JPS625064B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a laminate consisting of a vinyl chloride resin or vinylidene chloride resin layer, a polyolefin resin composition layer, and if necessary, this laminate and a polyolefin resin layer, and each layer is firmly adhered to each other. It is about things. Vinyl chloride resins or vinylidene chloride resins have low gas permeability and resistance to oil and chemicals, making them suitable for food packaging materials. However, on the other hand, vinyl chloride-based resins or vinylidene chloride-based resins have drawbacks such as being thermally unstable and easily decomposed, having poor heat sealability, being brittle, and having low low-temperature flexibility. Additionally, some of them are weak and have poor rigidity, and may lack self-support as packaging materials. On the other hand, polyolefin resins have high gas permeability, excellent heat sealability, and well-balanced mechanical and thermal properties. Therefore, a laminate made of both materials has low gas permeability, resistance to oil and chemicals, excellent heat sealability, and has excellent balanced mechanical and thermal properties. It is expected to be used as a material. However, vinyl chloride resin or vinylidene chloride resin and polyolefin resin are inherently difficult to adhere to, and it is necessary to use an adhesive between the two materials. Although various proposals have been made for such adhesives, none with sufficient properties has yet been found. For example, in Japanese Patent Publication No. 53-24464, ethylene-vinyl acetate copolymer or ethylene-acrylic acid ester copolymer is used as a thermal adhesive, but although the adhesiveness meets practical requirements, it is not sufficient. It had the disadvantage that its applications were limited due to its low heat resistance and oil resistance. Further, in JP-A No. 47-35053, a modified polyolefin grafted with an unsaturated carboxylic acid is used as a thermal adhesive, but the adhesiveness is low and it cannot be put to practical use depending on the application. However, as a result of intensive research into laminates in which vinyl chloride resin or vinylidene chloride resin and polyolefin resin are firmly bonded and have excellent heat resistance and oil resistance, the present inventors were able to complete the present invention. Ivy. That is, the present invention includes a resin layer (A) made of a vinyl chloride resin or a vinylidene chloride resin, 5 to 70 parts by weight of a thermoplastic polyurethane elastomer,
Modified polyolefin containing one or more functional groups selected from the group consisting of carboxylic acid groups, carboxylic acid bases, carboxylic acid anhydride groups, amide groups, hydroxyl groups, and epoxy groups in the main chain or side chain, or containing the above functional groups A copolymer mainly composed of olefins that
The present invention provides a laminate comprising a resin composition layer (B) comprising 95 to 30 parts by weight, and a laminate in which a polyolefin resin layer is laminated on this laminate, if necessary. In the present invention, the vinyl chloride resin or vinylidene chloride resin constituting the resin layer (A) is mainly a polymer or copolymer of vinyl chloride or vinylidene chloride. Possible comonomers for the copolymer include vinyl acetate, acrylic esters, acrylonitrile, olefins, maleic acid derivatives, and the like. In particular, the vinylidene chloride resin contains 70 to 90% by weight of vinylidene chloride and vinyl chloride.
