JPS6195047A - Photodegradable tape - Google Patents

Abstract

PURPOSE:A photodegradable tape for animal attraction that is obtained by adding a nitrile-butadiene rubber containing a specific amount of acrylonitrile to a vinyl chloride resin, thus being rapidly photodegradable after passage of desired days and controllable in its photodegradation rate. CONSTITUTION:(A) 100pts.wt. of a vinyl chloride resin with a polymerization degree of 600-2,500, preferably 700-1,300, preferably polyvinyl chloride, (B) 30-150pts.wt., preferably 60-100pts.wt. of a nitrile-butadiene rubber containing 15-35wt%, preferably 20-35wt% of acrylonitrile, (C) 0-50pts.wt., preferably 5-40pts.wt. of a plasticizer, e.g., 2-ethylhexyl adipate, further, when needed, stabilizers and fillers are kneaded and formed into films of 20-300 micron thickness to give the objective tape. The content of component B and selection of component C, plasticizers enable the tape to be controlled in its photodegradation rate.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a photodegradable tape that rapidly photodegrades after a certain period of time and is useful as a tape for attracting plants.

``Prior art'' Currently, polyethylene is used as a tape for attracting vines and vines of fruits and other plants, and as a bag to prevent pests from fruits.
Tapes made of polypropylene are often used. However, these tapes remain stronger than necessary even after a period of time has passed due to the necessary attraction or bagging, and the reality is that the tape must be removed manually, making this work difficult for those who operate fruit orchards. was complicated and required a considerable amount of effort.

As a tape for attracting, Q per width Losm, 1.5 kg
A tensile strength of -
Easily cut by small impacts. On the other hand, if a paper string such as paper is used for inducement or lending, inducement, 9! The hangings were easily cut before the required period of time, and their fiability diminished during rain, so they had little practical value.

[Problems to be Solved by the Invention] In view of the conventional technology, the inventor of the present invention has conducted intensive studies to develop a photodegradable tape that can be rapidly photodegraded by irradiation with sunlight after a predetermined period of time. Although the strength varies depending on the thickness of the tape, if the thickness is constant, if NBR containing a specific amount of 7-cryloetrile is blended and kneaded with vinyl chloride fan resin, it can be applied immediately after the desired number of days have passed. They discovered that it can be photodecomposed and that the rate of photodecomposition can be controlled by controlling the content of NBR, and have completed the present invention.

That is, an object of the present invention is to provide a photodegradable tape that can be used as a tape for attracting plants, which is rapidly photodegraded by sunlight after a predetermined period of time has elapsed.

``Means for solving the r problem and α'' Therefore, the gist of the present invention is that the degree of polymerization is 600.
~2500 vinyl chloride resin 100 parts by weight, 7crylonitrile content 15~35% by weight NBR20~150
The present invention is a photodegradable tape whose main component is a composition consisting of parts by weight of ffi and 0 to 50 parts by weight of a plasticizer.

In detail, the vinyl chloride resin, which is one component of the photodegradable tape of the present invention, is produced by suspension polymerization, bulk polymerization, or a mixture of vinyl chloride or vinyl chloride and a comonomer copolymerizable therewith. All products manufactured by conventional methods such as micro-suspension polymerization or emulsion polymerization are used. Therefore, examples of comonomers that can be copolymerized with vinyl chloride include vinyl acetate, vinyl propionate,
Vinyl esters such as vinyl laurate, acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, methacrylic esters such as methyl acrylate and ethyl methacrylate, and maleic esters such as butyl maleate and diethyl maleate. , diptyl 7-malate, diethyl 7-malate, etc. 77
- acid esters, vinyl ethers such as vinyl methyl ether, vinyl butyl ether, and vinyl octyl ether, vinyl cyanides such as acrylonitrile and methacrylonitrile, a of ethylene, propylene, styrene, etc.
- Examples include vinylidene halides or vinyl halides other than vinyl chloride such as olefin 11t, vinylidene chloride, and vinyl bromide, and these comonomers are contained in an amount of 30% or less, preferably 20% in the constituent components of the vinyl chloride resin.
It is used in a range of % by weight or less.

