JPH11335568A - Anti-fogging agent-containing master batch and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a master batch, which does not generate any acidic gas at the time of kneading and melting, by melt mixing a chlorine atom-free thermoplastic resin capable of being melt molded at a specified temperature, an F-containing anti-fogging agent, and a basic inorganic compound. SOLUTION: There are melt mixed, preferably, 100 parts by weight of a chlorine atom-free thermoplastic resin capable of being melt molded at 150 to 230 deg.C and, preferably, containing 80 wt.% or over of a polyolefin resin and/or an ethylene-vinyl acetate resin; preferably, 1 to 70 parts by weight of an F- containing anti-fogging agent; and, preferably, 0.01 to 14 parts by weight of a basic inorganic compound (e.g. calcium carbonate), which is in the form of a powder, preferably, having a particle size of 0.1 to 10 μm. The ratio by weight of the basic inorganic compound to the F-containing anti-fogging agent is preferably at 0.005 to 0.2. The F-containing anti-fogging agent includes, for example, one which is obtained by reacting a fluoroalkyl group-containing epoxy compound with a compound having one or more OH groups in the molecule in the presence of an acid catalyst such as BF3 or the like, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a masterbatch containing an antimisting agent, a method for producing the same, and a method for producing an agricultural film using the masterbatch containing the antimisting agent. More specifically, it has the ability to suppress fog generation near the inner surface of the film when used as an agricultural vinyl house (fog resistance) and the ability to exhibit the fog resistance over a long period of time (fog resistance). The present invention relates to a method for producing an agricultural film containing no chlorine atom, a raw material containing an antifog agent and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, so-called house cultivation or tunnel cultivation, in which useful plants are forcibly, semi-forcibly or suppressed under covered with an agricultural film, have been actively used in order to increase the productivity and market value of the useful plants. Is being done. A vinyl chloride resin is currently used as this agricultural film. This agricultural film contains an antifogging agent (such as a sorbitan fatty acid ester), which is a type of surfactant, in order to promote the flow of water droplets on the inner surface of the film and increase the amount of sunlight. Under such a film containing an anti-fogging agent, the temperature difference between inside and outside becomes large, and fog is generated near the inner surface. Therefore, a fluorine-containing anti-fog agent is added to impart anti-fog properties.

[0003] However, since vinyl chloride resin has chlorine atoms, it emits highly toxic dioxin when burned at a low temperature, and must be treated with a special high-temperature combustion treatment facility when it is discarded. Agricultural films having the above-mentioned properties with resins other than vinyl chloride resins have been studied, but changing the resin alone has not been put into practical use due to some problems. For example, when a thermoplastic resin containing no chlorine atom such as a polyethylene resin or a vinyl acetate resin is used, the temperature at which the resin can be melt-molded is higher than that of a vinyl chloride resin (15).
0 to 230 ° C.), so that kneading and melting at a high temperature, pelletization, and film forming processing are required.

As a fluorine-containing antifog agent currently used for a vinyl chloride resin film, a fluorine-containing antifoggant synthesized by ring-opening addition of a fluoroalkyl group-containing epoxy compound and an oxyethylene group-containing compound in the presence of a Lewis acid catalyst. Antifoggants (JP-A-59-93739, JP-A-61-13324)
4, JP-A-61-152745, JP-A-64-147,
It is described in JP-A-64-14263, JP-A-1-216947, JP-A-1-246237 and the like. ).

As the Lewis acid catalyst, boron trifluoride (BF ₃ ) or a complex thereof is used from the viewpoint of reactivity. However, the fluorine-containing antimisting agent synthesized by these methods has an acid content and a small amount. BF ₃ remains. This BF ₃ has a property of being decomposed by moisture in the air and remaining acid components to generate hydrofluoric acid (HF) gas. This property is particularly remarkable at high temperatures, and becomes a problem when a thermoplastic resin containing no chlorine atom is used, which has a higher melt forming temperature than a vinyl chloride resin.