A copolymer containing 10 to 30% by weight as a main component is preferred. In addition, modified resins such as post-chlorinated vinyl chloride resins, blend resins with ABS resins, MBS resins, chlorinated polyethylene, etc., and vinyl chloride graft copolymer resins with ethylene-vinyl acetate copolymers and polyolefins as the backbone polymers are also available. It is possible. It is also possible to use a mixture of the above-mentioned resins, and it goes without saying that various additives such as stabilizers, plasticizers, lubricants, fillers and the like can be used in combination. In the present invention, the resin composition constituting the resin composition layer (B) is a thermoplastic polyurethane elastomer 5
~70 parts by weight and a carboxylic acid group in the main chain or side chain,
Modified polyolefin containing one or more functional groups selected from the group consisting of carboxylic acid bases, carboxylic acid anhydride groups, amide groups, hydroxyl groups, and epoxy groups, or copolymers mainly composed of olefins containing the above functional groups 95 It is a resin composition consisting of ~30 parts by weight. The thermoplastic polyurethane elastomer used in the resin composition layer (B) used in the present invention includes polyether diols such as polyoxytetramethylene glycol and polyethylene ether glycol, polyethylene adipate, and poly(1,4- difunctional polyol components such as polyester diols such as butylene adipate), poly(1,6-hexane adipate), polytetramethylene sebacate, polycaprolactone, polyhexamethylene carbonate, or mixtures thereof, ethylene glycol, 1,4 -Butylene glycol 1,6
- Glycols such as hexamethylene glycol and bishydroxyethoxybenzene, diamines such as ethylenediamine, 1,4-butylenediamine, cyclohexanediamine, tolylenediamine, hydrazine, monoalkylhydrazine,
Hydrazines such as N,N'-diaminopiperazine, carbodihydrazides, dihydrazides such as adipic acid dihydrazide, difunctional low molecular weight compound components of water or mixtures thereof, diphenylmethane diisocyanate, zinc chlorhexyl diisocyanate components such as methane diisocyanate, isophorosocyanate, tolylene diisocyanate, xylylene diisocyanate, isopropylidene bis(4-phenyl isocyanate), tetramethylene diisocyanate, hexamethylene diisocyanate or mixtures thereof. . The thermoplastic polyurethane elastomer contains an active hydrogen group [AH] contained in a bifunctional polyol component and a difunctional low molecular weight compound component, and a diisocyanate component.
It is a linear polymer in which [NCO] groups are reacted at a molar ratio of [NCO]/[AH]≒1. In the present invention,
and a fully thermoplastic type synthesized with 0.5<[NCO]/[AH]≦1, preferably approximately 0.95<[NCO]/[AH]≦1, and approximately 1<[NCO]/
[AH]<1.2 preferably approximately 1<[NCO]/
[AH] Both incomplete thermoplastic types synthesized with <1.1 can be used. The former has a completely linear structure at the end of the hydroxyl group or amino group, and the latter has a partially linear structure with crosslinking points. Such thermoplastic polyurethane elastomers can be produced by various known methods such as bulk polymerization or solution polymerization. Further, TPU may contain additives such as a heat stabilizer, a plasticizer, a lubricant, a hydrolysis resistance improver, a yellowing improver, and a filler. The modified polyolefin or the copolymer mainly composed of olefin used in the resin composition layer (B) used in the present invention means that the main chain or side chain thereof contains a carboxylic acid group, a carboxylic acid base, or a carboxylic acid anhydride. basis,
Contains one or more functional groups selected from the group consisting of an amide group, a hydroxyl group, and an epoxy group,
For example, the following types are possible: One is a modified polyolefin in which a saturated carboxylic acid or its derivative, or other functional vinyl monomer is grafted onto the polyolefin. In this case, the polyolefins include high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene,
Polybutene, polymethylpentene-1, copolymer of ethylene and α-olefin, propylene and α
Polyolefins such as olefin copolymers, ethylene-propylene rubber, ethylene-propylene-diene ternary copolymer rubber, butyl rubber, butadiene rubber, low-crystalline ethylene-propylene copolymers or low-crystalline ethylene-butene copolymers Polyolefin thermoplastic elastomers consisting of
Includes polyolefin elastomers such as polyolefin thermoplastic elastomers that are mainly blends of polypropylene and ethylene-propylene rubber, as well as ethylene-vinyl ester copolymers, ethylene-acrylic ester copolymers, etc., and also includes blends of various polyolefins. . On the other hand, the unsaturated carboxylic acids or derivatives thereof and other functional vinyl monomers referred to in the present invention include, for example, carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and sorbic acid, maleic anhydride, Acid anhydrides such as itaconic anhydride, amides such as acrylic acid amide and methacrylic acid amide, epoxies such as glycidyl acrylate and glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-methacrylic acid
-Hydroxy compounds such as hydroxyethyl and polyethylene glycol monoacrylate, metal salts such as sodium acrylate, sodium methacrylate, and zinc acrylate, etc., and they can also be used in combination. Among them, acrylic acid, maleic acid, and maleic anhydride give preferable results. In addition, when using the above-mentioned monomer, it is also possible to use it simultaneously with other kinds of monomers such as styrene, vinyl acetate, acrylic ester, etc. to carry out co-graft copolymerization. The amount of unsaturated carboxylic acid or its derivative or other functional vinyl monomer contained in the graft-modified polyolefin is preferably 0.005 to 5 mol%, more preferably 0.01 to 1.0%.
