JPH09327893A - Multilayer laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to provide excellent transparency, flexibility, cold resistance and heat sealing strength and small aging change of the transparency in a novel multilayer laminate suitable for a film or sheet material. SOLUTION: The multilayer laminate comprises a surface layer (II) at least on one surface of a base layer (I). The layer (I) contains (a)/(b)=100 to 20/0 to 80wt.%, and the layer (II) contains (a)/(c)=95 to 50/5 to 50wt.%, wherein (a) is a polyolefin resin (b) is a hydrogenated diene copolymer having a double bond of conjugated diene of a conjugated diene polymer saturated at 80% or more and 50,000 to 700,000 of number-average molecular weight, and (c) is a hydrogenated diene copolymer having a hydrogenated block at the ends or at least one end of the polybutadiene polymer having 25% or less of butadiene content having 1,2-vinyl bond.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel multi-layer laminate suitable as a film or sheet material, and more specifically, it has excellent transparency, flexibility, cold resistance, heat seal strength, etc. Less multi-layer laminates.

[0002]

2. Description of the Related Art A large number of single-layer or multi-layer film and sheet materials have been developed so far, and among these materials, vinylon film is a typical film excellent in transparency, flexibility and texture. There is. However, because of its characteristics, the texture of vinylon is easily affected by temperature and humidity, and in particular, it has poor cold resistance, so there is a limit to its use in regions where temperatures drop in winter or in cold regions. In addition to the problems of residual acetic acid odor and easy blocking, there is also a drawback that the cost must be increased because the film forming method is limited to the solution casting method. To solve these problems, a large number of polyolefin single-layer and multi-layer film materials have been developed. Although these polyolefin-based materials are improved in cost and cold resistance, they have a problem that they are inferior in transparency and flexibility to vinylon film. More recently, vinyl aromatic compound polymer block, conjugated diene compound polymer block or random copolymer block of vinyl aromatic compound and conjugated diene compound, vinyl aromatic compound and conjugated diene compound, A sheet made of a composition containing a hydrogenated diene copolymer obtained by hydrogenating a block copolymer composed of two or more kinds of tapered blocks in which an aromatic compound is gradually increased, and a polyolefin resin as main components. It is generally disclosed that a film is subjected to secondary processing such as lamination (Open Technical Report 94-
12864), and a hydrogenated block copolymer comprising a polypropylene copolymer, a polymer block containing at least one vinyl aromatic group as a main component, and a polymer block containing a hydrogenated conjugated diene compound as a main component. It is disclosed that a film excellent in flexibility, transparency, heat resistance, low temperature impact resistance, and heat sealability can be obtained by laminating a skin layer composed mainly of a polypropylene resin on the compounded base layer. (See Japanese Patent Laid-Open No. 7-227938). However, these films and sheets are still unsatisfactory in terms of transparency, strength, heat-sealing property, and in terms of a comprehensive property balance in terms of changes in transparency over time and occurrence of stickiness at high temperatures.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art.
It is an object of the present invention to provide a multi-layered laminate which is excellent in transparency, strength, heat seal strength, etc., has little change in transparency with time, and is free from stickiness at high temperatures.

[0004]

That is, the present invention relates to a multilayer laminate having a skin layer (II) provided on at least one surface of a base layer (I), wherein the base layer (I) comprises the following (A)
/ (B) = 100 to 20/0 to 80% by weight, and the skin layer (II) has the following (a) / (c) = 95 to 50/5.
The gist is a multi-layer laminate consisting of ˜50% by weight. (A) Polyolefin resin (b) Hydrogenated diene copolymer having a number average molecular weight of 50,000 to 700,000, in which the double bond of the conjugated diene portion of the conjugated diene polymer is saturated by 80% or more. ) The content of butadiene having a 1,2-vinyl bond (hereinafter referred to as "1,2-vinyl bond content") is 25.
% Or less of a polybutadiene polymer having a hydrogenated block at least at one end thereof.

