Adhesive composition, intermediate laminate, laminate, and method for manufacturing the intermediate laminate

Abstract

To provide an adhesive composition which can bond two different kinds of base materials regardless of the kinds of the base materials, and is excellent in storage stability, an intermediate laminate having an adhesive layer composed of the adhesive composition, a laminate having an adhesive layer composed of the adhesive composition, and a method for manufacturing the intermediate laminate.SOLUTION: An adhesive composition contains a modified polyolefin resin and a solvent. In the modified polyolefin resin, a polyolefin resin is modified with a compound having both a block isocyanate group and a (meth)acryloyl group.SELECTED DRAWING: Figure 3

Description

TECHNICAL FIELD

[0001] The present invention relates to an adhesive composition, an intermediate laminate, a laminate, and a method for producing the intermediate laminate. BACKGROUND ART

[0002] Conventionally, in various fields such as packaging materials, two base materials of different types are sometimes used by being bonded to each other.

[0003] On the other hand, when the types of base materials are different, the adhesiveness may decrease in some cases.

[0004] Therefore, from the viewpoint of improving adhesiveness, it is known to provide an adhesive layer between two base materials.

[0005] As a material for forming such an adhesive layer, for example, a coating agent containing a maleic anhydride-modified propylene / 1-butene copolymer and a hydrocarbon-based synthetic oil has been proposed (see, for example, Example 1 of Patent Document 1). PRIOR ART DOCUMENTS PATENT DOCUMENTS

[0006] PATENT DOCUMENT 1 International Publication No. 2013 / 164976 Pamphlet SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION

[0007] However, the coating agent of Patent Document 1 has a problem that the adhesiveness decreases depending on the types of the two base materials.

[0008] In addition, depending on the purpose and application, there is a case where after forming an adhesive layer and storing it for a long period of time, lamination is performed using the adhesive layer. Therefore, the adhesive layer is required to have adhesiveness even after long-term storage (storage stability).

[0009] The present invention provides an adhesive composition that can bond two substrates of different types regardless of the type of substrate and has excellent storage stability, an intermediate laminate comprising an adhesive layer made of the adhesive composition, a laminate comprising an adhesive layer made of the adhesive composition, and a method for manufacturing the intermediate laminate. [Means for solving the problem]

[0010] The present invention [1] is an adhesive composition comprising a modified polyolefin resin and a solvent, wherein the modified polyolefin resin is modified by a compound having both a blocked isocyanate group and a (meth)acryloyl group.

[0011] The present invention [2] includes the adhesive composition described in [1] above, wherein the polyolefin resin has a heat of fusion of 0 J / g or more and 60 J / g or less, as measured according to JIS K7122.

[0012] The present invention [3] further comprises the adhesive composition described in [1] above, which includes another polyolefin resin.

[0013] The present invention [4] further comprises the adhesive composition described in [1] above, which includes a blocked isocyanate dissociation catalyst.

[0014] The present invention [5] comprises a substrate and an adhesive layer which is a dried product of any one of the adhesive compositions described in [1] to [4] above, in order toward one side in the thickness direction, wherein the adhesive layer includes an intermediate laminate in which the modified polyolefin resin has blocked isocyanate groups.

[0015] The present invention [6] includes a laminate comprising a first substrate, an adhesive layer which is a dried product of an adhesive composition described in any one of the above [1] to [4], and a second substrate of a different type from the first substrate, in order toward one side in the thickness direction.

[0016] The present invention [7] includes a method for manufacturing an intermediate laminate, comprising a first step of preparing a substrate and a second step of applying an adhesive composition described in any one of the above [1] to [4] to one side of the first substrate in the thickness direction and drying it at less than 200°C to form an adhesive layer. [Effects of the Invention]

[0017] In the adhesive composition of the present invention, the modified polyolefin resin is modified by a compound having both a blocked isocyanate group and a (meth)acryloyl group. Therefore, it can bond two substrates of different types, regardless of the type of substrate, and has excellent storage stability.

[0018] In detail, when using this adhesive composition to bond two substrates of different types, first, an adhesive layer, which is the dried product of the adhesive composition, is placed (formed) on one side in the thickness direction of one substrate. Then, the two substrates are bonded together by laminating the first substrate with the second substrate via this adhesive layer. When the adhesive layer is placed (formed), the modified polyolefin resin in the adhesive composition has blocked isocyanate groups. Therefore, even after long-term storage without performing the lamination described above, the adhesive layer retains its adhesive properties and exhibits excellent storage stability.

[0019] On the other hand, in the above bonding process, the blocked isocyanate groups are deblocked and become isocyanate groups. Then, the adhesion is improved by the interaction between these isocyanate groups and the two substrates of different types. Therefore, regardless of the type of substrate, two substrates of different types can be bonded together.

[0020] In the intermediate laminate of the present invention, the modified polyolefin resin in the adhesive layer has blocked isocyanate groups. Therefore, even after long-term storage, the adhesive layer of this intermediate laminate retains its adhesive properties and exhibits excellent storage stability.

[0021] The laminate of the present invention includes an adhesive layer made of the adhesive composition of the present invention between a first base material and a second base material of mutually different types. Therefore, the first base material and the second base material can be reliably bonded to each other.

[0022] The method for producing an intermediate laminate of the present invention includes a second step of applying the adhesive composition of the present invention to one surface in the thickness direction of a first base material, and drying the applied composition at a temperature lower than 200°C to dispose an adhesive layer. Therefore, in the adhesive layer, deblocking of the blocked isocyanate groups of the modified polyolefin resin can be suppressed, and an intermediate laminate having excellent storage stability can be produced. [Brief Description of the Drawings]

[0023] [Figure 1] Figure 1 is a schematic view showing one embodiment of the intermediate laminate of the present invention. [Figure 2] Figure 2A and Figure 2B are schematic views showing one embodiment of the method for producing an intermediate laminate of the present invention. Figure 2A shows a first step of preparing a first base material. Figure 2B shows a second step of disposing an adhesive layer on one surface in the thickness direction of the first base material. [Figure 3] Figure 3 is a schematic view showing one embodiment of the laminate of the present invention. [Figure 4] Figure 4A and Figure 4B are schematic views showing one embodiment of the method for producing a laminate of the present invention. Figure 4A shows a third step of preparing an intermediate laminate. Figure 4B shows a fourth step of disposing a second base material on one surface in the thickness direction of the adhesive layer in the intermediate laminate, and bonding the first base material and the second base material. [Modes for Carrying Out the Invention]

[0024] The adhesive composition contains a modified polyolefin resin and a solvent.