A range of mol % is desirable, and even if the amount is small, it can be effective if the functional group contained in the polyolefin has a strong interaction with the thermoplastic polyurethane elastomer. However, below the above range, the remarkable effects of the present invention cannot be obtained.
Moreover, if the amount exceeds the above range, the moldability, thermal stability, etc. of the composition will deteriorate, which is not preferable. In addition, unsaturated carboxylic acid or its derivative,
Various methods can be employed to prepare polyolefins graft-modified with other functional vinyl monomers. One method is to simultaneously mix polyolefins, unsaturated carboxylic acids or derivatives thereof, and other functional vinyl monomers with a radical generator to homogenize the melt. There is a method of adding an unsaturated carboxylic acid or its derivative, other functional vinyl monomer, and a radical generator to suspended polyolefin. On the other hand,
It is also possible to carry out the above reaction in the presence of the thermoplastic polyurethane elastomer referred to in the present invention. Another type of modified polyolefin referred to in the present invention is a saponified product of ethylene-vinyl ester copolymer,
Alternatively, a modified product in which the above-mentioned unsaturated carboxylic acid or its derivative, or other functional vinyl monomer is grafted onto a saponified product of an ethylene-vinyl ester copolymer can be used. In this case, ethylene
The vinyl ester copolymer is preferably a copolymer mainly composed of ethylene, and the ethylene content is preferably 50 mol% or more. Further, the degree of saponification is preferably in the range of 10 to 100%. Those within this range form thermoplastic polyurethane elastomers, compositions with good moldability and physical properties. On the other hand, a modified product obtained by grafting the above-mentioned unsaturated carboxylic acid, a derivative thereof, or another functional vinyl monomer onto the saponified product of the above-mentioned ethylene-vinyl ester copolymer can also be used in the present invention. The type, amount, and modification method of monomers are the same as those for the modified polyolefin described above. As copolymers mainly composed of olefins that can be used in the present invention, copolymers of α-olefins and unsaturated carboxylic acids or derivatives thereof, and other functional vinyl monomers are possible. Also possible are so-called ionomer resins consisting of partial metal salts of copolymers of. For example, it consists of partial metal salts of ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid-methacrylic acid ester copolymer, and ethylene-acrylic acid-methacrylic acid ester copolymer. There are ionomer resins and ionolamer resins made of partial metal salts of ethylene-acrylic acid copolymers. The above-mentioned various modified polyolefins and copolymers mainly composed of olefins can be used in mixtures with each other, or they can be used in mixtures with unmodified polyolefins to the extent that the concentration of the functional groups does not become too low. can. the thermoplastic polyurethane elastomer;
The blending ratio of the modified polyolefin or the copolymer mainly composed of olefin is in the range of 5 to 70 parts by weight for the former and 95 to 30 parts by weight for the latter. especially,
When such a resin composition is used as an adhesive resin layer (B) between a resin layer (A) made of vinyl chloride resin or vinylidene chloride resin and a polyolefin resin layer (C), the resin composition The blending ratio of the thermoplastic polyurethane elastomer and the modified polyolefin or olefin-based copolymer in the material layer is preferably within the inverted phase region of the "sea-island" dispersed structure of the two. That is,
For the resin layer (A) side, which has adhesive properties to thermoplastic polyurethane elastomer but has low adhesion to modified polyolefin or copolymer mainly composed of olefin, the thermoplastic polyurethane elastomer in the resin composition is used. is “sea” (continuous phase)
A dispersed state in which the modified polyolefin or the copolymer mainly composed of olefin forms "islands" (discontinuous phase) is desirable. Conversely, for the resin layer (C) side, which has adhesive properties to modified polyolefins or copolymers mainly composed of olefins, but has low adhesive properties to thermoplastic polyurethane elastomers, It is desirable to have a dispersed state in which the polyolefin or copolymer mainly composed of olefin is the "sea" (continuous phase) and the thermoplastic polyurethane elastomer is "islands" (discontinuous phase). Therefore, the resin composition layer (B) is the same as the resin layer (A) and the resin layer (C).