The present invention will be described in detail below. First, the base material layer (I) will be described. The polyolefin resin used as the component (a) in the base material layer (I) of the present invention is a resin obtained by polymerizing one or more monoolefins by either a high pressure method or a low pressure method, Polyethylene, polypropylene, polybutene-1 and poly-4-methylpentene-1 are preferable, and polypropylene is more preferable. The polyolefin resin may be a homopolymer or a copolymer obtained by copolymerizing the following other monomers.
In the component (a), preferable copolymerization components include, for example, ethylene (except when the main polymer is polyethylene), propylene (except when the main polymer is polypropylene), butene-1 (where the main polymer is (Except when it is polybutene-1), pentene-1, hexene-1, heptene-1, octene-1, and other linear α-
Olefin, 4-methylpentene-1 (except when the main polymer is 4-methylpentene-1), 2-methylpropene-1,3-methylpentene-1,5-methylhexene-1,4-methylhexene -1,4,4-Dimethylpentene-1 and other branched α-olefins, acrylic acid, methacrylic acid and other monocarboxylic acids, maleic acid, fumaric acid and other dicarboxylic acids and their monoesters, methyl methacrylate, methyl Acrylate, methacrylic acid esters such as ethyl acrylate, vinyl esters of saturated carboxylic acids such as vinyl acetate, aromatic vinyl compounds such as styrene and α-methyl-styrene, acid anhydrides such as maleic anhydride, acrylonitrile, etc. α, β-Unsaturated nitrile, dicyclopentadiene, ethylidene nor Diene monomer addition acrylamide such Runen and methacrylamide are used. Among these copolymerizable monomers, more preferred monomers in the polypropylene copolymer are linear α-olefins such as ethylene, butene-1, pentene-1, hexene-1, heptene-1, and octene-1. Particularly preferred are ethylene and butene-1.
These copolymerizable monomers may be used alone or in combination of two or more kinds. The amount of these copolymerization components is preferably 20% by weight or less, more preferably 10% by weight or less. There is no particular limitation on the form of the copolymer when these are copolymerized, and for example, any of a random type, a block type, a graft type, and a mixed type thereof may be used. In the polypropylene-based polymer, a homopolymer of propylene or a random copolymer with the above monomer is more preferable.

In the present invention, by using a propylene homopolymer or a random copolymer, a multilayer laminate having an excellent balance of physical properties such as transparency, heat resistance and flexibility can be obtained. The polyolefin resin (a) of the present invention may be used alone or in combination of two or more kinds. The melt flow rate (MFR: 230 ° C., 2.16 kg load) of the polyolefin resin is not particularly limited as long as it can be molded as a film or sheet, but in the case of a polypropylene resin, it is preferably 0.5 to 15 g / 10. Min, more preferably 1-10 g
By setting it as / 10 minutes, a multilayer laminate excellent in moldability, transparency and the like can be obtained. The content of the polyolefin resin in the base material layer (I) is 100 to 20% by weight, preferably 90 to 30% by weight, and most preferably 90 to 40% by weight. In this case, the blending amount of the polyolefin resin is 20
If it is less than wt%, the strength of the obtained multilayer laminate and the formability of the multilayer laminate will be reduced.

