JP2014043020A - Resin laminate and multilayer container made of resin having carbon-labeled surface layer containing plant-derived ethylene resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate and a multilayer container made of a resin having carbon-offset property with easy controllability of the carbon-offset property and excellent slipperiness and piercing resistance.SOLUTION: A resin laminate and a multilayer container made of a resin having a carbon-labeled surface layer containing a plant-derived ethylene resin are provided, which have a layer of the following resin composition as a surface layer. The resin composition comprises a resin component containing (A) 90 to 60% of an ethylene α-olefin copolymer having a density of 912 to 935 kg/cmand (B) 10 to 40% of a high-density polyethylene, and (C) 100 to 4000 ppm of a fatty acid amide having an unsaturated cis structure carbon double bond, in which (A) and (B) have modern carbon ratios (ASTM D6866-12) of 23.3 to 118 pMC and 0 to 8 pMC, respectively, or the resin composition has a modern carbon ratio of 14 to 118 pMC. A preferable example of (C) is (C):HN-CO-(-CH-)-CH=CH-(-CH-)-CH; (C):HN-CO-(-CH-)-CH=CH-(-CH-)-CH; or (C):HN-CO-(-CH-)-CH=CH-(-CH-)-CH(where n, m and k are 6 to 10).

Description

  The present invention relates to a resin laminate and a resin multilayer container, and in particular, is a carbon offset property suitable for a resin multilayer container with improved surface slipperiness and puncture resistance, and adjustment of the carbon offset property is possible. The present invention relates to an easy resin laminate and a resin multilayer container. More specifically, the carbon offset contributes to reducing greenhouse gas emissions, and exhibits optimal slipperiness in each process such as the manufacturing process, filling process, and packaging process of resin multilayer containers, and the filled contents The present invention relates to a resin laminate that contributes to the improvement of a resin multilayer container that does not lose its sealing performance during transportation, storage, and use, and a resin multilayer container.

  Containers are usually used for storing or transporting articles or materials. The contents of the container include various things such as viscous liquid materials such as mayonnaise, ketchup, sauce and jelly, liquid materials having relatively high fluidity such as juice and alcoholic beverages, and granular materials. There are a wide variety of container shapes in overall shape and partial shape. Metal, synthetic resin, paper, ceramics, glass, etc. are used as the material of the container, and these composites and laminates are also used. The

  For example, as a synthetic resin material container, it is obtained by extruding a cylindrical parison made of synthetic resin material and then blow molding into the shape of the container in a molding die, or by injection molding. An injection-molded container is known. The layer structure of the synthetic resin material container includes a single layer container or a multilayer container, and the synthetic resin material includes polyolefins such as ethylene resins and propylene resins, polyesters such as polyethylene terephthalate, polyamides such as nylon, etc. Is used (Patent Documents 1 to 4). As a multilayer synthetic resin material container, polyolefin is used as a surface layer (outer layer and / or inner layer), and an intermediate layer is formed from a resin laminate including a barrier layer such as ethylene / vinyl alcohol copolymer (EVOH). The multilayer structure is widely used.

  Examples of the metal container include a container formed by winding a thin metal plate such as aluminum or steel into a substantially cylindrical shape, or a metal thick plate formed by deep drawing in a substantially cup shape. In addition, as the paper container, there is a paper container in which a plate-shaped paper material is wound to have a substantially cylindrical shape or a prism shape.

[Container recycling]
These various types of containers are being recycled and separated due to the majority of household waste in volume ratios and the growing public opinion of building a recycling-oriented society. Combined with the enactment of the Containers and Packaging Recycling Law and the Law for Promotion of Effective Utilization of Resources, the recycling rate of aluminum containers and PET bottles has improved, and the resource reuse rate has also improved. Absent.

[Carbon offset]
When a synthetic resin such as polyolefin, which is an organic substance, or a molded product such as a container or cap made of the synthetic resin material is burned, carbon dioxide is generated. Carbon dioxide is one of the gases that warm the global environment, that is, greenhouse gas (also called “green house gas”), and has continued to increase along with industrial activities by people, especially after the industrial revolution. . In order to maintain a global environment where human survival is sustainable, the concept of carbon dioxide that does not increase the total amount of carbon dioxide circulating in the earth's oceans and atmosphere is shared.

  Currently, most of synthetic resin materials, such as polyolefins, are produced using compounds derived from fossil fuels such as petroleum, coal and natural gas as starting materials. As is well known, fossil fuels contain carbon that has been fixed in the ground for many years. Combustion of a fossil fuel or a product derived from a compound derived from fossil fuel and releasing carbon dioxide into the atmosphere means that carbon that is fixed deep in the ground and does not exist in the atmosphere will Since it is suddenly released into the atmosphere as carbon, carbon dioxide in the atmosphere greatly increases, causing global warming.

  On the other hand, even if organisms (plants, animals) that grow by nutrient sources that absorb carbon dioxide circulating in the global environment and convert it into organic matter are burned in the earth's atmosphere to generate carbon dioxide, Since this is a circulation of carbon dioxide existing in the interior, there is no change in the total amount of carbon constituting the carbon dioxide. This carbon entry / exit is said to be a state of carbon offset (carbon offset) or no entry / exit (carbon neutral), and carbon negative (carbon negative) increases carbon dioxide present in the global environment. ).

  Carbon that circulates in the global environment, and the existing carbon is renewable carbon, modern carbon (contemporary carbon), bio-derived carbon (bio-resourced carbon, biobased carbon, biogenic carbon) ), Biomass derived carbon, green carbon, atmospheric carbon, environmentally friendly carbon, or life-cycle carbon, etc. And carbon (fossil carbon, fossil fuel based carbon, petrochemical based carbon, carbon of fossil origin).

  In particular, plants are organisms that grow by absorbing carbon dioxide circulating in the global environment, performing photosynthesis reactions using carbon dioxide and water as raw materials, and assimilating and fixing as organisms. It is attracting attention as a source. For example, alcohol components, especially ethyl alcohol, are distilled and separated from fermented sugar or cellulose fermented products extracted from plant materials such as sugar cane and corn, and ethylene is obtained as an alkene by its dehydration reaction. Thus, an ethylene resin or an olefin resin can be obtained (Patent Document 5). Synthetic resins having this history are said to be carbon offset polyolefin, biogenic polyolefin, plant based resin, or the like.

Carbon constituting the carbon dioxide circulating in the global environment is radioactive carbon 14 (also referred to as “ ¹⁴ C”), which is an isotope, and stable carbon 12 (also referred to as “ ¹² C”). ) And metastable carbon 13 (sometimes referred to as “ ¹³ C”), the mass ratio of which is ¹² C (98.892 mass%), ¹³ C (1.18 mass%) and ¹⁴ it is well known that C (a trace amount 1.2 × ^{10 -12} wt% to 1.2 × ^{10 -10} wt%). The ratio between ¹² C and ¹³ C is stable. In addition, radioactive ¹⁴ C is generated when neutrons contained in secondary cosmic rays generated by primary cosmic rays in the upper atmosphere collide with nitrogen atoms ( ¹⁴ N) in the atmosphere. Although it fluctuates slightly depending on the level of activity, etc., it continues to be supplied.

Living organisms (plants and animals) that grow by nutrient sources that constantly absorb carbon dioxide circulating in the global environment and convert it into organic matter constitute the carbon dioxide circulating in the global environment during its life. Continue to carry on mass proportions of different carbon isotopes. When the organism is killed, the mass ratio of the three types of carbon isotopes inside the organism is fixed at the ratio at the time of death. The half-life of ¹⁴ C is 5730 years, and archaeological dating methods that use this to estimate the age of various samples are well known. On the other hand, ^{14 C} in fossil fuels for a long time is formed elapsed since killing of organisms inhabit the ancient a long time ago than the half-life 5730 years of ^{14 C,} a modern circulating in the global environment carbon dioxide When measured in isolation, it can be regarded as almost 0 (below the detection limit of the measuring instrument), so ¹⁴ C in the synthetic resin derived from fossil fuel can be regarded as almost 0.

Therefore, the plant-derived synthetic resin and the fossil fuel-derived synthetic resin can be distinguished by the ratio of ¹⁴ C contained. The time taken to harvest the growing plant, saccharify it into alcohol, and use ethylene, which is the alkene resulting from the dehydration reaction, as a raw material to produce a plant-derived synthetic resin through ordinary resin synthesis means. Is a few months, and can be neglected from the ¹⁴ C half-life of 5730 years. The time lag until the production of plant-derived synthetic resin is either plant-derived synthetic resin or fossil fuel-derived synthetic resin. There is no substantial effect on the discrimination.

The ratio of radioactive ¹⁴ C composing carbon dioxide circulating in the global environment has been diluted and reduced by humans burning large amounts of fossil fuels since the Industrial Revolution, but the atmosphere since 1950 AD It turned to increase by the inner core experiment. That is, the amount of radioactive ¹⁴ C produced by atmospheric nuclear tests exceeded the amount of radioactive ¹⁴ C produced by the nuclear reaction of ¹⁴ N caused by collision with neutrons generated by the action of cosmic rays. Subsequently, due to the 1964 nuclear test cessation treaty, the ratio of radioactive ¹⁴ C began to decrease after peaking in 1963, and there were fluctuations due to subsequent nuclear accidents, but the ratio of radioactive ¹⁴ C in 1950 Not reached.

Therefore, for the distinction between plant-derived synthetic resins and fossil fuel-derived synthetic resins, a standardization method based on the existence ratio of radioactive ¹⁴ C as of 1950 is known, and the National Bureau of Standards (NIST) ) By ASTM D6866-12 (Determining the Biobased Control of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis). ASTM D6866 is an ASTM (American Society for Testing and Materials) standard that determines the biogenic carbon concentration in solid, liquid, and gas samples using radiocarbon dating. Since it was approved, it has been revised and the current latest standard ASTM D6866-12 is the one revised in April 2012.

The principle defined by ASTM D6866-12 is roughly as follows. In other words, organic substances derived from fossil fuels have been killed or cut off by living organisms (animals and plants) in the era before 1950, and the ratio composition of carbon isotopes at that time is fixed. The abundance ratio of carbon constituting the organic substance is 0 (zero). Therefore, the ratio composition of carbon isotopes is derived from fossil fuel using the unit of modern carbon ratio (percent modern carbon: pMC) defined by the function of ¹³ C / ¹² C, which is a stable ratio, and radioactive ¹⁴ C. The modern carbon ratio of the organic substance is set to 0 pMC (meaning less than the detection limit of the measuring instrument). However, organic substances derived from fossil fuels may show 0.01 to 0.03 pMC due to contamination of radioactive ¹⁴ C derived from nuclear tests and nuclear accidents conducted after 1950. Further, the modern carbon ratio of a standard substance (oxalic acid supplied by NIST (SRM4990) or an equivalent organic substance) having a carbon isotope ratio composition as of 1950 is defined as 100 pMC. The ratio of the fossil fuel-derived organic substance and the plant-derived organic substance is determined by determining the modern carbon ratio of the sample with reference to 0 to 100 pMC. The modern carbon ratio of synthetic resins synthesized using only plant-derived raw materials currently produced is at least 90 pMC due to the influence of ¹⁴ C which has been artificially increased by atmospheric nuclear tests conducted since 1950. It does not fall below, and is about 107 pMC on average. The modern carbon ratio in 1963 before the nuclear test stop treaty was 118 pMC. Therefore, if the modern carbon ratio of a synthetic resin is 90-118pMC, it can be said that the synthetic resin derived from a plant is contained reliably.

  Moreover, from the value of the modern carbon ratio of the known plant-derived synthetic resin, a synthetic resin material (a modern carbon ratio is 0 pMC) that is a mixture of the plant-derived synthetic resin and a fossil fuel-derived synthetic resin ( The content ratio of the plant-derived synthetic resin in the resin composition) can be calculated, and the mass ratio of the plant-derived synthetic resin may be described as “% Corg.renew”. For example, the mass ratio of the plant-derived synthetic resin (modern carbon ratio is calculated as 107 pMC × 0.96 = 102.7 pMC) and the synthetic resin derived from fossil fuel in the resin composition of 96% When the ratio is 50:50, the resin composition has a modern carbon ratio of 51.4 pMC (calculated as 107 pMC × 0.96 × 0.50 = 51.36 pMC) and 48% Corg.renew ( It is calculated as 96% × 0.5). When the mass ratio of the resin composition is 55:45, the modern carbon ratio is 56.5 pMC (calculated as 107 pMC × 0.96 × 0.55 = 56.50 pMC). 52.8% Corg.renew (calculated as 96% × 0.55). Note that the “biologicalization rate” (%) is the mass ratio of the plant-derived synthetic resin in the synthetic resin, and may be referred to as “biomass plastic degree” or “biomass degree”. If the bio-ization rate is 25%, it is allowed to be referred to as “biomass plastic” as containing 25.0% by mass or more of biomass plastic based on the biomass plastic identification display system established by the Japan Bioplastics Association.

[Carbon labeling]
The resin composition containing no synthetic resin derived from plants and containing a synthetic resin derived from fossil fuel is essentially modern carbon ratio when measured separately from the modern carbon dioxide circulating in the global environment as described above. Is actually 0pMC, but in reality, radioactive ^14C derived from nuclear tests and nuclear accidents conducted after 1950 are mixed, or carbon dioxide circulating in the modern global environment is adsorbed or permeated on the surface. When carbon isotope exchange occurs, a modern carbon ratio greater than 0 pMC may be exhibited. However, in many cases, the ratio of the synthetic resin modern carbon derived from fossil fuel is in the range of 0.01 to 0.03 pMC, and can be said to be substantially 0 pMC. Moreover, the modern carbon ratio of the synthetic resin derived from fossil fuel does not exceed 8 pMC. Therefore, if the modern carbon ratio of a certain synthetic resin or a resin composition containing a synthetic resin is 0 to 8 pMC, the synthetic resin or the resin composition containing the synthetic resin is derived from a fossil fuel-derived synthetic resin or a fossil fuel. It can be said that it is a resin composition containing the synthetic resin.

In addition, the influence of radioactive ¹⁴ C derived from inorganic carbon such as calcium carbonate, which is a component of limestone and may be blended in a resin composition containing a synthetic resin derived from fossil fuel for various purposes, is observed. Sometimes, in measuring modern carbon ratios, methods that eliminate the effect are standardized. In addition, in a resin composition containing a synthetic resin derived from fossil fuel, radioactive ¹⁴ C derived from an additive or compounding agent containing organic carbon is affected and diluted, so that it is larger than 0 pMC. Although a modern carbon ratio may be shown, if it is a normal compounding quantity, the modern carbon ratio of the resin composition containing the synthetic resin derived from fossil fuel will not exceed 8 pMC.

