JPH032906B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an agricultural vinyl resin film. Specifically, the present invention relates to an agricultural vinyl resin film that has anti-fog and anti-fog properties and is durable even when exposed to rain and dew for a long period of time as a covering material for agricultural greenhouses or agricultural tunnels. In recent years, cultivation methods for promoting or suppressing the growth of vegetables, fruits, flowers, etc. in greenhouses or tunnels using agricultural films have become increasingly popular. Agricultural films made from vinyl resins, especially vinyl chloride resins, are relatively inexpensive and
Because it has good heat retention, flexibility, light transmittance, etc.
It has been widely used for a long time. However, in agricultural greenhouses or tunnels, moisture evaporates from the soil or crops, or water sprinkled on the film causes cloudiness due to water droplets condensing on the inner surface of the film, reducing light transmittance and causing crops to grow. In addition, the water droplets fall, and when combined with high temperatures and high humidity, the young shoots of crops are susceptible to rot and disease. Furthermore, when the morning and evening temperatures change rapidly, such as in autumn and winter, fog forms inside greenhouses and tunnels, reducing work efficiency and light transparency, and similarly to the cloudy conditions mentioned above, slowing down crop growth. It is also connected to things. The mechanism behind the formation of this fog has not been clearly elucidated, but it is subtly influenced by the electrostatic properties of the moisture evaporating from the ground surface and the degree of hydrophilicity of the film surface. It is presumed that this is because water vapor adheres smoothly to the inner surface of the film due to temperature changes and does not flow down, and some of the water vapor becomes a mist near the inner surface of the film. Various proposals have been made to suppress and improve the occurrence of cloudiness and fog. For example, JP-A-55
Publication No. 91663 is characterized in that an organic siloxane surfactant, that is, a siloxane-polyoxyalkylene copolymer, is added to the agricultural coating material, but when used for greenhouses, the outer surface of the film is exposed to rain and exposure. As a result, the inner surface of the film is eluted little by little as water droplets flow down, so there is a drawback that durable anti-fog and anti-fog properties are obtained.
In addition, JP-A-57-12070 discloses felt groups,
A method for incorporating a polysiloxane having a trifluoro group, an amino group, a mercapto group, a carboxyl group, a long-chain alkyl group, or an epoxy group into an agricultural coating material is described, and Japanese Patent Application Laid-Open No. 1983-1989
No. 104953 discloses a composition in which a vinyl chloride resin is blended with an antifogging agent such as polyethylene glycol alkyl ester and a silicone oil such as methylphenylpolysiloxane, dimethylpolysiloxane, diphenylpolysiloxane. However, since both organopolysiloxanes have no or almost no hydrophilicity, water vapor adheres to the film in the form of microspheres, and it takes a long time for the water droplets to grow and flow down. Further, even when the film flows down, transparent parts and cloudy parts due to water droplets are generated in the film part, which tends to form a striped pattern, and there is a drawback that uniform light transmittance cannot be obtained. Furthermore, since it does not have antistatic properties, it has the disadvantage that the film tends to become dark due to adhesion of salts and dust in the air, which impedes light transmittance. As a result of intensive research in order to solve the above-mentioned drawbacks, the present invention has been developed by adding hydrophilic polyoxyalkylene groups and reactive epoxy groups to organopolysiloxane to vinyl resin, thereby producing a film of the organopolysiloxane. It imparts wettability to the film, and the water vapor attached to the film surface immediately spreads to form a uniform water film, resulting in excellent anti-fogging and fog-proofing properties, and due to the crosslinking of the epoxy groups, it does not dissolve in rain or dew. The inventors have discovered that this effect improves durability, and have arrived at the present invention. That is, the present invention includes (a) 100 parts by weight of vinyl resin, (b) 0 to 100 parts by weight of a plasticizer, (c) 0.1 to 15 parts by weight of a compound selected from organic acid metal salts and organic amines, and ( d) General formula [wherein R is a substituted or unsubstituted monovalent hydrocarbon group, R ¹ is a group selected from R, A and B,
A is an epoxy-containing monovalent organic group, B is (-R ² -) _a O
(-C ₂ H ₄ O-) _b (-C ₃ H ₆ O-) _c R ³ (Here, R ² represents a divalent organic group, R ³ represents a hydrogen atom or a monovalent organic group, and a represents a 0 or 1, b is 0 to 40, c is 0 to 40, but b + c is 2 to 60),
is 0-300, m is 0-30, n is 0-50, however,
+m+n is 2-300. ], 1
Relating to an agricultural vinyl resin film formed into a film by blending 0.01 to 10 parts by weight of an organopolysiloxane having at least one epoxy group-containing organic group and at least one polyoxyalkylene group in the molecule. . Examples of the vinyl resin as component (a) used in the present invention include polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyacrylonitrile,
