JP4337448B2 - Fluorine-containing internal additive and synthetic resin film - Google Patents

Description

  The present invention relates to a fluorine-containing additive comprising a fluorine-containing polymer which is difficult to bleed out over a long period of time and maintains antifogging ability and transparency over a long period of time. The synthetic resin coating material to which a fluorine-containing additive is added is particularly useful as an agricultural synthetic resin coating material that retains antifogging properties, antifogging properties, and transparency over a long period of time.

  Fluorine-containing compounds are used as liquid surface tension reducing agents, surface treatment agents, and internal additives to modify solid surfaces that impart antifouling, water and oil repellency, and lubricity to solid surfaces such as fibers, films, and powders. It is used in the rubber industry and the plastics industry as an internal additive for plastics, an internal additive for rubbers, a wet film-forming aid for urethane, and a release agent for urethane. Particularly in the agricultural field, a fluorine-containing surfactant is blended and used to improve the coating material.

  For example, in recent years, greenhouse cultivation has been carried out in order to stably supply various vegetables and fruits throughout the year, and synthetic resin films such as polyvinyl chloride, polyethylene, and polyvinyl acetate are widely used as greenhouse coating materials. Although used, the original purpose of the greenhouse is to ensure the sunlight and temperature that are essential for the growth of cultivated crops, that is, to keep warm. In order to improve this heat retention, it is necessary to improve the hermeticity of the greenhouse and suppress the amount of heat that escapes by clearance ventilation.

  In recent years, especially in the trend of energy saving, efforts have been made to introduce sunlight as much as possible and raise the hermeticity of the greenhouse in order to make effective use of solar energy within the range that does not adversely affect the crops in the house. Has been. However, there is a tendency that the inside of the greenhouse becomes humid as the sealing degree increases, and as a result, there is a problem that fog generated in the greenhouse increases remarkably. Fog is considered to be closely related to the pest damage of cultivated crops or the quality of harvested products, and must be avoided as much as possible in greenhouse cultivation.

Fog is basically a phenomenon in which water vapor in the greenhouse is frequently generated in the morning and evening when the temperature difference inside and outside the greenhouse changes rapidly. Fog can be extinguished by ventilating the air inside and outside the greenhouse. However, in general, ventilation is not possible because importance is placed on the heat retention of the greenhouse, which has been a major problem in greenhouse cultivation.
Since the generation of fog is essentially a phenomenon caused by moisture in the greenhouse, the generation of fog can be reduced by reducing the amount of moisture supplied to the atmosphere in the greenhouse. Covering the soil surface in the greenhouse with multiple materials is one countermeasure against the generation of fog. However, the covering of the multi-material is not necessarily an advantageous method for the greenhouse grower because the covering operation is complicated and the material cost is high.

  In order to reduce the generation of fog, a method for improving the coating material by adding a fluorine-containing surfactant is proposed in, for example, Japanese Patent Application Laid-Open No. 57-14648 and Japanese Patent Publication No. 5-72942. This method is simple and can effectively suppress the generation of fog, but it is added to obtain a great effect, becomes cloudy when used for a long period of time, and brown spots are observed on the surface. Has a problem that the introduction of sunlight is hindered. This is because the fluoroalkyl group in the molecule of the fluorine-containing surfactant is strongly incompatible with the coating material, and the surfactant that has been uniformly dispersed on the surface or inside moves with time and associates with each other. This is thought to be due to the fact that it is easy to bleed out. Especially when the fluoroalkyl group of the fluorosurfactant has a large number of carbon atoms, this tendency is strong. Even if effective anti-fogging properties are exhibited at the beginning, the effect is maintained over a long period of time and solar energy is effectively used. It is disadvantageous to do. On the other hand, when the number of carbon atoms is small, the fluorine content in the molecule of the fluorine-containing surfactant is so small that effective fog prevention cannot be obtained.

An object of the present invention is to provide a fluorine-containing additive that has high affinity for a synthetic resin medium and is difficult to bleed out over a long period of time and retains antifogging ability, antifogging properties, and transparency over a long period of time.
Another object of the present invention is to provide a synthetic resin coating material that contains a fluorine-containing additive and maintains antifogging ability and transparency over a long period of time despite containing a high concentration of fluoroalkyl groups. is there.