In order to obtain the highest adhesion for both layers, it is desirable that both components in the resin composition have a structure in which both components form a "sea" (continuous phase). That is, in the laminate of the present invention, when the resin composition layer (B) acts as an intermediate adhesive layer between the resin layer (A) and the resin layer (C), the thermoplastic polyurethane elastomer in the resin composition and It is desirable that the dispersion structure with the modified polyolefin or the copolymer mainly composed of olefin is such that the "sea-island" dispersion state is reversed and the "sea-island" dispersion state is destroyed. The optimal blending ratio of both components to achieve such a dispersed state varies depending on their melt viscosity, chemical affinity, manufacturing method or molding method, etc. It is preferable to select 80 to 40 parts by weight of the modified polyolefin or the copolymer mainly composed of olefin, in order to obtain optimum adhesiveness, as well as from the viewpoint of moldability and economical efficiency. On the other hand, in order to simultaneously melt and bond the resin layer (A) made of vinyl chloride resin or vinylidene chloride resin and the polyolefin resin layer (e), the dispersion structure in the resin composition layer (B) must be A clear “sea”
Even if the dispersion structure of "islands" is exhibited, if the minor axis of the discontinuous phase particles forming the "islands" is finely dispersed with a short axis of 100/μ or less, the above-mentioned modified polyolefin or copolymer mainly composed of olefin can be used. “Sea-Island”
The same effect can be obtained as in a region where the dispersion state of is destroyed. In particular, the shorter diameter of the discontinuous phase particles is preferably as small as possible, more preferably 50μ or less, further preferably 20μ or less, still more preferably 10μ or less. If the minor axis of the discontinuous phase particles exceeds 100μ, the adhesive strength by thermal bonding will be particularly low, and both the physical properties and moldability will decrease. The concentration range of both components for achieving such a dispersed state can be selected within the above range, although the optimal blending ratio varies depending on the melt viscosity of both components, chemical affinity, manufacturing method or molding method, etc. Melt-kneading is the simplest method for producing such a resin composition. It can be produced by melt-kneading a mixture mixed at a predetermined blending ratio using a device such as a single-screw extruder, a multi-screw extruder, a Banbury mixer, a kneader, or a mixing roll. Points to be noted are that the degree of kneading affects the dispersion state and physical properties of the resin composition, and that the thermoplastic polyurethane elastomer has low thermal stability. It is desirable to sufficiently increase the degree of kneading within a range that does not impair the thermal stability of the thermoplastic polyurethane elastomer. In addition to the above-mentioned composition, other kinds of synthetic elastomers can be additionally added to such a resin composition. In addition, heat stabilizers, ultraviolet absorbers, lubricants, antistatic agents, fillers, flame retardants, tackifiers,
Various additives such as dyes and pigments can also be added. The polyolefin resin constituting layer (C) in the present invention includes the above-mentioned modified polyolefins in the resin composition constituting layer (B), the above-mentioned polyolefins that can be raw materials for the modified polyolefin, and the above-mentioned polyolefins that can be used as raw materials for the modified polyolefin. Includes copolymers based on olefins. In particular, for layer (C), it is desirable to use the same type of polyolefin as the modified polyolefin constituting layer (B) from the viewpoint of adhesiveness and moldability. The laminate of the present invention has (A)(B) both layers, or (A)(B)(C)
It is obtained by joining each layer, and any known method such as coextrusion molding, extrusion coating, dry lamination, multilayer injection molding, and various heat welding methods can be employed as the joining method. In particular, it is preferable to melt-extrude each component using separate extruders and join each layer inside a circular die or T-shaped die to obtain a multilayer film, multilayer sheet, multilayer blow-molded product, etc. in a desired shape. Molding is possible if the molding temperature is above the softening temperature and below the decomposition temperature of each component, but it is usually 150 to 210℃.
