JPS58125737A - Vinyl chloride resin film for agricultural purpose - Google Patents

Abstract

PURPOSE:The titled film that contains a combination of trixylenyl phosphate and a specific triazole, thus being suitable for use in covering greenhouses, because of its improved weather resistance, free from deterioration such as discoloration of embrittlement, especially deterioration on window cross supports. CONSTITUTION:A combination of trixylenyl phosphate with at least one from compounds of formulaI(R1 is 4-18C alkyl) and formula II (R2 is 5-13C alkyl; R3 is 1-18C alkyl; X is H, halogen, alkyl, alkoxy, aryloxy, aralkyloxy, aryl) is added to a vinyl chloride resin and the resultant composition is made into a film. Further addition of a compound of formula III (m is 1-5; X is 0-4, satisfying the relationship of m+x<6; R4 is halogen; R5, R6 are 1-24C alkoxy; y, z are 1-4 where at least one ortho-position in the phenyl ring has no substituent) is preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to agricultural vinyl chloride resin films, and more particularly, to prevent undesirable deterioration phenomena such as discoloration and embrittlement caused by stretching outdoors, especially
This invention relates to an agricultural vinyl chloride resin film with improved weather resistance so that so-called "on-board deterioration" is less likely to occur.

In recent years, farmers cultivating useful plants have widely adopted methods of promoting or suppressing cultivation of useful plants in greenhouses or tunnels for the purpose of improving profitability.

As materials for covering the house or tunnel, polyethylene films, ethylene-vinyl acetate copolymer films, vinyl chloride resin films, etc. are used.

Among them, vinyl chloride resin films have better light transmittance, heat retention, mechanical strength, and
It is widely used because it has the best overall durability, workability, economy, etc.

However, synthetic resin films used to cover greenhouses or tunnels, including vinyl chloride resin films, can become susceptible to sunlight, especially ultraviolet rays, after a year has passed since they were first used. Deterioration or
This causes changes over time such as a decrease in flexibility. Furthermore, recent labor-saving agricultural techniques require coating materials to withstand even more severe conditions than in the past.

In order to eliminate the above-mentioned drawbacks, vinyl chloride resin films used for covering houses or tunnels contain, for example, organic tin stabilizers, metal soap stabilizers, lead stabilizers, etc.
Additives to improve resistance to light, heat, oxidation, etc., such as organic barium stabilizers, antioxidants, and ultraviolet absorbers, are often added. However, to date, there has been no evidence that a small amount of addition produces a noticeable effect.

Some of the above additives can improve the rigidity of the film if added in large amounts, but on the other hand, they may affect workability during film formation, ease of handling after film formation, etc. This causes a problem of lowering the transparency of the film.

For example, if a large amount of metal soap stabilizer is added, plate-out (additives precipitating on the roll surface when forming into a film by calendar molding) may occur during film formation, reducing the film-forming work efficiency. and significantly reduce the appearance and transparency of the film.

In addition, epoxy compounds and organic phosphite esters have the effect of improving the weather resistance of films to some extent, but
There is a limit to the amount that these can be blended. If a large amount is added, bleed-out (various additives blowing out on the film surface) will occur, and the films will adhere to each other, making it difficult to peel off the adhered films, resulting in poor releasability. ).

Furthermore, organic phosphoric acid esters are also effective in improving the weather resistance of the film when added in small amounts, but when added in excess of a certain amount, tricresyl 7 phosphate reduces the weather resistance and at the same time reduces the heat resistance.

By the way, when constructing a house or a tunnel, a method is adopted in which a frame is made from aggregate prepared from wood, metal, synthetic resin, etc., and the frame is covered with a synthetic resin film and fixed at necessary points. Deterioration of synthetic resin film occurs in areas that are in contact with fixing devices such as frames that fix the film (referred to as ``on-piece deterioration''), and in areas that are not in contact with the fixing devices (referred to as ``flat surface deterioration''). (referred to as "partial deterioration")
This is remarkable compared to . For this reason, the lifespan of the film is
The film is significantly affected by the presence or absence of "deterioration on the pier", and even if "deterioration on the flat surface" is small, when the ``deterioration on the pier'' is a dog, the film is often torn and problems occur.