Polyacrylic acid ester, polymethacrylic acid ester, polyvinylidene chloride, polyvinyl fluoride and other vinyl homopolymers, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer Polymer, vinyl chloride-methyl acrylate copolymer, vinyl chloride-methyl methacrylate copolymer, vinyl chloride-acrinitrile copolymer, vinyl chloride-styrene copolymer, vinyl chloride-vinyl acetate-methacrylic acid ester copolymer Polymer, vinyl acetate-ethylene copolymer, vinyl acetate-acrylic acid copolymer, vinyl acetate-acrylic acid ester copolymer, vinyl acetate-maleic acid copolymer, vinyl acetate-vinyl chloride-polyvinyl alcohol copolymer Examples include vinyl acetate-vinyl chloride-ethylene copolymers, and copolymers of vinyl resins and non-vinyl resins. The vinyl resin may be a mixture of two or more thereof, or may be a mixture of a vinyl resin and a non-vinyl resin. Among these, vinyl chloride resin is most preferred from the viewpoint of economy, light transmittance, weather resistance, strength, etc. The forms of vinyl resin are solution, emulsion, paste,
It can be used in either powder or solid form. The plasticizer component (b) used in the present invention may be one that has been conventionally added to plastics, and a compatible one may be appropriately selected and used. Examples of plasticizers include diethyl phthalate, dihexyl phthalate, dioctyl phthalate, dioctyl adipate, didecyl adipate, tributyl phosphate, trichloroethyl phosphate, glycerin triacetate, ethylene glycol dibutyrate, and ethylene glycol monoethyl. Examples include ether laurate, epoxidized soybean oil, epoxidized castor oil, dipropylene glycol dibenzoate, ethyl phthalylethyl glycolate, chlorinated paraffin, and the like. These plasticizers may be used alone or in combination of two or more. However, some types of vinyl resin do not require a plasticizer, so in that case, it is not necessary to add it. The amount of plasticizer added varies greatly depending on the type of resin, and some resins do not require plasticizer at all, but when plasticizer is needed, it is usually because too much plasticizer makes the film too soft. , it becomes unsuitable for uses such as agricultural greenhouses and tunnels, and if the amount is too low, the film becomes too hard. Therefore, the amount is in the range of 0 to 100 parts by weight, particularly preferably 20 to 60 parts by weight, based on 100 parts by weight of vinyl resin. . The organic acid metal salt compound or organic amine compound as component (iii) used in the present invention is known as a stabilizer for vinyl chloride resins, and in the present invention, it is contained in the organopolysiloxane as component (ii). Used as a catalyst for ring-opening reactions of epoxy groups. Therefore, when using vinyl chloride resin as component (a), it has both effects,
Also from this point of view, it is preferable to use vinyl chloride resin. Examples of metals in the organic acid metal salt include calcium, zinc, barium, cadmium, zirconium, magnesium, tin, lead, antimony, and titanium. Specific examples of components (c) include zinc 2-ethylhexoate, zinc gluconate, zinc stearate, zinc carbonate, di-n-octyltin lauric acid, di-n-octyltin maleate, tin laurate, Aluminum 2-ethylhexoate, aluminum heptanoate, calcium 2-ethylhexoate, calcium stearate, barium stearate, barium ricinoleate, zirconium stearate, zirium 2-ethylhexoate, cadmium stearate, lead stearate, magnesium naphthenate, 2 Examples include composite stabilizers containing more than one type of metal. Examples of organic amine compounds include N,N'-diphenylethylenediamine, hexamethylenetetramine, benzyldimethylamine, tridimethylaminomethylbenzene, N,N'-di-0-tolylethylenediamine, dimethylaminopropylamine, and monohydroxyethyldiethylenetriamine. etc. are exemplified. These compounds may be used alone or in combination of two or more. The amount of component (c) added is in the range of 0.1 to 15 parts by weight per 100 parts by weight of vinyl resin, but in the case of vinyl chloride resin, it is also used as a stabilizer to suppress decomposition. Therefore, the preferred range in this case is 3 to 10 parts by weight. (d) An organopolysiloxane having at least one polyoxyalkylene group and at least one epoxy group-containing organic group in one molecule of the component is used to impart antifogging and fogging properties to agricultural films. component, which is represented by the general formula described above. In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group, such as a methyl group, ethyl group, propyl group, dodecyl group, vinyl group, phenyl group, β-phenylethyl group, 3,3,3-trifluoropropyl group. , 3-
Examples include chloropropyl group. All R's in one molecule do not have to be the same, but from the viewpoint of effectiveness and ease of production, R is most preferably a methyl group. The epoxy group-containing monovalent organic group represented by A is (c)
Due to the catalytic action of the components, the ring is opened and a crosslinking reaction occurs with, for example, the terminal hydroxyl group of a polyoxyalkylene group, thereby imparting durable anti-fogging and fog-proofing properties to agricultural films. This epoxy group-containing 1
The valent organic group has the general formula