A range of is desirable. In particular, in the case of coextrusion molding, it is desirable from the viewpoint of adhesiveness and moldability that the melt viscosities of the components constituting each layer are not extremely different. The structure of the laminate of the present invention includes not only a two-layer structure consisting of a resin layer (A) and a resin composition layer (B), but also
(B)／(A)／(B)、(A)／(B)／(A′)／(B)／(A)、(B)／
(A)／(B)(A′)／(B)、(A)／(A′)／(B)／(A′)／
A Sanderch structure as shown in (A) is also possible. (Here, A' indicates a vinyl chloride resin or vinylidene chloride resin different from A.) Furthermore, the resin layer
Add (C), (C)/(B)/(A), (C)/(B)/(A)/(B), (C
)／
(B)／(A)／(B)／(C), (C)／(B)／(A)／(B)／(A′)／
It is also possible to have a multilayer structure such as (B)/(C). In this case, by taking advantage of the characteristics of the resin layer (C), mechanical strength and
A laminate with excellent heat sealability, water resistance, chemical resistance, heat resistance, etc. can be obtained. Furthermore, combinations using other resins that have good adhesion to the resin composition layer (B), such as polyamide/(B)/(A),
Polyamide/(B)/(A)/(B)/(C), Polyester/
It can also be a laminate of (B)/(A), polyester/(B)/(A)/(B)/(C), etc. Furthermore, using the laminate of the present invention as a laminate base material, aluminum foil, polyethylene terephthalate biaxially stretched film, nylon 66 biaxially stretched film, OPP, polystyrene sheet, paper, and other laminate base materials, and methods such as dry lamination can be used. It can also be used by laminating it. The thickness structure of each layer of the laminate can be arbitrarily selected to meet requirements such as quality and economy. Further, the shape of the laminate may be a film, a sheet, a pipe or other irregularly extruded product, a hollow molded product, or various other molded product shapes. The laminate of the present invention not only has extremely good adhesion between resin layers, excellent gas permeation prevention properties, and is easy to heat seal, but also has excellent resistance to water, oil, and chemicals. Because it has excellent impact resistance and flexibility, it also has excellent pinhole resistance, low-temperature properties and transparency, and is economical, making it ideal as a film for food packaging. In particular, when a vinylidene chloride resin is used as the resin layer (A), a laminate with excellent heat resistance can be obtained so that it can be sterilized by boiling or high temperature. The embodiments of the present invention will be illustrated below with reference to Examples, but these are intended to explain the present invention in more detail and are not intended to limit the present invention. In addition, parts and % in Examples and Reference Examples are parts by weight and % by weight, respectively. Example 1 Maleic anhydride and low density polyethylene were melt-kneaded in the presence of a radical generator to give an MI of 1.0 and a density of
0.920 and a maleic anhydride graft modified low density polyethylene having a maleic anhydride content of 0.1% was obtained. This modified low-density polyethylene and thermoplastic polyurethane elastomer (manufactured by Nippon Polyurethane Co., Ltd., Paraprene P22S) were melt-mixed and extruded at 190°C using an extruder at the compounding ratio shown in Table 1 to obtain various resin composition pellets. . This resin composition was applied to a thickness of approx.
A film was formed with a thickness of 20μ. This film (B), an blown film (C) of about 40μ thick low-density polyethylene with MI2.0 and density 0.919, and vinylidene chloride 80
%, vinylidene chloride copolymer resin obtained by a charging composition of 20% vinyl chloride with a thickness of about 20μ
- Three types of film (A) (C) / (B) /
(A)/(B)/(C) were stacked in this order, hot-pressed using a press molding machine at 180°C and a pressure of 20 kg/cm ² , and then cooled to prepare various laminates. The obtained laminate was cut to a width of 10 mm and a length of 10 cm, and one end of the cut was forcibly peeled off to measure the peel strength. (180° peeling, 200
mm/min chuck speed) The results are shown in Table 1. Reference Example 1 Except for using unmodified low-density polyethylene with an MI of 1.0 and a density of 0.920 in place of the maleic anhydride graft-modified low-density polyethylene used in producing the resin composition (B) in Example 1. Various resin compositions were produced in the same manner as in Example 1. Using this resin composition, a laminate was produced in the same manner as in Example 1, and its peel strength was measured. The results are shown in Table 1.