7- Recently, there is a strong tendency for greenhouse cultivation to increase the size of greenhouses.
In the case of large greenhouses, metal materials are used as aggregate. In the case of aggregates made of metal materials, there is a problem in that "deterioration on crosspieces" occurs more easily than in the case of aggregates made of wood or synthetic resin materials. When used as a covering material for a house or tunnel, "plane part deterioration"
As a result of extensive research, we have developed the present invention with the aim of providing a vinyl chloride resin film for the blind industry that does not cause the peeling to easily deteriorate, but also prevents "deterioration on the board." It has been completed.

However, the gist of the present invention is that vinyl chloride is
1RBWK, (A) Trixylenyl 7m 7ate,
and (B) General formula [In formula (1), RI is the number of carbon atoms
8- Indicates a kill group. ] or C(II)
In the formula, R2 is an alkyl group having 1 to 73 carbon atoms, R
3 represents an alkyl group having 7 to 1 g carbon atoms, and X represents hydrogen, halogen, an alkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, or an aryl group. The present invention provides an agricultural vinyl chloride resin film with excellent weather resistance, which is made by blending seven or a combination of two or more of the compounds represented by the following and forming the film into a film.

The present invention will be explained in detail below.

In the present invention, the vinyl chloride resin includes not only polyvinyl chloride but also copolymers containing vinyl chloride as a main component. Monomers that can be copolymerized with vinyl chloride include vinylidene chloride, ethylene, propylene,
Examples include acrylonitrile, maleic acid, itaconic acid, acrylic acid, methacrylic acid, vinyl acetate, etc., but are not limited to the examples.

Vinyl chloride resins can be produced using suspension polymerization, emulsion polymerization, and emulsion polymerization.
It may be manufactured by any conventionally known manufacturing method such as suspension polymerization, solution polymerization, and bulk polymerization.

In the present invention, tricylenyl phosphate is blended into the vinyl chloride resin as component (A).

Trixylenyl phos-7 ethane can be produced from a phenol fraction containing xylenol as a main component. Xylenol has six types of isomers depending on the positions of the two methyl groups. When producing tricylenyl phosphate, each isomer component is reacted with phosphorus oxychloride without fractional distillation. Trixylenyl phosphate is therefore obtained as a mixture of compounds containing xylenyl groups with substituents in different positions.

According to the inventor's experiments, among the xylenyl group isomers of trixylenyl phosphate, -13 xylenyl group, 3. If the ratio of the xylenyl group-containing compound (total of both ministries) is equal to or higher than -C30M relative to the total amount of the isomer mixture, the flexibility of the agricultural vinyl chloride resin film can be maintained for a long period of time. It turns out.

If the amount of t in component (A) added to the vinyl chloride resin is too low, it cannot be expected to improve the weather resistance of the intended film, especially for improving the "deterioration on the crosspiece", and on the other hand, if it is too high, the film production will be affected. Problems such as plate-out problems occur when the film is used, the tackiness of the resulting film is too high, and heat resistance is reduced. A preferred blending ratio is in the range of 7 to 10 parts by weight per 100 parts by weight of the resin.

In the present invention, (A)
In addition to blending the ingredients, component (B) is further blended.

Among the components (B), the compounds represented by the general formula (f) include λ-(,2'-hydroxy-I-tert-butylphenyl)benzotriazole, r-(,2
'-Hydroxy-j'-tetramethylbuty-11-luphenyl)penztriazok,J-(,!'-
Examples include hydroxy-j'-amylphenyl)penztriazole, co(+2'-hydroxy-j'-n-hexylphenyl)benzotriazole, λ-(2'-hydroxy-j'-cyclohexylphenyl)benzotriazole, etc. It will be done. However, the examples of these compounds do not limit the present invention. Among component (B), compounds represented by general formula (I[) include the following compounds. However, the examples of these compounds do not limit the present invention.

Compound/.