Of course, the comonomers are limited to those mentioned above.
-1, but in order to bring the photodegradation period of the tape after NBR kneading closer to the desired constant period, it is preferable to use a vinyl chloride polymer, and the degree of polymerization of the vinyl chloride resin is between 600 and 2500. If the degree of polymerization is lower than 600, for example in the case of calendar processing, the adhesion to the mouth and roll will be large and it will be difficult to separate the film from the roll. , 2500, the shear heat during kneading increases, promoting thermal decomposition of vinyl chloride resin, etc., and making stable production difficult.

NBR, which is a component of the photodegradable tape of the present invention, is obtained by copolymerizing acrylonitrile and butane di,
and the content of acrylonitrile is in the range of 15 to 35% by weight, preferably in the range of 20 to 35% by weight, especially in the range of 25 to 3% by weight.
It may be manufactured by any method as long as it is within the range of 5% by weight.If the acrylonitrile content is lower than 15 parts by weight, the butadiene content will increase, so vinyl chloride-based Compatibility with the resin deteriorates, making uniform kneading difficult. In addition, since the decomposition mechanism of the photodegradable tape of the present invention starts from the double bond of butanoene in NBR, as the content of acrylonitrile increases, the photodegradability inevitably decreases. It is appropriate to keep it at around %.

Therefore, the amount of NBR contained in the photodegradable tape is
Vinyl chloride Q (desirably in the range of 30 to 150 parts by weight per 100 parts by weight of fat, preferably in the range of 60 to 100 parts by weight, if the amount of NBR is less than 30 parts by weight,
There is no doubt that the tape is less likely to be photodegraded and fully exhibits its photodegradable effect.On the other hand, if the tape exceeds 150, the composition constituting the tape becomes soft during the production of the photodegradable tape. If it is too long, even if the tape is obtained, it cannot function satisfactorily as an attraction tape or the like.

The plasticizer contained in the photodegradable tape is not particularly limited as long as it is used for vinyl chloride resin. Specific plasticizers include, for example, di-n-butyl heptalate,
Dihexyl 7-talate (11P), n-octyl 7-talate, 2-ditylhexyl 7-talate (DOP),
Neusooctyl 7talate, octyldecyl 7talate, 7
7-talic acid group plasticizers such as diindecyl tallate (DIDP), butylbenzene 7-talate (BBP), no-2-ethylhexyl isophthalate, or 7-talic acid esters of higher alcohols having about 11 to 13 carbon atoms, trimellitic acid n-octyl-n-decyl, trinoliftic acid tri2
- Trimellitic acid group plasticizers such as ethylhexyl (TOTM), triisodecyl 19mellistate, tri-octyl trinoliftate, di-2-ethylhexyl 7nobate (DO^), non-n-decyl anopinate, 7novin Noisodecyl acid, 7 gelain 1! 11! Fatty acid ester plasticizers such as C-2-ethylhexyl, butyl sebanate, C-2-ethylhexyl sepacate, tributyl phosphate, tri-2-ethylhexyl phosphate, and 2-ethyl phosphate.
Typical examples include phosphate ester plasticizers such as ethylhexyl 7-diol and tricresyl phosphate, and plasticizers obtained by polycondensation of 7-nobic acid and ethylene glycol, 1,3-butanediol, neopentyl glycol, etc. Epoxy plasticizers such as polyester plasticizers, epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil fatty acid-2-ethylhexyl, liquid epoxy resins, etc. are used, and one or more of these can be mixed. used. Among these plasticizers, DOP, DIP, Do
^ etc. have relatively large volatilization loss, DIDP%BBP%TO
It is preferable to select a plasticizer in consideration of the photodegradation period, as photodegradation tends to proceed more quickly than those with relatively low volatilization loss, such as 76M and polyester plasticizers.

Therefore, the amount of plasticizer to be used is appropriately selected depending on the moldability, processability, workability of the photodegradable tape molding composition, the use of the tape, etc. Generally, vinyl chloride resin 1001
! θ ~ 50 weight per part! parts, preferably in the range of 5 to 40 parts by weight. The blending amount of the plasticizer was specified as 0 to 50 parts by weight, but this is because the plasticizer serves as a type of lubricant and improves processability in the blend system of polyvinyl chloride resin and NBR. It is preferable to add 5 parts by weight, and if it exceeds 50 parts by weight, light
This is because the 5° disintegrating tape becomes too soft and tends to lose its tape function.