[0025] <Modified Polyolefin Resin> Modified polyolefin resins are obtained by modifying a polyolefin resin with a compound that contains both a blocked isocyanate group and a (meth)acryloyl group. More specifically, modified polyolefin resins are obtained by modifying a polyolefin resin with a compound that contains both a blocked isocyanate group and a (meth)acryloyl group.

[0026] [Polyolefin resin] Polyolefin resins are olefin polymers that contain constituent units derived from olefins.

[0027] Examples of olefins include α-olefins. Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0028] Preferably, the olefins are α-olefins having 2 to 6 carbon atoms, more preferably propylene, and 1-butene.

[0029] Olefins can be used alone or in combination of two or more types. Preferably, a combination of propylene and 1-butene is used. In other words, the polyolefin resin is preferably a propylene / 1-butene copolymer.

[0030] When the polyolefin resin is a propylene / 1-butene copolymer, the content of propylene-derived structural units is, for example, 60 mol% or more, preferably 70 mol% or more, and also, for example, 90 mol% or less, preferably 80 mol% or less, relative to the total amount of propylene-derived structural units and 1-butene-derived structural units (100 mol%). The content of 1-butene-derived structural units is, for example, 10 mol% or more, preferably 20 mol% or more, and also, for example, 40 mol% or less, preferably 30 mol% or less.

[0031] Polyolefin resins are obtained by polymerizing olefins using known methods. Furthermore, metallocene catalysts may be incorporated into the polymerization process as needed.

[0032] The heat of fusion of polyolefin resin, as measured according to JIS K7122, is, for example, 0 J / g or more, preferably 3 J / g or more, preferably 10 J / g or more, and also, for example, 110 J / g or less, preferably 60 J / g or less, more preferably 40 J / g or less.

[0033] If the above heat of fusion is above the lower limit and below the upper limit, the modified polyolefin resin can be dissolved or dispersed in the solvent. As a result, this adhesive composition can be prepared as a coating agent. In particular, if the above heat of fusion is 60 J / g or less, the modified polyolefin resin can be dissolved in the solvent, and the solution stability can be further improved.

[0034] [Compounds containing both a blocked isocyanate group and a (meth)acryloyl group] Compounds having both a blocked isocyanate group and a (meth)acryloyl group have one or more blocked isocyanate groups and one or more (meth)acryloyl groups. Preferably, compounds having both a blocked isocyanate group and a (meth)acryloyl group have one blocked isocyanate group and one (meth)acryloyl group. The (meth)acryloyl group is a methacryloyl group and / or an acryloyl group.

[0035] Examples of such compounds include the compound represented by formula (1) below (hereinafter referred to as compound (1)) and the compound represented by formula (2) below (hereinafter referred to as compound (2)). [ka] In formula (1) above, R1 represents a hydrogen atom or a methyl group. R2 represents an alkylene group having 1 to 20 carbon atoms. X represents a leaving group. Also, in formula (1) above, -NH-C(=O)-X is a blocked isocyanate group. [ka] In formula (2) above, R1 is equivalent to R1 in formula (1) above. R2 is equivalent to R2 in formula (1) above. R3 represents an alkylene group having 1 to 20 carbon atoms, which is the same as or different from R2. Also, in formula (2) above, -NH-C(=O)-X is a blocked isocyanate group.

[0036] Examples of alkylene groups having 1 to 20 carbon atoms include linear alkylene groups having 1 to 20 carbon atoms and branched alkylene groups having 1 to 20 carbon atoms.

[0037] Examples of linear alkylene groups having 1 to 20 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, tetradecylene, hexadecylene, octadecylene, and eicosilene. Preferably, linear alkylene groups having 1 to 4 carbon atoms are used as linear alkylene groups having 1 to 20 carbon atoms.

[0038] Examples of branched alkylene groups having 1 to 20 carbon atoms include isopropylene, isobutylene, s-butylene, t-butylene, isopentylene, s-pentylene, 2-methylhexylene, 2-ethylhexylene, and isodecylene. Preferably, branched alkylene groups having 2 to 4 carbon atoms are used as branched alkylene groups having 1 to 20 carbon atoms.

[0039] Preferably, the alkylene group having 1 to 20 carbon atoms is a linear alkylene group having 1 to 20 carbon atoms. More preferably, the alkylene group having 1 to 20 carbon atoms is a linear alkylene group having 1 to 4 carbon atoms. Even more preferably, the alkylene group having 1 to 20 carbon atoms is ethylene.

[0040] The leaving group is generally removed by deblocking the blocked isocyanate group, as shown in formula (3) below. Furthermore, the isocyanate group is regenerated by this removal. In formula (3) below, HX is the blocking agent.

[0041] [ka]

[0042] The blocking agents are not particularly limited and include, for example, guanidine compounds, imidazole compounds, alcohol compounds, phenol compounds, active methylene compounds, amine compounds, imine compounds, oxime compounds, carbamic acid compounds, urea compounds, acid amide (lactam) compounds, acid imide compounds, triazole compounds, pyrazole compounds, mercaptan compounds, bisulfites, imidazoline compounds, and pyrimidine compounds. Preferably, pyrazole blocking agents and oxime blocking agents are used.

[0043] Examples of pyrazole-based blocking agents include pyrazole, 3,5-dimethylpyrazole (dissociation temperature 120°C), 3,5-diisopropylpyrazole, 3,5-diphenylpyrazole, 3,5-di-t-butylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole. Preferably, 3,5-dimethylpyrazole is used as the pyrazole-based blocking agent.

[0044] Examples of oxime-based blocking agents include formaldehyde oxime, acetaldehyde oxime, acetooxime, methyl ethyl ketone oxime, cyclohexanone oxime, diacetyl monooxime, benzophenooxime, 2,2,6,6-tetramethylcyclohexanone oxime, diisopropyl ketone oxime, methyl t-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylpentyl ketone oxime, methyl 3-ethylheptyl ketone oxime, methyl isoamyl ketone oxime, n-amyl ketone oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4'-dimethoxybenzophenone oxime, and 2-heptanone oxime. Methyl ethyl ketone oxime is a preferred example of an oxime-based blocking agent.

[0045] Preferably, a pyrazole-based blocking agent is used.