In order to solve this problem, a method was studied in which BF ₃ did not remain in the fluorine-containing antifog and the acid content was reduced to a non-corrosive state. To eliminate this corrosiveness, the acid content must be less than 1 ppm in terms of HF,
It is further desired that it be less than pm.

A method for removing acid components such as BF ₃ in a fluorine-containing antifog by washing with water involves dissolving, emulsifying or uniformly dispersing in water and dissolving with water since the fluorine-containing antifog is a surfactant. Separation is difficult and not practical.

A method for removing acid components such as BF ₃ in a fluorine-containing antifog by washing with a mixed solvent (JP-A-61-4)
In 5973), since the fluorine-containing antifog contains a large amount of etheric oxygen atoms having high coordination properties, it is partially coordinated with BF ₃ and cannot be completely removed. 230 ° C for similar reasons
It cannot be completely removed even if it is removed under reduced pressure at a temperature below. 2
At 30 ° C. or higher, the catalytic action of the coordinated BF ₃ becomes active, causing the generation and decomposition of dioxane due to the cyclization reaction of the oxyethylene portion of the fluorine-containing antifog, and the anti-fog property is reduced. Light transmission decreases due to coloring.

Although there is a method of reducing the amount of the BF ₃ complex used in the reaction, in order to progress the reaction, 0.1% by weight or more of the BF ₃ complex is used with respect to the starting fluoroalkyl group-containing epoxy compound. Necessary, weight reduction below this is not possible. As described above, BF ₃ in the fluorine-containing antifog
It is difficult to reduce the residual amount of the acid and to remove the acid component.

When the above-mentioned fluorine-based antifogant containing BF ₃ and containing an acid component is used for a thermoplastic resin containing no chlorine atom, the remaining BF ₃ is kneaded and melted at a high temperature of 150 ° C. or more. ₃ is decomposed to generate HF gas. Therefore, the equipment requires acid gas elimination equipment, which causes problems in workability and cost. In particular, in a masterbatch containing an antimisting agent, since the content of the fluorine-containing antimisting agent is large, HF gas in which BF ₃ is decomposed is generated intensely, which is a problem. In addition, since a part of the generated HF gas remains in the antifoggant-containing masterbatch and generates HF gas during forming and film forming, mild steel or the like which is easily corroded by acid cannot be used as forming and film forming equipment. However, the material is restricted to expensive materials such as Hastelloy and titanium. Further, there is a possibility that acid content may remain in the film as a product, and there is also a problem of environmental pollution.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a masterbatch containing an antifog agent using a chlorine-free thermoplastic resin which does not involve the generation of an acid component based on BF ₃ or the like during the production of agricultural films. And a method for producing an agricultural film using the same, and a method for producing a masterbatch containing an antifog agent based on BF ₃ or the like without generating an acid component.

[0012]

SUMMARY OF THE INVENTION The present invention relates to
Provided is a master batch containing an anti-mist agent, which is obtained by melt-mixing a thermoplastic resin containing no chlorine atom, which can be melt-molded at 0 ° C., a fluorine-containing anti-mist agent, and a basic inorganic compound. Further, the present invention provides a method for producing the above-mentioned anti-mist agent-containing master batch, which comprises kneading and melting at 150 to 230 ° C. using an extruder. Further, the present invention provides a method for producing an agricultural film, which comprises mixing the above-mentioned master batch containing an antifog agent and a thermoplastic resin containing no chlorine atom to form a film.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION A master batch containing an antimisting agent of the present invention comprises a thermoplastic resin containing no chlorine atom, which can be melt-molded at 150 to 230 ° C., a fluorine-containing antimisting agent, a basic inorganic compound, Are melt-mixed. As a method of melt mixing, there is a method of kneading and melting after mixing.

The ratio of the raw materials for obtaining the master batch containing an antimisting agent is preferably 1 to 70 parts by weight, particularly 5 to 50 parts by weight, based on 100 parts by weight of the thermoplastic resin. , The basic inorganic compound is 0.01 to 14
Part by weight, especially 0.05 to 5 parts by weight is preferred.