Compound J 12- Compound 3゜ compound kyu It's a compound Compound 6゜ Compound 7 Compound.

The component (B) to be added to the vinyl chloride resin has the general formula (1
) or (II), seven types or two or more types. When using 7 types, any one of the compounds represented by formula (1) or (11) may be used.When using 1.2 or more types, the compounds represented by formula (1) and (old formula) can be It is preferable to use the ridge.

If the amount of component (B) added to the vinyl chloride resin is too small, there will be a significant decrease in flexibility during outdoor expansion during the second stage of the film.On the other hand, if it is too large, there will be a large amount of bleed-out when the film is used. transparency is also reduced. If there are many particles that bleed out, the surface of the film becomes easily stained and the transparency deteriorates more quickly, which is undesirable.

A suitable blending ratio is 0.3 to 3 parts by weight of the vinyl chloride resin.

In the present invention, it is essential to blend the above-mentioned (A) component and (B) component into the vinyl chloride resin, but if the (0) component represented by the general formula 1D is further blended, the film control Improves weather resistance and maintains UV shielding effect.
Furthermore, it is possible to prevent coloring and decrease in flexibility.

Examples of compounds represented by the general formula [phase] formula that can be used as component (0) include the following compounds. However, the exemplification of these compounds is not intended to limit the invention.

Bis(≠-methoxyphenyl)phthalate, bis(+-
1-butylphenyl) phthalate, bis(,2-ethoxy-+-1-butylphenyl) isophthalate, bisC
4t(/,/,3.3-tetramethylbutyl)phenyl]phthalate, bis(2,≠-di-n-amylphenyl)terephthalate, bis(4+!-isodecylphenyl)isophthalate, bis(,2-nonyl) phenyl) inphthalate, bis(3-nonylphenyl) inphthalate, bis(kunonylphenyl) isophthalate, bis[3(/,/-dimethyloctoxyl)phenyl coisophthalate, his(2,3゜g, j- Tetramethoxyphenyl) terephthalate, bis(3-octoxyphenyl) terephthalate, bis(rla-di-n-hexylphenyl) terephthalate, bis(-2-methoxy-≠
-1-butylphenyl)isophthalate, bis(3-impropoxyphenyl)isophthalate, bis(4t-
t-butylphenyl) 3,4t-dichlorophthalate,
Bis(!-1-butylphenyl)cuoctadecoxyisophthalate, bisCF (/, /, 3.3-tetramethylbutyl)phenyl]terephthalate, bis(≠-t
-butylphenyl)gubromoisophthalate, bis(4t-tetramethylphenyl)inphthalate, bis(l/L(2-ethylhexyl)phenyl]3゜'+,
j, A-tetrachlorophthalate, bis(Hiro-octadecylphenyl)isophthalate, bis(2,3,'I-
tridecylphenyl) inphthalate, bis(≠-t-
butylphenyl)11. , O-di-t-butyl isophthalate, Bis(3-butylphenyl) O-octadecyl inphthalate, Bis(Hiro-ethoxyphenyl) 6-dozosylisophthalate, Bis[3(/-ethyl-/-methylpentyl) ) phenyl] O-hexadecyloxyisophthalate, [4(/,/,3.3-tetramethylbutyl)phenyl) (,2,3,II,3-tetramethylphenyl)inphthalate), (4'- t-7” tylphenyl) (4t-methylphenyl) isophthalate,
tris(4L-t-butylphenyl) trimellitate,
Tris[g(i,i,3.3-tetramethylbutyl]phenyl]trimerite),! , Is (3-nonylphenyl) trimesate, tris (J, 1.t-diyneamylphenyl) trimezate, tris (couhexadecylphenyl) trimellitate, tris (4t-octadecylphenyl) trimezate, tris (3-imbutoxy) phenyl) trimesate, tris(≠-t-7” tylphenyl) hemimelisate, tris[Hiro(/, /, 3.3-
Tetramethylbutyl)phenyl]hemimellitate, tris(3-isopropyloxyphenyl)trimesate,
Tris(,2-n-butylphenyl)trimesate, (
≠-t-butylphenyl)bis(3-impropoxyphenyl)trimesate.