[0046] Blocking agents can be used alone or in combination of two or more types.

[0047] Compound (1) is a preferred example of a compound having both a blocked isocyanate group and a (meth)acryloyl group.

[0048] Preferably, such compounds (1) include 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (a compound represented by formula (4) below) and 2-[0-(1'-methylpropyleneneamino)carboxyamino]ethyl methacrylate (a compound represented by formula (5) below). [ka] [ka]

[0049] More preferably, compound (1) is 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate.

[0050] Compounds containing both an isocyanate group and a (meth)acryloyl group can be used alone or in combination of two or more.

[0051] [Preparation of Modified Polyolefin Resins] Modified polyolefin resins are obtained by modifying polyolefin resins with compounds that contain both blocked isocyanate groups and (meth)acryloyl groups.

[0052] Specifically, a polyolefin resin is mixed with a compound having both a blocked isocyanate group and a (meth)acryloyl group, and these are reacted. As a result, the compound having both the blocked isocyanate group and the (meth)acryloyl group is grafted onto the polyolefin resin.

[0053] The reaction temperature is, for example, 50°C or higher, preferably 80°C or higher, and also, for example, 250°C or lower, preferably 180°C or lower. The reaction time is, for example, 1 hour or more, and also 10 hours or less.

[0054] Furthermore, in the above reaction, a radical polymerization initiator may be added in an appropriate proportion as needed.

[0055] Examples of radical polymerization initiators include organic peroxides and azo compounds. Examples of organic peroxides include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate)hexine-3, 1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexine-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl benzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate, and tert-butyl perdiethyl acetate. Examples of azo compounds include azobis-isobutylnitrile and dimethylazoisobutylnitrile.

[0056] Preferably, organic peroxides are used as radical polymerization initiators. More preferably, di-tert-butyl peroxide is used as a radical polymerization initiator.

[0057] Radical polymerization initiators can be used alone or in combination of two or more types.

[0058] Furthermore, the above reaction may be carried out in the presence or absence of a solvent. From the viewpoint of maintaining the blocking agent more easily, the above reaction may be carried out in the presence of a solvent.

[0059] As a solvent, one that is inert to the isocyanate group is preferred. Examples of solvents include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ketones, alkyl esters, glycol ether esters, ethers, and polar aprotons. Examples of aliphatic hydrocarbons include n-hexane, n-heptane, and octane. Examples of alicyclic hydrocarbons include cyclohexane and methylcyclohexane. Examples of aromatic hydrocarbons include toluene and xylene. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of alkyl esters include methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate. Examples of glycol ether esters include methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, and ethyl-3-ethoxypropionate. Examples of ethers include diethyl ether, tetrahydrofuran, and dioxane. Examples of polar aprotons include N-methylpyrrolidone, dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphonylamide.

[0060] Preferred solvents include alicyclic hydrocarbons and alkyl esters. More preferably, methylcyclohexane and butyl acetate are used as solvents.

[0061] Solvents can be used alone or in combination of two or more types.

[0062] This process prepares a modified polyolefin resin (a solution of the modified polyolefin resin). Such a modified polyolefin resin has blocked isocyanate groups derived from a compound having both blocked isocyanate groups and (meth)acryloyl groups.

[0063] In a solution of modified polyolefin resin, the solid content concentration is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 50% by mass or less, preferably 30% by mass or less.

[0064] The amount of modification (graft amount) of the compound having both an isocyanate group and a (meth)acryloyl group to the modified polyolefin resin is, for example, 0.5% by mass or more, preferably 1.0% by mass or more, more preferably 1.5% by mass or more, and also, for example, 10% by mass or less, preferably 5.0% by mass or less, more preferably 3.0% by mass or less.

[0065] If the above modification amount is above the lower limit and below the upper limit, two substrates of different types (the first substrate and the second substrate, described later) can be bonded together, regardless of the type of substrate.

[0066] The above modification amount (graft amount) can be determined, for example, from the mixing ratio of each component when preparing the modified polyolefin resin. 1 This can also be confirmed by known methods such as 1H-NMR measurement.

[0067] The weight-average molecular weight of the modified polyolefin resin, measured by gel permeation chromatography (GPC) and converted to standard polystyrene, is, for example, 50,000 or more, preferably 70,000 or more, and also, for example, 200,000 or less, preferably 150,000 or less.

[0068] If the weight-average molecular weight is within the above range, the modified polyolefin resin can be dissolved in the solvent. As a result, this adhesive composition can be prepared as a coating agent.

[0069] The method for measuring the weight-average molecular weight described above will be explained in detail in the examples below.

[0070] Furthermore, the melt mass flow rate (MFR) of the modified polyolefin resin is, for example, 200 g / 10 min or more, and for example, 2000 g / 10 min or less.

[0071] If the above melt mass flow rate (MFR) is above the above lower limit, the modified polyolefin resin can be dissolved in the solvent. As a result, this adhesive composition can be prepared as a coating agent.

[0072] The melt mass flow rate (MFR) can be measured in accordance with JIS K 7210, under measurement conditions of a plastometer cylinder temperature of 230°C and a load of 2.16 kgf.

[0073] Modified polyolefin resins can be used alone or in combination of two or more types.

[0074] The content of the modified polyolefin resin is, for example, 1% by mass or more, 5% by mass or more, and for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less, relative to the adhesive composition.

[0075] <Other polyolefin resins> The adhesive composition may also contain other polyolefin resins from the viewpoint of improving adhesion (particularly AL-PP adhesion, as described later).

[0076] Other polyolefin resins are polyolefin resins other than the modified polyolefin resins described above. Specifically, examples of other polyolefin resins include unmodified polyolefin resins, acid-modified polyolefin resins, and hydroxyl group-containing vinyl monomer-modified polyolefin resins.

[0077] [Unmodified polyolefin resin] Examples of unmodified polyolefin resins include the polyolefin resins described in detail above in the section on modified polyolefin resins.

[0078] [Acid-modified polyolefin resin] Acid-modified polyolefin resins are obtained by modifying polyolefin resins with unsaturated carboxylic acids.

[0079] Examples of polyolefin resins include those described in detail above in the section on modified polyolefin resins. Preferably, a propylene / 1-butene copolymer is used as the polyolefin resin. Preferably, the same polyolefin resin as the polyolefin resin used in the section on modified polyolefin resins is used as the polyolefin resin.