In recent years, environmental labeling systems have begun to spread for the purpose of contributing to environmental conservation and reduction of environmental burdens. For example, environmental management is being operated as ISO 14000, which is an international standard. Attempts to “visualize” CO ₂ emissions through the entire life cycle from the procurement of raw materials to disposal and recycling in the manufacture and use of various products and services for carbon dioxide (CO ₂ ), a greenhouse gas. This is called carbon labeling and carbon footprint display. If carbon labeling or carbon footprint display becomes widespread, operators are expected to use it as an indicator for improving product design and manufacturing process management to reduce the environmental burden in the product life cycle. It can be used as one of product selection materials, and is expected to become one of the means for promoting efforts to reduce the environmental burden of manufacturers and suppliers. In addition, carbon labeling is effective for securing credits used for carbon offsets and guaranteeing reliability and transparency, and is becoming increasingly important as environmental accounting is expected to spread in the future.

  In principle, plant-derived synthetic resins and fossil-fuel-derived synthetic resins differ only in the modern carbon ratio. Except for the effects on the global environment, manufacturing resin products from these synthetic resins It is believed that there is no change or difference in handling for the process or the formed resin product. However, in reality, it is also known that there may be a difference in compatibility and mechanical properties, for example (Patent Document 6).

  On the other hand, a resin multilayer container formed from a resin laminate is often required to have a slipperiness on the container surface as well as transparency and gloss. That is, in a resin multilayer container formed from a resin laminate, a container molding process, a container transfer process, a content filling process such as food by a user, a transfer process after filling the contents, a container packaging process, etc. In each process with different environmental conditions such as temperature, humidity, etc., it is required to exhibit good slipperiness in order to ensure stable continuous production. For example, in a container forming process line or a container alignment line in a content filling process, even if containers contact each other, slipperiness is required so as not to affect the work and production speed in the process or the next process. . Moreover, in the transfer line after the container is filled with the contents, slipping between the transfer conveyor and the container is required in order to ensure smooth transfer. Furthermore, in the container packaging line, since the packaging of the container with the exterior film is usually performed at a high speed, the slipperiness between the container surface and the wrap film is required. Since each of these processes and lines has different environmental conditions such as temperature and humidity, a resin capable of forming an appropriate slipperiness of the surface of the resin multilayer container is required under various environmental conditions. There is a need for laminates. Further, in order to improve the liquid drainage of the contents filled in the container, the slip property of the inner surface of the resin multilayer container is required, and a resin laminate capable of forming the container is required. .

  In order to improve the slipperiness of the resin multilayer container formed from the resin laminate, conventionally, a lubricant is mainly added to the raw material resin of the outermost layer or the innermost layer. The lubricant is usually added to the raw material resin by a master batch method or kneaded in a resin lot of a resin supplier.

  As the lubricant, for example, fatty acid amide is widely used, and specifically, oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide (behenic acid amide) and the like are used. Among these, the lubricant having a low melting point is, for example, oleic acid amide, and by adding this, good slipperiness is exhibited when the temperature of the container is low. A lubricant having a relatively high melting point is, for example, behenic acid amide. By adding this, a good slip property can be obtained when the container becomes hot, such as when the contents such as food are filled at high temperature. It can be demonstrated. These lubricants have been used by mixing two or more kinds (Patent Documents 1 to 4).

  In a resin multilayer container formed from a resin laminate, when packaging or packing the multilayer container, when packing and transferring, or when storing the container, containers or containers Various members may come into contact with each other or, in some cases, may receive an impact. Due to these contacts and impacts, the bottom and body of the container may be damaged, and the sealing performance of the container may be lost. In particular, if the piercing resistance of the resin multilayer container is insufficient, the container is likely to break during transport and storage in winter, and the reliability of product distribution is impaired, so improvement is required. It was.

Japanese Patent Laid-Open No. 6-72422 JP-A-6-99481 JP-A-2005-307122 JP 2009-214914 A Special table 2010-511634 JP 2011-132525 A

  The object of the present invention is a carbon offset property, and the carbon offset property can be easily adjusted, and molding that is comparable to a resin multilayer container integrally formed from a resin laminate containing a synthetic resin derived from a fossil fuel. And containers, containers and devices, containers and packaging films or containers under different lines and environmental conditions from the container molding process, the container transfer process, the contents filling process, and the packaging process. Provided is a resin laminate suitable for a resin multi-layer container having appropriate slipperiness between contents, improved liquid drainage of the contents filled in the container, and sufficient puncture resistance. There is.

  As a result of earnest research on solving the above-mentioned problems, the present inventors refer to the surface layer of the resin laminate (in the resin laminate, a layer exposed on the front surface or the back surface other than the intermediate layer or the core layer. ) Is a layer made of a resin composition containing a plant-derived ethylene-based resin and a specific unsaturated fatty acid amide, and a resin multilayer container formed from the resin laminate, The present invention has been completed by finding that the problem can be solved by forming the resin composition comprising a plant composition-derived ethylene-based resin and a resin composition containing a specific unsaturated fatty acid amide as a surface layer. .

That is, according to the present invention, (A) a resin component containing 90 to 60% by mass of an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high density polyethylene. In contrast, (C) a resin laminate comprising as a surface layer a layer made of a resin composition containing 100 to 4000 ppm of fatty acid amide having an unsaturated cis structure carbon double bond,
(I) The ethylene / α-olefin copolymer of (A) has a modern carbon ratio defined by ASTM D6866-12 of 23.3 to 118 pMC,
(II) The high-density polyethylene of (B) includes a plant-derived ethylene-based resin having a modern carbon ratio of 0 to 8 pMC as defined in ASTM D6866-12, and includes a carbon-labeled surface layer. Is provided.

  According to the present invention, as an embodiment, the ethylene / α-olefin copolymer of (A) is a modern carbon ratio (hereinafter simply referred to as “modern carbon ratio”) defined in ASTM D6866-12. There is provided a resin laminate comprising the plant-derived ethylene-based resin having 74.5 to 118 pMC and having a carbon-labeled surface layer.

Furthermore, according to the present invention, (A) a resin containing 90 to 60% by mass of an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high density polyethylene. A resin laminate comprising, as a surface layer, a layer made of a resin composition containing 100 to 4000 ppm of a fatty acid amide having an unsaturated cis structure carbon double bond with respect to the component,
(III) The resin composition includes a plant-derived ethylene-based resin having a modern carbon ratio of 14 to 118 pMC defined in ASTM D6866-12, and a resin laminate including a carbon-labeled surface layer is provided. The

  According to the present invention, as an embodiment, the resin composition having a modern carbon ratio of 14 to 118 pMC is (I) the ethylene / α-olefin copolymer of (A) has a modern carbon ratio. (II) The high-density polyethylene of (B) above contains a plant-derived ethylene-based resin having a modern carbon ratio of 0 to 8 pMC, and has a carbon-labeled surface layer. A resin laminate is provided.

  Furthermore, according to the present invention, as an embodiment, the resin composition includes the plant-derived ethylene-based resin having a modern carbon ratio of 26.8 to 118 pMC, and includes a carbon-labeled surface layer. A resin laminate is provided.

  Furthermore, according to this invention, the resin laminated body provided with the surface layer by which the plant-derived ethylene-type resin of the following (1)-(15) was included and carbon-labeled as an aspect is provided.

(1) The fatty acid amide having the (C) unsaturated cis structure carbon double bond is the following (C ₁ ), (C ₂ ) and (C ₃ ):
(C ₁ ) H ₂ N—CO — (— CH ₂ —) _n —CH═CH — (— CH ₂ —) _n —CH ₃ (where n is an integer in the range of 6 ≦ n ≦ 10);
_{(C 2) H 2 N-} CO - (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH 3 ( however, m is an integer in the range of 6 ≦ m ≦ 10) And (C ₃ ) H ₂ N—CO — (— CH ₂ —) _{k + 4} —CH═CH — (— CH ₂ —) _k —CH ₃ (where k is an integer in the range of 6 ≦ k ≦ 10); ;
A resin laminate comprising a carbon-labeled surface layer containing the plant-derived ethylene-based resin containing at least one fatty acid amide represented by a formula selected from the group consisting of:

(2) The fatty acid amide having the (C) unsaturated cis-structured carbon double bond is a fatty acid amide represented by the formula (C ₁ ), and the (C ₂ ) or (C ₃ ) The resin laminated body provided with the surface layer by which the said plant-derived ethylene-type resin which is a mixture with the at least 1 sort (s) of fatty acid amide represented by a formula was carbon-labeled.

(3) m in the fatty acid amide represented by the formula of (C ₂ ) above contains a plant-derived ethylene-based resin in which m = n + 1 or m = n−1, and a carbon-labeled surface layer A resin laminate provided.

(4) A resin laminate comprising a surface layer that is carbon-labeled and contains the plant-derived ethylene-based resin in which k in the fatty acid amide represented by the formula (C ₃ ) is k = n.

(5) The fatty acid amide having the (C) unsaturated cis structure carbon double bond is a fatty acid amide represented by the above formula (C ₁ ) and the following (C ₁₁ ):
(C ₁₁ ) H ₂ N—CO — (— CH ₂ —) _j —CH═CH — (— CH ₂ —) _j —CH ₃ (where j is an integer in the range of 6 ≦ j ≦ 10, j ≠ n);
A resin laminate comprising a plant-derived ethylene-based resin which is a mixture with a fatty acid amide represented by the formula: and having a carbon-labeled surface layer.

(6) The above plant derived from (C) the fatty acid amide having an unsaturated cis-structured carbon double bond containing a compound having 2 to 4 bonds of unsaturated cis-structured carbon double bonds in the molecular structure. A resin laminate comprising an ethylene-based resin and a carbon-labeled surface layer.

(7) A resin laminate, wherein the resin composition further includes the plant-derived ethylene-based resin containing a saturated fatty acid amide, and includes a carbon-labeled surface layer.

(8) The ethylene / α-olefin copolymer (A) having a density of 912 to 935 kg / m ³ has a polydispersity (Mw / Mn), which is an index of molecular weight distribution, of 1.5 to 9. A resin laminate comprising a surface layer that contains the plant-derived ethylene-based resin and is carbon-labeled.

(9) The (A) ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ is an ethylene / α-olefin copolymer using a Ziegler / Natta catalyst. A resin laminate comprising a resin and a carbon-labeled surface layer.

(10) The (B) high-density polyethylene contains the plant-derived ethylene-based resin having a polydispersity (Mw / Mn), which is an index of molecular weight distribution, of 4 to 10, and is carbon-labeled. A resin laminate comprising a surface layer.

(11) The (B) high-density polyethylene is a resin laminate comprising a plant layer-derived ethylene-based resin, which is a low-pressure polymerization high-density polyethylene using a Ziegler-Natta catalyst, and having a carbon-labeled surface layer.

(12) A resin laminate comprising the plant-derived ethylene-based resin further provided with a barrier layer and having a carbon-labeled surface layer.

(13) A resin laminate in which the barrier layer includes the plant-derived ethylene-based resin which is an ethylene / vinyl alcohol copolymer or polyglycolic acid, and includes a carbon-labeled surface layer.

(14) A resin laminate comprising the plant-derived ethylene-based resin and further having a recovery layer and a carbon-labeled surface layer.

(15) A resin laminate comprising a surface layer that includes a plant-derived ethylene-based resin that includes a surface layer, a barrier layer, an adhesive layer, and a recovery layer, and includes a carbon-labeled surface layer.

  And according to this invention, the resin multilayer container formed from the resin laminated body containing the said plant-derived ethylene-type resin and provided with the carbon-labeled surface layer is provided.

  According to the present invention, as an embodiment, there is provided a resin multilayer container formed of a resin laminate including a plant-derived ethylene-based resin of the following (16) to (17) and having a carbon-labeled surface layer. Is done.

(16) The resin product, wherein the surface layer, which is a layer made of the resin composition containing (A), (B) and (C), is one or both of the outermost layer and the innermost layer of the resin multilayer container. Multi-layer container.

(17) The resin multilayer having the layer configuration of outermost layer / barrier layer / adhesive layer / recovery layer / innermost layer or outermost layer / adhesive layer / barrier layer / adhesive layer / recovery layer / innermost layer container.

According to the present invention, (A) a resin component containing 90 to 60% by mass of an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high-density polyethylene. And (C) a resin laminate comprising, as a surface layer, a layer made of a resin composition containing 100 to 4000 ppm of a fatty acid amide having an unsaturated cis structure carbon double bond, (I) The α-olefin copolymer has a modern carbon ratio of 23.3 to 118 pMC, and (II) the high-density polyethylene of (B) contains a plant-derived ethylene resin having a modern carbon ratio of 0 to 8 pMC. In addition, by being a resin laminate having a carbon-labeled surface layer, it is easy to adjust the carbon offset property and the carbon offset property. It has a moldability comparable to that of a resin multilayer container integrally formed from a resin laminate containing a synthetic resin derived from a material, and leads to a container molding process, a container transfer process, a content filling process, and a packaging process. Up to the proper slipperiness between containers, containers and equipment, containers and packaging film or between containers and contents under different lines and environmental conditions, improved contents filled in containers There is an effect that it is possible to provide a resin laminate that is suitable for a resin multilayer container having liquid breakage and sufficient puncture resistance.

Further, according to the present invention, (A) a resin component containing 90 to 60% by mass of an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high density polyethylene. And (C) a resin laminate comprising, as a surface layer, a layer made of a resin composition containing 100 to 4000 ppm of a fatty acid amide having an unsaturated cis structure carbon double bond, and (III) the resin composition described above Is a resin laminate comprising a plant-derived ethylene-based resin having a modern carbon ratio of 14 to 118 pMC, and having a carbon-labeled surface layer, whereby the resin composition forming the surface layer is carbon-labeled , A resin laminate containing a synthetic resin derived from fossil fuel, which is carbon offset and can be easily adjusted. In addition to having a moldability comparable to that of a resin multi-layer container molded integrally, under different line and environmental conditions from the container molding process, the container transfer process, the content filling process, and the packaging process, Proper slipperiness between containers, containers and devices, containers and packaging films or between containers and contents, improved drainage of contents filled in containers, and sufficient puncture resistance There exists an effect that the resin laminated body suitable for the resin multilayer container which it has can be provided.

  Furthermore, according to the present invention, it is a carbon multi-layer container formed of a resin laminate including a plant-derived ethylene-based resin and having a carbon-labeled surface layer. It is easy to adjust the carbon offset property, and has a moldability comparable to that of a resin multilayer container integrally formed from a resin laminate containing a synthetic resin derived from fossil fuel, and a container molding process, a container transfer process, Under different lines and environmental conditions up to the contents filling process and the packaging process, the container and the device, the container and the packaging film or between the container and the contents, the appropriate slipperiness, the container There is an effect that it is possible to provide a resin multilayer container having improved liquid drainage of the filled contents and sufficient puncture resistance.

