JPH0359046A - Antifogging agricultural polyolefin resin film - Google Patents

Abstract

PURPOSE:To obtain the title film improved in transparency, antifogging property at low temperatures and its persistence by forming a composition prepared by adding three specified surfactants to a polyolefin resin into a film. CONSTITUTION:A composition is obtained by mixing 100 pts.wt. polyolefin resin (A) (e.g. PE of a density of 0.910-0.935) with a sorbitan-glycerol condensation fatty acid ester-type surfactant (B) (e.g. sorbitan/glycerol condensation monostearate), a diglycerol fatty acid ester-type surfactant (B) (e.g. diglycerol monopalmitate), a glycerol fatty acid ester-type surfactant (C) (e.g. glycerol monostearate) and optionally 0.1-5.0 pts.wt. antifogging hindered amine compound (D) of any one of formulas I, II, etc., and 3-200 pts.wt. hydrotalcite-like compound (E) in such amounts that the weight ratio of components B, C and D to the total is 0.5-5.0, the weight ratio of component B to components C and D is 9/1-1/1, and the weight ratio of component C to component D is 9/1-1/2. This composition is formed into a film by melt extrusion, calendering or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an agricultural polyolefin resin film. More specifically, the present invention relates to an agricultural polyolefin resin film that has excellent transparency, excellent antifogging properties at low temperatures, and excellent antifogging durability.

(Prior art) Conventionally, methods for imparting antifogging properties to films in agricultural applications include methods of applying a liquid antifogging agent or a solution containing an antifogging agent, or methods of kneading an antifogging agent into the film. and some of them have been put into practical use.

In the coating method, an antifogging agent is applied to the surface of a hydrophobic synthetic resin such as polyolefin resin to impart hydrophilic properties. However, the antifogging agent is easily washed out by water droplets, and only products with insufficient antifogging durability have been obtained.

In addition, in the method of kneading an anti-fog agent, the anti-fog property is developed by the incorporated anti-fog agent bleed out to the resin surface, but this bleed-out of the anti-fog agent causes the film to bleed out. is required to occur in a moderate amount during the manufacturing process or use of the film.

However, if the antifogging agent bleeds excessively, it is not preferable because the film becomes sticky and the transparency decreases due to the whitening phenomenon of the bleed-out material, which adversely affects cultivation.

Furthermore, if the degree of bleed-out is low, sufficient antifogging properties are not exhibited. That is, unless the antifogging agent bleeds out appropriately during use, the antifogging property will not be lost after the antifogging agent is washed away by water droplets, and satisfactory antifogging durability cannot be expected.

Until now, methods for incorporating an antifogging agent to impart antifogging properties to the surface of a polyolefin resin film 0 have been proposed, for example, in Japanese Patent Publication No. 4Z, 5--, ? A O/←, Special Public Show II &
-1,3! ;2, Tokukai Akira! ;7-g235 JP-A-1986-
Examples include the method described in the 26θ4t publication.

However, these antifogging agents bleed out significantly, causing the film to become sticky, or the bleed out material becoming white, significantly impairing the transparency of the film, or because it is difficult for the film surface to bleed out appropriately. The current situation includes problems such as failure to exhibit antifogging properties, especially in low-temperature periods, and a satisfactory agricultural polyolefin resin film with appropriately controlled bleed-out has not yet been obtained.

(Problems to be Solved by the Invention) In view of the above-mentioned circumstances, the present inventors have made extensive studies to solve these problems, and have found that a specific amount of a specific surfactant consisting of three types is used in combination with a polyolefin resin. As a result, we have found a film that achieves appropriate bleed-out to the film surface, has excellent anti-fog corrosion properties and anti-fog durability at low temperatures, and does not reduce transparency due to whitening, etc., and has completed the present invention. .

In the present invention, when a hindered amine compound with a specific molecular weight is used as an additive in combination, the anti-fog durability is further improved, and when a hydrotalcite compound is used in combination, the bleed-out suppression, low-temperature anti-fog property, and anti-fog durability are further improved. I found out.

(Means for Solving the Problems) That is, the gist of the present invention is (1) 100 parts by weight of a polyolefin resin and a nrubitan-glycerin condensed fatty acid ester surfactant.
...A part by weight diglycerin fatty acid ester surfactant...8 parts by weight glycerin fatty acid ester surfactant...
An agricultural polyolefin resin film characterized by forming a film from a composition in which C parts by weight of three types of surfactants are added and the amount ratio is as follows.