[0080] Examples of unsaturated carboxylic acids include those having 3 to 8 carbon atoms. Examples of unsaturated carboxylic acids having 3 to 8 carbon atoms include monobasic acids and dibasic acids. Examples of monobasic acids include (meth)acrylic acid (acrylic acid and / or methacrylic acid), crotonic acid, and isocrotonic acid. Examples of dibasic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, allylsuccinic acid, nadic acid, methylnadic acid, tetrahydrofumaric acid, and methylhexahydrophthalic acid.

[0081] Furthermore, unsaturated carboxylic acids include the acid anhydrides of the unsaturated carboxylic acids mentioned above.

[0082] Preferably, unsaturated carboxylic acids include acid anhydrides of unsaturated carboxylic acids. More preferably, unsaturated carboxylic acids include acid anhydrides of dibasic acids. Even more preferably, unsaturated carboxylic acids include maleic anhydride.

[0083] Unsaturated carboxylic acids can be used alone or in combination of two or more types.

[0084] Acid-modified polyolefin resins are obtained by reacting a polyolefin resin with an unsaturated carboxylic acid. In this reaction, the unsaturated carboxylic acid is grafted onto the polyolefin resin.

[0085] The reaction temperature is, for example, 50°C or higher, preferably 80°C or higher, and also, for example, 250°C or lower, preferably 180°C or lower. The reaction time is, for example, 1 hour or more, and also 10 hours or less.

[0086] Furthermore, in the above reaction, a radical polymerization initiator may be added in an appropriate proportion as needed.

[0087] Examples of radical polymerization initiators include those described in detail above for modified polyolefin resins.

[0088] Preferably, organic peroxides are used as radical polymerization initiators. More preferably, di-tert-butyl peroxide is used as a radical polymerization initiator.

[0089] Furthermore, the above reaction may be carried out in the presence or absence of a solvent. Preferably, the above reaction is carried out in the presence of a solvent.

[0090] Examples of solvents include those detailed above for the modified polyolefin resin. Preferably, the solvents include alicyclic hydrocarbons and alkyl esters. More preferably, the solvents include methylcyclohexane and butyl acetate. In addition, preferably, the same solvents as those detailed above for the modified polyolefin resin are selected.

[0091] This process prepares an acid-modified polyolefin resin (a solution of acid-modified polyolefin resin).

[0092] In a solution of acid-modified polyolefin resin, the solid content concentration is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 50% by mass or less, preferably 30% by mass or less.

[0093] The amount of unsaturated carboxylic acid used to modify the acid-modified polyolefin resin (graft amount) is, for example, 0.5% by mass or more, preferably 0.8% by mass or more, and for example, 5.0% by mass or less, preferably 3.0% by mass or less, and more preferably 2.0% by mass or less.

[0094] The above modification amount (graft amount) can be determined, for example, from the mixing ratio of each component when preparing an acid-modified polyolefin resin. 1 This can also be confirmed by known methods such as 1H-NMR measurement.

[0095] [Hydroxygroup-containing vinyl monomer-modified polyolefin resin] A hydroxyl group-containing vinyl monomer-modified polyolefin resin is obtained by modifying a polyolefin resin with a hydroxyl group-containing vinyl monomer.

[0096] Examples of polyolefin resins include the polyolefin resins described in detail above in the section on modified polyolefin resins.

[0097] Examples of hydroxyl group-containing vinyl monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0098] Hydroxyl group-containing vinyl monomers can be used alone or in combination of two or more types.

[0099] Furthermore, hydroxyl group-containing vinyl monomer-modified polyolefin resin is obtained by reacting a polyolefin resin with a hydroxyl group-containing vinyl monomer. In this reaction, the hydroxyl group-containing vinyl monomer is grafted onto the polyolefin resin.

[0100] The reaction temperature is, for example, 50°C or higher, preferably 80°C or higher, and also, for example, 250°C or lower, preferably 180°C or lower. The reaction time is, for example, 1 hour or more, and also 10 hours or less.

[0101] Furthermore, in the above reaction, a radical polymerization initiator may be added in an appropriate proportion as needed.

[0102] Examples of radical polymerization initiators include those described in detail above for modified polyolefin resins.

[0103] Preferably, organic peroxides are used as radical polymerization initiators. More preferably, di-tert-butyl peroxide is used as a radical polymerization initiator.

[0104] Furthermore, the above reaction may be carried out in the presence or absence of a solvent. Preferably, the above reaction is carried out in the presence of a solvent.

[0105] Examples of solvents include those detailed above for the modified polyolefin resin. Preferably, the solvents include alicyclic hydrocarbons and alkyl esters. More preferably, the solvents include methylcyclohexane and butyl acetate. In addition, preferably, the same solvents as those detailed above for the modified polyolefin resin are selected.

[0106] This process prepares a hydroxyl group-containing vinyl monomer-modified polyolefin resin (a solution of the hydroxyl group-containing vinyl monomer-modified polyolefin resin).

[0107] In a solution of a hydroxyl group-containing vinyl monomer-modified polyolefin resin, the solid content concentration is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 50% by mass or less, preferably 30% by mass or less.

[0108] The amount of hydroxyl group-containing vinyl monomer used to modify the hydroxyl group-containing vinyl monomer-modified polyolefin resin (graft amount) is, for example, 0.5% by mass or more, preferably 1.0% by mass or more, and for example, 5.0% by mass or less, preferably 3.0% by mass or less, and more preferably 2.0% by mass or less.

[0109] Furthermore, the above modification amount (graft amount) can be determined, for example, from the mixing ratio of each component when preparing a hydroxyl group-containing vinyl monomer-modified polyolefin resin. 1 This can be confirmed by known methods such as 1H-NMR measurement.

[0110] Other polyolefin resins that are preferable include acid-modified polyolefin resins, from the viewpoint of improving adhesion (particularly AL-PP adhesion, as described later).

[0111] Other polyolefin resins can be used individually or in combination of two or more types.

[0112] The content of other polyolefin resins is, for example, 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and also, for example, 20% by mass or less, preferably 10% by mass or less, relative to the adhesive composition.

[0113] Furthermore, if the adhesive composition contains other polyolefin resins, the content of the other polyolefin resins is, for example, 10 parts by mass or more, preferably 40 parts by mass or more, and for example, 80 parts by mass or less, preferably 60 parts by mass or less, based on 100 parts by mass of the total amount of the modified polyolefin resin and the other polyolefin resins. Furthermore, the content of the modified polyolefin resins is, for example, 20 parts by mass or more, preferably 40 parts by mass or more, and for example, 90 parts by mass or less, preferably 60 parts by mass or less, based on 100 parts by mass of the total amount of the modified polyolefin resin and the other polyolefin resins.