I. Resin Component The resin laminate of the present invention contains (A) 90 to 60% by mass of an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high-density polyethylene. A resin laminate comprising, as a surface layer, a layer made of a resin composition containing 100 to 4000 ppm of a fatty acid amide having an unsaturated cis structure carbon double bond with respect to the resin component,
(I) The ethylene / α-olefin copolymer of (A) has a modern carbon ratio of 23.3 to 118 pMC,
(II) The high-density polyethylene of (B) is characterized in that it is a resin laminate comprising a plant-derived ethylene resin having a modern carbon ratio of 0 to 8 pMC and having a carbon-labeled surface layer.

Moreover, the resin laminated body of this invention contains (A) 90-60 mass% of ethylene-alpha-olefin copolymers whose density is 912-935 kg / m < ³ >, and (B) 10-40 mass% of high density polyethylene. A resin laminate comprising, as a surface layer, a layer made of a resin composition containing 100 to 4000 ppm of a fatty acid amide having an unsaturated cis structure carbon double bond with respect to the resin component,
(III) The above resin composition is characterized in that it is a resin laminate comprising a plant-derived ethylene-based resin having a modern carbon ratio of 14 to 118 pMC and having a carbon-labeled surface layer.

1. (A) Density 912~935kg / ^{m 3} a is ethylene · alpha-olefin copolymer resin laminate of the present invention is contained in the surface layer comprising (A) a density 912~935kg / ^{m 3} ethylene · alpha-olefin The copolymer is an ethylene resin that is a copolymer of ethylene and an α-olefin other than ethylene, and has a density of 914 to 935 kg / m ³ , preferably 915 to 932 kg / m ³ , more preferably 918. ˜930 kg / m ³ . When the density is lower than 912 kg / m ³ , sufficient puncture resistance and strength cannot be obtained, and the high-speed packaging machine suitability may be deteriorated. On the other hand, if the density exceeds 935 kg / m ³ , the haze increases and the transparency required for the container may be insufficient. In the present invention, the density is a value measured based on JIS K 6922-2.

  The α-olefin other than ethylene forming the ethylene / α-olefin copolymer of (A) is usually an α-olefin having 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms, specifically propylene, Examples include butene-1, pentene-1, hexene-1, heptene-1, octene-1, and 4-methylpentene-1. The content of α-olefin in the ethylene / α-olefin copolymer of (A) is 0.05 to 4 mol%, preferably 0.1 to 3.5 mol%, more preferably 0.2 to 3 mol%. The amount is mol%, more preferably 0.4 to 2.8 mol%, particularly preferably 0.8 to 2.5 mol%. As the ethylene / α-olefin copolymer of (A), a linear low density polyethylene commonly called LLDPE can be used, and LLDPE is a preferred ethylene / α-olefin copolymer of (A). Further, the ethylene / α-olefin copolymer (A) may be any of those polymerized by a metallocene catalyst, a Ziegler-Natta catalyst, a Phillips catalyst, or the like, but ethylene / α- using a Ziegler-Natta catalyst. It is preferable to use an olefin copolymer.

  The ethylene / α-olefin copolymer of (A) has an MFR (temperature 190 ° C., load 2.12 N), preferably 0.01 to 30 g / 10 minutes, more preferably 0.1 to 5 g / 10 minutes. More preferably, those within the range of 0.2 to 1 g / 10 min can be used. The ethylene / α-olefin copolymer (A) has a polydispersity (Mw / Mn), which is an index of molecular weight distribution, preferably 1.5 to 9, more preferably 2 to 8, and still more preferably. Those in the range of 2.5 to 7 are effective in terms of improving moldability. If the polydispersity (Mw / Mn) is less than 1.5, moldability may be difficult, and if it exceeds 9, the surface of the molded article may become sticky. The MFR of the ethylene / α-olefin copolymer was measured according to JIS K6922-2, and the polydispersity (Mw / Mn) was measured according to JIS K7252.

  In the resin composition contained in the surface layer of the resin laminate of the present invention, the content of the ethylene / α-olefin copolymer in (A) contains the above (A) and (B) high-density polyethylene. When the total mass of the resin components is 100% by mass, the range is 90 to 60% by mass, preferably 88 to 62% by mass, and more preferably 87 to 65% by mass. When the content of the ethylene / α-olefin copolymer (A) in the resin component is too small, for example, when a resin multilayer container is formed from a resin laminate by an extrusion blow molding method or the like, the melt viscosity of the resin May cause problems in molding, such as being small and difficult to handle. If the content of the ethylene / α-olefin copolymer (A) in the resin component is too large, for example, the slipperiness of a molded product such as a resin multilayer container formed from a resin laminate may be reduced, The piercing property may be reduced.

[(A) Modern carbon ratio of ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ ]
The resin laminate of the present invention comprises (A) a resin component containing 90 to 60% by mass of an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high density polyethylene. On the other hand, (C) a resin laminate comprising, as a surface layer, a layer made of a resin composition containing 100 to 4000 ppm of a fatty acid amide having an unsaturated cis structure carbon double bond, (I) The ethylene / α-olefin copolymer has a modern carbon ratio of 23.3 to 118 pMC, and (II) the high-density polyethylene of (B) has a modern carbon ratio of 0 to 8 pMC, or (III ) The resin composition containing (A), (B) and (C) described above contains a plant-derived ethylene resin having a modern carbon ratio of 14 to 118 pMC, and carbon labeline. It is a resin laminate comprising been surface.

  The resin laminate containing the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer has a modern carbon ratio of the ethylene / α-olefin copolymer of (A) of 23.3 pMC or more. For example, when the ethylene / α-olefin copolymer is a plant-derived ethylene / α-olefin copolymer having a bioavailability of 87%, the plant-derived ethylene / α-olefin copolymer is 25% by weight [based on results calculated as 107 pMC × 0.87 × 0.25 = 23.27 pMC. In terms of conversion, this corresponds to 21.8% Corg.renew (calculated as a bioavailability of 87% × 0.25). ] A resin laminate comprising, as a surface layer, a layer made of a resin composition containing the ethylene / α-olefin copolymer of (A) contained above.

  In the resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer, the ethylene / α-olefin copolymer (A) contained in the surface layer is plant-derived ethylene / α. -When the olefin copolymer and the fossil fuel-derived ethylene / α-olefin copolymer are contained, the modern carbon ratio of the fossil fuel-derived ethylene / α-olefin copolymer can be regarded as almost 0 pMC. If the value of the modern carbon ratio of the plant-derived ethylene / α-olefin copolymer is known, the content ratio of both, and the value of the modern carbon ratio of the plant-derived ethylene / α-olefin copolymer, The value of the modern carbon ratio of the ethylene / α-olefin copolymer (A) contained in the surface layer of the resin laminate (or used for forming the surface layer of the resin laminate) By comparison, it is possible to calculate. For example, the modern carbon ratio of the plant-derived ethylene / α-olefin copolymer having a bioavailability of 87% is 93.1 pMC (calculated as 107 pMC × 0.87 = 93.09 pMC). The value of the modern carbon ratio of the ethylene / α-olefin copolymer (A) contained in the surface layer of the resin laminate containing the plant-derived ethylene / α-olefin copolymer is 46.5 pMC. Then, the ethylene / α-olefin copolymer (A) in the synthetic resin material is 50% by mass of a plant-derived ethylene / α-olefin copolymer (107 pMC × 0.87 × 0.5 = 46). It is determined based on the result calculated as .545 pMC.) And 50% by mass of the fossil fuel-derived ethylene / α-olefin copolymer.

  In the present invention, the ethylene / α-olefin copolymer (A) is preferably the above-described plant-derived ethylene / α-olefin copolymer having a bioavailability of 87%, preferably 80% by mass or more [modern. This corresponds to a carbon ratio of 74.5 pMC (determined based on the result calculated as 107 pMC × 0.87 × 0.80 = 74.472 pMC) or more, 69.6% Corg.renew (87% It is calculated as x0.8). More preferably, it corresponds to 85 mass% or more (modern carbon ratio is 79.1 pMC (determined based on the result calculated as 107 pMC × 0.87 × 0.85 = 79.127 pMC)) or more. , 74.0% Corg.renew (calculated as 87% × 0.85) or higher. More preferably, it corresponds to 90 mass% or more (modern carbon ratio is 83.8 pMC (determined based on the result calculated as 107 pMC × 0.87 × 0.90 = 833.781 pMC)) or more. , 78.3% Corg.renew (87% × 0.9). It is desirable from the viewpoint of carbon offset property. The ethylene / α-olefin copolymer (A) is 100% by mass of a plant-derived ethylene / α-olefin copolymer [calculated as a modern carbon ratio of 93.1 pMC (107 pMC × 0.87 = 93.09 pMC). And 87% Corg.renew. (The upper limit of the modern carbon ratio is 118 pMC.)

  That is, in the resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer, the ethylene / α-olefin copolymer (A) contained in the surface layer has a modern carbon ratio. 23.3 to 118 pMC, preferably 74.5 to 118 pMC, more preferably 79.1 to 118 pMC, still more preferably 83.8 to 118 pMC, and particularly preferably 93.1 to 118 pMC.

  Therefore, the resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer is obtained from the fossil fuel-derived ethylene • α- in the ethylene / α-olefin copolymer of (A). An olefin copolymer can be contained in an amount of 75% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. It may not contain any coalescence (0% by mass). If the ethylene / α-olefin copolymer derived from fossil fuel exceeds 75% by mass, carbon negative may occur.

(A) As an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ , a synthetic product of an ethylene / α-olefin copolymer derived from a plant and / or fossil fuel may be used. A commercially available product can be used. Preferably, plant-derived and / or fossil fuel-derived LLDPE having a density of 912 to 935 kg / m ³ can be used. For example, as a commercially available ethylene / α-olefin copolymer having a plant-derived density of 912 to 935 kg / m ³ , a plant-derived ethylene / α-olefin copolymer (LLDPE) belonging to Green Polyethylene manufactured by Brasschem There are brand names such as SLH0820 / 30AF, which can be used as desired. Moreover, as a commercial item of the ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ derived from fossil fuel, an ethylene / α-olefin copolymer (LLDPE) brand name PE LH-118 manufactured by Brasschem Co., Ltd. is used. Etc. can be used.

2. (B) High-density polyethylene (B) High-density polyethylene contained in the surface layer of the resin laminate of the present invention means high-density polyethylene commonly referred to as HDPE, and generally has a density of 942 to 980 kg / m ³ . Polyethylene, preferably 945 to 970 kg / m ³ , more preferably 948 to 965 kg / m ³ . (B) The high density polyethylene has an MFR (temperature 190 ° C., load 2.12 N) of 0.01 to 30 g / 10 minutes, more preferably 0.1 to 5 g / 10 minutes, and still more preferably 0.2 to 1 g. / 10 minutes can be used. The polydispersity (Mw / Mn), which is an index of molecular weight distribution, is preferably in the range of 4 to 10, more preferably 5 to 9.5, and even more preferably 6 to 9 to improve the moldability. Effective in terms. If the polydispersity (Mw / Mn) is less than 4, moldability may be difficult, and if it exceeds 10, the surface of the molded article may become sticky.

  (B) As high-density polyethylene, a homopolymer of ethylene or a copolymer of ethylene and an α-olefin other than ethylene can be used. Examples of α-olefins other than ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and the like. You may use the above together. When the high density polyethylene is a copolymer of ethylene, the content of the α-olefin in the copolymer is 0.2 to 3 mol%, preferably 0.3 to 2.5 mol%. is there. A copolymer having an α-olefin content of more than 3 mol% may deteriorate the mechanical properties.

  (B) High density polyethylene can be obtained by polymerization using a Ziegler-Natta catalyst, a Phillips catalyst, a metallocene catalyst or the like. (B) The high-density polyethylene may be obtained by any one of a low pressure polymerization method and an intermediate pressure polymerization method, and gas phase polymerization (generally used for polymerization using a Ziegler-Natta catalyst) or slurry polymerization (using a Philips catalyst). It can be obtained by bulk polymerization, solution polymerization, etc., and can also be produced by one-stage polymerization, two-stage polymerization, or more multistage polymerization.

  (B) The high density polyethylene is preferably a low pressure polymerization high density polyethylene using a Ziegler-Natta catalyst. Further, according to the slurry polymerization method using a Philips catalyst, the molecular weight distribution can be a single distribution or a plurality of distributions, so that the melt extrusion moldability of high-density polyethylene can be controlled as desired.

  (B) As the high-density polyethylene, a low-pressure polymerization method using a Ziegler-Natta catalyst, a synthetic product of high-density polyethylene can be used. You can also select and use. Examples of commercially available plant-derived high-density polyethylene include plant-derived high-density polyethylene (Ziegler-Natta catalyst polymerization brand name SGF4950 for blow molding, etc.) belonging to green polyethylene manufactured by Braschem. Commercially available products of high-density polyethylene derived from fossil fuel include Novatec (registered trademark) HD brand name KB285N manufactured by Nippon Polyethylene Co., Ltd., Hyzex (registered trademark) manufactured by Prime Polymer Co., Ltd., Ziegler Natta for blow molding manufactured by Braschem Co., Ltd. There are catalyst polymerization brand name IE59U3 and the like.

  In the resin composition contained in the surface layer of the resin laminate of the present invention, the content of (B) high-density polyethylene is 100% by mass of the total mass of the resin components containing (A) and (B). Is usually in the range of 10 to 40% by mass, preferably 12 to 38% by mass, more preferably 13 to 35% by mass. When the content of the (B) high-density polyethylene in the resin component is too small, the rigidity of the molded body such as a resin multilayer container formed from the resin laminate is insufficient, or the puncture resistance is reduced. There is. If the content of the (B) high-density polyethylene in the resin component is too large, for example, when a resin multilayer container is formed from a resin laminate by an extrusion blow molding method, etc., the melt viscosity of the resin becomes small and handling is difficult. It may cause molding problems such as difficulty.

[(B) Modern carbon ratio of high-density polyethylene]
The resin laminate of the present invention comprises (A) a resin component containing 90 to 60% by mass of an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high density polyethylene. On the other hand, (C) a resin laminate comprising, as a surface layer, a layer made of a resin composition containing 100 to 4000 ppm of a fatty acid amide having an unsaturated cis structure carbon double bond, (I) The ethylene / α-olefin copolymer has a modern carbon ratio of 23.3 to 118 pMC, and (II) the high-density polyethylene of (B) has a modern carbon ratio of 0 to 8 pMC, or (III ) The resin composition containing (A), (B) and (C) described above contains a plant-derived ethylene resin having a modern carbon ratio of 14 to 118 pMC, and carbon labeline. It is a resin laminate comprising been surface.

