JP3959967B2 - Laminated body - Google Patents

Description

【００６７】
以上の実施例および比較例の結果から、本発明において、ブロックイソシアナートを含む接着性樹脂を用いることで、吸湿による発泡や架橋反応に伴う加工性の低下を抑制することが可能であり、かつ各種表面処理を施した熱可塑性樹脂フィルム、あるいは熱水変性を施したアルミニウム箔などのバリア性基材に対し、イソシアナート基を有する複合体をグラフト化させた接着性樹脂を積層させた積層体は、初期のラミネート強度だけでなく、強浸透性物質である内容物を充填しても、その内容物によりラミネート強度が低下することがないことが確認できた。
【００６８】
【発明の効果】
本発明により、アルミニウム箔等のバリア性基材に接着性樹脂を積層した積層体において、その接着性樹脂が、ブロックイソシアナートを用いることから、接着性樹脂の製造工程で発生する熱や吸湿による水分の影響でイソシアナート基が消費されることがなく、かつブロックイソシアナートの脱ブロック化反応が起こる加工温度条件で活性なイソシアナートが再生するために、各種バリア基材との優れた接着性を有することから、本発明の積層体を各種包装形態に加工して、内容物として強浸透性物質を充填した場合であっても、その強浸透性物質からなる内容物の影響でラミネート強度が低下することのない優れたラミネート強度を有する積層体を提供することが可能となった。
【００６９】
本発明の積層体は、従来内容物に対してラミネート強度が低下する問題が発生していた各種軟包装材分野や、液体用複合紙容器などの分野に広く展開することが可能となった。
【００７０】
また、本発明の積層体における、イソシアナート複合体をグラフト化させた接着性樹脂を、各種バリア基材上への押出ラミネートにおいて、接着剤を用いることなしに、優れたラミネート強度を有する積層体が得られる。
【００７１】
さらに、本発明の積層体は、環境対応に優れた各種包装材料として好適に用いられるものである。
【図面の簡単な説明】
【図１】本発明の１実施例としての積層体の構成を示す断面図。
【符号の説明】
１……基材層
２……接着性樹脂層[0001]
BACKGROUND OF THE INVENTION
  The present inventionAThe present invention relates to a laminate using an adhesive resin capable of imparting good adhesiveness to various barrier substrates such as a ruminium foil without using an adhesive, and more specifically, these laminates. It is related with the laminated body by which the laminate strength by the content does not fall even if it processes into various packaging forms and it fills with various strongly permeable content.
[0002]
[Prior art]
In the packaging field, different types of thermoplastic resin films are laminated by using various adhesives and bonding them by a known method such as dry lamination or extrusion lamination. Aluminum foil and aluminum vapor-deposited film are used as one of barrier materials for protecting contents from light shielding properties, oxygen, water vapor, and the like. Furthermore, since the aluminum foil can be maintained in its shape when it is bent (dead hold property), it is also used as a lid material for cup containers such as cup ramen. On the other hand, alumina vapor deposition films are used in various packaging forms because they have not only barrier properties but also transparency. In this way, metal foil, metal vapor-deposited film, and inorganic compound vapor-deposited film are used to provide barrier properties and other functionalities to packaging materials (packages). Examples of these include aluminum foil and aluminum vapor-deposited film. In many cases, an alumina vapor-deposited film is used as an intermediate layer of a laminate and processed into various packaging forms.
[0003]
Moreover, in making various packaging forms using a metal foil, a metal vapor-deposited film, or an inorganic compound vapor-deposited film, as a method for producing the laminate, not only a method using the above-described adhesive, but also a metal foil or a metal vapor-deposited film, Ethylene-α, β unsaturated carboxylic acid such as ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid copolymer ionic cross-linked product or ionic cross-linked product thereof Is laminated using a technique such as extrusion lamination.
[0004]
Not only the above-mentioned ethylene-α, β-unsaturated carboxylic acid copolymer and its ionic cross-linked product, but also general-purpose low-density polyethylene is extruded at a high temperature of 300 ° C. or higher so that a carboxyl group, a carbonyl group, a hydroxyl group, etc. And a method of laminating on a metal foil, a metal vapor-deposited film, or an inorganic compound vapor-deposited film using a two-component curable urethane adhesive.
