JPH0214281A - Anti-fogging and fog preventive agent - Google Patents

Abstract

PURPOSE:To obtain an anti-fogging and fog preventive agent, containing a fluorine-containing aromatic carboxylic acid ester consisting of constituent units expressed by a specific formula and capable of imparting excellent anti- fogging and fog preventing properties to the surfaces of agricultural synthetic resins. CONSTITUTION:The objective anti-fogging and fog preventing agent containing a fluorine-containing aromatic carboxylic acid consisting of constituent units expressed by formulas I and II [A is -CO C6H4.ORf (Rf is perfluoroalkenyl C6F11 or C9H17) or -CH2CH2Rf' (Rf' is 4-12C perfluoroalkyl); EO is ethylene oxide residue; PO is propylene oxide residue; R is H or 1-18C alkyl; R' is H, 1-18C alkyl or phenyl; X is 1-30; y is 0-29, provided that x and y are as follows; 5<=x+y<=30) m is 1-10; n is 0-9, provided that m and n are as follows; 1<=m+n<=10; m/n=(1/0)-(1/10)]. Furthermore, the content of the fluorine- containing aromatic carboxylic acid is preferably 0.01-3.0 pts.wt. based on 100 pts.wt. substrate resin.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to an anti-fog and anti-fog agent, particularly an anti-fog and anti-fog agent suitable for imparting excellent anti-fog and anti-fog properties to the surface of agricultural synthetic resins. Regarding.

Conventional Pinching Techniques - In order to increase the productivity and marketability of agricultural products, greenhouse cultivation, tunnel cultivation, and other facility cultivation using synthetic resin films have been widely practiced.

In this case, antifogging agents such as sorbitan fatty acid esters and glycerin fatty acid esters are used to turn water droplets that adhere to the surfaces of synthetic resin films inside greenhouses and tunnels into liquid films and prevent a decrease in sunlight transmittance. Although it is blended into the synthetic resin, there is a problem in that when the temperature difference between the inside and outside of a house or tunnel becomes large, fog is generated near the inside surface. In other words, the fog generated in this way not only causes disease outbreaks in the crops being cultivated, but also incurs extra costs for drying wet crops, and further reduces visibility and reduces work efficiency. .

In order to solve these problems, a method has been proposed in which a fluorine-containing compound is used in combination with an antifogging agent (for example, Japanese Patent Publication No. 59-35573 and Japanese Unexamined Patent Publication No. 1986
1-152745), a practically satisfactory anti-fog and anti-fog effect has not been obtained.

Problems to be Solved by the Invention The present invention provides an anti-fog and anti-fog agent, particularly an anti-fog and anti-fog agent suitable for imparting practically satisfactory anti-fog and anti-fog properties to the surface of agricultural synthetic resins. It was made for the purpose of

Means for solving the problem, that is, the present invention provides - Formulas [I] and [11 [wherein A
represents -Go-C, H, .0Rf (Rf represents a perfluoroalkenyl group CaF++ or CIF17) or -CH, CH, Rf'(Rf' represents a perfluoroalkyl group having 4 to 12 carbon atoms), EO represents an ethylene oxide residue, PO represents a propylene oxide residue, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms which may have a branched chain, and R' represents a hydrogen atom or a branched alkyl group. Represents an alkyl group having 1 to 18 carbon atoms or a phenyl group having a branched chain, which may have a chain, X represents a number of 1 to 30, and y represents a number of 0 or 1 to 29. 5≦x+y≦30), m indicates a number from 1 to 10, and n indicates a number from 0 to 9 (however, l≦m+n≦10,
The present invention relates to an anti-fogging fogging agent containing a fluorine-containing aromatic carboxylic acid ester consisting of a structural unit represented by m/n=110 to 1/l O)].

In the fluorine-containing aromatic carboxylic acid ester used in the present invention, the structural units represented by formulas [1'l and [I] may be bonded in a block form, or both may be bonded randomly. You can.

- In formula [8 in 11, Rf represents a perfluoroalkenyl group C6F11 or C*F+7, which is derived from, for example, a dimer module or trimer of tetrafluoropropene.

Such a perfluoroalkenyl group has the following formula (a
) to (d) are exemplified: (c) In the general formulas [I] and [I[], EO and PO
represent ethylene oxide residue and propylene oxide residue, respectively, these residues may be bonded in a block form, or both may be bonded randomly, and X is 1 to 30, preferably 5 to Showing the number 20,
y represents 0 or a number from 1 to 29, preferably from 5 to 20. However, 5≦x+y≦30.