  From this, the resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer has a modern carbon ratio of substantially 0 pMC as the high-density polyethylene of (B). It is preferable to use high-density polyethylene derived from fossil fuels. High density polyethylene derived from fossil fuels with a modern carbon ratio of substantially 0 pMC is readily available, stable in supply, and inexpensive. However, as long as the modern carbon ratio of the high-density polyethylene of (B) can be in the range of 0 to 8 pMC, or the resin composition containing the above (A), (B) and (C) As long as the modern carbon ratio of the product can be in the range of 14 to 118 pMC, the high density polyethylene of (B) can use the high density polyethylene of (B) whose modern carbon ratio exceeds 0 pMC. .

  For example, the resin laminated body provided with the layer which consists of a resin composition containing the high density polyethylene of (B) containing less than 7.5 mass% of plant-derived high density polyethylene as a surface layer may be sufficient. The high-density polyethylene of (B), together with the high-density polyethylene derived from fossil fuel, for example, is a plant-derived high-density polyethylene with a bioavailability of 96% (the modern carbon ratio is calculated as 107 pMC × 0.96 = 102.7 pMC) .) Is contained in an amount of 7.5% by mass, the modern carbon ratio of the high-density polyethylene in (B) is 7.7 pMC (107 pMC × 0.96 × 0.075 = 7.704 pMC). It can be contained in the resin composition that forms the surface layer of the resin laminate that includes the plant-derived ethylene-based resin of the present invention and that includes the carbon-labeled surface layer.

  The plant-derived high-density polyethylene that can be contained in the high-density polyethylene (B) having a biogenic rate of 96% is preferably 5% by mass [modern carbon ratio is 5.1 pMC (107 pMC × 0.96 × 0.05). = 5.136 pMC, determined based on the result. ], More preferably 1% by mass [modern carbon ratio is 1.0 pMC (determined based on the result calculated as 107 pMC × 0.96 × 0.01 = 1.070 pMC). ] Is desirable. As already described, (B) high-density polyethylene does not contain plant-derived high-density polyethylene, but is 100% by mass of fossil fuel-derived high-density polyethylene (corresponding to 0% Corg.renew). Most preferred.

3. Other resins In the resin composition contained in the surface layer of the resin laminate of the present invention, (A) an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) a high-density polyethylene In addition to the above (A) and (B), the resin component to be added can further contain other resins as desired. Other resins include propylene homopolymers or propylene random copolymers obtained using Ziegler-Natta catalysts, propylene homopolymers, propylene random copolymers or block copolymers obtained using metallocene catalysts. And resin components such as ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methyl acrylate copolymer, and maleic anhydride-modified polyolefin. The content of these other resins is usually 20% by mass or less, preferably 10% by mass or less, when the total mass of the resin components containing (A) and (B) is 100% by mass. Preferably it is 5 mass% or less.

  In the resin laminate or the resin multilayer container described in detail later, the polyolefin such as ethylene resin contained is a polyolefin obtained using a Ziegler-Natta catalyst or a metallocene catalyst. Alternatively, qualitative analysis can be performed and confirmed using a scanning electron microscope equipped with an energy dispersive X-ray detector using a resin-containing pellet or its incineration residue shaved from a resin multilayer container as a specimen. That is, a trace amount of catalyst element species remaining in the specimen (preferably the above incineration residue) is detected, and the Group IVa group Ti and the third period IIa group Mg, which are transition metals in the fourth period of the periodic table, Element pair, a peak corresponding to the energy of Group Va which is the transition metal of the fourth period or the energy of Cr of the group VIa which is the transition metal of the fourth period, and the energy of Al which is the promoter-derived element By confirming the presence of the corresponding peak (Ziegler-Natta catalyst), or Zr of group IVa which is the transition metal of the fifth period of the periodic table, or Hf of group IVa which is the transition metal of the sixth period This can be confirmed by confirming the presence of a peak corresponding to energy (metallocene catalyst).

4). (C) Fatty acid amide having an unsaturated cis-structured carbon double bond The resin laminate of the present invention comprises (A) an ethylene / α-olefin copolymer of 90 to 60% by mass having a density of 912 to 935 kg / m ³ and ( B) With respect to the resin component containing 10 to 40% by mass of high-density polyethylene, (C) a layer made of a resin composition containing 100 to 4000 ppm of fatty acid amide having an unsaturated cis structure carbon double bond is provided as a surface layer. It is a resin laminate. (C) A fatty acid amide having an unsaturated cis-structured carbon double bond (hereinafter sometimes referred to as “(C) unsaturated fatty acid amide” or simply “(C)”) is slippery. It functions as an agent for improving the resistance and puncture resistance. The unsaturated fatty acid amide (C) is an unsaturated fatty acid amide having a carbon double bond having at least one unsaturated cis structure in the molecular structure of the fatty acid amide. When it is an unsaturated fatty acid amide having a plurality of carbon double bonds in the molecular structure of the fatty acid amide, the unsaturated fatty amide in which all of the carbon double bonds are carbon double bonds of an unsaturated cis structure It is. If the unsaturated fatty acid amide has a carbon double bond with a trans structure, the homogeneous blending of the resin material becomes insufficient, or the unsaturated fatty acid amide with a carbon double bond with the trans structure In some cases, it may be deposited on the surface of a molded body such as a body or a resin multilayer container, resulting in deterioration of slipperiness and puncture strength.

  The content of unsaturated fatty acid amide (C) is preferably 150 to 3900 ppm, more preferably 200 to 3800 ppm, still more preferably 250 to 3700 ppm, and particularly preferably 300 to 3600 ppm. When the content of the unsaturated fatty acid amide (C) is too small, the slipping property is insufficient, and the resin is produced during the production of a molded body such as a resin laminate or a resin multilayer container, during transportation or filling of contents. There is a risk that defective products, production line stoppage, device failure, etc. may occur due to contact or collision between the laminates or molded bodies or with devices. In addition, when the molded body is a resin multilayer container, if the slipperiness of the innermost layer of the container is insufficient, the contents may not be filled smoothly, or the contents may not be sufficiently drained when used by consumers. It may become. When the content of the unsaturated fatty acid amide (C) is too large, the surface gloss of the obtained molded product such as the resin laminate or the resin multilayer container is deteriorated, or the stickiness during the carrying operation is increased. Sometimes. When the unsaturated fatty acid amide of (C) is a mixture of fatty acid amides having two or more kinds of unsaturated cis structure carbon double bonds as described later, the total amount of the mixture needs to be included in the above range. There is.

  (C) The fatty acid amide having an unsaturated cis structure carbon double bond is preferably a fatty acid amide having an unsaturated cis structure carbon double bond having one unsaturated cis structure carbon double bond in the molecular structure. is there.

  (C) The fatty acid amide having an unsaturated cis structure carbon double bond may be an unsaturated fatty acid amide having a plurality of unsaturated cis structure carbon double bonds in the molecular structure. A compound having 6 or less carbon bonds, more preferably 5 or less bonds, and still more preferably 4 or less bonds. Therefore, (C) the fatty acid amide having an unsaturated cis structure carbon double bond most preferably used in the present invention is an unsaturated cis having 1 to 4 bonds of an unsaturated cis structure carbon double bond in the molecular structure. It is a fatty acid amide having a structural carbon double bond.

Examples of (C) fatty acid amides having an unsaturated cis-structure carbon double bond having one unsaturated cis-structure carbon double bond include the following formulas (C ₁ ) to (C ₃ ):
(C ₁ ) H ₂ N—CO — (— CH ₂ —) _n —CH═CH — (— CH ₂ —) _n —CH ₃ (where n is an integer in the range of 6 ≦ n ≦ 10);
(C ₂ ) H ₂ N—CO — (— CH ₂ —) _m−2 —CH═CH — (— CH ₂ —) _m —CH ₃ (where m is an integer in the range of 6 ≦ m ≦ 10) And (C ₃ ) H ₂ N—CO — (— CH ₂ —) _{k + 4} —CH═CH — (— CH ₂ —) _k —CH ₃ (where k is an integer in the range of 6 ≦ k ≦ 10); ;
And at least one fatty acid amide compound represented by the formula selected from the group consisting of: (Hereinafter, (the fatty acid amide of the formula of _{C 1),} there may be referred to as "formula _{(C 1)} fatty acid amide of the" further may be simply referred to as a "formula _{(C 1)". (C} 2) The same applies to the fatty acid amide represented by the formula (C ₃ ).)

  Examples of the (C) fatty acid amide having an unsaturated cis-structure carbon double bond having one unsaturated cis-structure carbon double bond include the following compounds.

Formula (C ₁ ) H ₂ N—CO — (— CH ₂ —) _n —CH═CH — (— CH ₂ —) _n —CH ₃ (where n is an integer in the range of 6 ≦ n ≦ 10):
cis-8,9-hexadecenoamide [H ₂ N—CO — (— CH ₂ —) ₆ —CH═CH — (— CH ₂ —) ₆ —CH ₃ ] (corresponding to n = 6)
cis-9,10-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] (corresponding to n = 7)
cis-10, 11-eicosenoamide [H ₂ N—CO — (— CH ₂ —) ₈ —CH═CH — (— CH ₂ —) ₈ —CH ₃ ] (corresponding to n = 8)
cis-11,12-ethaeicosenoamide [H ₂ N—CO — (— CH ₂ —) ₉ —CH═CH — (— CH ₂ —) ₉ —CH ₃ ] (corresponding to n = 9)
cis-12, 13- tetraeicosenoamide (corresponding to n = 10) _{[H 2 N-CO - (-} CH 2 -) 10 -CH = CH - (- - CH 2) 10 -CH 3 ]

Formula (C ₂ ) H ₂ N—CO — (— CH ₂ —) _m−2 —CH═CH — (— CH ₂ —) _m —CH ₃ (where m is an integer in the range of 6 ≦ m ≦ 10) ):
cis-6,7-tetradecenoamide _{[H 2 N-CO - (-} CH 2 -) 4 -CH = CH - (- CH 2 -) 6 -CH 3 ] (corresponding to m = 6)
cis-7,8-hexadecenoamide [H ₂ N—CO — (— CH ₂ —) ₅ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] (corresponding to m = 7)
cis-8,9-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₆ —CH═CH — (— CH ₂ —) ₈ —CH ₃ ] (corresponding to m = 8)
cis-9,10-eicosenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₉ —CH ₃ ] (corresponding to m = 9)
cis-10, 11- ethaeicosenoamide (corresponding to m = 10) _{[H 2 N-CO - (-} CH 2 -) 8 -CH = CH - (- - CH 2) 10 -CH 3 ]

Formula (C ₃ ) H ₂ N—CO — (— CH ₂ —) _{k + 4} —CH═CH — (— CH ₂ —) _k —CH ₃ (where k is an integer in the range of 6 ≦ k ≦ 10):
cis-12,13-eicosenoamide [H ₂ N—CO — (— CH ₂ —) ₁₀ —CH═CH — (— CH ₂ —) ₆ —CH ₃ ] (corresponding to k = 6)
cis-13,14-docosenoamide [H ₂ N—CO — (— CH ₂ —) ₁₁ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] (corresponding to k = 7)
cis-14,15- tetracosenoamide (corresponding to k = 8) _{[H 2 N-CO - (-} CH 2 -) 12 -CH = CH - 8 -CH 3 (- - CH 2) ]
cis-15,16-hexacosenoamide [H ₂ N—CO — (— CH ₂ —) ₁₃ —CH═CH — (— CH ₂ —) ₉ —CH ₃ ] (corresponding to k = 9)
cis-16,17- octacosenoamide (corresponding to k = 10) _{[H 2 N-CO - (-} CH 2 -) 14 -CH = CH - (- - CH 2) 10 -CH 3 ]

Further, (C) fatty acid amide having an unsaturated cis structure carbon double bond, which is a compound having 2 to 4 bonds of unsaturated cis structure in the molecular structure, includes, for example, an unsaturated cis structure in the molecular structure. The following compounds having 4 carbon double bonds having a saturated cis structure are exemplified.
cis-5,6-8,9-11,12-14,15-arachidonic acid amide [H ₂ N—CO — (— CH ₂ —) ₃ —CH═CH—CH ₂ —CH═CH—CH ₂ — _{CH = CH-CH 2 -CH =} CH - (- CH 2 -) 4 -CH 3 ]

Examples of the (C) fatty acid amide having an unsaturated cis structure carbon double bond include the fatty acid amides of the above formulas (C ₁ ) to (C ₃ ), or a plurality of unsaturated cis structures in the molecular structure. If one type of fatty acid amide selected from fatty acid amides having a carbon double bond is used, a sufficient effect can be obtained, but two or more types of (C) unsaturated cis-structured carbon double bonds can be obtained. A mixture of fatty acid amides may be used. The mixture of fatty acid amides preferably contains the fatty acid amide of the above formula (C ₁ ).

Therefore, a preferred mixture of (C) fatty acid amides having an unsaturated cis structure carbon double bond is represented by the above formula (C ₁ ) fatty acid amide and the above formula (C ₂ ) or (C ₃ ). A mixture with at least one fatty acid amide. The proportion of the fatty acid amide of the formula (C ₁ ) in the mixture is usually 0.05 to 99.95% by mass, preferably 0.1 to 99.9% by mass, more preferably 0.5 to 99.5% by mass. %, More preferably in the range of 1 to 99% by mass. Therefore, the ratio of the fatty acid amide that is a mixture of the above formula (C ₂ ), formula (C ₃ ), or formula (C ₂ ) and formula (C ₃ ) is usually 99.95 to 0.05% by mass, preferably Is in the range of 99.9 to 0.1% by mass, more preferably 99.5 to 0.5% by mass, and still more preferably 99 to 1% by mass.

In particular, (C) a mixture of fatty acid amides having an unsaturated cis-structured carbon double bond is a fatty acid amide of the above formula (C ₁ ), ie H ₂ N—CO — (— CH ₂ —) _n —CH═ CH — (— CH ₂ —) _n —CH ₃ (where n is an integer in the range of 6 ≦ n ≦ 10) and the fatty acid amide of the above formula (C ₂ ), that is, H ₂ N—CO— ( —CH ₂ —) _{m− 2} —CH═CH — (— CH ₂ —) _m —CH ₃ (where m is an integer in the range of 6 ≦ m ≦ 10), and m = n + 1 or m = n It is preferable that it is a mixture with this fatty acid amide which is -1.

Specifically, the formula (C ₁ ) is cis-9,10-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] ( n = 7), and the formula (C ₂ ) is cis-6,7-tetradecenoamide [H ₂ N—CO — (— CH ₂ —) ₄ —CH═CH — (— CH ₂ —) ₆ —. CH ₃ ] (corresponding to m = 6 = n−1) or cis-8,9-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₆ —CH═CH — (— CH ₂ —) ₈ -CH _3] mixture combinations are (m = 8 = n + 1 corresponding to) and the like can be preferably used.