[0114] <Solvent> Examples of solvents include those described in detail above for modified polyolefin resins. Preferably, the solvents include alicyclic hydrocarbons and alkyl esters. More preferably, the solvents include methylcyclohexane and butyl acetate.

[0115] Furthermore, if a modified polyolefin resin and / or other polyolefin resin is manufactured in a solvent, that solvent can be used as is.

[0116] The solvent content is the remainder of the modified polyolefin resin, other polyolefin resins added as needed, a blocked isocyanate dissociation catalyst (described later) added as needed, and additives (described later) added as needed, and is, for example, 60% by mass or more, preferably 75% by mass or more, and for example, 90% by mass or less, relative to the adhesive composition. In other words, the total amount (solid content concentration) of the modified polyolefin resin and other polyolefin resins added as needed, relative to the adhesive composition, is, for example, 10% by mass or more, and for example, 40% by mass or less, and preferably 25% by mass or less.

[0117] <Blocked Isocyanate Dissociation Catalyst> The adhesive composition may include a blocked isocyanate dissociation catalyst as needed, from the viewpoint of improving adhesion.

[0118] Examples of blocked isocyanate dissociation catalysts include tertiary amines and metal compounds. Examples of tertiary amines include 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) and 1,6-diazabicyclo[3.4.0]nonene-5. Examples of metal compounds include dibutyltin dilaurate, lead octoate, and bismuth octoate.

[0119] Preferably, a tertiary amine is used as the blocked isocyanate dissociation catalyst. More preferably, 1,8-diazabicyclo[5.4.0]undecene-7 is used as the blocked isocyanate dissociation catalyst.

[0120] Blocked isocyanate dissociation catalysts can be used alone or in combination of two or more types.

[0121] The content of the blocked isocyanate dissociation catalyst is, for example, 0.01% by mass or more, and for example, 5% by mass or less, preferably 1% by mass or less, relative to the adhesive composition.

[0122] Furthermore, the content ratio of the blocked isocyanate dissociation catalyst is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, and for example, 5 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.8 parts by mass or less, per 100 parts by mass of the modified polyolefin resin.

[0123] <Additives> The adhesive composition may contain additives in appropriate proportions as needed.

[0124] Examples of additives include pigments, thickeners, tackifiers, defoamers, surface modifiers, anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents.

[0125] Additives can be used individually or in combination of two or more types.

[0126] <Preparation of adhesive composition> The adhesive composition is prepared by mixing a modified polyolefin resin, other polyolefin resins as needed, a solvent, a blocked isocyanate dissociation catalyst as needed, and additives as needed.

[0127] In such adhesive compositions, the modified polyolefin resin is modified by a compound having both a blocked isocyanate group and a (meth)acryloyl group. Therefore, it can bond two substrates of different types, regardless of the type of substrate, and exhibits excellent storage stability.

[0128] The following describes in detail a method for bonding two substrates of different types (a first substrate and a second substrate) using this adhesive composition. Specifically, firstly, an intermediate laminate used in the method of bonding two substrates of different types and a method for manufacturing the intermediate laminate will be described in detail. Secondly, the method of bonding two substrates of different types (method for manufacturing the laminate) will be described in detail.

[0129] <Intermediate Laminate> The intermediate laminate of the present invention comprises a substrate and an adhesive layer in order toward one side in the thickness direction.

[0130] As described above, the intermediate laminate is used in a method for bonding two substrates of different types (a first substrate and a second substrate). In the following description, we will focus on the intermediate laminate used in the embodiment where the substrate is the first substrate (in other words, the embodiment in which an adhesive layer is placed on one side in the thickness direction of the first substrate in the second step described later).

[0131] An embodiment of the intermediate laminate of the present invention will be described with reference to Figure 1.

[0132] In Figure 1, the vertical direction of the paper is the vertical direction (thickness direction), with the top of the paper being the top (one side in the thickness direction) and the bottom of the paper being the bottom (the other side in the thickness direction). The horizontal and depth directions of the paper are plane directions perpendicular to the vertical direction. Specifically, these correspond to the directional arrows in each figure.

[0133] As shown in Figure 1, the intermediate laminate 10 has a film shape (including a sheet shape) with a predetermined thickness. The intermediate laminate 10 extends in a planar direction perpendicular to the thickness direction. The intermediate laminate 10 has a flat top surface and a flat bottom surface.

[0134] The intermediate laminate 10 comprises a first base material 2 as a base material and an adhesive layer 3 in order toward one side in the thickness direction. Specifically, the intermediate laminate 10 comprises a first base material 2 and an adhesive layer 3 that is directly disposed on the upper surface (one side in the thickness direction) of the first base material 2.

[0135] [First base material] The first substrate 2 has a film shape. The first substrate 2 is positioned over the entire lower surface of the adhesive layer 3 so as to be in contact with the lower surface of the adhesive layer 3.

[0136] The type of the first base material 2 is different from the type of the second base material 4 (described later). The terms "different types" include the following: the materials constituting the first base material 2 and the materials constituting the second base material 4 (described later) are different resins; the materials constituting the first base material 2 and the materials constituting the second base material 4 (described later) are different metals; or one of the materials constituting the first base material 2 and the materials constituting the second base material 4 (described later) is a metal and the other is a resin.

[0137] Examples of materials constituting the first base material 2 include resins and metals. Examples of resins include high-polarity resin materials and low-polarity resin materials. Examples of high-polarity resin materials include acrylic resins, polyamide resins, polyimide resins, polyurethane resins, polycarbonate resins, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer resins, polysyl resins (e.g., polyethylene terephthalate (PET)), and acrylonitrile / styrene / butadiene copolymer resins (ABS resins). Examples of low-polarity resin materials include polyolefin resins (e.g., polyethylene, polypropylene). Examples of metals include iron, aluminum, zinc, stainless steel, and alloys thereof. Aluminum is preferably used as the metal.

[0138] [Adhesive layer] The adhesive layer 3 has a film shape.

[0139] The adhesive layer 3 is formed from the solid content (dried material) of the above-mentioned adhesive composition.

[0140] The adhesive layer 3 is obtained by applying an adhesive composition to one side in the thickness direction of the first substrate 2 and drying the solvent, as will be described in more detail later.