[0005]
However, a laminate obtained by directly laminating a metal foil, a metal vapor-deposited film or an inorganic compound vapor-deposited film and the thermoplastic resin, or a laminate obtained by laminating the thermoplastic resin using a two-component curable urethane adhesive. Is processed into various packaging forms such as pouches and liquid composite paper containers, and as a content, a permeable substance such as a fragrance or a foaming agent component of a bath preparation or a solvent-based content such as various disinfectants is used. When filled, the strong penetrating substance is trapped between the barrier layer and various thermoplastic resin layers due to the barrier properties of the metal foil, metal deposited film, and inorganic compound deposited film, resulting in a decrease in laminate strength at the interface. It is thought to happen. Further, when the content is mainly composed of a solvent component, particularly in the case of a configuration using a two-component urethane type adhesive, this adhesive layer is dissolved, causing a significant decrease in laminate strength.
[0006]
Laminates of thermoplastic resin films, metal foils, metal vapor-deposited films, inorganic compound vapor-deposited films, and thermoplastic resin films are indispensable as various packaging materials because of their functionality and excellent barrier properties. However, as described above, there is a problem that the laminate strength is lowered due to the influence of the contents made of the strong permeable substance.
[0007]
[Problems to be solved by the invention]
  The present invention has been made to solve the above problems.,aluminumFoil andaluminumVapor deposited film,aluminaEven when a laminate in which an adhesive resin is laminated on a barrier substrate such as a vapor-deposited film is processed into various packaging forms and filled with a strong permeable substance as a content, it consists of the strong permeable substance. An object of the present invention is to provide a laminate having an excellent laminate strength that does not lower the laminate strength due to the contents.
[0008]
[Means for Solving the Problems]
  In order to solve the above-mentioned problems, the present invention relates to an invention according to claim 1, which is an isocyanate having an unsaturated bond using a blocking agent capable of regenerating an active isocyanate by heating on a substrate. It includes at least a constitution in which an adhesive resin made of a polyolefin resin or an olefin copolymer resin modified with a monomer having a block isocyanate obtained by blocking the isocyanate group of a narate compound or a composite thereof is laminated.The base material is made of any one selected from an aluminum vapor-deposited film, an alumina vapor-deposited film, and an aluminum foil, and a hydrothermal denaturation treatment is applied to the vapor-deposited surface or aluminum surface in contact with the adhesive resin layer of the base material.It is the laminated body characterized by this.
[0009]
The invention according to claim 2 is the laminate according to claim 1, wherein the adhesive resin is a polyolefin resin or olefin copolymer having a melt index (MI) in the range of 0.1 to 200 according to ASTM D1238. It is characterized by being modified by grafting a block isocyanate-containing monomer or a complex thereof in the range of 0.001 to 10 parts by weight with respect to 100 parts by weight of the resin.
[0010]
The invention according to claim 3 is the laminate according to claim 1 or 2, wherein the blocking agent is at least one selected from oxime compounds, amide compounds, active methylene compounds, and pyrazole compounds. It consists of the compound of the above.
[0011]
The invention according to claim 4 is the laminate according to any one of claims 1 to 3, wherein the isocyanate compound having an unsaturated bond is a vinyl type or allyl type having a monofunctional or higher isocyanate group. , (Meth) acrylic isocyanate compound monomers, difunctional isocyanate monomers, or trifunctional or polyfunctional isocyanate monomer derivatives in the form of adducts, burettes and isocyanurates And an active hydrogen group having reactivity with an isocyanate and a compound having an unsaturated double bond such as vinyl, allyl or (meth) acryl in the structure, and at least one isocyanate group. It is characterized by comprising any isocyanate compound complex having a functionality or higher, or a mixture thereof.