Next, in the hydrogenated diene-based copolymer used as the component (b) of the base material layer (I), the hydrogenation rate of the double bond in the conjugated diene portion of the conjugated diene-based polymer is 80%. Or more, preferably 90% or more, more preferably 95% or more, and have a number average molecular weight of 50,000 to 700,000, preferably 10
It is a hydrogenated diene polymer having a molecular weight of 10,000 to 600,000. When the hydrogenation rate is less than 80%, transparency, mechanical strength, heat resistance,
Poor weather resistance. When the number-average molecular weight is less than 50,000, the obtained hydrogenated diene-based copolymer is easily blocked when pelletized, and when blended with another resin, the mechanical strength, the molded appearance is inferior, and when it exceeds 700,000. Poor workability. As the component (b), for example, a homopolymer of a conjugated diene, a random copolymer of a conjugated diene and a vinyl aromatic compound, a block copolymer of a polymer block of a vinyl aromatic compound and a polymer block of a conjugated diene, Polymer block of vinyl aromatic compound and vinyl aromatic compound /
Examples thereof include a hydrogenated product of a diene-based polymer such as a block copolymer composed of a copolymer block of a conjugated diene or a functional group-modified product thereof. The component (b) has a number average molecular weight of 50,000 to 70 in which the double bond of the conjugated diene portion of the polymer mainly composed of the random copolymerization portion of the conjugated diene compound and the aromatic vinyl compound is 80% or more saturated. The hydrogenated diene-based polymer (ro-a) is preferably used, and when it is used, a multilayer laminate excellent in transparency and flexibility can be obtained. The hydrogenated diene copolymer used as the (b-a) component of the base material layer (I) is a polymer mainly composed of a random copolymerized portion of a conjugated diene compound and an aromatic vinyl compound (hereinafter, referred to as “ (Also referred to as "pre-hydrogenated polymer"). The proportion of the random copolymerized portion in the polymer before hydrogenation is preferably at least 50% by weight, more preferably at least 60% by weight, further preferably at least 70% by weight. When the proportion of the random copolymer portion is less than 50% by weight, the transparency, flexibility, cold resistance and the like of the obtained multilayer laminate are reduced. In the above random copolymerization portion, the content of the conjugated diene having 1, 2, and 3,4 bonds (hereinafter, also referred to as “vinyl bond content”) with respect to all the conjugated dienes in the random copolymerization portion is preferably 60. %that's all,
It is more preferably at least 65%, further preferably at least 70%. If the proportion of this conjugated diene is less than 60%,
(A) The effect of improving transparency and flexibility when blended with a polypropylene resin is insufficient.

The (a) hydrogenated diene copolymer used in the present invention is composed of a conjugated diene compound and an aromatic vinyl compound. Examples of the conjugated diene compound used here include 1,3-butadiene, isoprene, and 2,3-
Dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene,
Examples thereof include 3-butyl-1,3-octadiene and chloroprene. In order to obtain a hydrogenated diene polymer which can be industrially used and has excellent physical properties, 1,3-butadiene,
Isoprene and 1,3-pentadiene are preferred, and 1,3
-Butadiene and isoprene are particularly preferred. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, divinylbenzene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene,
Vinyl pyridine and the like are exemplified, and styrene and α-methylstyrene are preferred.

The ratio of conjugated diene compound / aromatic vinyl compound constituting the polymer before hydrogenation is not particularly limited in the present invention, but is preferably 95/5 to 40.
/ 60, and more preferably 93/7 to 50/50. When the proportion of the aromatic vinyl compound is more than 60%, the obtained multilayer laminate has poor flexibility, and when it is less than 5%, the strength of the obtained multilayer laminate is poor.

The component (b-a) of the present invention can be obtained by hydrogenating a polymer mainly composed of a random copolymer portion as described above. And the following polymer blocks may be contained. Examples of the polymer block which may be contained in the pre-hydrogenated polymer include an aromatic vinyl compound polymer, a polybutadiene polymer mainly containing 1,4-bonds, and an aromatic vinyl compound comprising an aromatic vinyl compound and a conjugated diene. Examples include a tapered polymer in which the compound gradually increases. When these polymer blocks are present, the physical properties of the component (b-a) are slightly impaired, but the handling properties are improved due to a decrease in the blocking property of the material, and therefore, the polymer blocks may be industrially useful. . The ratio of the polymer block in the entire molecular chain in the polymer before hydrogenation is not particularly limited, but is preferably 50% by weight or less, more preferably 40% by weight or less, and further preferably 30% by weight or less. . When the proportion of the polymer block exceeds 50% by weight, transparency, flexibility, cold resistance and the like of the obtained multilayer laminate are reduced.

The pre-hydrogenated polymer may be a polymer in which a polymer molecular chain is extended or branched via a coupling agent residue by using a coupling agent. As the coupling agent used at this time, for example, diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin,
Butyltrichlorotin, dimethyldichlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, 1,4
-Chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate and the like. In addition, as the component (b-a) of the present invention, those obtained by hydrogenating a blend of two or more pre-hydrogenated polymers are also preferably used. Furthermore, a blend of two or more hydrogenated diene polymers is also suitable as the component (b) of the present invention.