[0141] As will be explained in more detail later, in the above drying process, the drying temperature is selected to be one that can suppress the deblocking of the blocked isocyanate groups of the modified polyolefin resin in the adhesive layer 3 (a temperature below the dissociation temperature of the blocking agent). Therefore, in the adhesive layer 3, the modified polyolefin resin has blocked isocyanate groups. As a result, even after long-term storage, the adhesive layer 3 of this intermediate laminate 10 retains its adhesive properties and exhibits excellent storage stability.

[0142] The thickness of the adhesive layer 3 is, for example, 1 μm or more, and for example, 10 μm or less.

[0143] <Method for manufacturing intermediate laminates> The present invention provides a method for manufacturing an intermediate laminate, comprising a first step of preparing a substrate and a second step of arranging an adhesive layer on one side of the substrate in the thickness direction.

[0144] An embodiment of the method for manufacturing the intermediate laminate of the present invention will be described with reference to Figures 2A and 2B.

[0145] The method for manufacturing the intermediate laminate 10 comprises a first step of preparing a first substrate 2 as a base material, and a second step of placing an adhesive layer 3 on one side of the first substrate 2 in the thickness direction.

[0146] [1st step] In the first step, the first substrate 2 is prepared as shown in Figure 2A.

[0147] [Second process] In the second step, as shown in Figure 2B, an adhesive layer 3 is placed on one side of the first substrate 2 in the thickness direction.

[0148] To place the adhesive layer 3 on one side of the first substrate 2 in the thickness direction, the adhesive composition is applied to one side of the first substrate 2 in the thickness direction and allowed to dry. This places (forms) the adhesive layer 3 on one side of the first substrate 2 in the thickness direction.

[0149] As for the drying conditions, the drying temperature is a temperature at which volatile components such as solvents contained in the adhesive composition volatilize and deblockization of the blocked isocyanate groups of the modified polyolefin resin in the adhesive layer 3 is suppressed (a temperature below the dissociation temperature of the blocking agent), for example, less than 200°C, preferably 150°C or lower, and for example, 10°C or higher. The drying time is, for example, 3 seconds or more, preferably 30 seconds or more, and for example, 1 hour or less, preferably 30 minutes or less, more preferably 5 minutes or less.

[0150] If the drying temperature is below 200°C, deblocking of blocked isocyanate groups is suppressed in the adhesive layer 3. Therefore, the modified polyolefin resin has blocked isocyanate groups. As a result, even after long-term storage, the adhesive layer 3 of this intermediate laminate 10 retains its adhesive properties and exhibits excellent storage stability.

[0151] The intermediate laminate 10 is manufactured as described above.

[0152] Such an intermediate laminate 10 is used in a method of bonding two different types of substrates (first substrate 2 and second substrate 4 (described later)), in other words, the intermediate laminate 10 is a component of the laminate 1 described later.

[0153] Next, we will describe in detail the laminate produced using this intermediate laminate 10 and the method for producing the laminate. <Laminate> An embodiment of the laminate of the present invention will be described with reference to Figure 3.

[0154] As shown in Figure 3, the laminate 1 has a film shape (including a sheet shape) with a predetermined thickness. The laminate 1 extends in a planar direction perpendicular to the thickness direction. The laminate 1 has a flat top surface and a flat bottom surface.

[0155] The laminate 1 comprises an intermediate laminate 10 (an intermediate laminate 10 comprising a first base material 2 and an adhesive layer 3 in order toward one side in the thickness direction) and a second base material 4 in order toward one side in the thickness direction. Specifically, the laminate 1 comprises an intermediate laminate 10 and a second base material 4 directly disposed on the upper surface (one side in the thickness direction) of the intermediate laminate 10. More specifically, the laminate 1 comprises a first base material 2, an adhesive layer 3, and a second base material 4 in order toward one side in the thickness direction.

[0156] [Second base material] The second substrate 4 has a film shape. The second substrate 4 is arranged on the entire upper surface of the intermediate laminate 10 (adhesive layer 3) so as to be in contact with the upper surface of the intermediate laminate 10 (adhesive layer 3).

[0157] The second substrate 4 is a different type of substrate from the first substrate 2.

[0158] The materials constituting the second base material 4 are the same as those constituting the first base material 2 described above. The materials constituting the second base material 4 are of a different type than those constituting the first base material 2. Specifically, combinations of materials constituting the first base material 2 and the second base material 4 include a combination of a metal and a high-polarity resin material, a combination of a metal and a low-polarity resin material, and a combination of a high-polarity resin material and a low-polarity resin material.

[0159] <Method for manufacturing laminates> An embodiment of the method for manufacturing the laminate of the present invention will be described with reference to Figures 4A and 4B.

[0160] The method for manufacturing the laminate 1 comprises a third step of preparing an intermediate laminate 10, and a fourth step of placing a second substrate 4 on one side in the thickness direction of the adhesive layer 3 in the intermediate laminate 10 and bonding the first substrate 2 and the second substrate 4 together.

[0161] [3rd step] In the third step, the intermediate laminate 10 is prepared as shown in Figure 4A. The method for preparing the intermediate laminate 10 is the same as the method for manufacturing the intermediate laminate described above.

[0162] [4th step] In the fourth step, as shown in Figure 4B, the second substrate 4 is placed on one side in the thickness direction of the adhesive layer 3 in the intermediate laminate 10, and the first substrate 2 and the second substrate 4 are bonded together.

[0163] Specifically, first, the second substrate 4 is placed on one side in the thickness direction of the adhesive layer 3 in the intermediate laminate 10, and the first substrate 2 and the second substrate 4 are heat-pressed together.

[0164] In thermocompression bonding, the thermocompression bonding temperature is the temperature at which the blocked isocyanate groups of the modified polyolefin resin in the adhesive layer 3 are deblocked (above the dissociation temperature of the blocking agent), for example, 120°C or higher, preferably 200°C or higher, and for example, 300°C or lower.

[0165] If the heat-pressing temperature is above the lower limit mentioned above, the blocked isocyanate groups of the modified polyolefin resin in the adhesive layer 3 are deblocked, and active isocyanate groups are regenerated. With such isocyanate groups, the first substrate 2 and the second substrate 4, which are of different types, can be reliably bonded together.