If the amount of the fluorine-containing antimisting agent exceeds 70 parts by weight, stickiness occurs during mixing using a Henschel mixer or the like, so that it is difficult to carry it into an extruder and exceeds the limit of compatibility with a resin, resulting in poor uniformity. On the other hand, if the amount is less than 1 part by weight, the anti-fog performance decreases. If the amount of the basic inorganic compound is less than 0.01 part by weight, the removal of the acid component cannot be sufficiently performed, and if the amount exceeds 14 parts by weight, molding becomes difficult. The weight ratio of the basic inorganic compound to the fluorine-containing antifog is preferably 0.005 to 0.2, particularly preferably 0.01 to 0.1.

As the basic inorganic compound, basic salts and hydroxides of alkali metals, alkaline earth metals, aluminum and other metals are preferred. Particularly preferred basic salts are carbonates and basic carbonates. Specifically, aluminum hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, potassium sodium carbonate, barium carbonate or a compound represented by the following formula 1 is preferable. Calcium carbonate, barium carbonate, magnesium carbonate Is particularly preferred.

[0017]

(M ²⁺ ) _1-x (Al ³⁺ ) _x (OH ⁻ ) ₂ (D ⁿ⁻ ) _{x / n} · mH ₂ O Formula 1

The symbols in the formula 1 have the following meanings. M: Mg, Ca, Co, Ni, Cu, Pb or Zn. D: Cl, F, CN, NO ₂ , NO ₃ , CO ₃ , C ₂ O
_4, S, SO _4, SCN, or PO _4. x: 0 ≦ x <0.5. m: 0 ≦ m <0.7. n: D anion value.

The compound represented by the formula 1 includes basic magnesium carbonate, basic cobalt carbonate, basic zinc carbonate,
Preferable examples include basic nickel carbonate, basic copper carbonate, basic lead carbonate, basic copper sulfate, basic aluminum magnesium carbonate, and magnesium hydroxide. For basic aluminum magnesium carbonate, (Mg ²⁺ ) _9/13
(Al ³⁺ ) _4/13 (OH ⁻ ) ₂ (CO ₃ ^2- ) ₂ / _13.7 / 1
Compounds having different composition ratios, such as 3H ₂ O, are commercially available (Kyowa Chemical Industry Co., Ltd., trade name Kyoward KW-100, etc.).

In order to neutralize the acid component contained in the fluorinated antifog and the acid component generated upon heating, the basic inorganic compound preferably has a smaller particle diameter, and more preferably has a particle size of 0.1 to 10 μm. 0.1 to 2 μm is preferred. If the particle size is less than 0.1 μm, the powder tends to flutter and it is difficult to perform a uniform dispersion. If it exceeds 10 μm, the surface area is small and it is necessary to increase the amount of addition, and when formed into a film, the light transmittance is reduced by 5% or more. These basic inorganic compounds may be used alone or in a combination of two or more.

A chlorine-free thermoplastic resin that can be melt-molded at 150 to 230 ° C. has transparency, ease of processing,
From the viewpoint of durability, a resin containing a polyolefin resin and / or an ethylene-vinyl acetate resin in a total amount of 80% by weight or more is preferable, and 100% by weight is particularly preferable. Ethylene-vinyl acetate resin (EVA) is preferable because of its good durability in cold regions.

Specific examples of the polyolefin resin include:
The following resins are exemplified. The homopolymer resin is preferably a polyethylene resin, and particularly preferably a low-density polyethylene resin (abbreviation: L
DPE). As the resin of the copolymer, ethylene-
Propylene resins and ethylene-butylene resins are preferred.

Further, the fluidity of the resin is JIS-K7
The melt index (MI value) according to 210 is 2 to 10.
0 (g / 10 minutes) is preferable, and especially 5 to 2
0 (g / 10 minutes) is preferable.