  In order to solve this problem, the present inventors have developed a synthetic resin medium comprising a fluoropolymer composed of a portion composed of a repeating unit having a fluoroalkyl group having 1 to 8 carbon atoms and a portion having a polyalkylene glycol. High affinity, difficult to bleed out over a long period of time, maintaining anti-fogging ability and transparency over a long period of time, and despite the fact that the synthetic resin coating containing this fluorine-containing additive contains a high concentration of fluoroalkyl groups The inventors have found that the anti-fogging ability, anti-fogging property and transparency are maintained over a long period of time, and have completed the present invention.

The present invention is a fluorine-containing additive comprising a fluorine-containing polymer,
The fluorine-containing polymer is
(A) a block composed of a repeating unit having a C1-C8 fluoroalkyl group, and (B) a repeating unit having an oxyalkylene group,
Provided is a fluorine-containing additive which is a fluorine-containing graft polymer or a fluorine-containing block polymer.
The present invention also provides a synthetic resin coating material comprising the fluorine-containing additive and a synthetic resin.

  The fluorine-containing additive of the present invention is less likely to associate in a synthetic resin medium due to a structure having a portion composed of a repeating unit having a fluoroalkyl group and a portion composed of a repeating unit having an oxyalkylene group. Due to high medium affinity, it is difficult to bleed out over a long period of time. The synthetic resin coating material to which the fluorine-containing additive is added retains the fog prevention ability and transparency particularly for a long period of time.

Preferred form of the invention

In the fluorinated polymer, repeating units having a fluoroalkyl group are adjacent to each other in a block form.
In the fluoropolymer, the fluoroalkyl group is preferably a perfluoroalkyl group. The carbon number of the fluoroalkyl group (especially perfluoroalkyl group) is 1-8, such as 1-7, especially 1-6, especially 1-4. The fluoroalkyl group (Rf group) is particularly preferably C ₄ F ₉ . The fluorine-containing additive having a C ₄ F ₉ fluoroalkyl group has good dispersibility in synthetic resin medium affinity (for example, polyvinyl chloride, polyethylene, polyvinyl acetate) despite its high fluorine content. Furthermore, the anti-fogging performance is high due to the adjacent assembly effect of the fluoroalkyl group, and the anti-fogging ability and transparency are maintained especially for a long period of time.

The fluorine-containing polymer constituting the fluorine-containing additive of the present invention may be a graft polymer or a block polymer. The fluorine-containing polymer may be a branched polymer or a linear polymer.
The fluorine-containing polymer is, for example,
(I) It has a branch polymer and a trunk polymer, at least one of the branch polymer and the trunk polymer has a block consisting of a repeating unit having a fluoroalkyl group having 1 to 8 carbon atoms, and the other has an oxyalkylene group It may be a fluorine-containing graft polymer having a repeating unit or (II) a fluorine-containing block polymer having a block having a repeating unit having a C1-C8 fluoroalkyl group and a block composed of an oxyalkylene repeating unit.

The graft polymer (I), which is one embodiment of the fluoropolymer, will be described below.
In the graft polymer, generally, at least one of the branch polymer and the trunk polymer has a block composed of a repeating unit having a fluoroalkyl group, and at least one of the branch polymer and the trunk polymer has a repeating unit having an oxyalkylene group.

In the graft polymer, at least one of the branch polymer and the trunk polymer may have both a fluoroalkyl group and an oxyalkylene group, but one of the branch polymer and the trunk polymer has a block composed of a repeating unit having a fluoroalkyl group. It is preferable that the other has a repeating unit having an oxyalkylene group. Therefore, the graft polymer is
(1) A branched polymer having a block composed of a repeating unit having a fluoroalkyl group, and a graft polymer having a trunk polymer having a repeating unit having an oxyalkylene group, or (2) a repeating unit having a fluoroalkyl group It may be a graft polymer comprising a trunk polymer having a block consisting of the above and a branch polymer having a repeating unit having an oxyalkylene group.