The amount of component (0) added to the vinyl chloride resin is 9 to 10 parts by weight or less, particularly preferably 0.3 to 10 parts by weight, per 100 parts by weight of the vinyl chloride resin.

The agricultural vinyl chloride resin according to the present invention is one in which the above-mentioned (A) component, (B) component, and if necessary, the (0) component are added and blended. Other additives such as plasticizers, lubricants, antifogging agents, heat stabilizers, pigments and dyes, etc. can be added.

Examples of plasticizers that can be used include phthalic acid derivatives such as di-n-octyl phthalate, di-2-ethylhexyl phthalate, dibenzyl phthalate, diisodecyl phthalate, didodecyl phthalate, and diisodecyl phthalate; isophthalic acid derivatives such as diisooctyl isophthalate; Acid conductors; adipic acid derivatives such as di-n-butyl adipate and dioctyl adipate; maleic acid derivatives such as di-n-butyl maleate; citric acid derivatives such as tri-n-butyl citrate; itaconic acid derivatives such as motuputyl itaconate Oleic acid conductors such as butyl oleate; Ricinoleic acid conductors such as glycerin monocitrate; Other examples include tricresyl phosphate, epoxidized soybean oil, and epoxy resin plasticizers.

In order to blend the above-mentioned component (A), component (B), and optionally component (0) with the vinyl chloride resin, it is preferable to use a soft blend. To obtain a soft blend, 19 parts of 3O-6O plasticizer may be blended with 10 parts by weight of the vinyl chloride resin.

Examples of lubricants or heat stabilizers that can be used include polyethylene wax, liquid paraffin, stearic acid, zinc stearate, fatty alcohols, calcium stearate, barium stearate, barium ricinoleate,
Examples include dibutyltin laurate and dibutyltin malate.

Antistatic agents or antifogging agents that can be used include those that have been conventionally used in agricultural coating films.
There are no restrictions. Specific examples include polyethylene glycol alkyl esters such as polyethylene glycol monostearate and polyethylene glycol dibehenate; sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; polyoxyethylene lauryl ether Polyoxyethylene fatty acid ethers such as glycerin behenyl ether; glycerin fatty acid ethers such as glycerin behenyl ether; fatty acid alkylolamine condensates such as stearic acid jetanolamine; these may be used alone or in combination of one or more. You may also use it.

Resin additives other than these plasticizers include vinyl chloride resin 1
It is used in an amount equal to or less than an sN amount for a 00M amount.

The above (A) component, (B
) component, component (0), and other resin additives, use conventional compounding techniques and mixing techniques, such as a T-bar ribbon blender, Banbury mixer, super mixer, and other compounding machines and mixers. It is possible with the technology that

In order to produce the agricultural vinyl chloride resin film according to the present invention, ordinary film manufacturing methods such as calendar molding, extrusion molding, inflation molding, etc. can be appropriately adopted. If the thickness of the vinyl chloride resin film is too thin, the strength will become opaque, which is undesirable.On the other hand, if it is too thick, it will be difficult to make the film and the subsequent handling (
It causes inconvenience in the work of cutting the film and joining it into a house shape (including the work of rolling it out into a square shape, etc.), so 0.
03-0,. It is preferable to set it in the range of 2 mm.

The agricultural vinyl chloride resin film according to the present invention has the following characteristics, and its agricultural utility value is extremely high.

(1) Even when the agricultural vinyl chloride resin film according to the present invention is used outdoors for a long period of time, the additives hardly bleed out, and therefore, the appearance deterioration such as a decrease in film transparency is unlikely to occur.

(2) The agricultural vinyl chloride resin film according to the present invention has little "deterioration on the flat surface" even when used outdoors for a long time, and has little "deterioration on the crosspiece", so it can be used for a long time. can.

(3) The agricultural vinyl chloride resin film according to the present invention can further improve weather resistance when the three components of component (A), component (B), and component (0) are used together.