Currently, LDPE is available from Sumitomo Chemical, Mitsui Chemicals,
Products with different MI values are commercially available from many companies including Asahi Kasei Kogyo, Tosoh, Showa Denko, Mitsubishi Chemical, Nippon Unicar, and Mitsui Dupont Polychemicals. The shape of the resin includes powder, pellet, and lump. EVA
Similarly, many products are commercially available from polyethylene manufacturers.

In the present invention, as the thermoplastic resin containing no chlorine atom, the above-mentioned polyolefin resin, E
Instead of VA or the above-mentioned polyolefin resin,
Resins that can be used in addition to EVA include propylene-
Examples include vinyl acetate resin, ethylene-vinyl acetate-propylene resin, styrene resin, ethylene-styrene resin, carbonate resin, ABS resin, acrylic resin, ethylene terephthalate resin, fluorine resin, nylon resin, urethane resin and the like. However, the melt molding temperature is 15
Limited to a thermoplastic resin containing no chlorine atom at 0 to 230 ° C.

As the fluorine-containing antifog in the present invention,
A fluorine compound represented by the following formula 2 or 3 is preferable.

[0027]

R ^fa -R ¹ -O (C ₂ H ₄ O) _h -R ² -R ^fb Formula 2 R ^fc -R ³ -O (C ₂ H ₄ O) _i- (CO ) _j -R ⁴ ·· formula 3

However, the symbols in the formulas 2 and 3 have the following meanings. R ¹ , R ² , R ³ : each independently represents a divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms in which an oxygen atom may be inserted between carbon atoms, and a hydrogen atom in the group. May be substituted with an acyloxy group such as an acetoxy group or a hydroxyl group. R ⁴ : a hydrogen atom, a phenyl group, a glycidyl group, or
A monovalent aliphatic hydrocarbon group having 2 to 16 carbon atoms, in which an oxygen atom may be inserted between carbon atoms and which may contain a double bond; R ^fa , R ^fb , and R ^fc each independently represent a C 4-16 polyfluoroalkyl group in which an oxygen atom may be inserted between carbon atoms. h, i: 2 to 30 numbers each independently. j: 0 or 1.

As R ¹ , R ² and R ³ , a divalent aliphatic hydrocarbon group having 3 to 5 carbon atoms which may have an oxygen atom inserted between carbon atoms is preferable. As the hydrogen atom-substituted group, one in which one of the hydrogen atoms is substituted with an acetoxy group or a hydroxyl group is preferable. R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The polyfluoroalkyl group is hereinafter referred to as ^Rf group. The R ^f group is a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms. The carbon number of the R ^f group is 4-1.
6 is preferred. The R ^f group preferably has a linear structure, and the number of fluorine atoms is [(the number of fluorine atoms in the R ^f group) / (the number of hydrogen atoms contained in the corresponding alkyl group having the same carbon number)].
When expressed by × 100 (%), it is preferably at least 60%, particularly preferably at least 80%. As the fluorine-containing antifog agent, specifically, the following compounds are preferable. In the formula, Ph represents a phenyl group, and G represents a glycidyl group.

[0031]

Embedded image F (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ O (C ₂ H ₄ O) _n ——CH ₂ CH (OH) CH ₂ (CF ₂ ) ₈ F ... Compound (A) (In the above formula, n is 22.8, indicating the average number of the groups.) F (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ O (C ₂ H _{4
O) 5 --CH 2 CH (OH} ) CH 2 (CF 2) 8 F, F (CF 2) 5 C 2 H 4 OCH 2 CH (OH) CH 2 O
_{(C 2 H 4 O) 18} --CH 2 CH (OH) CH 2 OCH
₂ (CF ₂ ) ₅ F, H (CF ₂ ) ₈ CH ₂ OCH ₂ CH (OH) CH ₂ O
(C ₂ H ₄ O) ₅ H, F (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ O (C ₂ H _{4
O) 5 CH 3, F (} CF 2) 10 CH 2 CH (OH) CH 2 O (C 2 H 4
O) ₅ CH ₃ , F (CF ₂ ) ₁₆ CH ₂ CH (OH) CH ₂ O (C ₂ H ₄
O) ₅ CH ₃ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH
_{2 --O (C 2 H 4 O} ) 5 CH 3, H (CF 2) 10 CH 2 CH (OH) CH 2 O (C 2 H 4
O) ₅ CH _3.