In the graft polymer, it is preferable that the branched polymer has a block composed of a repeating unit having a fluoroalkyl group, and the trunk polymer has a repeating unit having an oxyalkylene group.
The branch polymer and the backbone polymer may be a homopolymer or a copolymer. When the branch polymer and the backbone polymer are copolymers, the copolymer is a random or block polymer, preferably a block polymer.

The repeating unit having a fluoroalkyl group is included in a trunk polymer or a branch polymer, for example, a branch polymer. The repeating unit having a fluoroalkyl group can be derived from a fluoroalkyl group-containing vinyl monomer.
The fluoroalkyl group-containing vinyl monomer may be a (meth) acrylate having a fluoroalkyl group or an acrylate in which the α-position having a fluoroalkyl group is substituted with a halogen atom, CF ₃ , CF ₂ H or CFH ₂ .

The fluoroalkyl group-containing acrylate may be represented by the following general formula.
^{Rf-A 2 -OC (= O} ) CR 3 = CH 2
[Wherein, Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms,
R ³ is hydrogen, F atom, Cl atom, CF ₃ group, CF ₂ H group, CFH ₂ group or methyl group,
A ² is a divalent organic group. ]

Examples of the fluoroalkyl group-containing acrylate include the following.

[Wherein Rf is a fluoroalkyl group having 1 to 21 carbon atoms, R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ² is an alkylene group having 1 to 10 carbon atoms, R ³ is a hydrogen atom, F atom , Cl atom, CF ₃ group, CF ₂ H group, CFH ₂ group or methyl group, Ar is an arylene group which may have a substituent, and n is an integer of 1 to 10. ]

Specific examples of the fluoroalkyl group-containing (meth) acrylate are as follows.
_{CF 3 (CF 2) p (} CH 2) q OCOCH = CH 2,
CF ₃ (CF ₂ ) _p CH═CH (CH ₂ ) _q OCOCH═CH ₂ ,
(CF ₃ ) ₂ CF (CF ₂ ) _p (CH ₂ ) _q OCOCH═CH ₂ ,
H (CF ₂ ) _p (CH ₂ ) _q OCOCH═CH ₂ ,
CF ₃ CHFCF ₂ (CH ₂ ) _q OCOCH═CH ₂ ,
_{CF 3 (CF 2) p (} CH 2) q OCOC (CH 3) = CH 2,
CF ₃ (CF ₂ ) _p CH═CH (CH ₂ ) _q OCOC (CH ₃ ) ═CH ₂ ,
_{(CF 3) 2 CF (CF} 2) p (CH 2) q OCOC (CH 3) = CH 2,
_{H (CF 2) p (CH} 2) q OCOC (CH 3) = CH 2,
CF ₃ CHFCF ₂ (CH ₂ ) _p OCOC (CH ₃ ) ═CH ₂ ,

_{CF 3 (CF 2) p SO} 2 N (C s H 2s + 1) (CH 2) q OCOCH = CH 2,
_{CF 3 (CF 2) p SO} 2 N (C s H 2s + 1) (CH 2) q OCOC (CH 3) = CH 2,
_{CF 3 C 6 F 10 (CF} 2) p SO 2 N (CH 3) (CH 2) q OCOCH = CH 2,
CF ₃ C ₆ F ₁₀ (CF ₂ ) _p SO ₂ N (CH ₃ ) (CH ₂ ) _q OCOC (CH ₃ ) ═CH ₂ ,
(CF ₃ ) ₂ CF (CF ₂ ) _p CH ₂ CH (OCOCH ₃ ) CH ₂ OCOCH═CH ₂ ,
(CF ₃ ) ₂ CF (CF ₂ ) _p CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) ═CH ₂ ,
(CF ₃ ) ₂ CF (CF ₂ ) _p CH ₂ CH (OH) CH ₂ OCOCH═CH ₂ ,
_{(CF 3) 2 CF (CF} 2) p CH 2 CH (OH) CH 2 OCOC (CH 3) = CH 2,
[P = 0-20, q = 1-10, s = 1 or 2]

  Of course, a mixture of two or more of the above-mentioned fluoroalkyl group-containing (meth) acrylates can be used.