In the (a) hydrogenated diene polymer of the present invention, the hydrogenation rate of the double bond of the conjugated diene moiety in the molecular chain is preferably 80%, more preferably 85% or more, and further preferably Is 90% or more. If it is less than 80%, the transparency, mechanical strength, heat resistance, weather resistance, etc., decrease. Furthermore, the (b) hydrogenated diene-based polymer of the present invention has a polystyrene reduced number average molecular weight (hereinafter simply referred to as “number average molecular weight”) of 50,000 to 700,000, preferably 50,000 to
600,000. If the molecular weight is less than 50,000, the hydrogenated diene copolymer is easily blocked when pelletized, and (a) the mechanical strength is reduced when blended with the polyolefin resin. Properties etc. decrease.

The hydrogenated diene copolymer can be produced, for example, by the method disclosed in Japanese Patent Application Laid-Open No. 3-72512. Further, (b) of the base material layer (I)
The hydrogenated diene-based copolymer used as a component may be a modified product obtained by introducing one or more functional groups into the hydrogenated diene-based copolymer. Examples of the functional group include a carboxyl group, an acid anhydride group, a hydroxyl group, an epoxy group, an amino group, an ammonium group, a halogen atom-containing group, a sulfonic acid group, and the like, and a group derived from these functional groups, for example, an ester group. Etc. Such functional groups are introduced before or after hydrogenation of the hydrogenated diene-based copolymer (b), depending on their type.

The base material layer (I) of the present invention comprises the above-mentioned components (a) and (b), and the content of the component (b) in the resin composition is 0 to 80% by weight, preferably. 10-70%,
Most preferably, it is 10 to 60%. In this case, (b)
When the content of the component is more than 80% by weight, the strength and moldability of the obtained multilayer laminate are reduced.

Next, the surface layer (II) will be described. Polyolefin resin (a) forming the surface layer (II) of the present invention
The same as that used for the base material layer (I) is used, but a polypropylene resin is preferable as in the case of the base material layer (I). The compounding amount of the polyolefin resin (a) in the surface layer (II) is 100 to 50% by weight, preferably 95 to 60% by weight, and most preferably 90 to 70% by weight. In this case, the blending amount of polyolefin resin is 50
If it is less than 10% by weight, the blocking resistance of the resulting multi-layer laminate is deteriorated.

Next, (c) used in the surface layer (II) of the present invention is water having a block to which at least one end is added a polybutadiene polymer having a 1,2-vinyl bond content of 25% or less. It is an added diene-based copolymer, and those described in (ha-a) and (ha-b) below are preferable. (A) A polymer block (A) mainly composed of a vinyl aromatic compound [hereinafter also referred to as "(A) block"] and a conjugated diene having a vinyl bond content of 25 to 95% by weight. Polymer block (B) [hereinafter also referred to as "(B) block"] and 1,2-vinyl bond content of 25
% Of polybutadiene polymer block (C) [hereinafter also referred to as "(C) block"] (A)-
(B)-(C) block copolymer or modified functional group thereof, wherein (A) block content is 4 to 60% by weight, (B) block content is 30 to 90% by weight, (C) The block copolymer having a block content of 4 to 60% by weight, [(A) + (B) + (C) = 100], or the block copolymer unit is bonded via a coupling agent residue. A hydrogenated diene system having a number average molecular weight of 50,000 to 700,000 obtained by hydrogenating a block copolymer in which a polymer molecular chain is extended or branched, and a double bond of a conjugated diene portion is saturated by 80% or more. Copolymer or modified functional group thereof.

(H-b) The above (C) block and (B)
And (C)-(B) or (C)-
(B)-(C) block copolymer, or a block copolymer in which the block copolymer unit has a polymer molecular chain extended or branched through a coupling agent residue, is hydrogenated and conjugated. A hydrogenated diene-based copolymer having a number average molecular weight of 50,000 to 700,000 in which double bonds in the diene portion are saturated by 80% or more, or a functional group-modified product thereof. In the above (ha-a) and (ha-b), the ratio of 1,2 or 3,4 bonded conjugated dienes to all conjugated dienes in the b block is (a) the polyolefin resin described in claim 2. In the case of polypropylene resin, preferably 60% or more,
It is more preferably at least 65%, further preferably at least 70%. If the proportion of this conjugated diene is less than 60%,
(A) The effect of improving transparency and flexibility when blended with a polypropylene resin is insufficient. The above-mentioned (ha-a) and (ha-b) are described in, for example, JP-A-3-72.
It can be manufactured by the method disclosed in Japanese Patent Laid-Open No. 512.