[0032]

Embedded image H (CF ₂ ) ₈ CH ₂ OCH ₂ CH (OH) C
H ₂ O (C ₂ H ₄ O) ₆ CH ₃ , H (CF ₂ ) ₈ CH ₂ OCH ₂ CH (OH) CH ₂ O
(C ₂ H ₄ O) ₆ Ph, H (CF ₂ ) ₈ CH ₂ OCH ₂ CH (OH) CH ₂ O
_{(C 2 H 4 O) 6} G, H (CF 2) 8 CH (CH 3) OCH 2 CH (OH) C
H ₂ —O (C ₂ H ₄ O) ₉ H, (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH
_{2 --O (C 2 H 4 O} ) 10 C 2 H 5, (CF 3) 2 CF (CF 2) 6 CH 2 CH (OH) CH
₂ --O (C ₂ H ₄ O) ₁₀ Ph, F (CF ₂ ) ₁₆ CH ₂ CH (OH) CH ₂ O (C ₂ H ₄
O) ₁₄ C ₂ H ₅ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH
_{2 --O (C 2 H 4 O} ) 10 H, F (CF 2) 6 CH 2 CH (OH) CH 2 O (C 2 H 4
O) ₂₀ H, F (CF ₂ ) ₁₀ CH ₂ CH (OCOCH ₃ ) CH ₂ O
_{(C 2 H 4 O) 10} H, F (CF 2) 10 CH 2 CH (OCOCH 3) CH 2 O
_{(C 2 H 4 O) 10} CH 3, (CF 3) 2 CF (CF 2) 6 CH 2 CH (OH) -
_{O (C 2 H 4 O)} 8 COC (CH 3) = CH 2, (CF 3) 2 CF (CF 2) 2 (CH 2) 6 CH (O
_{H) - CH 2 O (C} 2 H 4 O) 5 H, F (C 3 F 6 O) 4 CF (CF 3) CH 2 CH (OH)
_{--CH 2 O (C 2 H 4} O) 3 H, F (CF 2) 10 CH 2 CH (OH) CH 2 --O (C 2
_{H 4 O) 5 (C 3} H 6 O) 5 CH 3.

These compounds are prepared by combining a fluoroalkyl group-containing epoxy compound and a compound having one or more hydroxyl groups in a molecule with BF ₃ or a complex thereof with an ether or alcohol, sulfuric acid, or an acid catalyst such as NaHSO _4. (Japanese Patent Application Laid-Open No. 61-59773).
etc). Further, it can be synthesized by reacting a fluorinated alcohol with a compound having one or more glycidyl groups in the molecule in the presence of the above-mentioned acid catalyst. In these catalysts, BF ₃
Complexes are most used because they have the advantage of high reaction rates and low by-products. Acid content of 1 ppm or more remains in the fluorine-containing antifog agent synthesized by the above production method, and B
F ₃ remains.

The antifoggant-containing masterbatch of the present invention may further contain, as a fluorine-containing antifoggant, a copolymer having a fog-proof property containing a polymerized unit based on a monomer represented by the following formula (4). By containing this copolymer, the anti-fog durability is improved, which is preferable. R ^fd -Q-OCOCR ⁵ = CH ₂ Formula 4 where the symbols in Formula 4 have the following meanings. R ^fd : a polyfluoroalkyl group having 4 to 16 carbon atoms. Q: a single bond or a divalent linking group. R ⁵ : a hydrogen atom or a methyl group.

The copolymer containing the polymerized unit based on the monomer represented by the formula 4 undergoes a crosslinking reaction due to BF ₃ remaining in the fluorine-containing antifog during melt-kneading at 150 ° C. or more, and the viscosity rapidly increases. The crosslinking reaction can be suppressed by adding a basic inorganic compound.