(2) In addition to this, anti-fog hindered amine compounds are added.
, i to 3.0 parts by weight of an antifogging agricultural polyolefin resin film.

(3) Furthermore, 3 to 20 hydrotalcite compounds
This invention relates to an antifogging agricultural polyolefin resin film containing parts by weight.

The present invention will be explained in detail below.

Polyolefin resins that can be used in the present invention include homopolymers of α-olefins and copolymers with different monomers containing α-olefins as a main component, such as low-density polyethylene, medium-density polyethylene, High-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-gumethyl-7-pentene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer , ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer.

Examples include ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, and ionomer resin.

Among these, polyethylene and ethylene-α-olefin copolymers with a density of 0.910 to 0.93 and ethylene-vinyl acetate copolymers with a vinyl acetate content of 30% or less have excellent transparency, weather resistance, and price. It is preferable from the point of view.

More preferably, the vinyl acetate content is 3 to 40% by weight.

The surfactants used in the present invention are three types of nonionic surfactants.

■ As the first surfactant, sorbitan-glycerin condensed esters of fatty acids having carbon number/, 2 to = 2 or θ,! -! Sorbitan-glycerin condensed fatty acid ester surfactant with mol of ethylene oxide or propylene oxide added (abbreviated as antifogging agent a), such as sorbitan-glycerin condensed monostearate, sorbitan-glycerin condensed distearate, sorbitan-
Glycerin-fused monopalmitate, sorbitan-glycerin-fused dipalmitate, sorbitan-glycerin-fused monobehenate, sorbitan-glycerin-bound dibehenate, sorbitan-glycerin-fused monomyristate,
Sorbitan-glycerol fused simiristate, sorbitan-glycerol fused monolaurate, sorbitan-glycerol fused trilaurate, sorbitan-glycerol fused monolaurate monostearate, sorbitan-glycerol fused monostearate dipalmitate, sorbitan-glycerol fused monostearate・, 2EO adduct, sorbitan-glycerin condensed monostearate・
Examples include dipalmitate, 7EO adduct, sorbitan-glycerol-bound simiristate/PO adduct, and the like. These can be used alone or in combination of two or more.

■ As the second surfactant, diglycerol esters of fatty acids having 1 to 2.2 carbon atoms or θ,! ~!
Diglycerin fatty acid esters (abbreviated as antifogging agents) with moles of ethylene oxide or propylene oxide added, such as diglycerin monopalmitate, diglycerin monomyristate, diglycerin monolaurate.

Diglycerin monobehenate, diglycerin dibehenate, diglycerin distearate, diglycerin dipalmitate, diglycerin sesquistearate, diglycerin monostearate/3EO adduct, diglycerin monopalmitate/PO-addition and diglycerol monostearate monopalmitate.

These can be used alone or in combination of more than one type.

■ As the third surfactant, glycerin esters of fatty acids having 12 to 12 carbon atoms or θ,! ~! Glycerin fatty acid ester with moles of ethylene oxide or propylene oxide added (abbreviated as antifogging agent C),
For example, glycerin monostearate, glycerin monopalmitate, glycerin monobehenate, glycerin monomyristate, glycerin monolaurate, glycerin distearate, glycerin dipalmitate, glycerin monostearate/2EO adduct, glycerin dipalmitate/ /PO adducts and the like. these are,
Seven types or two or more types can be used.

If the amounts of these three antifogging agents a, b, and c are respectively A, B, and C parts by weight relative to ioo parts by weight of the polyolefin resin, then A+B+C=0.3~! Must be parts by weight.

0,! If the amount is less than 1 part by weight, antifogging properties will be poor, so this is not preferable.

or! If the amount exceeds 1 part by weight, it becomes difficult to mix into the polyolefin resin, and bleed-out significantly reduces transparency, which is not preferable.

Also, the amount of each antifogging agent added is A/CB+C)=q/t~
l/l and B/C=? It is necessary to satisfy the relational expression /1S-7/.