[0166] Furthermore, the heat-sealing pressure is, for example, 0.1 MPa or higher, and for example, 1.0 MPa or lower. The heat-sealing time is, for example, 1 second or higher, and for example, 120 seconds or lower.

[0167] Afterward, aging is performed as necessary. The aging temperature is, for example, above 20°C and below 80°C. The aging time is, for example, above 1 day and below 7 days.

[0168] As a result, the first substrate 2 and the second substrate 4 are bonded together via the adhesive layer 3, and a laminate 1 is obtained.

[0169] <Effects and Effects> In adhesive compositions, the modified polyolefin resin is modified by a compound having both a blocked isocyanate group and a (meth)acryloyl group. Therefore, regardless of the type of the first substrate 2 and the second substrate 4, different types of the first substrate 2 and the second substrate 4 can be bonded together, and storage stability is excellent.

[0170] More specifically, when using this adhesive composition to bond a first substrate 2 and a second substrate 4 of different types, first, an adhesive layer 3, which is a dried product of the adhesive composition, is placed (formed) on one side in the thickness direction of the first substrate 2 (specifically, after the second step described above). Then, the first substrate 2 and the second substrate 4 are bonded together via this adhesive layer 3 (specifically, in the fourth step described above). When the adhesive layer 3 is placed (formed), the modified polyolefin resin in the adhesive composition has blocked isocyanate groups. Therefore, even after long-term storage without performing the bonding described above, the adhesive layer 3 retains its adhesive properties and exhibits excellent storage stability.

[0171] On the other hand, in the above bonding process, the blocked isocyanate groups are deblocked and become isocyanate groups. Then, the adhesion is improved by the interaction of these isocyanate groups with the first substrate 2 and / or the second substrate 4, which are of different types. Therefore, regardless of the type of substrate, the first substrate 2 and the second substrate 4, which are of different types, can be bonded together.

[0172] Furthermore, the adhesive composition contains a solvent. In other words, the adhesive composition is prepared as a varnish. When the adhesive composition is prepared as a varnish, workability is improved, especially compared to when a solid adhesive composition is melted and laminated onto the substrate.

[0173] In the adhesive layer 3, the intermediate laminate 10 contains a modified polyolefin resin with blocked isocyanate groups. Therefore, the intermediate laminate 10 retains its adhesive properties and exhibits excellent storage stability even after long-term storage.

[0174] The laminate 1 includes an adhesive layer 3 made of the adhesive composition between a first substrate 2 and a second substrate 4 of different types. Therefore, the first substrate 2 and the second substrate 4 can be reliably bonded together.

[0175] The method for manufacturing the intermediate laminate 10 includes a second step of applying the adhesive composition to one side in the thickness direction of the first substrate 2 and drying it at a temperature of less than 200°C to form the adhesive layer 3. As a result, the deblocking of the blocked isocyanate groups of the modified polyolefin resin can be suppressed in the adhesive layer 3, and an intermediate laminate 10 with excellent storage stability can be manufactured.

[0176] The laminate 1 can be suitably used in various fields, such as packaging materials.

[0177] Furthermore, the above description details the case where the base material is the first base material 2 (in other words, the case in which the adhesive layer 3 is placed on one side in the thickness direction of the first base material 2 in the second step), but even if the base material is the second base material 4 (in other words, the case in which the adhesive layer 3 is placed on one side in the thickness direction of the second base material 4 in the second step), the intermediate laminate and the laminate can be manufactured using the same procedure as described above. [Examples]

[0178] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, "parts" and "%" are based on mass. Furthermore, specific numerical values ​​such as blending ratios (content), physical properties, and parameters used in the following description may be replaced with the corresponding upper limits (numerical values ​​defined as "less than or equal to" or "less than") or lower limits (numerical values ​​defined as "greater than or equal to" or "greater than") of the blending ratios (content), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above.

[0179] <Details of ingredients> Details of the active ingredients used in the manufacturing examples, examples, and comparative examples are shown below. PBR: Propylene / 1-butene copolymer (75 mol% propylene units and 25 mol% 1-butene units, melting point 75°C), heat of fusion: 30 J / g AOI-BP: 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (compound represented by formula (4) above) AOI-VM:2-Acryloyloxyethyl isocyanate (deblocked form of AOI-BP) MAH: Maleic anhydride DBU:1,8-Diazabicyclo[5.4.0]undecene-7 AL: Aluminum base material PP: Polypropylene base material PET: Polyethylene terephthalate substrate PC: Polycarbonate base material ABS: Acrylonitrile styrene-butadiene copolymer resin base material PVC: Polyvinyl chloride base material

[0180] <Manufacturing of Modified Polyolefin Resins> Manufacturing Example 1 In a 1.0 L autoclave equipped with a stirrer, 100 parts by mass of PBR and 283 parts by mass of butyl acetate were placed, and the temperature was raised to 145°C while stirring to completely dissolve the PBR. Then, while maintaining this solution at 145°C, AOI-BP and di-tert-butyl peroxide were added dropwise over 6 hours while stirring. After the addition was complete, the mixture was stirred at 145°C for another 3 hours to allow further reaction. The resulting solution was cooled to 80°C and then diluted with 283 parts by mass of methylcyclohexane to a solid content concentration of 15% to obtain a modified polyolefin resin solution. The amount of modification of the modified polyolefin resin by AOI-BP was 1.9% by mass. The weight-average molecular weight of the modified polyolefin resin was 90,000. The melt mass flow rate (MFR) of the modified polyolefin resin was 300 g / 10 min.

[0181] <Manufacturing of other polyolefin resins> Manufacturing Example 2 A modified polyolefin resin solution was obtained using the same procedure as in Production Example 1. However, MAH was used instead of AOI-BP. The amount of MAH used to modify the modified polyolefin resin was 1.0% by mass.

[0182] <Other modified polyolefin resins> Manufacturing Example 3 A modified polyolefin resin solution was obtained using the same procedure as in Production Example 1. However, AOI-VM was used instead of AOI-BP. The amount of modification by AOI-VM to the modified polyolefin resin was 2.1% by mass.

[0183] <Manufacturing of adhesive compositions> Reference Examples 1, 3, 2, 4 Comparative Example 1 and Reference Example 1 Adhesive compositions were prepared by mixing each component (modified polyolefin resin, other polyolefin resins, other modified polyolefin resins, blocked isocyanate dissociation catalyst, and solvent) according to the formulations shown in Table 1. The solid content concentration of the obtained adhesive composition was 12% by mass.