By using these (ha-a) and (ha-b), it is possible to obtain a multi-layer laminate which is excellent in transparency, heat seal strength, etc., has little change in transparency with time, and does not cause stickiness at high temperatures. Obtainable. The content of the hydrogenated diene-based copolymer (C) in the surface layer (II) is 5 to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30%.
% By weight. In this case, hydrogenated diene copolymer (C)
If the compounding amount is less than 5% by weight, the transparency of the obtained multilayer laminate is lowered, and if it exceeds 50% by weight, the blocking resistance of the obtained multilayer laminate is lowered.

The multi-layer laminate of the present invention comprises a resin composition (a)
The double bond of the conjugated diene portion of the polyolefin resin and the (b) conjugated diene polymer is 80% or more saturated,
On at least one surface of the base material layer (I) formed of a hydrogenated diene-based copolymer having a number average molecular weight of 50,000 to 700,000, (a) a polyolefin resin and (c) 1,2-
A surface layer formed from a hydrogenated diene-based copolymer having a block to which a polybutadiene polymer having a vinyl bond content of 25% or less is added at least at one end (I
In such a multilayer laminate, the base layer and the surface layer complement or synergize with each other to form a multilayer laminate having excellent properties. Therefore, in the present invention, the combination of the component (a) and the component (b) in the base material layer (I), the blending amount of the component (b), the component (a) and the component (c) in the surface layer (II). Combination with,
Various conditions such as the compounding amount of the component (c) are appropriately selected according to the desired characteristics of the multilayer laminate.

In the present invention, if necessary, ethylene-propylene copolymer (EPM), ethylene-butene-1 copolymer (EBM), ethylene-propylene are used as long as the characteristics of the present invention are not impaired. -Olefin-based (co) polymers such as non-conjugated diene copolymer (EPDM), polybutene-1, polyethylene; ionomer, ethylene-
Vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (E
Other resins such as VOH) can be incorporated in the base layer (I) and / or the surface layer (II). The base material layer (I) and / or the surface layer (II) may include, if necessary, an antiblocking agent, an organic antibacterial agent, an inorganic antibacterial agent, and an antistatic agent as long as the characteristics of the present invention are not substantially impaired. Agent,
Known additives such as an antioxidant, a lubricant, an anti-fogging agent, a colorant, and an ultraviolet absorber can also be blended. As the antiblocking agent, for example, silica and zeolite are suitable, and these may be natural or synthetic. As the antistatic agent, N, N-bis- (2-hydroxyethyl) -alkylamines having an alkyl group having 12 to 18 carbon atoms and glycerin fatty acid ester are preferable.
Further, as the lubricant, a fatty acid amide is preferable,
Specific examples include erucic acid amide, behenic acid amide, stearic acid amide, oleic acid amide and the like.

The mixing of the component (a) and the component (b) in the base material layer (I) of the present invention and the mixing of the component (a) and the component (c) in the surface layer (II) are carried out by, for example, Banbury-
It can be carried out by using an appropriate mixer such as a mixer, a roll mill, an extrusion molding machine, etc., but melt kneading is preferably carried out in the extruder, and particularly preferably a twin screw extruder is used for melt kneading. By using the resin composition melt-kneaded by the twin-screw extruder as described above, the fish eyes in the film and the sheet are reduced, and the film and the sheet having not only excellent appearance but also further excellent transparency can be obtained. . The resin composition melt-kneaded using a twin-screw extruder is usually pelletized and used. The multilayer laminate of the present invention is, for example, (a) a method in which a base material layer and a surface layer are formed into a film or sheet by an ordinary method such as an inflation method or a T-die method, and then heat-bonded, (b) coextrusion Type inflation molding machine and T
A method of directly laminating with a die extruder, (c)
For example, it can be manufactured by laminating by a known method such as a method of extruding and laminating the other layer on at least one surface of the base material layer or the surface layer preformed by the method (a). The T-die of the T-die extruder used in the method (b) may be either a multi-manifold type or a feed block type. Of these methods,
The method (b) is preferable, and the most preferable method is a method using a co-extrusion type T-die extruder.

