JP2017218511A - Temperature-time accumulated history display composition and temperature-time accumulated indicator using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a temperature-time accumulated history display composition which gives an indicator capable of recognizing an accumulated history of a temperature and a time by visual sensation, and to provide a temperature-time accumulated indicator using the same.SOLUTION: A temperature-time accumulated history display composition contains a polyvinylidene chloride resin and a basic compound. Preferably, the basic compound is at least one selected from the group consisting of an alkali metal hydroxide and amine. Preferably, the amine is piperidine. A temperature-time accumulated indicator includes the composition. Preferably, the indicator has a laminate containing a resin layer containing the polyvinylidene chloride resin and a layer containing the basic compound. Preferably, in the indicator, a region containing the polyvinylidene chloride resin and a resin containing the basic compound are separated to each other through a peelable junction.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a temperature-time integration history display composition and a temperature-time integration indicator using the composition.

  Conventionally, it has been studied to use a substance having a change in color tone as a time-delay indicator composition. For example, a time-indicating agent composition comprising a mixture of a developer such as a vinylidene chloride polymer compound, an electron-donating color-forming organic compound, and a desensitizer is known (Patent Document 1). ).

Japanese Patent Laid-Open No. 06-122863

  The invention described in Patent Document 1 relates to a time-determining indicator composition that uses a change in color tone of a colored or color-forming organic compound, etc., so that the reaction that gives the change in color tone is not affected by environmental conditions such as temperature. Making it a part of the problem.

  By the way, in the preservation of fresh food, etc., the temperature is not always kept constant, and the desired temperature may be reduced due to the frequency of switching the refrigerated or frozen storage device, power failure, human error in temperature setting, etc. There may be cases where it is not maintained. For this reason, there is a demand for easily recognizing an integration history that takes into account temperature as well as time. However, in the conventional aging indicator composition as described in Patent Document 1, the passage of time can be visually recognized, but it is extremely difficult to visually recognize the accumulated history of both temperature and time. there were.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a temperature-time integration history display composition that provides an indicator capable of visually recognizing the integration history of temperature and time, and to use this composition. To provide a temperature-time integration indicator.

  The present inventors have found that the above problems can be solved by combining a polyvinylidene chloride resin and a basic compound, and have completed the present invention.

  The first aspect of the present invention is a temperature-time integration history display composition containing a polyvinylidene chloride resin and a basic compound. The basic compound is preferably at least one selected from the group consisting of alkali metal hydroxides and amines. The amine is preferably piperidine.

  The second aspect of the present invention is a temperature-time integration indicator comprising the composition. The indicator preferably includes a laminate including a resin layer containing the polyvinylidene chloride resin and a layer containing the basic compound. In the indicator, it is also preferable that the region containing the polyvinylidene chloride resin and the region containing the basic compound are separated by a peelable joint.

  ADVANTAGE OF THE INVENTION According to this invention, the temperature-time integration history display composition which provides the indicator which can recognize the integration history of temperature and time visually, and a temperature-time integration indicator using the same can be provided.

In Examples 1-5, it is a graph which shows the result of having measured the change of the Hunter whiteness accompanying progress of storage days. It is a top view which shows typically the temperature-time integration | stacking indicator used in Example 10. FIG.

<Temperature-time integration history display composition>
The temperature-time integration history display composition according to the present invention contains a polyvinylidene chloride resin and a basic compound. By using a combination of a polyvinylidene chloride resin and a basic compound, the composition can provide an indicator that can visually recognize the accumulated history of temperature and time.

[Polyvinylidene chloride resin]
In the temperature-time accumulation history display composition according to the present invention, the polyvinylidene chloride resin (hereinafter also referred to as “PVDC”) may be a homopolymer of vinylidene chloride, but is usually 60 to 98% by mass of vinylidene chloride. And 2 to 40% by mass of another monomer copolymerizable with vinylidene chloride. Examples of other monomers copolymerizable with vinylidene chloride include, for example, vinyl chloride; alkyl acrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and lauryl acrylate (alkyl group having 1 to 18 carbon atoms). ); Methacrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate, lauryl methacrylate (C1-C18 of alkyl group); Vinyl cyanide such as acrylonitrile; Aromatic vinyl such as styrene; Carbon number such as vinyl acetate 1 to 18 vinyl esters of aliphatic carboxylic acids; alkyl vinyl ethers having 1 to 18 carbon atoms; vinyl polymerizable unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid; maleic acid, fumaric acid and itaconic acid Alkyl esters of vinyl polymerizable unsaturated carboxylic acids such as It includes, and the number 1 to 18), and carbon atoms in the alkyl group. More preferably, it is at least one selected from the group consisting of vinyl chloride, methyl acrylate or lauryl acrylate. Other monomers copolymerizable with vinylidene chloride may be used alone or in combination of two or more. The copolymerization ratio of the other monomer is more preferably 3 to 35% by mass, still more preferably 3 to 25% by mass, and particularly preferably 4 to 22% by mass. When the copolymerization ratio of the other monomer is 2 to 40% by mass, it is easy to maintain good melt processability and stability. PVDC may be used alone or in combination of two or more in order to improve melt processability. PVDC can be synthesized by any polymerization method such as a suspension polymerization method, an emulsion polymerization method, or a solution polymerization method.