In addition, (C) a mixture of fatty acid amides having an unsaturated cis-structured carbon double bond is a fatty acid amide of the above formula (C ₁ ), that is, H ₂ N—CO — (— CH ₂ —) _n —CH═ CH — (— CH ₂ —) _n —CH ₃ (where n is an integer in the range of 6 ≦ n ≦ 10) and the fatty acid amide of the above formula (C ₃ ), that is, H ₂ N—CO— ( —CH ₂ —) _{k + 4} —CH═CH — (— CH ₂ —) _k —CH ₃ (where k is an integer in the range of 6 ≦ k ≦ 10) and k = n It is preferable that it is a mixture.

Specifically, the formula (C ₁ ) is cis-9,10-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] ( n = 7), and the formula (C ₃ ) is cis-13,14-docosenoamide [H ₂ N—CO — (— CH ₂ —) ₁₁ —CH═CH — (— CH ₂ —) ₇ — CH ₃ ] (corresponding to k = 7 = n) is preferably used.

Further, (C) a mixture of fatty acid amides having an unsaturated cis structure carbon double bond is a mixture of two or more compounds belonging to the fatty acid amide of the above formula (C ₁ ) and having different values of n. be able to. That is, (C ₁ ) H ₂ N—CO — (— CH ₂ —) _n —CH═CH — (— CH ₂ —) _n —CH ₃ (where n is an integer in the range of 6 ≦ n ≦ 10) And (C ₁₁ ) H ₂ N—CO — (— CH ₂ —) _j —CH═CH — (— CH ₂ —) _j —CH ₃ (where j is an integer in the range of 6 ≦ j ≦ 10) , J ≠ n) can be used.

Specifically, for example, the formula (C ₁ ) is cis-9,10-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ —CH ₃ (Corresponding to n = 7), and the formula (C ₁₁ ) is cis-10, 11-eicosenoamide [H ₂ N—CO — (— CH ₂ —) ₈ —CH═CH — (— CH ₂ —) ₈ -CH ₃ ] (corresponding to j = 8) is preferably used.

Furthermore, (C) a fatty acid amide having an unsaturated cis-structured carbon double bond having 2 to 4 carbon double bonds of an unsaturated cis structure in the molecular structure alone or other (C) It can also be used as a mixture with a fatty acid amide having an unsaturated cis structure carbon double bond. As the other (C) fatty acid amide having an unsaturated cis structure carbon double bond, the fatty acid amides of the above formulas (C ₁ ) to (C ₃ ) are preferably used, and in particular, the fatty acid amide of the formula (C ₁ ) Amides are preferred. Specifically, cis-5,6-8,9-11,12-14,15-arachidonic acid amide [H ₂ N—CO — (— CH ₂ —) ₃ —CH═CH—CH ₂ —CH═ _{CH-CH 2 -CH = CH-} CH 2 -CH = CH - (- CH 2 -) 4 and -CH _3], a mixture such as is preferably used in the cis-9,10-octadecenoamide is formula _{(C 1)} it can.

5. (C) Method for Producing Fatty Acid Amide Having Unsaturated cis-Structure Carbon Double Bond The unsaturated fatty acid amide (C) contained in the resin composition in the present invention may be a commercially available product or a commercially available product. May be obtained by separating the desired unsaturated fatty acid amide by extraction or the like. However, for example, fatty acid amides of the formula _{(C 2), i.e., (C 2) H 2 N} -CO - (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH ₃ (where m is an integer in the range of 6 ≦ m ≦ 10) can be produced by the following method.

The following (formula a) having a CH ₃ O—CO— terminal group and a hydroxyl group terminal or a carboxylic acid terminal at the α, ω positions and a (m−1) -linked methylene group (—CH ₂ —) _m−1 ):
(Formula _{a) CH 3 O-CO -} (- CH 2 -) m-1 -OH
As a starting material. ((Formula a) illustrates a compound having a hydroxyl terminal.)

The hydroxyl terminal of the compound represented by the formula (a) is bromine-substituted using carbon tetrabromide (CBr ₄ ), and then methyl cyanide (CH ₃ ) using triphenylphosphine (PPh ₃ , triphenylphosphine). CN) bromine is reacted with PPh ₃ in a solvent and the following (formula b):
(Formula b) [CH ₃ O—CO — (— CH ₂ —) _m−1 -PPh ₃ ] ⁺ + Br ⁻
To obtain an ionic intermediate represented by:

The ionic intermediate (formula b) is reacted with decyl aldehyde to make the PPh ₃ group an alkyl group terminal having a carbon double bond with an unsaturated cis structure (formula c):
(Formula _{c) CH 3 O-CO -} (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH 3
The α, ω structural compound represented by

Next, lithium hydroxide is reacted with the CH ₃ O—CO— terminal group of the α, ω structure compound of the formula (c) to form a hydroxyl terminal, which is saturated with ammonium in a solvent of oxalyl chrolide and methylene chloride. To the amide group terminal by reaction with (Formula d):
(Wherein _{d) H 2 N-CO -} (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH 3
A fatty acid amide having an unsaturated cis structure carbon double bond represented by

  By changing the carbon number m (where m is an integer in the range of 6 ≦ m ≦ 10), a fatty acid amide having an unsaturated cis structure carbon double bond having a desired carbon number can be obtained using this synthetic route. Can be obtained.

In the synthesis of fatty acid amide having an unsaturated carbon double bond, as is well known, a compound having an unsaturated cis structure carbon double bond and a compound having an unsaturated trans structure carbon double bond are simultaneously prepared. As a result, chromatographic development is performed using a mixed solvent with a concentration gradient of 100% (initial development) to 40% of ethyl acetate and hexane, and isomers of unsaturated cis structure and unsaturated trans structure are obtained. To separate. At that time, using a proton ¹ H-NMR nuclear magnetic resonance apparatus, identification according to the chemical shift value was performed on the fractionated solution at each chromatography development time based on the Aldorich standard substance, and fractionation was performed. Identify the liquid. The fraction solution is dried under reduced pressure to recover the desired fatty acid amide having an unsaturated cis structure carbon double bond.

6). Other compounding agents In the resin composition contained in the surface layer of the resin laminate of the present invention, if necessary, as other compounding agents, an inorganic filler, a heat stabilizer, a light stabilizer, a water repellent, Various compounding agents, such as an antistatic agent, an antiblocking agent, a mold release agent, a coupling agent, and an oxygen absorber, can be contained. Content of these various compounding agents is 10 mass% or less normally in a resin composition, Preferably it is 5 mass% or less, More preferably, it is 2 mass% or less. In particular, as will be described later, when the bio-setting ratio of the resin composition is increased to increase the carbon offset property, the content of other compounding agents needs to be 5000 ppm or less, preferably 2000 ppm or less. is there.

  As various compounding agents, lubricants other than the unsaturated fatty acid amide (C) can also be used. As the other lubricant, a saturated fatty acid amide is preferable. By using the saturated fatty acid amide in combination, effects such as further improvement of slipperiness and surface gloss can be achieved. As the saturated fatty acid amide, a compound usually used as a lubricant can be used, for example, butyramide, valeric acid amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, Examples thereof include palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, and preferably stearic acid amide and behenic acid amide.

  When the saturated fatty acid amide is contained, the content thereof is preferably 10% by mass or less, more preferably 8% by mass or less, based on the total content of the unsaturated fatty acid amide (C) and the saturated fatty acid amide. More preferably, it is 6 mass% or less, and the lower limit of the content is about 0.5 mass%, and if it is 1 mass%, a sufficient effect can be realized. In addition, the total content of the unsaturated fatty acid amide (C) and the saturated fatty acid amide is within the range of 100 to 4000 ppm with respect to the total mass of the resin components containing (A) and (B). Is preferred.

7). Modern carbon ratio of resin composition The resin laminate of the present invention is also composed of (A) an ethylene / α-olefin copolymer of 90 to 60% by mass having a density of 912 to 935 kg / m ³ and (B) a high density polyethylene 10. A resin laminate comprising, as a surface layer, a layer made of a resin composition containing 100 to 4000 ppm of a fatty acid amide having an unsaturated cis structure carbon double bond with respect to a resin component containing ˜40 mass%, (III) The resin composition is a resin laminate including a plant-derived ethylene-based resin having a modern carbon ratio of 14 to 118 pMC and having a carbon-labeled surface layer. More preferably, the resin composition contains a plant-derived ethylene resin having a modern carbon ratio of 26.8 to 118 pMC, particularly preferably a modern carbon ratio of 85.6 to 118 pMC, and is labeled with carbon. It is a resin laminated body provided with the made surface layer.

  From this, the resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer is a plant-derived ethylene-based resin, for example, the plant-derived ethylene having a bioavailability of 87%. It can be said that it is a resin laminate comprising, as a surface layer, a layer comprising a resin composition of the ethylene / α-olefin copolymer of (A) containing 25% by mass or more of an α-olefin copolymer (107 pMC × 0.87). Based on results calculated as x 0.25 x 0.60 = 13.96 pMC).

  Further, as a resin composition for forming the surface layer provided in the resin laminate of the present invention, a resin composition containing a plant-derived ethylene resin having a more preferable modern carbon ratio of 26.8 to 118 pMC is 25% Corg. Since it corresponds to renew (calculated as 107 pMC × 0.25 = 26.75 pMC) or more, it is extremely desirable from the viewpoint of carbon offset property. The modern carbon ratio particularly preferably corresponds to 53.5 to 118 pMC [50% Corg.renew (calculated as 107 pMC × 0.5 = 53.5 pMC)] or more. ] If necessary, the modern carbon ratio corresponds to 64.2 to 118 pMC [60% Corg.renew (calculated as 107 pMC × 0.60 = 64.2 pMC)] or more. Further, if desired, the modern carbon ratio corresponds to 74.9 to 118 pMC [70% Corg.renew (calculated as 107 pMC × 0.7 = 74.9 pMC)] or more. The resin composition containing a plant-derived ethylene resin is a carbon of a resin laminate comprising a plant-derived ethylene resin provided with a layer comprising the resin composition on the surface and a carbon-labeled surface layer. The offset property can be remarkably enhanced, which is preferable.

The resin composition containing 25% by mass or more of a plant-derived ethylene resin that forms the surface layer of the resin laminate of the present invention is (A) an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ^3. Resin composition containing 100 to 4000 ppm of fatty acid amide having (C) unsaturated cis structure carbon double bond with respect to resin component containing 90 to 60% by mass of coal and (B) 10 to 40% by mass of high density polyethylene (I) The ethylene / α-olefin copolymer of (A) has a modern carbon ratio of 23.3 to 118 pMC, and (II) the high density polyethylene of (B) is modern carbon. Although it can be easily obtained by preparing the resin composition having a ratio of 0 to 8 pMC, it may be prepared by other methods. In addition, about the bio-ization rate derived | led-out from the modern carbon ratio of the said resin composition, the influence of the modern carbon ratio of the fatty acid amide which has (C) unsaturated cis structure carbon double bond is contained in this (C) component. Since the amount is small, it can be ignored.

Moreover, as a resin composition which forms the surface layer with which the resin laminate of the present invention is provided, a resin composition containing a plant-derived ethylene-based resin having a more preferable modern carbon ratio of 26.8 to 118 pMC has a modern carbon ratio. It can be prepared by adopting an ethylene / α-olefin copolymer having a high density of 912 to 935 kg / m ³ or adjusting its content.

II. Resin Laminate The resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer is a layer comprising the resin composition containing the above (A), (B) and (C). Is a resin laminate provided on the surface layer. The resin laminate of the present invention includes a resin laminate having a multilayer structure of two layers, three layers, four layers, five layers or more provided with a layer made of the resin composition as a surface layer.

1. Surface layer As described above, in the resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer, the “surface layer” is exposed on the surface or the back surface other than the intermediate layer or the core layer The layer which is doing. The resin laminate of the present invention comprises a layer made of the above resin composition, that is, a layer made of the resin composition containing the above (A), (B) and (C). One or both of them.

  The resin laminate of the present invention is a resin laminate comprising on its surface a layer comprising the resin composition containing the above (A), (B) and (C), so that the surface of the resin laminate is slippery. Will improve. Molded bodies such as resin multilayer containers formed from the resin laminate usually improve the slipperiness of the outermost layer of the molded body, so the content of the molded body during manufacture, transportation or container While filling the product, it has the effect of preventing the occurrence of defective products, production line stoppage, equipment failure, etc. due to contact or collision between molded products or equipment, etc., and excellent surface gloss It can be a thing.

  The resin laminate of the present invention is a resin laminate provided on the back surface with a layer comprising the resin composition containing the above (A), (B) and (C), so that the back surface of the resin laminate is slippery. Will improve. Molded products such as resin multilayer containers formed from the resin laminate are usually improved in the slipperiness of the innermost layer of the molded product. There are effects such as smooth filling of contents and excellent drainage of contents when used by consumers.

  The resin laminate of the present invention is provided with a layer made of the resin composition on both the front surface and the back surface, thereby providing an effect when the resin laminate has a layer made of the resin composition on the surface, Both effects can be realized together with the effect in the case of a resin laminate comprising a layer composed of the resin composition on the back surface.

2. Intermediate layer or core layer The resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer is obtained from the resin composition containing (A), (B) and (C). As long as the layer to be provided is provided on one or both of the front and back surfaces of the resin laminate, the intermediate layer or core layer other than the surface layer is not particularly limited, and uses various materials or compositions. can do. In addition, the intermediate | middle layer in a resin laminated body means the layer with which the intermediate | middle position of the surface or back surface of a resin laminated body provided with three or more layers is equipped. The core layer in the resin laminate is a layer having the largest thickness or mass other than the resin composition containing (A), (B) and (C). Means a layer conforming to the above, sometimes referred to as a base material layer. For example, the resin laminate of the present invention contains a thin layer made of the resin composition containing the above (A), (B) and (C), and the above (A), (B) and (C). The laminated body formed from two layers with the core layer (base material layer) which is a relatively thick layer which consists of other than the resin composition to perform may be sufficient. Examples of the layer that can be provided as the intermediate layer or the core layer include the following layers.

(1) Barrier layer The resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer can further include a barrier layer in order to enhance the storage stability of the contents. As the barrier layer, those having gas barrier properties such as oxygen barrier properties and carbon dioxide gas barrier properties, and barrier properties against water or water vapor can be used. The barrier layer is not particularly limited, and a resin film layer on which a metal or an inorganic oxide is deposited, a metal foil, a barrier resin layer, or the like can be used depending on the type of container.