(4) A film made by blending ultraviolet absorbers with agricultural vinyl chloride resin FILNO® to block ultraviolet rays of 370 to 3 θnm or less. It is known to be able to suppress the activity of bacteria and arthropods, but its property of blocking ultraviolet rays is
It often worsened over time. In the agricultural vinyl chloride resin film according to the present invention, component (B) absorbs ultraviolet rays, and when used in combination with component (A) and also component (0), the film absorbs ultraviolet rays. The shielding property is
Even after long-term use (2 years), it still shows particularly remarkable properties.

Hereinafter, the present invention will be explained in detail based on examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Examples 7-7, Comparative Examples 7-7 Polyvinyl chloride (p=/'100)...10ON parts Dioctyl phthalate...G j #
Epoxy resin (product name [gp-, r, zyJ).../
l Barium-zinc-based composite liquid stabilizer
／、j#Barium stearate・・・・・・・・・
・0.2tr zinc stearate・・・・・・・・・・・・
...θ, l...Nrubitan monostearate...
- Prepare a resin composition consisting of parts i and jxx, and (A)
The components (B) component, (0) component, and other components (mainly in the case of comparative examples) were blended in the proportions shown in Table 1.

Each formulation was stirred and mixed with a super mixer for io minutes, then kneaded on a roll mill heated to /lj'c, o,
With a film of iwn thickness.

The following evaluation tests were conducted on each film, and the results are shown in Table 2.

(a) Evaluation of weather resistance was performed as follows.

A large amount of film was exposed on a window frame-shaped exposure test stand facing south and inclined at ≠j degrees with respect to the plane, and some films were periodically removed for evaluation.

"Flat surface deterioration" refers to the appearance (observation with the naked eye) of the exposed film where both the front and back sides are free and not held down by the crosspieces, and the residual elongation rate (, Tl5K-t73.2
By tensile test in accordance with . The results of evaluating the ratio of the elongation of the original film to the elongation of the original film are shown.

``Deterioration on the crosspiece'' refers to the state in which the open side of the exposed film is brought into contact with a galvanized iron plate and the film is fixed on the crosspiece, and the appearance of this part of the film and the residual elongation rate are evaluated. shows.

The evaluation results were displayed as follows.

○: There is no change in appearance and the remaining elongation rate is go% or more.

○×: There is no change in appearance, and the remaining elongation rate is in the range of to to dθ.

△...Appearance changes to yellow, residual elongation rate is 0~60%
Those within the range of.

U: Discolors to brown, tears occur, and residual elongation is in the range of 2O- (10%).

×: The entire surface turns brown, there are many tears, and only the remaining elongation rate can be measured.

[Total light transmittance in the ultraviolet region] was measured using a spectrophotometer [Newly manufactured by Hitachi, Model 323] at a wavelength of 370 nm and 3 nm.
Or the transmittance measured at 3 Onm. The surface of the film stretched outdoors was sufficiently washed with water to remove dirt, and then subjected to measurement. Regarding the film of Example 6.7, similar measurements were carried out 20 days after the start of stretching, and the results are shown in Table 2.

(b) Bleed-out of additives was evaluated as follows. Leave the prepared sample film indoors,
After two months and/or two months had elapsed, the surface of the film was lightly touched with a finger, and the extent of the marks on the film surface was observed with the naked eye.

The evaluation results were displayed as follows.

○: Almost no finger marks left.

○X: Finger marks are left and slight bleed-out is observed.

△: Finger marks are left, and bleed-out is clearly observed.

△X: There is bleed-out and it is slightly sticky.

(c) "Deterioration on crosspiece" test using a spreading house The ≠glazed films of Example 3, Example 6, Comparative Example 6, and Comparative Example 7 were actually spread in a horizontal direction, and the parts that came into contact with the aggregate were The deterioration status was observed.

Is the house 100n wide? Using the framework shown in the perspective view in Figure 1, and fixing the film as shown in the same figure, a roof-shaped house extending long from east to west was constructed.