In the method (b), a two-layer coextrusion method in which a surface layer is laminated on one surface of a base material layer, a three-layer coextrusion method in which a surface layer is laminated on both surfaces of the base material layer, and 4 A multilayer extrusion method of more than one layer can be employed. In addition, it is preferable to laminate a surface layer on both surfaces of the base material layer from the viewpoints of blocking resistance and change in transparency over time. In the multilayer laminate of the present invention, the surface layer is laminated on one surface or both surfaces of the base material layer, but the respective surface layers laminated on both surfaces of the base material layer may be the same or different. Two or more surface layers may be laminated on one surface or both surfaces of the layer. Two or more of the multi-layer laminate of the present invention can be used by laminating. Furthermore, the multi-layer laminate of the present invention may be used by pasting it onto a cloth such as cotton or polyester, or paper. The thickness of the multilayer laminate of the present invention is appropriately selected depending on the desired characteristics and application of the multilayer laminate, but from the viewpoint of moldability and strength,
It is preferably 10 μm or more, more preferably 2
0 μm or more. Further, the thickness ratio of the base material layer to the surface layer in the multilayer laminate of the present invention is appropriately selected according to the desired characteristics and application of the multilayer laminate, but the base material layer / surface layer = 1.
It is preferably in the range of / 1 to 20/1, and more preferably in the range of base material layer / surface layer = 2/1 to 8/1.

[0023]

[For 40 μm thick film]

 Haze is 2% or less ∘ ○ Haze is higher than 2% and 3% or less ・ ・ ・ △ Haze is higher than 3% ・ ・ ・ × [For a film having a thickness of 100 μm] Haze is 3% or less ・ ・ ・ ○ Haze Is higher than 3% and 4% or less ... △ Haze is higher than 4% ... ×

Heat-sealing strength : After heat-sealing at a temperature of 135 ° C. for a load of 2 kg / cm 2 for 1.5 seconds, the peel strength was measured and evaluated according to the following criteria. Peel strength is 800 g / 2.5 cm or more ... ○ Peel strength is 800 g / 2.5 cm or less ... × Change in transparency over time The film haze (%) after being left in a constant temperature bath at 50 ° C. for 2 weeks It was measured according to ASTM D 1003 and evaluated according to the following criteria. The difference from the initial haze is 0.5 or less ... O The difference from the initial haze is greater than 0.5 and 1.0 or less ... △ The difference from the initial haze is greater than 1.0 ... × At high temperature Evaluation of Stickiness After standing for 2 weeks in a thermostat at 80 ° C., evaluation was made according to the following criteria. Not sticky when touched with fingers ... ○ Sticky or slightly sticky when touched with fingers △ △ Sticky when touched with fingers ・ ・ ・ ×

The components used in the formulation of the examples and comparative examples are as follows. (B) Component (B-1) Polypropylene (manufactured by Chisso Petrochemical Co., Ltd., trade name FM831B) (B-2) Polypropylene (manufactured by Mitsubishi Chemical Co., trade name F)
X4) (b) Component The hydrogenated diene copolymers (b-1) to (b-2) shown in Table 1 were synthesized. Table 1 shows the microstructure, number average molecular weight, and hydrogenation rate of these hydrogenated diene-based copolymers.

[0026]

[Table 1] * 1) BD: butadiene * 2) St: styrene

Component (c) Hydrogenated diene copolymers (c-1) to (c-c) shown in Table 2
8) was synthesized. Miku of these hydrogenated diene-based copolymers
Table 2 shows the structure, number average molecular weight and hydrogenation rate.
You.