【table】

[Table] Example 2 60 parts of the maleic anhydride graft modified polyethylene used in producing the resin composition (B) in Example 1 and 40 parts of the various thermoplastic polyurethane elastomers listed in Table 2 were used as an example. Various resin compositions were produced by melt-kneading in the same manner as in 1. Using this resin composition, various laminates were manufactured in the same manner as in Example 1, and their peel strengths were measured. Second result
Shown in the table. In addition, in order to evaluate the heat resistance and oil resistance of these laminates, they were immersed in animal oil (pork fat) at 100℃.
The laminate was soaked for 30 minutes, but there was no change in appearance. Reference Example 2-1 Example 2 except that a styrene-butadiene thermoplastic elastomer (manufactured by Asahi Kasei Corporation, trade name: Tuffrene A) was used instead of the thermoplastic polyurethane elastomer. A laminate was produced and evaluated in the same manner as in Example 2. The results are shown in Table 2. Reference Example 2-2 In Example 2, a polyolefin thermoplastic elastomer (Mitsui Petrochemical Industries, Ltd. product name: Tafmer) was used instead of the thermoplastic polyurethane elastomer.
A laminate was produced and evaluated in the same manner as in Example 2, except that 90680) was used. The results are shown in Table 2. Reference Example 2-3 In Example 2, instead of the resin composition layer (B)
A laminate was produced and evaluated in the same manner as in Example 2, except that MI3 and an ethylene-vinyl acetate copolymer film (thickness 20 μm) having a vinyl acetate content of 26% were used. The results are shown in Table 2.

[Table] Example 3 Instead of the maleic anhydride-grafted modified polyethylene used in Example 1, 60 parts of various modified polyolefins listed in Table 3 or a copolymer mainly composed of ethylene and used in Example 1 were used. 40 parts of the thermoplastic polyurethane elastomer prepared above were melt-kneaded in the same manner as in Example 1 to produce various resin compositions. These resin compositions were formed into a 20μ thick film by the inflation method to form the (B) layer, the (A) layer used the same vinylidene chloride copolymer resin as in Example 1, and the (C) layer Laminates were produced in the same manner as in Example 1 using the various polyolefin resins listed in Table 3, and their peel strengths were measured. The results are shown in Table 3.

[Table] Reference Example 3 The thickness of various modified polyolefins or ethylene-based copolymers listed in Table 3 used in Example 3 was measured by the inflation method alone.
A 20μ film was deposited. This film was used as the (B) layer, the (A) layer was made of the same vinylidene chloride copolymer resin as in Example 3, and the (C) layer was made of various polyolefins listed in Table 4, as in Example 3. A laminate was produced in the same manner as in Example 3 using the resin, and its peel strength was measured. The results are shown in Table 4.

[Table] Example 4 MI0.3, density 0.953, maleic anhydride content 0.2%
A resin composition was prepared by melt-kneading 60 parts of maleic anhydride graft-modified high-density polyethylene and 40 parts of the thermoplastic polyurethane elastomer used in Example 1 in the same manner as in Example 1. This resin composition and vinyl chloride resin of the following formulation were each melted in separate extruders and heated to 180°C.
and feed it into a two-layer blow molding die. Concentric resin passages are provided inside the die, with the resin composition passing through the outside and the vinyl chloride resin passing through the inside, and the parison that flows out is molded into a 500ml bottle. The bottle has an outer diameter
75mm, height 160mm, outer resin composition layer thickness 0.5
mm, and the thickness of the inner vinyl chloride resin layer was 0.1 mm. The properties of the bottles are shown in Table 4. Compound Zeon 103EP-8 (manufactured by Nippon Zeon Co., Ltd.) 100 parts Hy-Blen 203 (manufactured by Nippon Zeon Co., Ltd.) 10 Ca/Zn composite stabilizer 2 Butyl stearate 1 Reference example 4 Substitute for the resin composition used in Example 4 A two-layer blow-molded product was molded in the same manner as in Example 4, except that maleic anhydride graft-modified high-density polyethylene, which was the raw material for the resin composition of Example 4, was used alone. The properties of the bottles are shown in Table 5.