What is the ratio A/CB+C)? If it is larger, the antifogging property and antifogging durability at low temperatures will be poor, which is not preferable. Also A/CB
+C) is! If it is smaller, bleed-out will increase and transparency will be significantly impaired, which is not preferable.

What is the ratio B/C? If it is larger, the antifogging property at low temperatures will be poor, which is not preferable. Also, B/C is 0! If it is smaller, bleed-out will be significantly larger and transparency will be significantly lower, so it is not preferable.

As the hindered amine compound that contributes to further performance improvement when used in combination in the present invention, any hindered amine compound that is added to films for boat fishing and agricultural use can be used. For example, the compounds exemplified in Japanese Patent Application Laid-Open No. 10-120011 and OLIi, specifically, the compounds shown below, can be exemplified.

Molecular weight: approx. 40 θθ (manufactured by Ciba Geigy) 2 Molecular weight: approx. 720 (Sanol LS-2626, manufactured by Sankyo Co.) Molecular weight: approx. 3600 (TlNUVlN 6 Coco LD, manufactured by Ciba Geigy) Molecular weight: approx. 7'10 (Adeca Argus, Inc.) (manufactured by) (b) Molecular weight of approximately JT (ARK LA-Aλ manufactured by Adeka Argus) αG Molecular weight of approximately ItA (ARK LA-67 manufactured by Adeka Argus) However, Diadol-/j of aO is manufactured by Mitsubishi Chemical ■
It is an alcohol with 13 carbon atoms manufactured by the company.

Molecular weight: approximately i1θO (CHIMASSORB manufactured by Ciba Geigy) //
? FL) α Enoki Yu, Yu, 6,6-titramethylbiperidinyl ruderpenzoate (19bis=(co,2,56-titramethylbiperidinyl)sebacate kan /, 3.!;-) riazo , 7,7,9.9-tetramethyl-3-n-octyl-spiro [: q, s ]]
(2zll-stearoyloxyco, t, A, 4-tetramethylpiperidine terbenzyloxyyl,!, Aj-tetramethylpiperidine (c) 'I-(7enylcarbamoyloxy)-2
゜, l, A, l, -tetramethylpiperidine ■ trilq-acetoxyco, co, 6,6-titramethylbiperidine]-amine (4) +-7cetoxyl, co, 6. A-Tetramethylpiperidine fl) Hiro-(p-)luenesulfonyloxy)-!
, J, A, A-tetramethylpiperidine (to) bis(
Co, λ, 6,6-titramethyl-q-piperidyl) terephthalate tris(2, co, 6,6-titramethyl-tahiberidyl) phosphite (1) /, 3. t-) Reasor 7.7. '? ,? -tetramethyl2. 'I-diokylyspiro(a,r)decanec3υ (2,IA,6-tetramethylpiperidine)-goosespiro-λ/ (,/,,/-cymethylhyhelysine) al-spiro-yo'-hindantoin (to) One or more types of these hindered amine compounds can be used.The blending amount must be selected within the range of O, S-S weight parts based on the polyolefin resin ioθ weight parts.The blending amount should be 3 weight parts. If it exceeds 1 part by weight, bleed-out will be significantly worsened, and the transparency of the film and the anti-fogging property at low temperatures will be deteriorated. This is the overlapping part.

The hydrotalcite compounds that contribute to further performance improvement when used in combination in the present invention are the compounds exemplified below.

■ Hydrotalcite stone is a hydrous carbonate mineral represented by the general formula % (where fi, = AI, Cr, Fe), and is a natural mineral found in the Ural region of the Soviet Union, the Snarm region of Norway, etc.

■ Synthetic hydrotalcites shown below General formula % Formula % M2+: Divalent metal ion selected from Mg, Ca, Zn An-: N-valent anion, such as CI-, Br-, I-, N01- , ClO4.

So, “, CO3”-, 5i03”-, HPO4”-H
PO3"-, PO4"-, Fe(CN),'-CH,C
OO-, (COO), "-, C, H4 (coo),"-
, C, H, (OH) (COO)--These hydrotalcite compounds can be used alone or in combination of two or more. The blending amount is preferably up to 20 parts by weight per 100 parts by weight of the polyolefin 4-in resin. If the blending amount exceeds 20 parts by weight, the transparency will be poor and the antifogging durability will also deteriorate, which is not preferable.