[0028]

[Table 2] * 1) BD: butadiene * 2) IP: isoprene * 3) St: styrene

[0029]

【Example】

Example 1 50 parts by weight of the component (a-1) and 50 parts by weight of the component (b-1) were melt-kneaded using a twin screw extruder PCM-45 manufactured by Ikegai Co., Ltd., and then pelletized. Pellets of the composition for the material layer (I) were obtained. Similarly, 85 parts by weight of the component (a-1), 15 parts by weight of the component (c-1) and 0.2 parts by weight of silica as an anti-blocking agent were melt-kneaded and then pelletized to obtain a composition for the surface layer (II). Of pellets were obtained. An extrusion molding machine (manufactured by Modern Machinery Co., Ltd., for base material layer: 65 mmφ, for surface layer: 5) capable of forming a three-layer film equipped with a T-die with a feed block is used for each composition obtained.
0 mmφ), the extrusion temperature is 240 ° C., the chill roll temperature is 20 ° C., and three layers are coextruded to obtain a thickness of 40 μm
A three-layer laminate in which the thickness ratio of each layer was 1/4/1 was obtained. Then, after performing normal aging, various evaluations were performed. As a result, the obtained three-layer laminate has transparency, flexibility,
The cold resistance, fusing seal strength, and film strength were excellent, and the change in transparency with time was extremely small. Table 2 shows the evaluation results.

Examples 2 to 7 Various evaluations were made in the same manner as in Example 1 except that the composition, thickness and thickness ratio of the base material layer to the surface layer were as shown in Table 3. As a result, all of the obtained three-layer laminates were excellent in transparency, flexibility, cold resistance, fusing seal strength and film strength, and the change in transparency with time was extremely small. Table 3 shows the evaluation results.

[0031]

[Table 3]

Comparative Examples 1 to 7 Various evaluations were carried out in the same manner as in Example 1 except that the composition, thickness and thickness ratio of the base material layer to the surface layer were as shown in Table 4. In the three-layer laminate of Comparative Example 1, the composition ratio of the component (a) and the component (b) of the base material layer was out of the range of the present invention and the heat-sealing property was excellent, but the film strength was poor, which was not preferable. In the three-layer laminate of Comparative Example 2, the composition ratio of the surface layer (A) component and the (C) component was out of the range of the present invention, and although the film strength was sufficient, the blocking resistance was poor, which was not preferable. Comparative Examples 3-6
In the three-layer laminate, the surface layer (c) component was outside the range of the present invention, and the film strength was sufficient in all cases, but Comparative Examples 3, 4 and 6 were inferior in transparency, and Comparative Example No. 5 was inferior in terms of blocking resistance. In the three-layer laminate of Comparative Example 7, the composition ratio of the surface layer (A) component and the (C) component was outside the range of the present invention, and although the film strength and the like were sufficient, the transparency and heat sealability were poor, which is preferable. There wasn't. Table 4 shows the evaluation results.
Shown in

[0033]

[Table 4]

[0034]

As shown in the above examples, the multi-layer laminate of the present invention is excellent in transparency, strength, heat sealability, anti-blocking property, etc., and has little change in transparency with time, and is sticky at high temperature. Since it does not occur, clothing materials such as ponchos,
Various packaging materials such as clothing packaging film, stationery packaging film, medical packaging film, book cover, electronic circuit board molding film, dicing film, medical waste bag, stationery, medical hygiene material transfer film, surface protection film, It can be suitably used in various fields such as various decorative films and table cloths.

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Claims (1)

[Claims] 1. In a multilayer laminate in which a surface layer (II) is provided on at least one surface of the base layer (I), the base layer (I) has the following (A) / (B) = 100 to 20/0 to 80.
The surface layer (II) is composed of the following (a) / (c) =
A multilayer laminate comprising 95 to 50/5 to 50% by weight. (A) Polyolefin resin (b) Hydrogenated diene copolymer having a number average molecular weight of 50,000 to 700,000, in which the double bond of the conjugated diene portion of the conjugated diene polymer is saturated by 80% or more. ) A hydrogenated diene copolymer having a hydrogenated block of a polybutadiene polymer having a 1,2-vinyl bond and having a butadiene content of 25% or less.