R ^fd is the same as the R ^f group described above, and particularly preferably has 6 to 10 carbon atoms. As the monomer represented by Formula 4, the following are preferable.

[0037]

Embedded image F (CF ₂ ) ₈ CONHCH ₂ CH ₂ OCOC
H = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (C ₄ H ₉ ) CH ₂ CH ₂ OC
_{OCH = CH 2, F (CF} 2) 8 CH 2 CH 2 OCOCH = CH 2.

The copolymer containing a polymerized unit based on the monomer represented by the formula (4) is a copolymer of the monomer represented by the formula (4) and a compound copolymerizable with the monomer (JP-A-59-80).
468), and those having a number average molecular weight in the range of 1,000 to 50,000 are preferred.

Compounds that can be copolymerized with the monomer represented by Formula 4 include ethylene, vinyl acetate, vinyl fluoride, styrene, α-methylstyrene, p-methylstyrene,
(Meth) acrylic acid, (meth) acrylic acid alkyl ester, poly (oxyalkylene) (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide,
Examples thereof include vinyl alkyl ether, vinyl alkyl ketone, butadiene, isoprene, glycidyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, maleic anhydride, aziridinyl (meth) acrylate, and N-vinyl carbazole. The copolymer oligomer is a fluorine-containing copolymer oligomer obtained by copolymerizing one or more of these compounds with a monomer represented by Formula 4. In this specification,
Acrylate and methacrylate are collectively referred to as (meth)
Acrylate. The same applies to other notations such as (meth) acrylic acid.

As commercially available fluorine-containing antifog agents, Surflon "KC-20", Surflon "KC-40" and "AF-EP-5" manufactured by Asahi Glass Co., Ltd., and Unidyne "DS-401" manufactured by Daikin Industries, Ltd. ”, Unidyne“ DS-4 ”
03 ", Neos Corporation's" Futant "251 and Dainippon Ink and Chemicals, Inc. Megafac" F-142D ". In addition, in Table 2, these commercially available fluorine-containing antifog agents were abbreviated by the above-mentioned "".

The method for producing a masterbatch containing an antifog agent of the present invention is characterized by kneading and melting at 150 to 230 ° C. using an extruder. As a specific example, using a mixer such as a Henschel mixer or a ribbon mixer, a thermoplastic resin containing no chlorine atom, a fluorine-containing antifog and a basic inorganic compound are mixed, and the mixture is extruded by twin-screw molding. By kneading and melting at 150 to 230 ° C. using a kneader such as a kneader, a screw extruder, and a roll kneader, an antifog agent-containing master batch can be easily produced. This masterbatch containing the antifog agent is usually formed into a predetermined shape.

The shape of the master batch containing the antifog agent is preferably a pellet having good workability such as charging during film forming. It is difficult to charge in the form of a lump, and it flutters in the case of a powder, resulting in poor workability. As a specific example of forming into a pellet, there is a method of cutting into a strand of a thread and cutting with a pelletizer.

Furthermore, by mixing the master batch containing the antifog agent and the thermoplastic resin containing no chlorine atom and forming a film, an agricultural film can be manufactured without generating HF gas during the film forming process. it can. The thermoplastic resin containing no chlorine atom used at this time is not particularly limited, but is preferably the same as the thermoplastic resin contained in the antifoggant-containing masterbatch from the viewpoint of workability. This film has anti-fog performance, is useful as an agricultural film, and has little effect on the environment at the time of disposal.

As described above, by adding a basic inorganic compound, a masterbatch containing an antifog agent and an agricultural film having antifog performance can be produced by a method that does not generate an acidic gas such as HF.

[0045]

EXAMPLES Examples 1 to 3 are synthesis examples of a fluorine-containing antifog, Examples 4 to
14 and Examples 25 to 27 are Examples, and Examples 15 to 24 and Example 28 are Comparative Examples.