[Basic compounds]
In the temperature-time integration history display composition according to the present invention, the basic compound accelerates the dehydrochlorination reaction of the polyvinylidene chloride resin, thereby causing color development. Color development progresses with time, and it tends to progress as the temperature increases. Therefore, by measuring the change in color tone of the composition, it is possible to visually recognize the accumulated history of temperature and time. A basic compound can be used individually or in combination of 2 or more types.

It does not specifically limit as a basic compound, For example, an alkali metal hydroxide and an amine are mentioned. It does not specifically limit as said alkali metal hydroxide, For example, sodium hydroxide, potassium hydroxide, etc. are mentioned, Sodium hydroxide is preferable from viewpoints, such as handleability, availability, and cost. The amine is not particularly limited, and examples thereof include alicyclic amines, acyclic aliphatic amines, and aromatic amines, and alicyclic amines are preferable from the viewpoint of safety and the like. Carbon number in the said amine is not specifically limited, For example, it is 1-10, Preferably it is 2-8, More preferably, it is 3-6. The total number of amino groups (that is, —NH ₂ ) and substituted amino groups (groups obtained by substituting hydrogen atoms of amino groups with organic groups) in the amine is not particularly limited, and is, for example, 1 to 3 Preferably, it is 1 or 2. More preferably, it is 1. The amine may have a substituent. The substituent is not particularly limited, and examples thereof include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; nitro group and the like. The amine may have a hetero atom in the carbon chain. The alicyclic amine is not particularly limited, and examples thereof include piperidine, morpholine and the like, and piperidine is preferable from the viewpoint of reactivity and the like. The acyclic aliphatic amine is not particularly limited, and examples thereof include trimethylamine and triethylamine. Trimethylamine is preferable from the viewpoint of reactivity and the like. The aromatic amine is not particularly limited, and examples thereof include aniline. In particular, the amine is preferably piperidine from the viewpoint of reactivity and the like.

  In the temperature-time integrated history display composition according to the present invention, the amount of the basic compound is not particularly limited, but is 0.01 to 20 parts by mass, for example, with respect to 100 parts by mass of the polyvinylidene chloride resin. From the viewpoint of properties and the like, it is preferably 0.03 to 15 parts by mass, and more preferably 0.05 to 15 parts by mass.

[Other ingredients]
The temperature-time integration history display composition according to the present invention may contain other components as long as the effects of the present invention are not impaired. Examples of other components include solvents; known additives such as heat stabilizers; and other resins.

(solvent)
For example, the solvent is added to the temperature-time accumulation history display composition according to the present invention as necessary in order to dissolve the basic compound and / or disperse the polyvinylidene chloride resin. It does not specifically limit as a solvent, For example, an organic solvent, water, etc. are mentioned. It does not specifically limit as an organic solvent, For example, alcohol, such as ethanol, etc. are mentioned. From the viewpoint of solubility of the basic compound, when an alkali metal hydroxide is used as the basic compound, the solvent is preferably water, and when an amine is used as the basic compound, the solvent is preferably ethanol.

(Additive)
When the additive is used in the form of a polyvinylidene chloride resin, for example, in the form of a film containing a polyvinylidene chloride resin, in the form of a fragment of the film, or in the form of a pulverized product of the film, To be added. Examples of the additive include a heat stabilizer, a plasticizer, a processing aid, a colorant, an ultraviolet absorber, a pH adjuster, and a dispersion aid added for the purpose of improving various properties and moldability of the film. And various other additives.

(Other resins)
Other resins include various characteristics of the film when the polyvinylidene chloride resin is used, for example, in the form of a film containing the polyvinylidene chloride resin, in the form of a fragment of the film, or in the form of a pulverized product of the film. And for the purpose of improving the moldability, it is added to the film as necessary. Examples of other resins include polyethylene wax, oxidized polyethylene wax, polyethylene (low density polyethylene or high density polyethylene), ethylene-vinyl acetate copolymer, homopolymer or copolymer of acrylate ester, and methacrylate ester. A homopolymer or a copolymer, a methyl methacrylate-butadiene-styrene copolymer, etc. are mentioned.