[0012]
The invention according to claim 5 is characterized in that in the laminate according to any one of claims 1 to 4, the adhesive resin is laminated on a base material by an extrusion laminating method.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, preferred embodiments of the present invention will be described in detail. The laminate of the present invention is a block isocyanate in which an isocyanate group of an isocyanate compound having an unsaturated bond is blocked using a blocking agent capable of regenerating an active isocyanate by heating on a substrate. At least a structure in which an adhesive resin made of a polyolefin resin or an olefin-based copolymer resin modified with a monomer or a complex thereof is laminated.The base material is made of any one selected from an aluminum vapor-deposited film, an alumina vapor-deposited film, and an aluminum foil, and a hydrothermal denaturation treatment is applied to the vapor-deposited surface or aluminum surface in contact with the adhesive resin layer of the base material.It is characterized by that.
[0019]
A characteristic of the adhesive resin layer used in the laminate of the present invention is that an isocyanate compound having excellent reactivity is grafted, and in particular, by using this isocyanate compound in the form of a block isocyanate. The following advantages arise. Since the isocyanate compound has a very high reactivity, it may be easily consumed by the influence of moisture absorption or the like in the process from resin production to film formation. However, by blocking isocyanate, consumption of functional groups due to moisture absorption and other effects is suppressed, and foaming due to moisture absorption during manufacturing of laminates and significant reduction in workability due to crosslinking reaction of isocyanate groups are suppressed. Is possible. In addition, since block isocyanate easily regenerates active isocyanate groups by heating, even if the reactivity is controlled by blocking, it is possible to easily regenerate isocyanate by heating during the production of laminates. Is possible.
[0020]
The isocyanate compounds in the present invention are roughly classified into two types. (1) One is that the isocyanate compound having an unsaturated bond before blocking is a vinyl, allyl or (meth) acrylic isocyanate compound having at least one or more isocyanate group It is a body. As typical isocyanate compounds of the monomer, vinyl isocyanate, allyl isocyanate, (meth) acryloxyoxyethyl isocyanate, (meth) acryloxyoxybutyl isocyanate, and the like can be used. However, it is not limited to these.
[0021]
(2) The other is that the isocyanate compound having an unsaturated bond before being blocked is difunctionalized in the form of a difunctional isocyanate monomer, adduct, burette or isocyanurate, or more than 4 functionalities. And a multifunctional isocyanate monomer derivative of a compound containing an active hydrogen reactive with isocyanate and a compound having an unsaturated double bond such as vinyl, allyl or (meth) acryl, It is an isocyanate compound complex having at least one isocyanate group. Representative examples of the complex include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, as isocyanate compounds. Various diisocyanate monomers such as 4,4'-diphenylmethane diisocyanate can be used. In addition, an adduct type obtained by reacting these diisocyanate monomers with trifunctional active hydrogen-containing compounds such as trimethylolpropane and glycerol, a burette type reacted with water, and self-polymerization of isocyanate groups are used. Trifunctional derivatives such as trimer (isocyanurate) type and higher polyfunctional derivatives can also be used.
[0022]
The complex shown in (2) above is compounded by reacting the isocyanate compound with a compound having reactivity with an isocyanate group and having an unsaturated double bond in the structure. It is a thing. Compounds having reactivity with this isocyanate group and having an unsaturated double bond in the structure include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (Meth) acrylate, glycerol di (meth) acrylate, ethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, allyloxyethyl alcohol and the like. Moreover, as a compound which has the unsaturated double bond mentioned above, although the hydroxyl group is mainly mentioned as active hydrogen, you may use the compound containing other active hydrogen groups like an amine, for example. In addition, a complex obtained from an isocyanate monomer may be further complexed with various monomers to form a derivative such as an adduct type, a burette type, or an isocyanurate type. The complex in this case is a bifunctional isocyanate compound having an unsaturated bond.
[0023]
The isocyanate compound monomers or complexes described above can be used as a mixture even if they are used alone.
[0024]
Examples of the blocking agent for blocking the isocyanate group include oxime, amide, active methylene, and pyrazole compounds. Examples thereof include acetone oxime, methyl ethyl ketone oxime, ε-caprolactam, dimethyl malonate, and methyl acetoacetate. 3,5-dimethylpyrazole, and the like. Other than these, blocking agents such as phenols, alcohols, imidazoles, and ureas can be used and are not particularly limited. These blocking agents may be used alone or in combination of two or more.