  Preferable examples of the barrier resin for forming the barrier layer include ethylene / vinyl alcohol copolymers or partially saponified products of ethylene / vinyl acetate copolymers (hereinafter sometimes collectively referred to as “EVOH”). Can be mentioned. Furthermore, since it is excellent not only in oxygen gas barrier properties but also in carbon dioxide gas barrier properties, a polyglycolic acid (co) polymer, preferably a polyglycolic acid or a copolymer thereof with lactic acid is used as the gas barrier resin. can do. Moreover, aromatic polyamide (MXD6) formed from metaxylylenediamine and adipic acid, polyvinylidene chloride, and the like can be used.

  As EVOH, an ethylene / vinyl acetate copolymer having an ethylene content of 20 to 60 mol%, preferably 25 to 55 mol%, more preferably 30 to 50 mol%, has a saponification degree of 90 mol% or more, A saponified copolymer obtained by saponification is preferably used in an amount of 95 mol% or more, more preferably 97 mol% or more, particularly preferably 99 mol% or more. This EVOH has a molecular weight sufficient to form a film.

(2) Adhesive layer The resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer can have an adhesive layer interposed between the respective layers for the purpose of increasing the delamination strength. The adhesive layer is preferably one that can be extruded and exhibits good adhesion to each resin layer. For example, when the resin laminate is formed in a container by blow molding, which will be described later, there is a case where an adhesive layer may not be interposed from the viewpoint of heat resistance and molding processability. It is preferable to interpose an adhesive layer for applications that require high resistance to impact or the like.

  Examples of the adhesive layer include acid-modified polyolefins such as maleic anhydride-modified polyethylene and maleic anhydride-modified polypropylene, glycidyl group-containing ethylene copolymers, thermoplastic polyurethanes, ethylene / vinyl acetate copolymers, polyamides / ionomers, polyacrylimides, and the like. Can be mentioned.

  If desired, the adhesive layer may contain various additives such as an inorganic filler, a plasticizer, a heat stabilizer, a light stabilizer, and a dye.

(3) Collection layer The resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer is a molded product such as a resin laminate or a resin multilayer container formed from the resin laminate. In order to increase the strength and improve the recyclability of resources, a recovery layer may be provided.

  The recovery layer is a material that is recovered from a molded product such as a resin multilayer container or a resin multilayer container formed from the resin laminate of the present invention (unusable parts of burrs and containers, recovered products of bottles that are out of product specifications, etc.) Or it is a layer which contains the material collect | recovered in the process of manufacturing the resin laminated body of this invention as a main component. In particular, when the resin multilayer container formed from the resin laminate of the present invention is manufactured by blow molding described later, the head of the container after introducing blow air into the parison that is a preformed product (Hereinafter, it may be referred to as “bag portion”) needs to be excised, but the excised bag portion can be used as a recovery layer by using a recovered resin pulverized by a pulverizer as a raw material. Further, it contains as a main component a resin recovered by cutting away the portion other than the bag portion of the blow molded container, a parison before molding, and materials and raw materials for forming each layer of the resin multilayer container. It may be a thing.

  The recovery layer may further contain raw materials for forming each layer of the resin multilayer container of the present invention, for example, various resin raw materials, compounding agents, adhesives, and the like.

3. Therefore, the resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer is a resin laminate having a barrier layer in addition to the surface layer, and / or further A resin laminate including a recovery layer is preferable, and a resin laminate including a surface layer, a barrier layer, an adhesive layer, and a recovery layer is more preferable. Furthermore, the resin laminate comprising the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer may be added to other layers, for example, a strength reinforcing layer or a printing layer formed from a resin film, if necessary. Etc. may be provided.

  The thickness and shape of the resin laminate containing the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer are not particularly limited, and the shape is a sheet, a film, a plate-like body, and the like. The sheet-like resin laminate may be formed into a tubular body (hereinafter sometimes collectively referred to as “sheet”). The total thickness of the resin laminate containing the plant-derived ethylene-based resin of the present invention and having a carbon-labeled surface layer is, for example, a resin laminate for the purpose of forming a resin multilayer container. Usually, it is in the range of 20 μm to 5 mm, preferably 100 μm to 3 mm, more preferably 200 μm to 1 mm. The thickness of the surface layer containing the above (A), (B) and (C) relative to the total thickness (meaning the total thickness on the front side and / or the back side) is usually 50 to the total thickness. 90% by mass. In addition, since the ratio of the thickness of each layer in a sheet-like resin laminated body is substantially equivalent to the ratio of mass, it can describe with mass%.

  The surface layer is preferably 55 to 85% by mass, more preferably 60 to 80% by mass. A collection layer is 5-30 mass% normally, Preferably it is 10-27 mass%, More preferably, it is 15-25 mass%. A barrier layer is 1-10 mass% normally, Preferably it is 2-9 mass%, More preferably, it is 3-8 mass%. The total amount of the adhesive layer is usually 0.005 to 2% by mass, preferably 0.007 to 1.5% by mass, and more preferably 0.008 to 1.2% by mass.

  The ratio of the surface layer of the surface layer (surface side and / or back surface side) in the resin laminate of the present invention to the entire surface layer is not particularly limited, but is usually 10 to 80% by mass, preferably 15 to 75% by mass. More preferably, it is 20-70 mass%, Most preferably, it is 25-65 mass%.

III. Resin multilayer container According to the present invention, there is provided a resin multilayer container formed of a resin laminate including a carbon-labeled surface layer containing the plant-derived ethylene-based resin of the present invention. The resin laminate of the present invention is a resin laminate comprising a layer made of the resin composition containing the above (A), (B) and (C) on the surface layer. The resin laminate of the present invention is a resin laminate having a multilayer structure of two layers, three layers, four layers, five layers or more provided with a layer made of the resin composition as a surface layer (front side and / or back side). Since it is a body, the resin multilayer container of this invention is a resin multilayer container provided with the layer which consists of said resin composition in an outermost layer and / or an innermost layer. Therefore, in the resin multilayer container of the present invention, the surface layer which is a layer composed of the resin composition containing the above (A), (B) and (C) is one of the outermost layer and the innermost layer of the resin multilayer container. Or it can be said that it is a resin multilayer container which is both.

1. Outermost layer and / or innermost layer The resin multilayer container of the present invention is provided with a layer made of the resin composition containing the above (A), (B) and (C) in the outermost layer and / or the innermost layer. Thereby, the slipperiness of the outer surface and / or inner surface of the container is improved. When the slipperiness of the outer surface of a resin multilayer container formed of a resin laminate comprising a plant-derived ethylene-based resin according to the present invention and having a carbon-labeled surface layer is improved, the container is being manufactured, being conveyed, or the container There is an effect that it is possible to prevent the occurrence of defective products, the stop of the production line, the failure of the apparatus, and the like due to the contact or collision between the containers or the containers and the devices during the filling of the contents. Further, when the slipperiness of the inner surface of the resin multilayer container formed from the resin laminate is improved, the contents are smoothly filled into the container, and the liquid of the contents is used when the consumer uses it. There are effects such as excellent cutting performance. The resin multilayer container of the present invention can realize both of the effects described above by providing the outermost layer and the innermost layer of the container with a layer made of the resin composition.

2. Intermediate layer or core layer The resin multilayer container of the present invention has an excellent effect when the resin laminate includes the above-described barrier layer, adhesive layer, recovery layer, etc. as the intermediate layer or core layer. Can do.

3. Configuration of Resin Multilayer Container The resin multilayer container of the present invention includes a layer made of the resin composition containing the above (A), (B) and (C) as a surface layer, preferably a layer configuration. As a resin multilayer container including a surface layer, a barrier layer, an adhesive layer, and a recovery layer. More preferably, the outermost layer / barrier layer / adhesive layer / recovery layer / innermost layer structure or the outermost layer / adhesive layer / barrier layer / adhesive layer / recovery layer / innermost layer structure made of resin It is.

  The resin multilayer container of the present invention is formed from a resin laminate comprising as a surface layer a layer composed of the resin composition containing the above (A), (B) and (C), specifically, A blow molded container (including a stretch blow molded container) formed from a resin laminate as a parison, a bag-like container prepared by bending and bonding from a sheet-like resin laminate, and a sheet-like resin laminate by vacuum molding and It can be made into various shapes such as a container formed by pressure forming. Among these, blow molded containers are preferable, and direct blow molded containers are more preferable.

  The resin multilayer container of the present invention may be formed from a single resin laminate, and the thickness of the entire container may be substantially uniform. For example, when a resin multilayer container is formed by integral molding such as blow molding, the thickness of the entire container is substantially uniform. However, depending on the purpose, it is also possible to form a container by combining a plurality of types of resin laminates. In that case, the container may have a different thickness depending on the portion of the container.

Volume of the resin multilayer container of the present invention is not particularly limited, is preferably 100～3000Cm ^3, more preferably 200～2000Cm ^3, more preferably a resin multilayered container having a volume in the range of 300～1000Cm ³ .

4). Characteristics of plastic multilayer containers (sliding friction)
The resin multilayer container of the present invention contains a plant-derived ethylene-based resin having a layer made of the resin composition containing the above (A), (B) and (C) as a surface layer, and is carbon-labeled surface layer It is a container excellent in slipperiness by being formed from the resin laminated body provided with. When the surface layer is one or both of the outermost layer and the innermost layer, the slipperiness of the outer surface and / or inner surface of the resin multilayer container can be improved. The slipperiness of the resin multilayer container can be evaluated by a surface sliding friction coefficient measured by a method according to JIS K7125. Specifically, after the multilayer container is fully filled with water at a temperature of 23 ° C., a two-layer seal (aluminum / LDPE) is used, and the LDPE side of the seal is placed on the mouth of the multilayer container and heated. Weld and seal the mouth of the multi-layer container. The mouth of the multilayer container is provided with a thread for screwing a lid around the outer periphery of the mouth. A wire for pulling the multilayer container is fixed to the lid, and then the lid is screwed to the mouth of the multilayer container. The multilayer container is placed horizontally on a stainless steel flat plate, and the maximum when a wire attached to the mouth of the multilayer container is pulled about 2 cm horizontally at a speed of 86 mm / min using a tensile and compression tester is used. A tensile load value is obtained, and the load value is divided by the total mass of the multilayer container to obtain a surface sliding friction coefficient of the multilayer container (hereinafter sometimes referred to as “sliding friction”). If the sliding friction is 0.40 or less, it can be said that the sliding property is good, and is preferably 0.39 or less, more preferably 0.38 or less.

[Puncture strength]
The resin multilayer container of the present invention is excellent in that it is formed from a resin laminate comprising a layer composed of a resin composition containing the above (A), (B) and (C) as a surface layer. It is a container having puncture resistance. The puncture resistance of the resin multilayer container can be evaluated by measuring the puncture strength by a method according to JIS T8051. Specifically, a body part in a range of 90 to 130 mm above the bottom of the multilayer container is cut into a ring, and a sheet obtained by cutting the ring is used as a sample. Using a Tensilon universal tester (compression tester), a semicircular piercing jig with a tip diameter of 1.0 mm and a tip shape radius of 0.5 mm is placed on the surface of the sample in an air-conditioned atmosphere at a temperature of 23 ° C. It can be evaluated by measuring the maximum puncture load (unit N) when pierced at a right angle at a puncture speed of 50 mm / min and penetrating it, and using the value converted to the sample thickness of 390 μm as the puncture strength of the multilayer container. . If the puncture strength is 10 N or more, it can be said that the puncture resistance is excellent, and preferably 11 N or more.

[Haze]
The resin multilayer container of the present invention is formed of a resin laminate including a layer made of the resin composition containing the above (A), (B) and (C) as a surface layer, thereby making a resin The haze on the surface of the multilayer container is small, and the appearance as a multilayer container is excellent. The haze of the resin multilayer container is measured at a temperature of 23 ° C. (unit%) using a turbidity meter (haze meter) according to JIS K7361. If the haze on the surface of the multilayer container is 40% or less, it can be said that the multilayer container is excellent in appearance, and the haze is preferably 39% or less.

IV. 1. Manufacturing method of resin laminate and resin multilayer container The manufacturing method of the resin laminated body The manufacturing method of the resin laminated body of this invention is a plant-derived ethylene resin provided with the layer which consists of a resin composition containing said (A), (B) and (C) as a surface layer. It is not particularly limited as long as a resin laminate including a carbon-labeled surface layer can be obtained, and can be based on co-extrusion molding, multilayer injection molding (co-injection molding), an adhesive lamination method, or the like. It is preferable in terms of efficiency to manufacture a resin laminate having a predetermined layer structure by coextrusion molding. Examples of the method for producing the resin laminate of the present invention by coextrusion include methods such as a coextrusion method using a tubular die, a coextrusion method using a T die, and a coextrusion method by inflation molding.

  From a resin laminate comprising a plant-derived ethylene-based resin according to the present invention and having a carbon-labeled surface layer, a so-called container-shaped resin multilayer container having a neck portion, a trunk portion and a bottom portion is blow molded to be described in detail later. When forming and manufacturing, a resin laminate comprising a plant-derived ethylene-based resin and a carbon-labeled surface layer as a tubular (pipe-shaped) multi-layer parison by a coextrusion method using a tubular die. It is preferable to manufacture. When producing a multi-layer parison by the coextrusion method using a tubular die, the number of extruders corresponding to the type of resin is used, and the resin corresponding to each layer is expanded into a tubular shape while the molten resin is formed in the die passage. Are joined together in the order of the laminated body. When the innermost layer and the outermost layer, which are the surface layers, are made of the same type of resin, they are further branched through a branch channel so as to sandwich the resin raw materials forming other layers, and then merged in an extrusion die, and are tubular Resin is extruded from a die head having a shape in a state of being laminated in a predetermined layer configuration. The temperature of the die head is usually 120 to 240 ° C, preferably 130 to 230 ° C, more preferably 140 to 220 ° C. As the shape of the diorifice, it is possible to use a circular or flat shape. According to the co-extrusion method using a tubular die, it is possible to relatively easily change the thickness of the multilayer parison.

  In addition, as mentioned above, the multilayer parison which is a resin laminated body containing the plant-derived ethylene-type resin and provided with the carbon-labeled surface layer can also be manufactured by co-injection molding. Using a molding machine equipped with a plurality of injection cylinders, the melted surface layer (outermost layer and / or outer layer and / or from a single gate in a single parison injection mold cavity in a single clamping operation. The resin composition forming the innermost layer) and the resin material forming the other layer are co-injected to form a bottomed multilayer parison. The barrier layer may not be present on a part or all of the bottom of the multilayer parison. Generally, since the thickness of the bottom portion is larger than the thickness of the body portion, the barrier property can be exhibited even if the bottom portion is substantially only the resin composition layer. By disposing the barrier layer only on the trunk, it is easy to prevent the mechanical strength of the multilayer container from being lowered and to control the thickness of the barrier layer uniformly.