The repeating unit having an oxyalkylene group can be derived from a vinyl monomer having an oxyalkylene group. A vinyl monomer having an oxyalkylene group constitutes a branched polymer or a trunk polymer, for example, a trunk polymer.
A vinyl monomer having an oxyalkylene group is a monomer having an oxyalkylene group and a carbon-carbon double bond. The oxyalkylene group may have 2 to 6 carbon atoms, and the oxyalkylene group is preferably an oxyethylene group or an oxypropylene group.

The following are mentioned as an example of the vinyl monomer which has a polyoxyalkylene group.
HO (C ₂ H ₄ O) _n COC (R ¹⁰ ) C═CH ₂
[R ^10: H or CH _3, n = 1~100],
_{HO (C 3 H 6 O)} n COC (R 10) C = CH 2
[R ^10: H or CH _3, n = 1~100],
_{HO (C 2 H 4 O)} m - (C 3 H 6 O) n COC (R 10) C = CH 2
[R ^10: H or _{CH 3, m = 1~20, n} = 1~20],
_{H (CH 2) p O (} C 2 H 4 O) n COC (R 10) C = CH 2
[R ^10: H or _{CH 3, p = 1~20, n} = 1~100],
_{H (CH 2) p O (} C 3 H 6 O) n COC (R 10) C = CH 2
[R ^10: H or _{CH 3, p = 1~20, n} = 1~100],
_{H (CH 2) p O (} C 2 H 4 O) m - (C 3 H 6 O) n COC (R 10) C = CH 2
[R ^10: H or _{CH 3, p = 1~20, m} = 1~20, n = 1~20],
_{H (CH 2) p O (} C 2 H 4 O) m - (C 3 H 6 O) n COC (R 10) C = CH 2
[R ^10: H or _{CH 3, p = 1~20, m} = 1~20, n = 1~20],

［Ｒ¹⁰：ＨまたはＣＨ₃、ｍ＝１〜２０、ｎ＝１〜２０］、

[R ^10: H or _{CH 3, m = 1~20, n} = 1~20],

  The branch polymer and the backbone polymer may contain other copolymerizable monomers in addition to the fluoroalkyl group-containing vinyl monomer and the oxyalkylene group-containing vinyl monomer. The other copolymerizable monomer may be any addition-polymerizable monomer (that is, a compound having a carbon-carbon double bond). The other copolymerizable monomer may be a non-fluorinated monomer or a fluorine-based monomer. Either may be sufficient.

  As a non-fluorine-type monomer, (meth) acrylate ester is mentioned, for example. The (meth) acrylate ester may be an ester of (meth) acrylic acid and an aliphatic alcohol, for example, a monohydric alcohol or a polyhydric alcohol (for example, a dihydric alcohol).

Examples of non-fluorinated monomers include the following.
2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, hydroxyalkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, polyoxyalkylene (meth) acrylate, alkoxy Polyoxyalkylene (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Benzyl (meth) acrylate glycidyl methacrylate, hydroxypropyl monomethacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxyethyl acrylate, glycerol Methacrylate, β-acryloyloxyethyl hydrogen succinate, β-methacryloyloxyethyl hydrogen phthalate, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2 -Hydroxyethylphthalic acid, hydroxypropyltrimethylammonium chloride methacrylate, 2-acryloyloxyethyl acid phosphate, glucosylethyl methacrylate, methacrylamide, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-methacryloyloxyethyl acid phosphate (Meth) acrylates such as hydroxypivalic acid neopentyl glycol diacrylate; styrene, p-isopropylstyrene and the like (Meth) acrylamide, N, N-dimethylacrylamide, acryloylmorpholine, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, etc. (Meth) acrylamides; Vinyl ethers such as vinyl alkyl ethers.

Further, vinyl halides such as ethylene, butadiene, vinyl acetate, chloroprene and vinyl chloride, vinylidene halides, acrylonitrile, vinyl alkyl ketones, maleic anhydride, N-vinyl carbazole, vinyl pyrrolidone, (meth) acrylic acid, etc. .
Further, the non-fluorine-based monomer may be a silicon-based monomer (for example, (meth) acryloyl group-containing alkylsilane, (meth) acryloyl group-containing alkoxysilane, (meth) acryloyl group-containing polysiloxane).