[0025]
The polyolefin resin or olefin copolymer to which such a composite is grafted is a polyolefin resin having a melt index (MI) in the range of 0.1 to 200, more preferably 3 to 50, according to ASTM D1238. The olefin copolymer is preferably a resin having high-speed processability. For example, low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-α olefin copolymer, poly α olefin, polypropylene, Propylene-ethylene copolymer, propylene-α olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene- From methacrylate ester copolymer It is selected from a single piece or two or more of the blend of the barrel resin. In particular, it is not limited to the resin mentioned above.
[0026]
Moreover, various additives, such as antioxidant, a tackifier, a filler, various fillers, can also be added with respect to the said resin as needed.
[0027]
This adhesive resin is produced by a graft graft reaction in the presence of peroxide, and a known apparatus can be used as an apparatus used for it, including a twin screw extruder, various kneaders, The graft reaction can be performed by using various mixers. As the peroxide used for the grafting reaction, it is possible to use a peroxide that is generally used for the grafting reaction in the molten state, and can be selected according to the grafting reaction temperature and reaction time. is there. Preferably, one having a half-life temperature of 1 to 280 ° C, preferably 150 to 230 ° C can be used. Examples include, but are not limited to, t-butyl peroxybenzoate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and the like.
[0028]
When the graft reaction is performed using a twin screw extruder, a predetermined amount of a mixture of an isocyanate compound and an organic peroxide is dropped onto the molten resin using a liquid feeder. Alternatively, a predetermined amount of the isocyanate compound and the organic peroxide are dispensed by using another liquid feeder. In this case, the amount of dropping is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and the organic peroxide is 0.001 to 100 parts by weight with respect to 100 parts by weight of the resin. 5 parts by weight, preferably 0.01 to 3 parts by weight. Under these conditions, the grafting amount of the obtained adhesive resin is 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin.
[0029]
In the above graft reaction, the unreacted complex and the peroxide residue after decomposition greatly affect the adhesion and other factors, so it is necessary to remove the unreacted product and the peroxide residue. If it is a manufacturing method by biaxial extrusion, it can be removed by extrusion under reduced pressure. If it is a batch type production method, it is possible to remove unreacted substances and peroxide residues by dissolving the purified adhesive resin in hot xylene and then performing reprecipitation, washing and drying. is there.
[0030]
If the isocyanate compound is not blocked by the blocking agent, the isocyanate compound may be consumed due to heat during the grafting reaction, moisture during water-cooled pelletization, or moisture absorption over time. In that sense, it is effective to use a block isocyanate that suppresses consumption of the isocyanate compound by heat or moisture. However, if the graft reaction is not performed in consideration of the temperature and time at which the blocked isocyanate compound is deblocked, the deblocking reaction may proceed during the graft reaction. In this sense, it is necessary to process under conditions that do not cause deblocking of the block isocyanate. Although it depends on the type of deblocking agent, 150 to 200 ° C. or lower is preferable as a guide.
[0031]
  As a base material for extruding the adhesive resin obtained by the manufacturing method described above,Aluminum vapor deposition film, alumina vapor deposition film, aluminum foilEtc. can be selected.
[0034]
  on the other handAAs the luminium foil, the aluminum vapor deposition film, and the alumina vapor deposition film, those prepared by a known method can be used. Especially in the case of aluminum vapor deposition or alumina vapor deposition film, various substrates such as stretched polyester film, stretched polypropylene film, stretched nylon film can be used as the substrate for vapor deposition. Can be selected.
[0035]
The various barrier substrates are preferably subjected to a hot water denaturation treatment on the surface in contact with the adhesive resin. By applying hydrothermal modification treatment, it is possible to functionalize the surface layer of the barrier layer by introducing a hydroxyl group into the outermost layer of the aluminum foil, aluminum vapor deposition surface, and alumina vapor deposition surface. Adhesion with an adhesive resin having an isocyanate group introduced From the viewpoint of sex, it is very preferable.
[0036]
The following content is mentioned as an index of the hydrothermal modification treatment in the various surface layers of the barrier layer.
First, when X-ray photoelectron spectroscopy is measured, the spectral peak position derived from the oxide and hydroxide of Al2p orbital is 75 eV or less.