[expression] or

[Formula] (Here, R ⁴ is any divalent organic group, including methylene group, ethylene group, propylene group,
Phenylene group, hydroxylated hydrocarbon residue, chloroethylene group, fluoroethylene group, -
CH ₂ OCH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ OCH ₂ CH ₂ −,

[Formula] - CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ - is exemplified. ). The polyoxyalkylene group represented by B is for imparting hydrophilicity to the agricultural film, and this hydrophilicity provides anti-fog and anti-fog properties. For example, even if water evaporates from the soil in a greenhouse and condenses on the inner surface of the film to form minute water droplets, the film surface is hydrophilic, so it immediately becomes wet and spreads, forming a uniform water film that reflects light. It has the effect of transmitting light. This polyoxyalkylene group is (-R ² -) _a O (-C ₂ H ₄ O-) _b (-C ₃ H ₆ O-) _c R
³
(Here, R ² is preferably an alkylene group having 1 to 5 carbon atoms, and in addition to this, -C ₆ H ₄ - group, -CO-
or a group to which an NHCO- group is attached.
^R3 is most preferably a hydrogen atom in the sense of reacting with an epoxy group, but by appropriately selecting the component (iii), it can be an alkyl group, cycloalkyl group, aryl group, acyl group, aralkyl group, or carbamyl group. be able to. a is 0 or 1, b is 0 to 40,
c is 0 to 40, but b+c is 2 to 60. )
It is a group represented by R ¹ is a group selected from R, A and B. Also, is 0~300, m
is 0 to 30, n is 0 to 50, but +m+n is 2
~300. Component (2) may have at least one epoxy group-containing organic group and at least one polyoxyalkylene group in one molecule, and it does not matter where these groups are present in the molecule. (d) The amount of component added varies depending on its molecular weight, number of functional groups, and type of vinyl resin, but usually vinyl resin 100%
0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight
It is blended in an amount of 5 parts by weight. (d) Component is, for example, Japanese Patent Publication No. 33-9969 and Japanese Patent Publication No. 36-1293.
It can be produced using the addition reaction described in the publication. When producing a vinyl resin film, particularly preferably a vinyl chloride resin film, 4 of (a) to (d)
After mixing the ingredients uniformly with a brain mixer,
It can be formed into a film by extruding it through a slit while melting at 150 to 230°C, or it can be easily formed into a film by a calender method or the like, and at this time, it may be stretched and oriented. The final thickness of the film is generally 50~
It is 500 microns. When producing the film of the present invention, in addition to components (a) to (d), a lubricant such as liquid paraffin or petroleum wax;
Surfactants such as sorbitan monostearate and polyethylene glycol monostearate, organic solvents, curing agents for epoxy resins, ultraviolet absorbers, colorants, kaolin, bentonite, silica and titanium dioxide as light shielding agents to suppress growth. There is no problem in adding fillers such as , Tatalk, calcium carbonate, carbon black, etc. Next, the present invention will be explained by giving examples. In Examples and Comparative Examples, parts mean parts by weight;
Viscosity is a measured value at 25°C. In chemical structural formula