In addition, the polyolefin resin film in the present invention includes:
The following various compounding agents can be used as necessary.

That is, plasticizers such as diconitylphthalate and diconithyladipate, organic phosphorus esters such as tricresyl phos7ate, yatricylenyl phos7ate, etc., organic phosphoric acid metal salts such as stearic zinc phosphate and dipalmityl phosphate barium salt, Epoxy compounds such as bisphenol A diglycidyl ether and epoxidized soybean oil, chelators such as triphenyl phosphite and indecyl phenyl phosphite, lubricants such as methylene bis stearamide and ethylene bis stearamide, barium stearate, etc. Heat stabilizers such as calcium oleate, cohydroxy cedar octoxybenzophenone and! = UV absorbers such as (J'-hydroxy-5l-methylphenyl)hensotriazole, stabilizing aids such as dehydroacetic acid and dibenzoylmethane, antioxidants such as 6-di-t-butyl-p-cresol, Examples include antistatic agents such as polyoxyethylene amine, benzimidazole-based and 7-talimide-based fungicides, algaecides, fluorine-based and silicone-based fog preventive agents, and colorants such as ultramarine blue.

The above various additives can be used alone or in combination of two or more. The amount of the various resin additives mentioned above can be selected within a range that does not deteriorate the performance of the film, usually within a range of 3 parts by weight or less per 100 parts by weight of the base polyolefin resin.

In order to blend the surfactant, or if necessary, hindered amine, hydrotalcite compounds, and other additives into the polyolefin resin of the present invention, the necessary amounts of each are weighed out, and the mixture is heated using a ribbon blender, Banbury mixer,
A conventionally known compounding machine, mixer, etc. such as a super mixer may be used.

The resin composition thus obtained can be formed into a film by a method known per se, such as a melt extrusion method (T-die method, inflation method, etc.), a calender molding method, etc. According to

These can also be formed as single layer films, but
It is also possible to form a multilayer film of two or more types.

In particular, when the composition has three or more layers, the additive may be added to any layer, but the amount added is the amount converted to a single layer film.

The film according to the present invention may be transparent or matte, and can be used for covering agricultural greenhouses, tunnels, etc., as well as for mulching, tearing, etc.

(Effect of the invention) The film according to the present invention contains specific amounts of three types of essential components: sorbitan-glycerin condensed fatty acid ester surfactant, diglycerin fatty acid ester surfactant, and glycerin fatty acid ester surfactant. The polyolefin-based resin film containing the resin achieves appropriate fleet out to the film surface and has excellent low-temperature antifogging properties and antifogging durability. Moreover, transparency does not deteriorate due to whitening or the like.

(Examples) Next, the present invention will be explained with reference to Examples, but these Examples are merely illustrative and are not limited thereto.

In addition, various tests in Examples and Comparative Examples were conducted as follows.

(Transparency of film) It shows the haze value measured by a haze meter.

The initial measurement value indicates the turbidity of the film itself, but the measurement value over time indicates changes in transparency due to bleeding, blooming, whitening, etc.

(Low temperature anti-fogging property) 3θOCC water (20℃) in a s o c cc beaker
and covered with sample film, then placed in a constant temperature water bath (S
The beaker was tilted 70 degrees from the ground surface and immersed in water up to two-thirds from the bottom, and left in a constant temperature room at θ°C for a predetermined period of time, after which the condition of the film surface was observed with the naked eye. The flow state of droplets on the film surface was evaluated based on the following criteria.

○: Some parts with micro water droplets) No parts ○ Fill a θOCC beaker with 3θOcc water (aO℃), cover it with a sample film, and then place it in a constant temperature water bath (daθ℃).
Tilt the beaker 70 degrees from the ground surface and
The film was immersed in water up to part 3 and left in a constant temperature room at 20° C. for a predetermined period of time, after which the condition of the film surface was observed with the naked eye. The flow state of droplets on the film surface was evaluated using the same criteria as the low-temperature antifogging properties.

Example-l Ethylene-vinyl acetate copolymer (VA content: 10 wt%
, Density: 0.92g, MI:/,! ;) were added with /J parts of nrubitan-glycerin condensed monostearate as surfactants, 0.1 part of diglycerin distearate, and 0.4 parts of glycerin monostearate, and ethylene bis as other compounding agents. After mixing 0.2 parts of Stearoa □do, the resin temperature was 130~130 in a test Banbury.
After kneading at /30°C for about S minutes, granulated pellets were obtained using an extruder.