[Form of composition and production method]
The form of the temperature-time integrated history display composition according to the present invention is not particularly limited as long as the polyvinylidene chloride resin and the basic compound are combined. For example, the polyvinylidene chloride resin and the basic compound A laminate comprising a resin layer containing a polyvinylidene chloride resin and a layer containing a basic compound; a region containing a polyvinylidene chloride resin and a region containing a basic compound are separated via a peelable joint And a structure isolated from each other.

  In the above mixture, examples of the form of the polyvinylidene chloride-based resin include a pulverized product of a film containing the polyvinylidene chloride-based resin. In the above structure, examples of the basic compound include a solution of the basic compound. The said mixture can be obtained by mixing a polyvinylidene chloride resin and a basic compound by a well-known method.

  Examples of the laminate include a laminate in which a resin layer containing a polyvinylidene chloride-based resin and a layer containing a basic compound are laminated adjacently, a resin layer containing a polyvinylidene chloride-based resin, and a basic compound. A layered product in which a layer containing the material is laminated via an intervening layer can be given. In the laminate, examples of the resin layer include a film containing a polyvinylidene chloride resin. The thickness of the polyvinylidene chloride resin film is not particularly limited, and is, for example, 5 to 15 μm. Examples of the layer containing the basic compound in the laminate include filter paper impregnated with the solution of the basic compound. Examples of the intervening layer include a film containing a resin other than a polyvinylidene chloride resin. Specifically, a film containing a linear low density polyethylene, a film containing an ethylene vinyl acetate copolymer, ethylene acrylic Examples thereof include a film containing an acid methyl copolymer and a film containing Ionomer. The intervening layer may be composed of one layer or may be composed of two or more layers. The laminate includes, for example, laminating a film containing a polyvinylidene chloride resin and a filter paper impregnated with the basic compound solution, or a laminate comprising a film containing a polyvinylidene chloride resin and the intervening layer. And the filter paper impregnated with the solution of the basic compound can be obtained by laminating so that the intervening layer and the filter paper are in contact with each other.

  In the structure, the forms of the polyvinylidene chloride resin and the basic compound are the same as those described for the mixture. For example, the structure is separated by dividing the inside of a bag made of a transparent barrier film into two regions, putting polyvinylidene chloride resin in one region, and weakly sealing the boundary between the two regions. After forming a possible joint, it can be obtained by putting a basic compound in the other region, and sealing and sealing the bag.

  In any form, as a raw material for the polyvinylidene chloride-based resin, offcuts generated in the process of manufacturing a film containing the polyvinylidene chloride-based resin can be used. Such offcuts are usually discarded, but in the present invention, resource saving is achieved through effective utilization of the offcuts as raw materials, and the temperature-time integrated history display composition is realized at low cost. Objects and temperature-time integration indicators using the same can be manufactured.

<Temperature-time integration indicator>
The temperature-time integration indicator according to the present invention comprises the temperature-time integration history display composition according to the present invention. In the said indicator, by providing the said composition composition, it becomes possible to recognize the integration history of temperature and time visually.

  In one embodiment (hereinafter, also referred to as “embodiment 1”), the indicator includes a laminate including a resin layer containing the polyvinylidene chloride resin and a layer containing the basic compound. In the indicator according to the first embodiment, the polyvinylidene chloride resin and the basic compound form the laminate described in the section of “form of the composition”, and the indicator produces, for example, the laminate. Optionally, the laminate can be obtained by hermetically packaging with a transparent barrier film.

  In another embodiment of the indicator (hereinafter, also referred to as “embodiment 2”), the region containing the polyvinylidene chloride resin and the region containing the basic compound are connected via a peelable joint. Isolated. In the indicator according to the second embodiment, the polyvinylidene chloride resin and the basic compound form the structure described in the section of “form of the composition”, and the indicator is similar to the structure, for example. Can be manufactured. In the indicator according to the second embodiment, since the polyvinylidene chloride resin and the basic compound are isolated, each component can be stably stored until the detection of the accumulated history of temperature and time is started. it can. Since it is a peelable joint that separates the polyvinylidene chloride resin and the basic compound, the joint can be easily peeled off by applying force from the outside of the structure. As a result, the polyvinylidene chloride resin and the basic compound are mixed, and the color tone change can be started at a desired time.