Example 1 Synthesis of Compound (A) In a 100 ml glass reaction flask, 47.6 g (0.10 mol) of 3-perfluorooctyl-1,2-epoxypropane (manufactured by Daikin Industries, Ltd.) Ethylene glycol (product name: PEG1000, manufactured by NOF Corporation)
51.1 g (0.05 mol) and 0.4 g of the BF ₃ ether complex were charged and reacted for 4 hours while stirring on a hot water bath controlled at 60 ° C. to obtain an unpurified compound (A). The obtained unpurified compound (A) is designated as Sample 1. For analysis, a part of the unpurified compound (A) was replaced with (CH ₃ ) ₃
Silylation with SiCl, gas chromatography (G
C) As a result of analysis, it was confirmed that the entire amount of epoxide was consumed and that 92.6% of polyoxyethylene glycol was consumed.

Example 2 Vacuum Treatment of Compound (A) The unpurified compound (A) obtained in Example 1 was subjected to a vacuum treatment at a temperature of 80 ° C. and a pressure of 2 mmHg for 3 hours. The acid content before and after the decompression treatment was 1720 ppm and 62 pp, respectively.
m. The compound (A) after the reduced pressure treatment is designated as Sample 2.

Example 3 25 g of perfluorooctylethyl acrylate was placed in a 200 ml glass reaction flask.
(Polyoxyalkylene) acrylate (manufactured by NOF Corporation, trade name: PE-200) 25 g, ethyl acetate 50
g, a mercaptan-based molecular weight regulator 2.5 g, and a polymerization initiator (AIBN: azobisisobutylnitrile) 0.
5 g was charged and reacted at 70 ° C. for 10 hours. After cooling to room temperature, GC analysis confirmed consumption of all of the monomers. The solvent was removed from the obtained reaction solution by drying under reduced pressure to obtain a light yellow viscous liquid copolymer. As a result of gel permeation chromatography (GPC) analysis, the average molecular weight of the obtained copolymer was 5,000 in terms of styrene. This copolymer and Sample 1 were mixed at the same weight ratio to obtain Sample 3.

[Examples 4 to 24]
Mix with a Henschel mixer at the mixing ratio shown in Table 2,
Using an axial extrusion molding machine, the mixture was kneaded and melted at a temperature of 170 to 200 ° C. and molded to obtain a pellet-shaped master batch containing an antifog agent. Hereinafter, the pellet-containing antifog agent-containing master batch is referred to as a pellet. For each of the obtained pellets, acid content, corrosiveness evaluation, and presence or absence of HF were measured by the following methods. Table 2 shows the results.

Fluorine-containing antifog (samples 1, 2, 3 or commercially available fluorinated antifog). Tri (n) as a basic inorganic compound or a comparative example thereof
- butyl) amine [Bu ₃ N]. In Table 2, "KW-
"100" indicates a basic aluminum magnesium carbonate (Kyowa Chemical Industry Co., Ltd., trade name Kyoward KW-100). Thermoplastic resin (LDPE: trade name LJ-605, manufactured by Mitsubishi Chemical Co., Ltd., having an MI value of 8. EVA: EVA powder).

Because of the high accuracy of the analysis, the fluorine content was used for the measurement of the acid content. Although the presence of an acid other than HF is also conceivable, since 50 to 400 ppm of boron was detected in all of the fluorine-containing antimist agents including commercially available products, it was determined that BF ₃ or a BF ₃ complex was used as a catalyst during synthesis. It was considered that most of the generated acid content was HF, and the HF amount calculated from the fluorine ion concentration was used as the acid content.

As a measuring method, a fixed amount of pellets was put in a fluororesin container, heated to 150 ° C. (melted) under a nitrogen stream, and the acid content accompanying nitrogen was absorbed into ion-exchanged water. After the operation was continued until no acidic gas was recognized, the absorbed aqueous solution was neutralized with a 0.1 N KOH aqueous solution, and the concentration of the contained fluorine ion was measured with a fluorine ion selective electrode. The acid content contained in the pellet was calculated from the measured value.