Me is an abbreviation for methyl group. The films of each Example and Comparative Example were evaluated according to the following method. (1) Transparency of film Observe the transparency of the produced film with the naked eye,
Judgment was made in the following three stages. ◎ Very good transparency. 〇 It's a little cloudy. × It is cloudy. (2) Anti-fog properties of the film A test film was placed on top of a thermostatic bath with a water temperature of 40°C prepared in advance, and the anti-fog properties were visually observed after 24 hours, one week, and one month. Next 3
Evaluated in stages. ◎...A thin water film is observed on the entire surface and it is transparent. 〇…Water droplets are observed, and the transparency is slightly poor. ×...Many fine water droplets adhere, and the film appears cloudy. (3) Contact angle measurement The contact angle of water was measured on the film surface immediately after molding and on the film surface after being left in a 40°C water bath for one month. The device used was Elma contact angle measuring device M-2010A-aG-1 manufactured by Elma Optical Co., Ltd. (4) Residual amount of organopolysiloxane To examine the durability of the film's antifogging properties, the test film was immersed in running water for one month, and then treated with running water using a fluorescent X-ray analyzer manufactured by Rigaku Denki Kogyo Co., Ltd. The number of counts before and after was measured to determine the amount of organopolysiloxane remaining after the running water treatment. (5) Fog-proof properties of the film A box assembled with a wooden frame with length, width, and height of 50 (cm) x 50 (cm) x 50 (cm) was heated to a temperature of 40 ± 1.5
After being left for 3 hours in a constant temperature and humidity room adjusted to 95±1.5% relative humidity, a test film immediately after molding was applied to the entire surface, sealed, and left for 2 hours. Next, this film-covered box was moved to a constant temperature and humidity room with a temperature of 3 ± 1.5°C and a relative humidity of 65 ± 1.5%, and the occurrence of fog inside the box was examined.
Rated in stages. ◎…There is no fog and the inside of the box is transparent. △: Very little fog was generated, and the transparency inside the box was slightly inferior. ×: There is a lot of fog, and the inside of the box appears pale white. Furthermore, in order to investigate the durability of fog-proofing properties, we used a running water treated film that had been immersed in running water for one month.
A fog proof test was conducted in exactly the same manner as above. Example 1 In order to compare the present invention with a conventional example, eight types of organopolysiloxanes from I to below were produced as component (2).

【table】

[Table] Next, as shown in Table 1, the component (a) is 100 parts of polyvinyl chloride (P=1300), the component (b) is 50 parts of dioctyl phthalate, and the component (c) is vinyl chloride. Three parts of the Ba-Zn composite stabilizer used in the resin and one part each of component (2) shown above were blended and calendered at 190°C to produce a film with a thickness of 100 microns. The properties of each film were measured according to the evaluation method described above, and the results are shown in Table 2.