The pellets thus obtained were formed into a film using a 1.30096 single-layer inflation die at a resin temperature of 70° C. to obtain a film having a thickness of 100 μm and a width of 3θOCm.

The performance of the obtained film is shown in Table 7.

Example-2 The surfactant used in Example-l was sorbitan-
A film was molded in the same manner as in Example 7 except that the amount of glycerin condensed monostearate O (1 g part, diglycerin monopalmitate) was changed to 0.11 parts, and the evaluation results are shown in Table 2.

Example-3 The surfactant used in Example-7 was sorbitan-
A film was formed in the same manner as in Example 7, except that the amount of glycerin condensed monopalmitate was changed to 0 parts, and the evaluation results are shown in Table 7.

Example--A film was prepared in the same manner as in Example-/, except that the compounding agents used in Example-7 were not changed, and Kimasorp 9*ll FL (manufactured by Ciba-Geigi Co., Ltd.) θ, s part oil was added as a hindered amine compound. was molded, and the evaluation results are shown in Table 7.

Example - The compounding agents used in Example -7 were not changed, and in addition, hydrotalcite compound Alkamizer l (Kyowa Chemical Co., Ltd.) was used.
A film was formed in the same manner as in Example 7 except that 70 parts (manufactured by Co., Ltd.) was added, and the evaluation results are shown in Table 7.

Example-6 The compounding agent used in Example-7 was not changed, and Kimasorb 911pFL (manufactured by Ciba-Geigi) O1 was added as a hindered amine compound! A film was formed in the same manner as in Example 1, except that 77 parts of hydrotalcite compound Alkamizer 1 (manufactured by Kyowa Kagaku Co., Ltd.) was added, and the performance evaluation results are shown in Table 1. .

Comparative Example-l The surfactant used in Example-7 was sorbitan-
Example except that 70.3 parts of glycerin condensed monostearate and 1.2 parts of diglycerin distearate were used.
A film was formed in the same manner as in 7, and the evaluation results are shown in the table below.
7.

Comparative Example-2 A film was formed in the same manner as in Actual Example-7, except that the surfactant used in Example-7 was changed to 0.1 part of diglycerine distearate and 0.6 part of glycerin monostearate. The evaluation results are shown in Table 7.

Comparative Example 3 A film was molded in the same manner as in Sister Example 7, except that the hindered amine compound used in Example DA was changed to the IQ portion, and the evaluation results are shown in Table 7.

Comparative Example - A film was formed in the same manner as in Example 1, except that the hydrotalcite compound used in Example 3 was changed to 30 parts, and the evaluation results are shown in Table 7.

Comparative Example-3 The surfactant used in Example-7 was sorbitan-
A film was formed in the same manner as in Example 7, except that 0.1 part of glycerin condensed monostearate (O, C part, diglycerin distearate) and 10.7 parts of glycerin monostearate were used, and the evaluation results were as follows. are shown in Table-7.

Comparative Example 6 The surfactant used in Practical Example 7 was sorbitan.
Glycerin condensed monostearate J, 0 parts, diglycerin distearate) 2.0 parts, glycerin monostearate 1. A film was molded in the same manner as in Example 1 except that the θ portion was changed, and the evaluation results are shown in Table 7.

Claims (3)

[Claims] (1) 100 parts by weight of polyolefin resin, sorbitan-glycerin condensed fatty acid ester surfactant...A part by weight diglycerin fatty acid ester surfactant... B Part by weight Glycerin fatty acid ester surfactant... C Part by weight of three types of surfactants are added, and the amount ratio is as follows: A+B+C=0.5-5.0 A/ (B+C)=9/1~1/1, B/C=9/1~1
An agricultural polyolefin resin film characterized by being formed from a composition having a composition of: /2. (2) Anti-fog hindered amine compound from 0.1 to 5.0
The antifogging agricultural polyolefin resin film according to claim 1, in which part by weight is added. (3) The antifogging agricultural polyolefin resin film according to claim 1 or 2, to which 3 to 20 parts by weight of a hydrotalcite compound is added.