[Table] Example 5 Maleic anhydride and medium density polyethylene were melt-kneaded in the presence of a radical generator to give MI1.0 and density
0.933, maleic anhydride modified polyethylene with a maleic anhydride content of 0.6% [], MI8, maleic anhydride modified polyethylene with a density of 0.933 and a maleic anhydride content of 0.2% [], [] 5 parts of maleic anhydride modified medium density polyethylene and MI2 , MI2, density by melt-mixing 95 parts of low-density polyethylene with a density of 0.919.
Maleic anhydride-modified low-density polyethylene with a maleic anhydride content of 0.923% and a maleic anhydride content of 0.03% were prepared, respectively. For reference with these modified polyethylene
Using unmodified low-density polyethylene (MI2) with a density of 0.919, the thermoplastic polyurethane elastomer used in Example 1 was melt-mixed at 190°C using an extruder at the compounding ratio shown in Table 6. A composite resin composition pellet was obtained. The obtained pellets were formed into a film with a thickness of 20 μm by using an inflation film forming machine. These films were used as the (B) layer, the vinylidene chloride resin film used in Example 1 was used as the (A) layer, and the polyethylene film was used as the (C) layer. (A)/(B)/(C) were heat-sealed in the order and the interlayer peel strength was measured. In addition, in order to confirm the dispersed structure of the resin composition, the above film was dyed with a disperse dye and only the polyurethane phase was stained and observed under a microscope. The dispersion structure in which the polyurethane phase is an "island" and the polyethylene phase is a "sea" is expressed as α/β, and the opposite is expressed as β/α. In addition, cases where the “sea-island” dispersion structure is confused are indicated as α×β. Also, if the short axis of the "island" is less than 10μ, no mark is given, and if it is more than 10μ, an asterisk is added. The results are shown in Table 6.

[Table] Example 6 Example 1 except that a vinyl chloride resin with the following formulation was used instead of the vinylidene chloride copolymer resin used as the layer (A) in the laminate of Examples 1-2. A laminate was produced in the same manner as in -2, and its peel strength was measured. The result is over 1000g/10mm,
The adhesion was so strong that the adherend was deformed. Compound Zeon 103EP (manufactured by Nippon Zeon) 100 parts Butylphthalyl-butyl glycolate 10 Octyl diphenyl phosphate 20 Organotin maleate 3 Bis fatty acid amide 0.2 Zinc stearate 0.1

Claims (1)

[Scope of Claims] 1. A resin layer (A) made of a vinyl chloride resin or vinylidene chloride resin, 5 to 70 parts by weight of a thermoplastic polyurethane elastomer, and a carboxylic acid group, a carboxylic acid group, or a carboxylic acid group in the main chain or side chain. 95 to 30 parts by weight of a modified polyolefin containing one or more functional groups selected from the group consisting of a carboxylic acid anhydride group, an amide group, a hydroxyl group, and an epoxy group, or a copolymer mainly composed of an olefin containing the above functional groups. At least two resin composition layers (B) consisting of
A laminate consisting of layers. 2. A resin layer (A) made of vinyl chloride resin or vinylidene chloride resin, 5 to 70 parts by weight of thermoplastic polyurethane elastomer, and a carboxylic acid group, carboxylic acid base, or carboxylic acid anhydride group in the main chain or side chain, A resin composition comprising 95 to 30 parts by weight of a modified polyolefin containing one or more functional groups selected from the group consisting of an amide group, a hydroxyl group, and an epoxy group, or a copolymer mainly composed of an olefin containing the above functional groups. The layer (B) is a laminate of two or more layers in contact with each other, and the layer (B) is arranged in at least one outermost layer of the laminate, and at least one layer is arranged in the outermost layer. A laminate made by laminating one layer (B) and a polyolefin resin layer (C) in contact with it.