Similarly, the ratio of oxygen atom (O) / aluminum atom (Al) when X-ray photoelectron spectroscopy is measured is 1.7 or more.
[0037]
Secondly, when time-of-flight secondary ion mass spectrometry is performed, the ratio of hydroxyl group (OH) / oxygen atom (O) is 0.9 or more.
[0038]
Finally, the result of surface observation by a scanning electron microscope shows a form in which the surface is finely roughened in a micro-order uneven shape.
[0039]
The aluminum foil layer, aluminum vapor deposition layer, and alumina vapor deposition layer that have been subjected to such hydrothermal modification treatment form an extremely oxidized / hydroxylated structure, and hydroxylation is particularly preferred from the viewpoint of the reactivity of the isocyanate compound. Furthermore, the surface form is very preferable because not only the isocyanate compound but also the anchoring effect and the adhesion area between the polyolefin resin and the olefin copolymer laminated thereon are expanded.
[0040]
The resistance of the laminate of the present invention to the strongly permeable substance includes primary and secondary bonds between various substrates whose surface layers are functionalized and an adhesive resin. In particular, when aluminum foil with hot water modification is taken as an example, when general-purpose low density polyethylene is extruded directly onto the aluminum hot water modification surface, the initial adhesion state is good, but strong permeability When a substance, particularly a solvent-based content such as a bactericide is filled, the laminate strength tends to gradually decrease. This is because the initial adhesion state was good due to the influence of the anchoring effect due to the undulation of the surface formed by the hydrothermal treatment, but due to the melt viscosity of the resin, Since the solvent component is not filled, the solvent component enters the void portion and the laminate interface is eventually affected by the effect of capillary action.
[0041]
As described above, in the case of a two-component curable urethane adhesive, when an adhesive layer of several μm order is formed between the barrier layer and the polyolefin resin layer, a urethane bond with low solvent resistance is formed. Therefore, the solvent component will invade the two-component curable urethane adhesive layer.
[0042]
On the other hand, by laminating an adhesive resin grafted with an isocyanate group, various bonds can be formed not only by the same anchoring effect as in LDPE but also by reaction with hydroxide groups by hydrothermal modification of the aluminum surface. It is thought that resistance can be imparted by forming and expanding the adhesion area.
[0044]
The hot water denaturation treatment applied to the aluminum foil, aluminum vapor deposition film or alumina vapor deposition film is 0.01 to 1 wt%, preferably 0.1 to 0.5 wt% in distilled water with an additive such as ammonia or triethanolamine. The treatment liquid is prepared, and the treatment liquid is heated in the range of 75 to 100 ° C, preferably in the range of 85 to 100 ° C, more preferably in the range of 90 to 100 ° C, and the various barrier layers described above are heated for 1 minute or more. It is possible to obtain various barrier layers subjected to hydrothermal treatment modification by immersing preferably for 2 minutes or more, more preferably for 3 minutes or more. This process may be a web process or a batch process.
[0045]
  The adhesive resin is applied to the treated surfaces of the various barrier layers that have undergone the hydrothermal modification treatment.PressIt is possible to obtain a laminate by applying the outgoing laminate.
[0046]
Extrusion of adhesive resin is not particularly limited, and it is possible to extrude with various types of extruders, die designs, and screw designs. If necessary, adhesive resin can be extruded by coextrusion. I do not care.
[0047]
The various laminates thus obtained can be developed into various packaging forms, and by combining with a paper from a soft packaging body such as a pouch, a liquid composite paper container or the like can be developed. Moreover, in these packaging containers, since the laminate strength does not decrease with respect to the contents, it is possible to develop applications for the contents that have been difficult to fill.
[0048]
【Example】
Hereinafter, specific examples of the present invention will be described. The present invention is not limited to the following examples.
[0049]
The following materials were used for the production of the adhesive resin of the present invention.