Moreover, in - formula [I] and/or [I[],
R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, which may have a branched chain;
R' is a hydrogen atom, an optionally branched alkyl group of 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, or an optionally branched alkyl group of 1 to 18 carbon atoms, preferably 1- Indicates a phenyl group having an alkyl group of 12, m
represents a number of 1 to 101, preferably 1 to 6, and n is 0 to 9
, preferably a number from 1 to 9. However, 2≦m+n≦l
O and m/n-110-1/10.

The method for producing the fluorine-containing aromatic carboxylic acid ester consisting of the structural units represented by the above general formulas [I] and [11] is not particularly limited, but the methods illustrated in Examples are simple, for example.

Two or more of the above fluorine-containing aromatic carboxylic acid esters may be used in combination, if desired.

The antifogging agent according to the invention may optionally contain conventional additives,
For example, plasticizers (e.g. di-n-octyl phthalate,
Heptalic acid derivatives such as di-2-ethylhexyl phthalate and diisodecyl heptalate, isophthalic acid derivatives such as diisooctyl isophthalate, adipic acid derivatives such as di-n-butyl adipate, tricresyl phosphate,
epoxidized soybean oil, etc.), heat stabilizers (e.g., zinc stearate, calcium stearate, barium stearate, phosphites, etc.), lubricants (e.g., stearic acid, polyethylene wax, etc.), ultraviolet absorbers (e.g., benzene Triazole type, benzoate type, benzophenone type, cyanoacrylate type, phenyl salicylate type, etc.), coloring agent (for example, carbon black, phthalocyanine blue, titanium oxide, etc.), etc. may be appropriately blended.

The anti-fogging and fogging agent according to the present invention contains the above-mentioned fluorine-containing aromatic carboxylic acid ester and other optional additives in a suitable solvent such as isopropyl alcohol, chloroform,
Dissolved in methylene chloride, carbon tetrachloride, Freon 113, etc.
; may be prepared as a dispersed solution or I; may be prepared as a dispersion liquid, and this may be applied to the surface of the agricultural synthetic resin by spray coating, dipping coating, roll coating, brush coating, etc.

In this case, the concentration of the fluorine-containing aromatic carboxylic acid ester is usually 0. O1-3.0% by weight, preferably 0.1-2.
0% by weight, and the concentration of the antifogging agent is usually 0.01~
2.0% by weight, preferably 0.1-1.0% by weight.

The anti-fogging and fogging agent according to the present invention is produced by kneading the above-mentioned fluorine-containing aromatic carboxylic acid ester with a base resin and conventional additives such as the above-mentioned plasticizer, and using the kneaded product to form a molding material such as a film or sheet. It may also be used in the preparation of

Base resins include vinyl chloride, ethylene, propylene,
Examples include 7-mer homopolymers or copolymers such as acrylic esters and methacrylic esters,
Vinyl chloride resin, that is, polyvinyl chloride and a copolymer containing 50% by weight or more of a vinyl chloride component, such as one or more selected from the group consisting of vinyl acetate, propylene, vinyl ether, acrylic ester, and methacrylic ester. Copolymers with vinyl chloride are preferred in terms of weather resistance, light transmittance, strength, cost, and the like.

In this embodiment, the amount of the fluorine-containing aromatic carboxylic acid ester blended is not particularly limited, but is usually 100% of the base resin.
0.01 to 3.0 parts by weight, preferably 0
．． If the amount is 1 to 2.0 parts by weight, and if it is less than 0.01 part by weight, it is difficult to achieve the initial objective of the present invention, and
If too large a quantity is blended, the formed film or sheet will become cloudy and lose its transparency, which is not preferable.

After kneading the above-mentioned ingredients using a conventional compounding machine or mixer, a regular burr pump blender, a super mixer, a Banbury mixer, etc., the mixture is kneaded using a known molding method such as melt extrusion method, calendar method, press method or For example, agricultural molding materials such as films and sheets can be manufactured by a casting method or the like.

In this case, the thickness of the molded film or sheet is not particularly limited, but for example, the thickness of the vinyl chloride resin film is about 20 to 400 μm from the viewpoint of strength, transparency, workability, etc.
It is preferable to

Hereinafter, the present invention will be explained by examples.

Examples 1 to 3 A mixture according to the formulation shown in Table 1 was kneaded for 3 minutes using two rolls heated to 160°C, and then a 100μ thick film (1) was kneaded using a press heated to 170°C. Examples 1), 2 (Example 2) and 3 (Example 3) were prepared.