In order to maintain thermal stability during molding, the photodegradable tape may contain a stabilizer in addition to the above-mentioned essential components.Stabilizers include tin fatty acid salts, tin mercaptide, barium- Zinc-based, lucium-zinc-based, magnesium-
Examples include zinc-based materials, and at least one of these is used. The amount of the stabilizer to be used is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, and preferably 1%, per 100 parts by weight of the vinyl chloride resin.

Furthermore, the photodegradable tape of the present invention can contain a filler, and a preferred filler includes calcium carbonate.

The photodegradable tape of the present invention is manufactured, for example, as follows. After hot tri-blending the vinyl chloride resin, NBR, plasticizer, and if necessary stabilizers, fillers, etc. using a high-speed stirrer, etc., the composition was uniformly stirred using a Banbury mixer, and then the composition was stirred uniformly using a calender roll at a roll temperature of about 180°C. After kneading, the film is slit to a required width by a molding method such as calender roll, extrusion, or in-seven lamination to form a photodegradable tape. The thickness of the photodegradable tape varies depending on its use, but it is preferably in the range of 20 to 300 μm for functionality and handling reasons. If it is thinner than 20 μm, it will not be able to fully demonstrate its function as a tape, and it will not function properly. If the tape becomes thicker, the period required for photodegradation becomes extremely long, so that it cannot function as a photodegradable tape.

To explain the photodegradable tape of the present invention more specifically, for example, 100 parts by weight of vinyl chloride resin with a degree of polymerization of 1050 and D
It takes one year for a 100 μ thick film made of 50 parts by weight of O^ to have a tensile elongation of 10% or less and a residual tensile strength of 10% or less, but this includes 7crylonitrile. If 50 parts by weight of NBR with a ratio of 33% is added, the period will be shortened to 3 months, and if 100 parts by weight of the same NBR is added, the period will be 2 months. Therefore, through some preliminary tests by adjusting the amount of NBR added, it was found that 1% of light irradiation
It is possible to know the period during which the decomposition phenomenon occurs in a crisis, and to control the photodegradation period of the film.Furthermore, by utilizing this phenomenon, it is possible to create a photodegradable tape that suddenly loses its function as a tape after a desired period of time. In addition, the function of photodegradable tapes varies depending on the wall thickness, type of plasticizer, etc., but in any case, the period during which decomposition occurs can be determined through some preliminary testing. That makes me feel better.

When this phenomenon is utilized in a tape for attracting plants, the photodegradable tape retains its function as a tape until the attraction agent liI is reached, and once the attraction period has passed, it is rapidly photodegraded, eliminating the need to remove the tape.

"Effects of the Invention" The tNA destructible tape of the present invention is decomposed by sunlight after 4 to 6 months of outdoor exposure, and its strength and function as a tape are lost. Therefore, the use of the photodegradable tape of the present invention eliminates the need to manually remove the tape after a predetermined period of time required for attracting plants or hanging bags. Its utility value as a tape is extremely high.

"Example" Next, the photodegradable tape of the present invention will be described in detail in Examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 Polyvinyl chloride (average degree of polymerization f'=1050) 10011 parts DOA, 2G epoxidized soybean oil 3 Ba-Zn stabilizer 2 Lubricant (stearic acid) 3 Calcium carbonate
5O NBR (7crylonitrile content 33%) 1 (t.

The above compound number was mixed with high-speed stirring, then kneaded with a calendar roll at a roll temperature of 180°C, and the kneaded composition was formed into calendered films with various wall thicknesses <50μ, 100μ, 300μ, 500μ). This was used as a test piece. A sunshine weatherometer irradiation test is performed on the test piece.
ζゝ Fig. 1 is a graph showing the results, where the horizontal axis shows the fill at the time of sunshine weatherometer irradiation ($ ambient temperature 40°C), and the vertical axis shows the tensile strength (kg/am).

Also, when 00^ is replaced with polyester plasticizer, 1
The relationship between irradiation time and tensile strength at 00μ is shown in FIG. The horizontal and vertical axes in FIG. 2 have the same meanings as in FIG.