[Isocyanate compound]
I-1: Methacryloxyoxyethyl isocyanate monomer
I-2: Hexamethylene diisocyanate / allyloxyethyl alcohol complex
I-3: Isophorone diisocyanate / hydroxyethyl methacrylate complex
I-4: 2,4-tolylene diisocyanate / hydroxyethyl methacrylate complex
[0050]
[Blocking agent]
B-1: Methyl ethyl ketone oxime
B-2: 3,5-dimethylpyrazole
B-3: ε-Caprolactam
[0051]
[Resin used]
[0052]
PO-1: Polyolefin resin (MI = 35, low density polyethylene)
PO-2: Olefin copolymer resin (MI = 22, ethylene-ethyl acrylate copolymer)
[0053]
[Peroxide]
2,5-Methyl 2,5-di (t-butylperoxy) hexyne
[0054]
(Method for producing adhesive resin)
Manufactured using a twin screw extruder. The liquid addition device was adjusted so that the isocyanate compound blocked with the blocking agent and the above peroxide could be added so as to have the following blending ratio, and each was added dropwise to the molten resin (resin / isocyanate) Compound / peroxide = 100/5 / 0.5). As processing conditions, the processing temperature is 180 ° C. and the residence time is 180 to 300 sec so that deblocking reaction of the block isocyanate does not occur. The rotation was performed at 100 rpm and the discharge was 12 kg / h, and the processing was performed under reduced pressure to remove the residual monomer. Further, the obtained strand sample was subjected to pelletization after water cooling and dried, and then used for evaluation shown below. Moreover, the graft rate of the obtained adhesive resin was 0.5-2 wt%.
[0055]
Next, the following base materials were used for sample preparation.
S-1: Atmospheric pressure plasma-treated polyamide film 25 μm in He gas atmosphere
S-2: N₂Corona-treated polyethylene terephthalate film 25μm in atmosphere
S-3: Hot water-modified aluminum foil 40 μm
[0056]
(Initial strength evaluation method)
The adhesive resin obtained by the above method was processed with a single screw extruder at a processing temperature of 260 ° C. and a processing speed of 80 m / min. And laminated on various substrates at 30 μm. At that time, using a polyester film / low density polyethylene laminate prepared in advance, lamination was performed so that the adhesive resin was sandwiched by sand lamination. The laminate strength (crosshead speed 300 mm / min. T-type peeling) and peeling interface between the various substrates and the adhesive resin of the samples thus obtained were evaluated.
[0057]
(Method for evaluating suitability of content resistance)
In producing the sample for initial strength measurement, a configuration excluding the base material for sand lamination (a laminated body composed only of various base materials and adhesive resin) was prepared, and a pouch was prepared using the structure. The pouch was filled with a foaming agent, a bathing agent, and a solvent-based disinfectant, and the laminate strength and release interface were evaluated when stored in a 40 ° C.-90% RH atmosphere for 1 month.
[0058]
<Example 1>
As the adhesive resin material, PO-1 was used as the resin, I-1 was used as the isocyanate compound, and B-1 was used as the blocking agent, and an adhesive resin was prepared based on the above adhesive resin production method. . The sample for evaluation was created based on the above sample creation method. Table 1 shows the results of evaluating the obtained sample based on the above evaluation method.
[0059]
<Example 2>
A sample was prepared in the same manner as in Example 1 except that the isocyanate compound was changed to I-2 as the adhesive resin material, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0060]
<Example 3>
A sample was prepared in the same manner as in Example 1 except that the isocyanate compound was changed to I-3 and the blocking agent was changed to B-3 as the adhesive resin material, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
[0061]
<Example 4>
A sample was prepared in the same manner as in Example 1 except that the isocyanate compound was changed to I-4 and the blocking agent was changed to B-2 as the adhesive resin material, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
[0062]
<Example 5>
A sample was prepared in the same manner as in Example 1 except that the resin was changed to PO-2 as the adhesive resin material, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0063]
<Example 6>
A sample was prepared in the same manner as in Example 4 except that the resin was changed to PO-2 as the adhesive resin material, and evaluated in the same manner as in Example 4. The results are shown in Table 1.
[0064]
<Comparative Example 1>
A sample was prepared in the same manner as in Example 1 except that the resin PO-1 not grafted with an isocyanate complex was used as the adhesive resin material, and the processing temperature was set to 340 ° C. Evaluation was performed in the same manner as in Example 1. did. The results are shown in Table 1.