The antifogging properties, antifogging properties, and contact angle with water of these films were investigated as follows, and the results are shown in Table 1.

The method for preparing the fluorine-containing compound (1) is as follows.

In a reaction vessel equipped with a thermometer, cooling tube, stirrer, and dropping funnel, 200 g of polyoxyethylene nonylphenol formaldehyde condensate, 44 g of p(perfluorononenyloxy)benzoic acid chloride, and 150 ml of benzene were added.
was added, and while cooling in an ice-water bath, 12.7 g of triethylamine was added dropwise to the solution and reacted for 1.5 hours.
The mixture was heated to 0-60°C and reacted for 5 hours. The reaction solution was subjected to filtration treatment, 100 ml of benzene and 100 ml of n-hexane were added to the filtrate, and after being left for day and night, it was subjected to silica gel column treatment, and then the solvent was removed under reduced pressure to obtain fluorine-containing compound (1) 2309. . (Yield 95.3%) (1) Evaluation of antifogging property Add 50cc of hot water (50°0) to a beaker (300cc)
The mouth was covered with the above film and sealed with a rubber band and tape. This sealed beaker was left standing in a dryer at 50°C for about 1 hour, then transferred to a constant temperature room at 5°C, and after being left for 60 minutes, the state of water adhesion on the inner surface of the film was observed with the naked eye.

The evaluation criteria for antifogging properties are as follows: 5: Water adheres in the form of a film, but no water droplets are observed; 4: Water adheres in the form of a film, but large water droplets are observed in some areas.

3: Water adheres as a film, but large or small water droplets are visible. 2: Large and small water droplets are observed. Small water droplets adhere to the knee surface and the bottom of the beaker is not visible.

(2) Fog-proof evaluation Make a frame using 1cm square lumber and tilt the ceiling at an angle of 30°.
The fog evaluation box, with the above film attached to the sides and ceiling and the bottom immersed in a water tank, was left in a water bath at 50°C for 2 hours, then transferred to a constant temperature room at 5°C, and after 15 minutes the inside of the film was exposed. The state of fog generation near the surface was observed.

The fog proof evaluation criteria are as follows.

5: No fog occurs, 4: Slight fog occurs, 3: Fog occurs, 2: A slightly thick fog occurs, l: Very thick fog occurs.

(3) Measurement of contact angle with water The film used in the above antifogging evaluation test was dried,
The contact angle of this dried film with water after 1 minute was measured using a goniometer type 2 G-1 contact angle measuring device manufactured by Elma Optical Co., Ltd.

Comparative Examples 1 and 2 Films 1'' (Comparative Example 1) and 2' (Comparative Example 2) prepared according to the formulations in Table 1 according to Examples 1 to 3
The anti-fog properties, anti-fog properties, and contact angle with water were investigated, and the results are shown in Table 1.

(Hereinafter, blank space) Effects of the Invention Synthetic resin films or sheets coated with the anti-fog and anti-fog agent of the present invention, or synthetic resin films or sheets containing the anti-fog and anti-fog agent, can be used in greenhouses, tunnels, etc. By deploying it in a cultivation facility, the above-mentioned conventional problems such as the occurrence of diseases in cultivated crops can be solved based on the excellent anti-fogging and fog-proofing effects.

Claims (1)

[Claims] 1. General formulas [I] and [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, A is - CO・C_5H_4・ORf (Rf is a perfluoroalkenyl group C_6F_1_1 or C_
9F_1_7) or -CH_2CH_2Rf'
(Rf' represents a perfluoroalkyl group having 4 to 12 carbon atoms), EO represents an ethylene oxide residue, PO represents a propylene oxide residue, and R may have a hydrogen atom or a branched chain. represents an alkyl group having 1 to 18 carbon atoms, R' represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a branched chain, or a phenyl group having a branched chain, and x represents 1 to 18 carbon atoms; Showing the number 30,
y indicates 0 or a number from 1 to 29 (5≦x+y
≦30), m indicates a number from 1 to 10, and n indicates a number from 0 to 9 (however, 1≦m+n≦10, m/n=1/0 to 1/
10)] An anti-fogging and fogging agent containing a fluorine-containing aromatic carboxylic acid ester consisting of the structural unit represented by [10]. 2. The antifogging and fogging agent according to claim 1, which contains 0.01 to 3.0 parts by weight of the fluorine-containing aromatic carboxylic acid ester per 100 parts by weight of the base resin.