  The temperature-time integration indicator according to the present invention visually stores the integration history of the temperature and time received by the object by storing it together with the object, for example, when storing the object such as fresh food. Can be used to recognize. The temperature range that can be detected by the indicator is not particularly limited, and examples thereof include −40 to 60 ° C., and preferably −30 to 50 ° C.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, the scope of the present invention is not limited to these Examples.

[Examples 1 to 9]
A 2.5 cm square filter paper is impregnated with 0.5 ml of the basic compound solution shown in Table 1, and a 2 cm square PVDC film (NEW Kurelap, Kureha Co., Ltd., thickness: 10 μm) is placed on the filter paper. Transparent barrier film made into a bag of 3.5 cm (laminated film in which 13 μm GL, 15 μm Ny, and 80 μm CPP are laminated in this order via an adhesive layer, GL: transparent vapor deposition film manufactured by Toppan Printing Co., Ltd. Ny: nylon, CPP: unstretched polypropylene) and hermetically packaged. The resulting package was exposed to the temperatures shown in Table 1 and examined for color change. For color change, use a color difference meter SE6000 manufactured by Nippon Denshoku Industries Co., Ltd. and measure Hunter whiteness (W = 100-((100-L * 2) + a * 2 + b * 2) 1/2) over time. It was quantified. More specifically, the Hunter whiteness was plotted against the storage days, and the absolute value of the slope of the obtained graph was used as the reaction speed, which was used as an index of color tone change. The results are shown in Table 1. In addition, about Examples 1-5, the said graph was each shown to Fig.1 (a)-(e).

[Example 10]
A temperature-time integration indicator schematically shown in FIG. 2 was produced. That is, first, the edges of the two transparent barrier films were strongly sealed (relative seal strength: 10) to produce a transparent barrier film bag. 0.1 g of a pulverized product of a PVDC film (Kureha Co., Ltd. Kurewrap, thickness: 10 μm) was put on the inner side of the bag, and the center of the bag was weakly sealed (relative seal strength: 5). 100 μl of 10% by mass piperidine solution (solvent is ethanol) was added to the front side of the inside of the bag, and the bag mouth was tightly sealed and sealed to produce a temperature-time integrating indicator. The region where the piperidine solution was sealed was pushed strongly, the weak seal at the center was broken, and the pulverized product and the piperidine solution were brought into contact with each other to initiate the reaction. After the start of the reaction, the indicator was stored in a freezer at −20 ° C. and the color change was measured in the same manner as described above. As a result, the reaction rate was 4.6. As a result of measuring the color tone change in the same manner as above except that the temperature was changed from -20 ° C to -40 ° C and -60 ° C, the reaction rates were 0.57 and 0.1, respectively.

[Example 11]
A multilayer barrier film (VLDPE (3 μm) / EVA (22 μm) formed by impregnating 0.5 cm square filter paper with 0.5 ml of a 1 mass% piperidine solution (solvent: ethanol) and making a bag of 3.5 cm × 3.5 cm. ) / EMA (1.5 .mu.m) / PVDC (7 .mu.m) / EMA (1.5 .mu.m) / EVA (10 .mu.m) / Ionomer (10 .mu.m), manufactured so that the surface on the Ionomer side is in contact with the filter paper. VLDPE: linear low density polyethylene, EVA: ethylene vinyl acetate copolymer, EMA: ethylene methyl acrylate copolymer, /: adhesive layer) and hermetically packaged. The obtained package was stored at 37 ° C., and the color change was examined in the same manner as described above. As a result, the reaction rate was 4.8.

  The filter paper is in contact with the ionomer in the multilayer barrier film, and the piperidine solution is presumed to have penetrated the ionomer layer, the EVA layer, and the EMA layer and reached the PVDC layer.

Claims (8)

  A temperature-time integration history display composition containing a polyvinylidene chloride resin and a basic compound.   The composition according to claim 1, wherein the basic compound is at least one selected from the group consisting of alkali metal hydroxides and amines.   The composition of claim 2, wherein the amine is piperidine.   A temperature-time integration indicator comprising the composition according to any one of claims 1 to 3.   The indicator of Claim 4 provided with the laminated body containing the resin layer containing the said polyvinylidene chloride type-resin and the layer containing the said basic compound.   The indicator according to claim 5, wherein in the laminate, a resin layer containing the polyvinylidene chloride-based resin and a layer containing the basic compound are laminated adjacent to each other.   The indicator according to claim 5, wherein in the laminate, a resin layer containing the polyvinylidene chloride resin and a layer containing the basic compound are laminated via an intervening layer.   The indicator according to claim 4, wherein the region containing the polyvinylidene chloride-based resin and the region containing the basic compound are separated via a peelable joint.

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