strength test after hot water immersion" except that the stainless steel foil was replaced with a nylon 6 sheet (100 μm) with no special surface treatment, and the peel strength after production was measured. The results are shown in Table 4 as "Before immersion test." The state of the peel interface was also evaluated according to the following items, and the results are shown in Table 4. The peel strength of the hot-melt adhesive resin laminates of Examples 9 and 12 and Comparative Example 3 was measured after immersion in hot water or acid solution. The results are shown in Table 4 as "After immersion in hot water" or "After immersion in acid solution." The state of the peel interface was also evaluated according to the following items, and the results are shown in Table 4.

[0082] ·State of peeling interface A: When observing the peeling interface, there are some peeled areas on the adherend side and some peeled areas on the base layer side, and the adhesion between the adherend side and the base layer side is consistent. Below It was found that the adhesive strength was above B: When the peeled interface was observed, there was a large amount of peeled off area on the adherend side. C: When the peeled interface was observed, there was a large amount of peeled off area on the base layer side.

[0083] [Table 4]

[0084] As shown in the above results, Examples 9 and 12, which are five-layer laminates to which the present invention is applied, maintained their peel strength even after immersion in hot water or acid solution when the adherend was nylon. [Explanation of symbols]

[0085] 30: Hot melt adhesive resin laminate, 31, 32: Stainless steel foil, 33, 34: Grip

Claims

1. A hot melt adhesive resin laminate having a base layer made of one or more resins selected from the group consisting of polyether ether ketone, polyphenylene sulfide resin, polyphenylene ether, syndiotactic polystyrene resin, polyethylene naphthalate, polyethylene terephthalate, polyimide resin, phenolic resin, epoxy resin, acrylic resin, polyketone, cyclic olefin resin, polymethylpentene, polypropylene, and polyethylene, and an adhesive layer, An adhesive layer is provided on at least one surface of the base material layer, the substrate layer has, on a surface in contact with the adhesive layer, acidic groups generated on the surface of the substrate layer by corona treatment or oxygen plasma treatment; a metal is used as an adherend of the adhesive layer, a hot melt adhesive resin laminate, characterized in that the adhesive composition constituting the adhesive layer contains an adhesive polyolefin-based resin, the adhesive polyolefin-based resin is an imine-modified polyolefin, and the melt flow rate of the imine-modified polyolefin is 2 g / 10 min or more and 25 g / 10 min or less.

2. 2. The hot melt adhesive resin laminate according to claim 1, wherein the imine-modified polyolefin is an imine-modified polypropylene.

3. A hot melt adhesive resin laminate as described in claim 1 or 2, wherein the base layer is formed from one or more resins selected from the group consisting of polyphenylene sulfide resin and polyethylene terephthalate.

4. A hot melt adhesive resin laminate having a base layer made of a resin comprising polyethylene terephthalate as a forming material and an adhesive layer, An adhesive layer is provided on at least one surface of the base material layer, the substrate layer has, on a surface in contact with the adhesive layer, acidic groups generated on the surface of the substrate layer by corona treatment or oxygen plasma treatment; a metal is used as an adherend of the adhesive layer, a hot melt adhesive resin laminate, characterized in that the adhesive composition constituting the adhesive layer contains an adhesive polyolefin-based resin, the adhesive polyolefin-based resin is a modified polyolefin having a carbodiimide group, and the melt flow rate of the modified polyolefin having a carbodiimide group is 2 g / 10 min or more and 25 g / 10 min or less.

5. The hot melt adhesive resin laminate according to any one of claims 1 to 4, wherein the thickness of the substrate layer is 10 µm or more and 200 µm or less.

6. The hot melt adhesive resin laminate according to any one of claims 1 to 5, wherein the base layer is a film formed from the resin, or a composite of the resin and one selected from a nonwoven fabric or a woven fabric.

7. The hot melt adhesive resin laminate according to any one of claims 1 to 6, wherein the adhesive composition contains an olefin-based elastomer.

8. 8. The hot melt adhesive resin laminate according to claim 1, wherein the adhesive composition comprises an unmodified polyolefin having a melt flow rate of 2 g / 10 min or more and 25 g / 10 min or less.

9. A laminate comprising the hot melt adhesive resin laminate according to any one of claims 1 to 8 and the adherend.

10. A method for producing a hot melt adhesive resin laminate having a base layer and an adhesive layer, the base layer being made of one or more resins selected from the group consisting of polyether ether ketone, polyphenylene sulfide resin, polyphenylene ether, syndiotactic polystyrene resin, polyethylene naphthalate, polyethylene terephthalate, polyimide resin, phenolic resin, epoxy resin, acrylic resin, polyketone, cyclic olefin resin, polymethylpentene, polypropylene, and polyethylene, generating acidic groups on the first surface of the substrate layer by corona treatment or oxygen plasma treatment; laminating an adhesive layer on the first surface of the base material layer; Including, a metal is used as an adherend of the adhesive layer, a method for producing a hot melt adhesive resin laminate, wherein the adhesive composition constituting the adhesive layer contains an adhesive polyolefin-based resin, the adhesive polyolefin-based resin being an imine-modified polyolefin, and the melt flow rate of the imine-modified polyolefin is 2 g / 10 min or more and 25 g / 10 min or less.

11. The method for producing a hot melt adhesive resin laminate according to claim 10, wherein the imine-modified polyolefin is an imine-modified polypropylene.

12. A method for producing a hot melt adhesive resin laminate described in claim 10 or 11, wherein the base layer is formed from one or more resins selected from the group consisting of polyphenylene sulfide resin and polyethylene terephthalate.

13. A method for producing a hot melt adhesive resin laminate having a base layer made of a resin comprising polyethylene terephthalate as a forming material and an adhesive layer, comprising: generating acidic groups on the first surface of the substrate layer by corona treatment or oxygen plasma treatment; laminating an adhesive layer on the first surface of the base material layer; Including, a metal is used as an adherend of the adhesive layer, a method for producing a hot melt adhesive resin laminate, characterized in that the adhesive composition constituting the adhesive layer contains an adhesive polyolefin-based resin, the adhesive polyolefin-based resin is a modified polyolefin having a carbodiimide group, and the melt flow rate of the modified polyolefin having a carbodiimide group is 2 g / 10 min or more and 25 g / 10 min or less.

14. The method for producing a hot melt adhesive resin laminate according to any one of claims 10 to 13, wherein the thickness of the base layer is 10 µm or more and 200 µm or less.

15. The method for producing a hot melt adhesive resin laminate according to any one of claims 10 to 14, wherein the base material layer is a film formed from the resin, or a composite of the resin and one selected from a nonwoven fabric or a woven fabric.

16. The method for producing a hot melt adhesive resin laminate according to any one of claims 10 to 15, wherein the adhesive composition contains an olefin-based elastomer.

17. The method for producing a hot melt adhesive resin laminate according to any one of claims 10 to 16, wherein the adhesive composition contains an unmodified polyolefin having a melt flow rate of 2 g / 10 min or more and 25 g / 10 min or less.

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