[0065]
<Comparative Example 2>
A sample was prepared in the same manner as in Example 1 except that the resin PO-2 not grafted with an isocyanate complex was used as the adhesive resin material, and the processing temperature was set to 300 ° C., and evaluation was performed in the same manner as in Example 1. did. The results are shown in Table 1.
[0066]
[Table 1]

[0067]
From the results of the above examples and comparative examples, in the present invention, by using an adhesive resin containing a block isocyanate, it is possible to suppress a decrease in workability due to foaming or a crosslinking reaction due to moisture absorption, and A laminate in which an adhesive resin obtained by grafting a composite having an isocyanate group to a barrier substrate such as a thermoplastic resin film subjected to various surface treatments or an aluminum foil subjected to hydrothermal modification is laminated. In addition to the initial laminate strength, it was confirmed that even when the content which is a strong permeable material was filled, the laminate strength was not lowered by the content.
[0068]
【The invention's effect】
  According to the present invention,aluminumIn a laminate in which an adhesive resin is laminated on a barrier substrate such as a foil, the adhesive resin uses block isocyanate, so isocyanate is affected by the heat generated during the adhesive resin manufacturing process and moisture due to moisture absorption. Because the active isocyanate is regenerated under the processing temperature conditions in which the nate group is not consumed and the deblocking reaction of the blocked isocyanate occurs,eachEven if it is a case where the laminate of the present invention is processed into various packaging forms and filled with a strong osmotic substance as a content because it has excellent adhesion with the seed barrier substrate, the strong osmotic substance Thus, it is possible to provide a laminate having an excellent laminate strength that does not lower the laminate strength due to the contents of the above.
[0069]
The laminate of the present invention can be widely deployed in the fields of various soft packaging materials and the composite paper containers for liquids, which have been problematic in that the laminate strength has been reduced with respect to the conventional contents.
[0070]
  In the laminate of the present invention,IAdhesive tree grafted with a soynate complexFat,VariousbarrierIn extrusion lamination onto a substrate, a laminate having excellent laminate strength can be obtained without using an adhesive.
[0071]
Furthermore, the laminate of the present invention is suitably used as various packaging materials excellent in environmental friendliness.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a configuration of a laminate as one embodiment of the present invention.
[Explanation of symbols]
1. Base material layer
2 ... Adhesive resin layer

Claims (5)

A monomer having a blocked isocyanate in which an isocyanate group of an isocyanate compound having an unsaturated bond is blocked using a blocking agent, which can regenerate an active isocyanate by heating on a substrate, or a either at least seen including a structure in which an adhesive resin comprising a modified polyolefin resin or olefin-based copolymer resin is laminated by the complex, wherein the substrate, aluminum deposition film, selected from alumina deposited film or an aluminum foil A laminate comprising: a vapor deposition surface or an aluminum surface that is in contact with the adhesive resin layer of the base material ;   Block adhesive-containing monomer with respect to 100 parts by weight of the resin made of polyolefin resin or olefin copolymer resin having a melt index (MI) in the range of 0.1 to 200 according to ASTM D1238. The laminate according to claim 1, wherein the composite is modified by being grafted in an amount of 0.001 to 10 parts by weight.   The laminate according to claim 1 or 2, wherein the blocking agent comprises at least one compound selected from oxime compounds, amide compounds, active methylene compounds, and pyrazole compounds.   The isocyanate compound having an unsaturated bond is a vinyl, allyl or (meth) acrylic isocyanate compound monomer having one or more functional isocyanate groups, a bifunctional isocyanate monomer, or an adduct, It contains an isocyanate monomer derivative that is trifunctional or polyfunctionalized in the form of burette or isocyanurate, and an active hydrogen that is reactive with isocyanate, and has vinyl, allyl, (meta) in the structure. 2. An isocyanate compound complex having at least one isocyanate group complexed with a compound having an unsaturated double bond such as acrylic, or a mixture thereof. The laminated body of any one of -3.   The laminate according to any one of claims 1 to 4, wherein the adhesive resin is laminated on a substrate by an extrusion lamination method.

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