2. Manufacturing method of resin multilayer container The manufacturing method of the resin multilayer container of the present invention includes the plant-derived ethylene-based resin, and forms a resin multilayer container from a resin laminate including a carbon-labeled surface layer. It is not particularly limited as long as it can be produced. For example, a method of blow molding (including stretch blow molding) using a resin laminate containing a plant-derived ethylene-based resin and having a carbon-labeled surface layer as a parison, folding and bonding a sheet-like resin laminate A method for vacuum forming and / or pressure forming a sheet-shaped resin laminate, and sealing a three- or four-sided sheet-shaped resin laminate to manufacture a resin multilayer container as a packaging bag A method for producing a resin multilayer container known per se can be employed.

  When producing a resin multilayer container by blow molding, it contains a plant-derived ethylene-based resin provided with a layer composed of a resin composition containing the above (A), (B) and (C) as a surface layer, A blow-molded product is obtained by blow-molding a multi-layer parison (hereinafter sometimes referred to as “multi-layer parison”), which is a resin laminate having a carbon-labeled surface layer, in a split mold having a container-shaped cavity wall. A resin multilayer container is manufactured. The blow molding may be performed by a cold parison method in which a multilayer parison is manufactured and then cooled to room temperature or room temperature and heated to a predetermined temperature when blow molding is performed, or a multilayer parison is manufactured and subsequently blow molded. The hot parison system to be performed may be used. The multi-layer parison can be produced by multi-layer injection molding, but a method of producing a tubular (hereinafter sometimes referred to as “tubular” or “pipe”) multi-layer parison by melt coextrusion is preferred. It is preferable to produce the multi-layer parison by direct blow molding in which blow molding is performed continuously.

  In the method for producing the resin multilayer container of the present invention by direct blow molding, a cylinder which is a resin laminate comprising a plant-derived ethylene-based resin produced by co-extrusion by the above-described method and having a carbon-labeled surface layer A multi-layered parison is sandwiched between split molds, and the lower end of the parison is fused and closed, and the upper end of the parison is cut, and then a pressurized fluid is blown from the opening at the upper end of the parison to form a container shape. The upper part (head part or bag part) of the container mouth part which becomes becomes a resin multilayer container.

As the mold for blow molding, either a mirror-finished one or a sandblasted one can be used, and the surface temperature of the mold is generally preferably in the range of 10 to 50 ° C. Moreover, it is preferable to use sterilized air as the fluid for blow molding, and the pressure is suitably in the range of 1.0 to 15 kg / cm ² .

  When manufacturing a heat-resistant resin multilayer container suitable for hot filling of contents, the temperature of the blow molding mold is set to 100 ° C or higher in order to prevent thermal shrinkage and deformation of the container during hot filling. The temperature may be raised and heat treatment (heat setting) may be performed in the mold. The mold temperature is in the range of 100 to 165 ° C., preferably in the range of 145 to 155 ° C. in the case of a general heat resistant container, and in the range of 160 to 165 ° C. in the case of a high heat resistant container. The heat treatment time varies depending on the thickness of the resin multilayer container and the heat treatment temperature, but is usually 1 to 30 seconds, preferably 2 to 20 seconds.

  The resin multilayer container of the present invention can also be produced by stretch blow molding. In the stretch blow molding step, the multilayer parison, which is a resin laminate, is adjusted to a temperature at which it can be stretched, and then inserted into a cavity of a blow molding die, and a blown fluid such as air is blown to perform stretch blow molding. In order to perform the stretching in the length direction, a stretching rod may be used. Stretch blow molding can be performed by either a hot parison system or a cold parison system. The total draw ratio is usually 6 to 9 times, 8 to 9.5 times for a pressure resistant container, 6 to 7.5 times for a heat resistant container, and 7 to 8 times for a large container.

  The resin multilayer container of the present invention can also be produced by sheet blow molding. That is, a multilayer parison that is a sheet-shaped resin laminate of two sheets is inserted into a cavity of a split mold for blow molding, and is fused with the end portions of the two sheet-shaped multilayer parison interposed therebetween. Then, a pressurized fluid such as air is blown into a container to perform blow molding.

  EXAMPLES The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to the examples. The measuring method of the characteristic or physical property of the resin raw material and the resin multilayer container in Examples and Comparative Examples is as follows.

[Density, MFR and polydispersity]
The density and MFR (temperature 190 ° C., load 2.12 N) of the ethylene-based resin were measured according to JIS K6922-2. The polydispersity (Mw / Mn) was measured according to JIS K7252.

[Crystal melting point]
The crystal melting point of the resin was measured according to JIS K7122.

[Sliding friction]
The surface sliding friction coefficient of the resin multilayer container was measured by a method according to JIS K7125. Specifically, after the multilayer container is fully filled with water at a temperature of 23 ° C., a two-layer seal (aluminum / LDPE) is used, and the LDPE side of the seal is placed on the mouth of the multilayer container and heated. The mouth of the multilayer container was sealed by welding. The mouth of the multilayer container is provided with a thread for screwing a lid around the outer periphery of the mouth. A wire for pulling the multilayer container was fixed to the lid, and then the lid was screwed into the mouth of the multilayer container, and then the multilayer container was placed horizontally on a stainless steel flat plate. Using a tensile and compression tester manufactured by Imada Manufacturing Co., Ltd., product name SV50, the maximum tensile load value when the wire attached to the mouth of the multilayer container is pulled horizontally about 2 cm at a speed of 86 mm / min is obtained. Dividing by the total weight of the container, the surface sliding friction coefficient (sliding friction) of the multilayer container was taken (average value of n = 3).

[Puncture strength]
The puncture strength of the resin multilayer container was measured by a method according to JIS T8051 for the multilayer container used for measurement of the surface sliding friction coefficient. Specifically, the body portion 90 to 130 mm above the bottom of the multilayer container was cut into a ring, and a sheet cut into the ring was used as a sample. Using a Tensilon universal testing machine RC-121OA manufactured by Orientec Co., Ltd., a semicircular piercing jig with a tip diameter of 1.0 mm and a tip shape radius of 0.5 mm in an air-conditioned atmosphere at a temperature of 23 ° C. The maximum puncture load (unit N) when pierced perpendicularly to the surface of the sample at a speed of 50 mm / min was measured, and the value converted to the sample thickness of 390 μm was taken as the puncture strength of the multilayer container (n = 3 Average value).

[Haze]
The haze of the resin multilayer container surface was measured at a temperature of 23 ° C. using an turbidimeter (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7361 (average value of n = 3). ).

[Example 1]
Using a plurality of extruders and multi-layer dies, a cylindrical parison that is a resin laminate of outermost layer / adhesive layer / barrier layer / adhesive layer / recovery layer / innermost layer is extruded, and rotary direct blow molding A multi-layer resin multi-layer container (hereinafter referred to as “multi-layer container”) having an internal volume of 500 cm ³ was formed by a machine. The mass of the multilayer container was 17 g.

(1) Surface layer (outermost layer and innermost layer):
(A) Ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ derived from a plant [manufactured by Brasschem, brand name SLH0820 / 30AF, density 920 kg / m ³ , MFR (temperature 190 ° C., load 2.12 N ) 0.80 g / 10 min, polydispersity (Mw / Mn) 2.8, modern carbon ratio 93.1 pMC. Hereinafter, it may be referred to as “plant-derived ethylene / α-olefin copolymer”. The ethylene / α-olefin copolymer is 87% Corg.renew. ] 72% by mass, and (B) fossil fuel-derived high-density polyethylene [Novatec (registered trademark) HD manufactured by Nippon Polyethylene Co., Ltd., Ziegler-Natta catalyst polymerization brand name KB285N (density 964 kg / m ³ , MFR (temperature 190 ° C. , Load 2.12 N) 0.2 g / 10 min, polydispersity (Mw / Mn) 7.8, crystal melting point 136 ° C., modern carbon ratio 0 pMC, hereinafter sometimes referred to as “fossil fuel-derived high-density polyethylene”. ] 28% by mass of resin component,
And
(C) Fatty acid amide having an unsaturated cis structure carbon double bond: cis-9,10-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ — CH ₃ ; unsaturated fatty acid amide of formula (C ₁ ) 98% by mass, cis-5,6-8,9-11,12-14,15-arachidonic acid amide [H ₂ N—CO — (— CH _2- ) ₃ -CH═CH—CH ₂ —CH═CH—CH ₂ —CH═CH—CH ₂ —CH═CH — (— CH ₂ —) ₄ —CH ₃ ] with 2% by mass 390 ppm [provided that , (C) is the total content (ppm) of (A) and (B) relative to the total mass. The same applies to the following examples and comparative examples. ]
The modern carbon ratio of the resin composition consisting of [The resin composition consisting of (A), (B) and (C) was 67.0 pMC. ]

(2) Barrier layer: Trade name EVAL (registered trademark) manufactured by Kuraray Co., Ltd. [EVOH having an ethylene content of 44% by molar ratio. Density 1140 kg / m ³ , MFR (temperature 190 ° C., load 21.18 N) 1.7 g / 10 min, crystal melting point 165 ° C.]

(3) Recovery layer: The resin (recovered resin) obtained by cutting the container head (bag portion) generated when direct blow molding the resin multilayer container manufactured according to the present embodiment and pulverizing it with a pulverizer It was.

(4) Adhesive layer: maleic anhydride-modified polyolefin manufactured by Mitsubishi Chemical Corporation, trade name Modic (registered trademark)

  The total thickness of (1) to (4) was 390 μm, and the thickness ratio (mass ratio) of the layers (1) to (4) was 74: 6: 19: 1.

  Table 1 shows the results of measuring the surface sliding friction coefficient (hereinafter referred to as “sliding friction”), piercing strength, and haze of the molded multilayer container.

[Example 2]
(C) Fatty acid amide having an unsaturated cis structure carbon double bond is converted to 99.8% by mass of cis-9,10-octadecenoamide [formula (C ₁ )] and cis-8,9-octadecenoamide [H ₂ N— CO — (— CH ₂ —) ₆ —CH═CH — (— CH ₂ —) ₈ —CH ₃ ; unsaturated fatty acid amide of formula (C ₂ )] A multilayer container was molded in the same manner as in Example 1 except that the amount was changed to 400 ppm. Table 1 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Example 3]
(C) an unsaturated cis structure fatty acid amide having a carbon-carbon double bond, cis- 9,10-octadecenoamide [formula _{(C 1)]} and 90 wt%, cis-8,9-octadecenoamide [formula _{(C 2)]} A multilayer container was molded in the same manner as in Example 1 except that the mixture was changed to a mixture with 10% by mass and the total content was changed to 3500 ppm. Table 1 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Example 4]
(C) Fatty acid amide having an unsaturated cis structure carbon double bond is converted into 85 mass% of cis-9,10-octadecenoamide [formula (C ₁ )] and cis-6,7-tetradecenoamide [H ₂ N—CO— (—CH ₂ —) ₄ —CH═CH — (— CH ₂ —) ₆ —CH ₃ ; Unsaturated Fatty Acid Amide of Formula (C ₂ )] 15% by mass, and the total content is 350 ppm A multilayer container was molded in the same manner as in Example 1 except that the change was made. Table 1 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Example 5]
(C) A fatty acid amide having an unsaturated cis structure carbon double bond was changed to cis-8,9-octadecenoamide [formula (C ₂ )] (single use), except that the content was changed to 400 ppm. A multilayer container was formed in the same manner as in Example 1. Table 1 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Example 6]
(C) A fatty acid amide having an unsaturated cis-structured carbon double bond is converted to 98% by mass of cis-9,10-octadecenoamide [formula (C ₁ )] and cis-13,14-docosenoamide [H ₂ N—CO— (—CH ₂ —) ₁₁ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ; Unsaturated Fatty Acid Amide of Formula (C ₃ )] 2% by mass to change to a total content of 1500 ppm A multilayer container was molded in the same manner as in Example 1 except that the change was made. Table 1 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Example 7]
(C) Fatty acid amide having an unsaturated cis structure carbon double bond is converted into cis-13,14-docosenoamide [formula (C ₃ )] 95% by mass, cis-9,10-octadecenoamide [formula (C ₁ )] A multilayer container was formed in the same manner as in Example 1 except that the mixture was changed to a mixture with 5% by mass and the content was changed to 250 ppm. Table 1 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Example 8]
(C) Fatty acid amide having an unsaturated cis structure carbon double bond is converted into 95 mass% of cis-9,10-octadecenoamide [formula (C ₁ )] and cis-13,14-docosenoamide [formula (C ₃ )] Example 1 except that the mixture was changed to a mixture with 3% by mass, and behenic acid amide, which is a saturated fatty acid amide, was further contained at a rate of 2% by mass, and the total content of these fatty acid amides was changed to 1000 ppm. In the same manner, a multilayer container was formed. Table 1 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Example 9]
(C) Fatty acid amide having an unsaturated cis-structured carbon double bond is converted into cis-9,10-octadecenoamide [formula (C ₁ )] 92% by mass and cis-13,14-docosenoamide [formula (C ₃ )] Example 1 except that the mixture was changed to a mixture with 3% by mass, further containing stearic acid amide, which is a saturated fatty acid amide, at a rate of 5% by mass, and the total content of these fatty acid amides was changed to 1000 ppm. In the same manner, a multilayer container was formed. Table 1 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Comparative Example 1]
(C) The fatty acid amide having an unsaturated cis structure carbon double bond corresponds to trans-9,10-octadecenoamide [corresponding to the trans form of the unsaturated fatty acid amide of the formula (C ₁ ). ] A multilayer container was molded in the same manner as in Example 5 except that it was changed to (single use). Table 1 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Comparative Example 2]
trans-9,10-octadecenoamide [corresponds to the trans form of the unsaturated fatty acid amide of the formula (C ₁ ). ] (Single use) was changed to a mixture of 98% by mass of trans-9,10-octadecenoamide and 2% by mass of stearic acid amide, which is a saturated fatty acid amide, in the same manner as in Comparative Example 1, and a multilayer container Was molded. Table 1 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Comparative Example 3]
The resin component of the resin composition contained in the surface layer is a fossil fuel-derived ethylene / α-olefin copolymer [manufactured by Brasschem, brand name PE LH-118, density 916 kg / m ³ , MFR (temperature 190 ° C., load 2.12N) 1.0 g / 10 min, polydispersity (Mw / Mn) 5.9, modern carbon ratio 0 pMC. Hereinafter, it may be referred to as “fossil fuel-derived ethylene / α-olefin copolymer”. ] And the above-described high-density polyethylene derived from fossil fuel, a resin multilayer container was molded in the same manner as in Example 3. The modern carbon ratio of the resin composition was 0 pMC. Table 1 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

From Table 1, (A) with respect to a resin component containing 90 to 60% by mass of an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high density polyethylene, (C) A resin laminate comprising, as a surface layer, a layer made of a resin composition containing 100 to 4000 ppm of a fatty acid amide having an unsaturated cis-structured carbon double bond, wherein (I) the ethylene / α- of (A) above The olefin copolymer has a modern carbon ratio of 23.3 to 118 pMC, (II) the high-density polyethylene of (B) has a modern carbon ratio of 0 to 8 pMC, and (III) a resin composition The modern carbon ratio is 14 to 118 pMC, and contains plant-derived ethylene-based resin and is formed from a resin laminate including a carbon-labeled surface layer. The multi-layer plastic container has a sliding friction of 0.25 to 0.32, a good surface slipperiness, a puncture strength of 12 N, excellent piercing resistance, and a haze of 26 to 37%. It can be seen that the molded product has practicality.