【table】

【table】

[Table] The film of the present invention not only has excellent transparency, antifogging properties, and wettability, but also has extremely excellent durability of these effects, as seen from the residual amount of organopolysiloxane. The results of using sodium acetate (Experiment No. 3), which is also used as a vinyl chloride stabilizer, in place of the Ba-Zn composite stabilizer showed excellent transparency and initial antifogging properties, but
Lack of long-lasting effects. Also, polysiloxane-
The polyoxyalkylene copolymer (Experiment No. 8) also has excellent transparency and initial antifogging properties, but does not have the durability of its effects. Example 2 Organopolysiloxane I used in Example 1
using 0.1 parts by weight, 0.5 parts by weight, 2.5 parts by weight.
Example 1 except that the parts were changed to 4 parts by weight and 5 parts by weight.
Films were prepared and evaluated under the same conditions as described above. As a comparative example, a film to which organopolysiloxane I was not added was also evaluated. The results are shown in Table 3. Even though the amount of added organopolysiloxane I was changed, the test results were all excellent, with almost no noticeable difference due to the change in the amount added.
Comparative examples without additives have good transparency, but are poor in antifogging properties and wettability.

[Table] Example 3 The following organopolysiloxane having a viscosity of 3200 cs was produced. 95 parts of polyvinyl chloride (P=1100), 5 parts of vinyl chloride/vinyl acetate copolymer (vinyl acetate content: 5 mol%), 30 parts of dibutyl phthalate, 20 parts of dioctyl phthalate, 1 part of Ba-Zn composite stabilizer ,
Blend 3 parts of N,N'-diphenylethylenediamine and 2 parts of the above organopolysiloxane,
A 100 micron thick film was prepared by calendaring at 180°C. This film was subjected to the same test as in Example 1, and the results showed that it had excellent transparency and antifogging properties after one month, and the contact angle of water was 10° immediately after molding, and 1° even on a water bath.
After standing for several months, the temperature was 26°, and the residual amount of organopolysiloxane was 95.2%. Example 4 100 parts of ethylene/vinyl acetate copolymer (vinyl acetate content 10 mo%), 5 parts of dihexyl phthalate,
Monohydroxyethyldiethylenetriamine 1
One part of the organopolysiloxane used in Example 1 was blended and calendered to form a film with a thickness of 100 microns. The transparency and antifogging properties of this film after one month were excellent, and the residual amount of organopolysiloxane was 94.5%, indicating that the antifogging properties were durable. Example 5 100 parts of isotactic polypropylene, 2.0 parts of calcium stearate, 2,2'-methylene-bis(4-methyl-6-t-
butylphenol) 1.0 part, organopolysiloxane with the same structure except that both terminal groups of the polysiloxane were changed to dimethylphenylsilyl groups instead of the organopolysiloxane used in Example 3, 1.5
A portion of the mixture was put into an extruder, melted and kneaded at 190 to 230°C, and extruded through a slit to form a film with a thickness of 80 microns. The film obtained by hot stretching this film had excellent transparency and antifogging properties after one month, and the residual amount of organopolysiloxane was 94.6%, indicating that the antifogging properties were durable.

Claims (1)

[Scope of Claims] 1 (a) 100 parts by weight of vinyl resin, (b) 0 to 100 parts by weight of a plasticizer, (c) 0.1 to 15 parts by weight of a compound selected from organic acid metal salts and organic amines, and (d) general formula [wherein R is a substituted or unsubstituted monovalent hydrocarbon group, R ¹ is a group selected from R, A and B,
A is an epoxy-containing monovalent organic group, B is (-R ² -) _a O
(-C ₂ H ₄ O-) _b (-C ₃ H ₆ O-) _c R ³ (Here, R ² represents a divalent organic group, R ³ represents a hydrogen atom or a monovalent organic group, and a represents a 0 or 1, b is 0 to 40, c is 0 to 40, but b + c is 2 to 60),
is 0-300, m is 0-30, n is 0-50, however,
+m+n is 2-300. ], 1
An agricultural vinyl resin film prepared by blending 0.01 to 10 parts by weight of an organopolysiloxane having at least one epoxy group-containing organic group and at least one polyoxyalkylene group in the molecule and forming the mixture into a film. 2. The film according to claim 1, wherein component (a) is a vinyl chloride resin. 3. The film according to claim 1, wherein the R ³ group of the organopolysiloxane as component (2) is a hydrogen atom.