While cultivating useful plants in the greenhouse, we observed ``beam deterioration'' by visually inspecting the area A surrounded by the dotted line in Figure 1 and by touching it with our fingers. The results are shown in Table 3.

In Figure 1, / indicates aggregate (made of galvanized steel plate);
2 indicates a film, and 3 indicates a holding spring (made of galvanized steel wire).

-j5LI- Table 3 From Tables 1 to 3, the following becomes clear.

(1) The agricultural vinyl chloride resin film according to the present invention has excellent weather resistance with less "deterioration on the flat surface" and "deterioration on the crosspiece."

(2) The agricultural vinyl chloride-based tung fat film according to the present invention has less bleed-out of additives, and therefore is less likely to suffer deterioration in appearance such as decreased transparency of the film.

(3) Films using the three components of component (4), component φ), and component (C) (Example 6, Example 7) are not the same as the one with excellent weather resistance, but the films containing component 0) and component (C). Compared to films in which component (C) was used frequently (Comparative Example 7, Comparative Example G), the property of blocking ultraviolet rays did not change over a long period of time.

[Brief explanation of the drawing]

FIG. 1 is a perspective view showing a state in which a film is stretched and fixed to a house frame. In the figure, l indicates the bone phase, C indicates the film, 3 indicates the holding spring, and section A indicates the location where "deterioration on the crosspiece" is likely to occur. Applicant Mitsubishi Monsanto Chemicals Co., Ltd. Agent Patent Attorney Hase Yo - (7 people)

Claims (8)

[Claims] (1) Vinyl chloride resin, (A) tricylenyl phosphate, and (B)
In the general formula (Formula! Shikil), R1 represents an alkyl group having q to /g carbon atoms. ] or [: In the formula (If), R2 is an alkyl group having 5 to 73 carbon atoms, R9 is an alkyl group having 7 to 7 g carbon atoms, and X is hydrogen, halogen, alkyl group, alkoxy group , aryloxy group, aralkyloxy group, and aryl group. ]
An agricultural vinyl chloride resin film with excellent weather resistance, characterized in that it is formed into a film by blending /glaze or a combination of two or more of the compounds represented by the following. (2) ((1ri General formula ((In formula 119, m is an integer from / to j, X is m+x
An integer of O-Hiroshi, provided that there is a relationship of
R4 is a halogen, an alkyl group or an alkoxy group having 7 to 7.2 carbon atoms, R6 and R6 are an alkyl group having 7 to 217 carbon atoms, and an alkyl group having 24 to 7 carbon atoms. , y and 2 each represent a desired number from / to ≠, provided that at least one ortho-position of each phenyl ring has no substituent. The agricultural vinyl chloride resin film according to claim (1), characterized in that it contains a compound represented by the following formula. (3) Trixylenyl phosphate, component (A), contains xylenyl groups having substituents at different positions.
．． 2.The proportion of compounds containing 3 xylenyl groups and 3J xylenyl groups in the total trixylenyl phosphate is 3
Claim No. (1), characterized in that it is 0-fold or more! The agricultural vinyl chloride resin film described in item (2) above. (4) Among the compounds that are component (B), the compound represented by formula (1) is -1(hydroxy-j-tert-butylphenyl)benzotriazole, and the compound represented by formula (n) is octyl Claims (1) and (2) are
) Agricultural vinyl chloride resin film as described in item 2. (5) Claim No. (0) characterized in that the compound which is component (0) is a compound represented by the general formula
2) Agricultural vinyl chloride resin film as described in item 2). (6) Claim (1) characterized in that 7 to 70 parts by weight of component (A) and 0.3 to 3 parts by weight of component (B) are blended with 700 parts by weight of vinyl chloride resin. ) to (2) above. (7) For vinyl chloride fruit tree M'Fj /QOM quantity part,
The agricultural vinyl chloride resin film according to claims (2) and (5), which contains 0.3 to 10 cumulative parts of component (C). (8) Claims (1) to (7), characterized in that the base vinyl chloride resin contains 3 O-tO parts by weight of plasticizer per 70 ON parts of the resin. agricultural vinyl chloride resin film.