[Evaluation of Corrosion Property]
The degree of corrosivity of the surface of the mild steel sheet after 500 hours at a temperature of 180 to 200 ° C was evaluated for appearance. As the evaluation criteria, the degree of corrosion was visually evaluated based on the criteria in Table 1 and quantified out of 5 points.

[0054]

[Table 1]

[Presence or absence of generation of HF gas] The presence or absence of HF gas in the gas generated at the time of kneading and melting at 170 to 200 ° C. by a twin-screw extruder is measured by a detector tube at the vent port of the molding machine. did.

[0056]

[Table 2]

As shown in Table 2, by adding a basic inorganic compound, HF during melt-kneading in an extruder was determined.
It was confirmed that generation of gas could be prevented, and a master batch containing an antifoggant containing no acid component could be produced. Further, since the pellets do not contain an acid component, there is no need to worry about corrosion of the metal material during the film forming process. It was also found that when tri (n-butyl) amine was used instead of the basic inorganic compound, generation of HF could not be prevented.

[Examples 25 to 28] The blending ratios of Examples 12 to 14 and the three pellets produced by the production method were mixed at the blending ratios shown in Table 3 to form a film to form films (Example 25, respectively).
To 27). As a comparative example, a film was prepared in the same manner except that no pellet was added (Example 28). Table 4 shows the results of evaluating the film appearance and the anti-fog property of the produced film by the following methods.

[0059]

[Table 3]

[Film Appearance] Compared to a film containing no pellet, the film was visually checked for differences in transparency and coloring.

[Evaluation of anti-fog property] A vinyl house was prepared from a film and installed outdoors. The observation period is one month (Heisei 1
The observation frequency was once each in the morning and evening, and it was visually checked whether fog had occurred, and the number of fog occurrences was counted.

[0062]

[Table 4]

As shown in Table 4, it was confirmed that the inclusion of the anti-mist agent-containing masterbatch of the present invention did not affect the appearance of the film and showed good anti-mist properties.

[0064]

According to the method for producing a masterbatch containing an antifog agent of the present invention, the generation of acidic gases such as HF during kneading and melting can be prevented, and the working environment can be prevented from lowering. The resulting anti-fog agent-containing masterbatch has no acid content and corrosiveness, and is easy to handle, so it is a raw material for agricultural films that have a fog-proof performance made of a chlorine-free thermoplastic resin for agricultural vinyl houses. As excellent.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/22 C08K 3/22 3/26 3/26 5/06 5/06 C08L 23/00 C08L 23/00 23/08 23 / 08

Claims (7)

[Claims] 1. A masterbatch containing an antifogging agent obtained by melt-mixing a chlorine-free thermoplastic resin which can be melt-molded at 150 to 230 ° C., a fluorinated antimisting agent, and a basic inorganic compound. 2. The method according to claim 1, wherein the fluorine-containing antifogant is contained in an amount of 1 to 70 parts by weight and the basic inorganic compound in an amount of 0.01 to 14 parts by weight based on 100 parts by weight of the thermoplastic resin. Masterbatch containing antifog. 3. The method according to claim 1, wherein the basic inorganic compound has a particle size of 0.1 to 10 μm.
The anti-mist agent-containing master batch according to claim 1 or 2, which is in the form of a powder. 4. The thermoplastic resin according to claim 1, wherein the total weight of the thermoplastic resin is at least 80% by weight of a polyolefin resin and / or an ethylene-vinyl acetate resin.
A masterbatch containing the described antifog. 5. The method according to claim 1, which has a pellet-like shape.
The antifoggant-containing master batch according to 3 or 4. 6. An extrusion molding machine at 150 to 230 ° C.
The composition is kneaded and melted in the following manner.
Or a method for producing a master batch containing an antimisting agent according to item 5. 7. An agricultural film characterized by mixing the masterbatch containing the antifog agent according to claim 1, 2, 3, 4 or 5 and a thermoplastic resin containing no chlorine atom to form a film. Manufacturing method.