[0184] <Manufacturing of intermediate laminates> [1st step] As the first substrate, aluminum (30 μm thick) was prepared.

[0185] [Steps 2 and 3] The adhesive compositions of each example and comparative example were applied to one side of the AL in the thickness direction and dried at 100°C for 1 minute to form an adhesive layer (3 μm thick). This prepared an intermediate laminate.

[0186] [4th step] Immediately after forming the adhesive layer, a sheet of PP (25mm x 50mm x 2mm) was placed on one side in the thickness direction of the adhesive layer. Then, it was heat-pressed under the conditions of 200°C, 0.3 MPa, and 3 seconds, and subsequently aged at 60°C for 3 days. After that, it was left to stand at room temperature overnight. This produced the laminate.

[0187] Furthermore, in the fourth step, intermediate laminates were prepared one month and three months after the formation of the adhesive layer, and the laminate was manufactured according to the same procedure.

[0188] Furthermore, the same procedure as described above was used to manufacture laminates in the following cases: when the first substrate is aluminum and the second substrate is PET; when the first substrate is a PP film (100 μm thick) and the second substrate is PET; when the first substrate is a PP film and the second substrate is PC; when the first substrate is a PP film and the second substrate is ABS; and when the first substrate is a PP film and the second substrate is PVC.

[0189] Furthermore, the dimensions of PET, PC, ABS, and PVC are 25mm x 50mm x 2mm.

[0190] <Rating> [Measurement of heat of fusion] The heat of fusion of polyolefin resin (PBR) was determined using a differential scanning calorimeter (TA Instruments; DSC-Q1000). The temperature was raised from 30°C to 180°C at a rate of 10°C / min, then cooled to 0°C at a rate of 10°C / min, and then raised again to 150°C at a rate of 10°C / min. The heat of fusion was determined from the thermogram taken during the second heating cycle, in accordance with JIS K 7122.

[0191] [Measurement of weight-average molecular weight] The weight-average molecular weight of the modified polyolefin resin in Production Example 1 was measured. Specifically, the weight-average molecular weight (Mw) was measured using gel permeation chromatography (Shimadzu Corporation; LC-10 series) under the following conditions. • Detector: Shimadzu Corporation; C-R4A • Columns: TSKG 6000H, TSKG 4000H, TSKG 3000H, TSKG 2000H (manufactured by Tosoh Corporation) • Mobile phase: tetrahydrofuran ·Temperature: 40℃ ·Flow rate: 0.8ml / min The weight-average molecular weight (Mw) was calculated using a calibration curve created from monodisperse standard polystyrene.

[0192] [Meltmass Flow Rate (MFR)] The melt mass flow rate (MFR) of the modified polyolefin resin in Production Example 1 was measured in accordance with JIS K 7210, under measurement conditions of a plastometer cylinder temperature of 230°C and a load of 2.16 kgf.

[0193] [Adhesiveness] For each example and comparative example, a strip of 15 mm width was cut into the laminate using a cutter. Then, a 180° peel test was performed using a universal tensile strength measuring device at a crosshead speed of 50 mm / min. Specifically, the peel strength between AL and PP (AL-PP adhesion), the peel strength between AL and PET (AL-PET adhesion), the peel strength between PP and PET (PP-PET adhesion), and the peel strength between PP and PC (PP-PC adhesion) were measured. The peel strength between PP and ABS (PP-ABS adhesion) and the peel strength between PP and PVC (PP-PVC adhesion) were measured. Adhesion was evaluated based on the following criteria. The results are shown in Table 1. {standard} ◎: The peel strength was 15 N / 15 mm or higher. ○: The peel strength was 8 N / 15 mm or more, and less than 15 N / 15 mm. △: The peel strength was 4N / 15mm or higher, and less than 8N / 15mm. ×: The peel strength was less than 4N / 15mm.

[0194] <Consideration> The adhesive composition includes a modified polyolefin resin that is modified with a compound having both a blocked isocyanate group and a (meth)acryloyl group. Reference Examples 1, 3, Examples 2 and 4 This demonstrates that, regardless of the type of substrate, it is possible to bond first and second substrates of different types to each other.

[0195] On the other hand, Comparative Example 1, in which the adhesive composition did not contain a modified polyolefin resin modified with a compound having both blocked isocyanate groups and (meth)acryloyl groups, could not adhere to certain types of substrates (e.g., PP and PC).

[0196] Furthermore, the adhesive composition includes a modified polyolefin resin that has been modified with a compound having both a blocked isocyanate group and a (meth)acryloyl group. Reference Examples 1, 3, Examples 2 and 4 This shows that even when using intermediate laminates one month and three months after the adhesive layer has been formed, it is possible to bond different types of first and second substrates together.

[0197] On the other hand, in Reference Example 1, which includes a modified polyolefin resin in which the adhesive composition is modified with a compound having both isocyanate groups and (meth)acryloyl groups, it was found that the adhesiveness decreased when the intermediate laminate was used one month and three months after the formation of the adhesive layer.

[0198] [Table 1] [Explanation of symbols]

[0199] 1. Laminate 2 First base material 3 Adhesive layer 4 Second base material 10 Intermediate Laminate

Claims

1. It contains a modified polyolefin resin and a solvent, Furthermore, it includes a blocked isocyanate dissociation catalyst, The modified polyolefin resin is an adhesive composition in which the polyolefin resin is modified with a compound having both a blocked isocyanate group and a (meth)acryloyl group.

2. The adhesive composition according to claim 1, wherein the heat of fusion of the polyolefin resin, as measured according to JIS K7122, is 0 J / g or more and 60 J / g or less.

3. Furthermore, the adhesive composition according to claim 1, further comprising other polyolefin resins.

4. Substrate and The adhesive layer, which is a dried product of the adhesive composition according to any one of claims 1 to 3, is provided sequentially toward one side in the thickness direction, In the adhesive layer, the modified polyolefin resin is an intermediate laminate having blocked isocyanate groups.

5. First substrate and An adhesive layer which is a dried product of the adhesive composition according to any one of claims 1 to 3, A laminate comprising the first substrate and a second substrate of a different type, arranged sequentially toward one side in the thickness direction.

6. The first step is to prepare the base material, A method for manufacturing an intermediate laminate, comprising: a second step of applying an adhesive composition according to any one of claims 1 to 3 to one surface in the thickness direction of the first substrate and drying it at a temperature of less than 200°C to form an adhesive layer.

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