  On the other hand, instead of the fatty acid amide having an unsaturated cis structure carbon double bond (C), the resin multilayer containers of Comparative Examples 1 and 2 containing a fatty acid amide having an unsaturated trans structure carbon double bond are: Although the puncture resistance is equivalent to that of the resin multi-layer container of Examples 1 to 9, the sliding friction is as large as 0.45 or 0.42, there is a sticky feeling, and the haze is 41 to 42% and somewhat. Turbidity is observed.

  Further, from the result of comparison with the resin multilayer container of Comparative Example 3 formed from a resin composition containing a resin component comprising a combination of fossil fuel-derived ethylene / α-olefin copolymer and fossil fuel-derived high-density polyethylene. In addition, the resin multilayer container formed from the resin laminate including the plant-derived ethylene-based resin of Examples 1 to 9 of the present invention and having a carbon-labeled surface layer has no inferiority in moldability, slipperiness and resistance. It can be confirmed that the piercing property is excellent.

[Example 10]
The resin component of the resin composition contained in the surface layer was changed to (A) 86% by mass of plant-derived ethylene / α-olefin copolymer and (B) 14% by mass of fossil fuel-derived high-density polyethylene. (The modern carbon ratio of the resin composition was 80.1 pMC) and (C) the total content of fatty acid amides having unsaturated cis structure carbon double bonds was changed to 3000 ppm. In the same manner as in Example 3, a resin multilayer container was molded. Table 2 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Example 11]
In the resin component of the resin composition contained in the surface layer, (A) as the plant-derived ethylene / α-olefin copolymer, instead of using the plant-derived ethylene / α-olefin copolymer alone, the plant-derived Change in blending of resin components with 50% by mass of ethylene / α-olefin copolymer and 50% by mass of the fossil fuel-derived ethylene / α-olefin copolymer [ethylene / α-olefin copolymer of (A)] The coalescence was 50% Corg.renew and the modern carbon ratio was 46.5 pMC. In addition, a resin multilayer container was molded in the same manner as in Example 3 except that the total content of fatty acid amides having (C) unsaturated cis structure carbon double bonds was 3000 ppm. The modern carbon ratio of the resin composition was 33.5 pMC. Table 2 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Example 12]
(C) Fatty acid amide having an unsaturated cis structure carbon double bond is converted into 95 mass% of cis-9,10-octadecenoamide [formula (C ₁ )] and cis-13,14-docosenoamide [formula (C ₃ )] A resin multilayer container was molded in the same manner as in Example 11 except that the mixture was changed to a mixture with 5% by mass. Table 2 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Comparative Example 4]
The resin component of the resin composition contained in the surface layer was changed to 100% by mass of (A) plant-derived ethylene / α-olefin copolymer [(B) fossil fuel-derived high-density polyethylene was not used. In the same manner as in Example 10, a resin multilayer container was molded. Table 2 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

[Comparative Example 5]
Except that the resin component of the resin composition contained in the surface layer was changed to (A) 55% by mass of a plant-derived ethylene / α-olefin copolymer and (B) 45% by mass of fossil fuel-derived high-density polyethylene. In the same manner as in Example 10, a resin multilayer container was molded. The modern carbon ratio of the resin composition was 51.2 pMC. Table 2 shows the results of measuring the sliding friction, puncture strength and haze of the molded multilayer container.

From Table 2, (A) with respect to the resin component containing 90 to 60% by mass of ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high density polyethylene, (C) A resin laminate comprising, as a surface layer, a layer made of a resin composition containing 100 to 4000 ppm of a fatty acid amide having an unsaturated cis-structured carbon double bond, wherein (I) the ethylene / α- of (A) above The olefin copolymer has a modern carbon ratio of 23.3 to 118 pMC, (II) the high-density polyethylene of (B) has a modern carbon ratio of 0 to 8 pMC, and (III) the resin composition Tree of Example 10 formed from a resin laminate comprising a plant-derived ethylene-based resin having a modern carbon ratio of 14 to 118 pMC and having a carbon-labeled surface layer Manufacturing multilayer container,
And
(A) With respect to a resin component containing 90 to 60% by mass of an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high density polyethylene, A resin laminate comprising, as a surface layer, a layer made of a resin composition containing a fatty acid amide having a saturated cis structure carbon double bond of 100 to 4000 ppm, (I) the ethylene / α-olefin copolymer of (A) Contains a plant-derived ethylene / α-olefin copolymer and a fossil fuel-derived ethylene / α-olefin copolymer, has a modern carbon ratio of 23.3 to 118 pMC, and (II) the high density of (B) above Polyethylene is a plant-derived ethylene tree having a modern carbon ratio of 0 to 8 pMC and (III) a modern carbon ratio of the resin composition of 14 to 118 pMC. The resin multilayer containers of Examples 11 and 12 formed from a resin laminate including a carbon-labeled surface layer have a sliding friction of 0.33 to 0.38 and a good surface slipperiness. The puncture strength was 12N, the puncture resistance was excellent, and the haze was 31 to 32%, which proved to be a practical product.

  On the other hand, the resin component contained in the resin composition forming the surface layer (which forms the innermost layer and the outermost layer of the resin multilayer container) does not contain the high-density polyethylene of (B), and is derived from a plant. (A) The resin-made multilayer container of Comparative Example 4 containing a plant-derived ethylene-based resin, which is only an ethylene / α-olefin copolymer, and having a carbon-labeled surface layer is slippery. It was found that the friction was as large as 0.41, there was a sticky feeling, the puncture strength was as small as 8, and the puncture resistance was insufficient. Moreover, the resin component contained in the resin composition forming the surface layer includes a plant-derived ethylene-based resin containing 45% by mass of the high-density polyethylene (B), and includes a carbon-labeled surface layer. The resin multilayer container of Comparative Example 5 formed from the resin laminate had a puncture strength as low as 9, insufficient puncture resistance, and had a haze of 42% and was slightly turbid.

The present invention is based on (A) a resin component containing 90 to 60% by mass of an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high density polyethylene. (C) A resin laminate comprising a layer composed of a resin composition containing 100 to 4000 ppm of fatty acid amide having an unsaturated cis structure carbon double bond as a surface layer,
I: (I) The ethylene / α-olefin copolymer of (A) has a modern carbon ratio of 23.3 to 118 pMC, and (II) the high density polyethylene of (B) has a modern carbon ratio of 0. ~ 8pMC, or
II: (III) The resin composition has a modern carbon ratio of 14 to 118 pMC.
A resin laminate comprising a plant-derived ethylene-based resin and having a carbon-labeled surface layer, and a resin laminate formed from the plant-derived ethylene-based resin and having a carbon-labeled surface layer By being a multi-layer container, carbon labeling makes it easy to adjust the carbon offset and the carbon offset, and is a resin molded integrally from a resin laminate containing a synthetic resin derived from fossil fuel While having a moldability comparable to multilayered containers made, containers, containers and devices under different lines and environmental conditions ranging from container molding process, container transfer process, contents filling process, and packaging process, Proper slipperiness such as between container and packaging film or between container and contents, improved contents filled in container Cutting resistance, and it is possible to provide a resin laminate which is suitable for resin multilayered container having sufficient 耐突 penetration resistance, has high industrial applicability.

Claims (23)

(A) With respect to a resin component containing 90 to 60% by mass of an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high density polyethylene, A resin laminate comprising, as a surface layer, a layer made of a resin composition containing a fatty acid amide having a saturated cis structure carbon double bond of 100 to 4000 ppm,
(I) The ethylene / α-olefin copolymer of (A) has a modern carbon ratio defined by ASTM D6866-12 of 23.3 to 118 pMC,
(II) The high-density polyethylene of (B) includes a plant-derived ethylene-based resin having a modern carbon ratio of 0 to 8 pMC as defined in ASTM D6866-12, and includes a carbon-labeled surface layer. .   The ethylene / α-olefin copolymer (A) contains a plant-derived ethylene-based resin according to claim 1, wherein the modern carbon ratio defined in ASTM D6866-12 is 74.5 to 118 pMC. A resin laminate comprising a labeled surface layer. (A) With respect to a resin component containing 90 to 60% by mass of an ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ and (B) 10 to 40% by mass of high density polyethylene, A resin laminate comprising, as a surface layer, a layer made of a resin composition containing a fatty acid amide having a saturated cis structure carbon double bond of 100 to 4000 ppm,
(III) The resin composition includes a plant-derived ethylene-based resin having a modern carbon ratio of 14 to 118 pMC as defined in ASTM D6866-12, and includes a carbon-labeled surface layer. (I) The ethylene / α-olefin copolymer of (A) has a modern carbon ratio defined by ASTM D6866-12 of 23.3 to 118 pMC,
(II) The high-density polyethylene of (B) has a modern carbon ratio defined by ASTM D6866-12 of 0 to 8 pMC, and contains a plant-derived ethylene-based resin according to claim 3 and is carbon-labeled surface layer A resin laminate comprising:   The resin composition comprising a plant-derived ethylene-based resin according to claim 4 and comprising a carbon-labeled surface layer, wherein a modern carbon ratio defined in ASTM D6866-12 is 26.8 to 118 pMC. body. The (C) fatty acid amide having an unsaturated cis structure carbon double bond is represented by the following (C ₁ ), (C ₂ ) and (C ₃ ):
(C ₁ ) H ₂ N—CO — (— CH ₂ —) _n —CH═CH — (— CH ₂ —) _n —CH ₃ (where n is an integer in the range of 6 ≦ n ≦ 10);
_{(C 2) H 2 N-} CO - (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH 3 ( however, m is an integer in the range of 6 ≦ m ≦ 10) And (C ₃ ) H ₂ N—CO — (— CH ₂ —) _{k + 4} —CH═CH — (— CH ₂ —) _k —CH ₃ (where k is an integer in the range of 6 ≦ k ≦ 10); ;
A plant-derived ethylene-based resin according to any one of claims 1 to 5 containing at least one fatty acid amide represented by a formula selected from the group consisting of: and a carbon-labeled surface layer. Resin laminate. The fatty acid amide having the (C) unsaturated cis structure carbon double bond is represented by the fatty acid amide represented by the formula (C ₁ ) and the formula (C ₂ ) or (C ₃ ). A resin laminate comprising a plant-derived ethylene-based resin according to claim 6 and comprising a carbon-labeled surface layer which is a mixture with at least one fatty acid amide. The m in the fatty acid amide represented by the formula (C ₂ ) is m = n + 1 or m = n−1. The plant-derived ethylene-based resin according to claim 7, and a carbon-labeled surface layer A resin laminate provided. The resin laminate comprising a plant-derived ethylene resin and a carbon-labeled surface layer, wherein k in the fatty acid amide represented by the formula (C ₃ ) is k = n. The fatty acid amide having the (C) unsaturated cis structure carbon double bond is the fatty acid amide represented by the above formula (C ₁ ) and the following (C ₁₁ ):
(C ₁₁ ) H ₂ N—CO — (— CH ₂ —) _j —CH═CH — (— CH ₂ —) _j —CH ₃ (where j is an integer in the range of 6 ≦ j ≦ 10, j ≠ n);
A resin laminate comprising a plant-derived ethylene-based resin according to claim 6 and a carbon-labeled surface layer which is a mixture with a fatty acid amide represented by the formula:   The fatty acid amide having (C) an unsaturated cis-structured carbon double bond contains a compound having 2 to 4 bonds of unsaturated cis-structured carbon double bonds in the molecular structure. A resin laminate comprising the plant-derived ethylene resin according to claim 1 and a carbon-labeled surface layer.   A resin laminate comprising the plant-derived ethylene resin according to any one of claims 1 to 11, wherein the resin composition further contains a saturated fatty acid amide, and comprising a carbon-labeled surface layer. The polydispersity (Mw / Mn), which is an indicator of molecular weight distribution, of the (A) ethylene / α-olefin copolymer having a density of 912 to 935 kg / m ³ is 1.5 to 9. A resin laminate comprising the plant-derived ethylene-based resin according to any one of 1 to 12 and having a carbon-labeled surface layer. 14. The ethylene / α-olefin copolymer having a density of (A) 912 to 935 kg / m ³ is an ethylene / α-olefin copolymer using a Ziegler-Natta catalyst. A resin laminate comprising a plant-derived ethylene-based resin as described in 1 and comprising a carbon-labeled surface layer.   The plant-derived ethylene-based resin according to any one of claims 1 to 14, wherein the (B) high-density polyethylene has a polydispersity (Mw / Mn) as an index of molecular weight distribution of 4 to 10. And a resin laminate comprising a carbon-labeled surface layer.   The (B) high-density polyethylene is a low-pressure polymerization high-density polyethylene using a Ziegler-Natta catalyst, containing the plant-derived ethylene-based resin according to any one of claims 1 to 15, and carbon-labeled. A resin laminate having a surface layer.   Furthermore, a resin laminated body provided with the carbon-labeled surface layer containing the plant-derived ethylene-type resin of any one of Claims 1 thru | or 16 provided with a barrier layer.   A resin laminate comprising a plant-derived ethylene-based resin according to claim 17 and comprising a carbon-labeled surface layer, wherein the barrier layer is an ethylene / vinyl alcohol copolymer or polyglycolic acid.   Furthermore, the resin laminated body provided with the surface layer by which the plant-derived ethylene-type resin of any one of Claims 1 thru | or 18 provided with a collection layer is carbon-labeled.   A resin laminate comprising a plant-derived ethylene-based resin according to any one of claims 1 to 19 and comprising a carbon-labeled surface layer, comprising a surface layer, a barrier layer, an adhesive layer, and a recovery layer.   A resin multilayer container formed of a resin laminate including the plant-derived ethylene-based resin according to any one of claims 1 to 20 and having a carbon-labeled surface layer.   The resin product according to claim 21, wherein the surface layer, which is a layer made of the resin composition containing (A), (B) and (C), is one or both of the outermost layer and the innermost layer of the resin multilayer container. Multi-layer container.   23. The resin multilayer according to claim 22, which has a layer configuration of outermost layer / barrier layer / adhesive layer / collection layer / innermost layer or outermost layer / adhesive layer / barrier layer / adhesive layer / recovery layer / innermost layer. container.