As is clear from FIG. 1, the photodegradable tape of the present invention is
It can be seen that the tensile strength decreases extremely after a certain period of time has passed, and that the decomposition time differs depending on the wall thickness for the same composition.

Therefore, in manufacturing the photodegradable tape of the present invention, the composition and wall thickness can be adjusted by determining the composition and wall thickness through some preliminary experiments.

Furthermore, from FIG. 2, it can be seen that the photodegradation rate of the photodegradable tape varies depending on the type of plasticizer, and that the type of plasticizer is also an important factor in determining the composition of the tape.

Examples 2 to 5, Comparative Examples 1 to 3 In Example 1, the amounts of DO^ and NBR used were changed as shown in Table 1 (next page) to keep the hardness of the vinyl chloride resin composition constant. After that, an outdoor exposure test was conducted on the photodegradable tape with a wall thickness of 100μ manufactured in the same manner as in Example 1, and the relationship between the number of exposure days and the tensile strength is shown in Figure 3. The relationship is shown in Figure 4. The horizontal axis in Figure 3 is expressed as the number of days of exposure.
Shows the same meaning as the figure.

Figures v&3 and 4 show that there is a clear correlation between the number of exposure days and the sunshine weatherometer irradiation time.

A photodegradable tape using a composition whose hardness was kept constant by changing the amount of plasticizer and DO added did not show photodegradation when the amount of NBR was 10 parts by weight per 100 parts by weight of vinyl chloride resin (Comparative Example 1). It takes a long time to process, and its value as a tape for attracting plants is extremely small.However, NBR30-150
The timing at which photodegradation of the tape occurs is almost clearly visible between 1 part and 1 part weight, and it is understood that it is possible to manufacture a tape that can be induced for a desired period by adjusting the amount of NBR. NBR
Those containing 200 parts by weight or more of NBR, or those containing only NBR, do not have enough initial strength (1.5 kgh theory) to be used as an attraction tape, and cannot be photodegradable tapes. is obvious.

Examples 6 to 8, Comparative Examples 4 to 5 Table 2 (next page) shows the relationship between the degree of polymerization of vinyl chloride resin, roll tackiness, and decomposition time using Brabender Plastogra 7. Furthermore, the relationship between the number of exposure days and the tensile strength of a tape with a thickness of 100 μm is shown in FIG.

Roll adhesion and decomposition time indicate the difficulty of forming the photodegradable tape, and the former is 0 (no adhesion).
Evaluation was made on the 4a floor of −〇−Δ−× (adhesive), and the latter was expressed as the time until decomposition (carbonization time).

The roll crosstalk temperature is 180℃, the plastic bender conditions are cell temperature 180℃, rotation speed 10Or, p, m, and charging amount 5.
It was shot at 5g/batch.

In addition, the blending composition is as follows: vinyl chloride resin 100 parts by weight 11 parts DOA

2 Phaeboquinated soybean oil 6 8a-Zo stabilizer 2 Lubricant
2 Calcium carbonate 5ONBR (AN3
3%) 6G Table 2 As is clear from Table 2, when p is about 400, the roll adhesion becomes poor, and when it exceeds 3000, decomposition occurs in a short period of time, so it is difficult to use as a photodegradable tape. It is unsuitable for this purpose.

[Brief explanation of the drawing]

FIG. 1, FIG. 2, FIG. 3, FIG. 4, and FIG. 5 are graphs showing changes in tensile strength as a function of light irradiation time or exposure days of the photodegradable tape, respectively. Patent applicant 3i! ! 4. Agent for Nsanto Vinyl Co., Ltd. Patent attorney Long diameter - (1 idiot)

Claims (2)

[Claims] (1) Vinyl chloride resin with a degree of polymerization of 600 to 2500 10
0 parts by weight, nitrile-butadiene rubber (hereinafter referred to as NBR) with an acrylonitrile content of 15 to 35% by weight 30
A photodegradable tape whose main component is a composition consisting of ~150 parts by weight and 0 to 50 parts by weight of a plasticizer. (2) Claim 1 in which the wall thickness is 20 to 300μ
Photodegradable tape as described in Section 1.