  Silicon monomers include (meth) acryloxytrialkylsilane, (meth) acryloxytrialkoxysilane, (meth) acryloxypolysiloxane, (meth) acryloxypropyltrialkylsilane, (meth) acryloxypropyltrialkoxy Examples include silane, (meth) acryloxypropyl polysiloxane, allyltrialkylsilane, allyltrialkoxysilane, allylpolysiloxane, vinyltrialkylsilane, vinyltrialkoxysilane, and vinylpolysiloxane.

［式中、Ｒ²⁰、Ｒ²¹、Ｒ²²およびＲ²³のそれぞれは、ＨまたはＣＨ₃、ｎは１〜１００である。］
で示される化合物であってよい。（メタ）アクリロキシプロピルポリシロキサンの例は、（メタ）アクリロキシプロピルポリジメチルシロキサンである。 (Meth) acryloxypropylpolysiloxane has the formula:

[In the formula, each of R ²⁰ , R ²¹ , R ²² and R ²³ is H or CH ₃ , and n is 1 to 100. ]
It may be a compound shown by these. An example of (meth) acryloxypropyl polysiloxane is (meth) acryloxypropyl polydimethylsiloxane.

As fluorine-based monomers,
Fluorinated olefins (carbon number, eg 1-20), eg CF ₃ (CF ₂ ) ₇ CH═CH ₂ ,

などが挙げられる。

Etc.

  The graft polymer has a backbone polymer and a branch polymer. The weight ratio of the backbone polymer to the branch polymer may be 5:95 to 95: 5, preferably 10:90 to 90:10, especially 30:70 to 70:30.

In the graft polymer, the amount of the non-fluorinated monomer including the vinyl monomer having a polyoxyalkylene group is 40% by weight, for example, 60% by weight, particularly 70% by weight, based on the trunk polymer and the branch polymer. The upper limit may be 99% by weight, for example 98% by weight, in particular 95% by weight, in particular 90% by weight. The amount of the vinyl monomer having a polyoxyalkylene group may be 1 to 100% by weight, for example 10 to 100% by weight, based on the amount of the non-fluorinated monomer.
The amount of the fluorinated monomer including the vinyl monomer having a fluoroalkyl group may be 1% by weight, for example, 2% by weight, and 60% by weight, for example, with respect to the trunk polymer and the branch polymer. It may be 30% by weight. The amount of the vinyl monomer having a fluoroalkyl group may be 50 to 100% by weight, for example 70 to 100% by weight, based on the amount of the fluorine-based monomer.

It is preferred that the fluoroalkyl group-containing vinyl monomer is contained in the branch polymer and the oxyalkylene group-containing vinyl monomer is contained in the trunk polymer. In this case, the amount of the fluoroalkyl group-containing vinyl monomer is 50 to 100% by weight, for example 75 to 100% by weight, in particular 90 to 100% by weight, based on the branched polymer, and the amount of the oxyalkylene group-containing vinyl monomer is 1 to 100% by weight, for example 75 to 100% by weight, in particular 90 to 100% by weight, based on the trunk polymer.
The number average molecular weight (GPC, styrene equivalent, in THF) of the graft polymer may be 1,000 to 200,000, for example, 5,000 to 100,000.

In the present invention, the graft polymer may be a graft polymer in which a branch polymer is grafted to the isocyanate group portion of the trunk polymer.
In one embodiment, the backbone polymer is a repeating unit derived from an isocyanate group-containing vinyl monomer and other copolymerizable monomers (eg, vinyl monomers having fluoroalkyl groups and / or vinyl monomers having oxyalkylene groups, in particular A vinyl monomer having an oxyalkylene group). Isocyanate groups present in repeating units derived from isocyanate group-containing vinyl monomers can react with the active hydrogen groups of the branch polymer to bond with the branch polymer.

  In this specification, the isocyanate group-containing vinyl monomer means a polymerizable compound having a carbon-carbon double bond and an isocyanate group. Generally, in the isocyanate group-containing vinyl monomer, the number of each of the carbon-carbon double bond and the isocyanate group is 1. Usually, a molecule of an isocyanate group-containing vinyl monomer has a carbon-carbon double bond at one end of the molecule and an isocyanate group at the other end.

Examples of isocyanate group-containing vinyl monomers are:
(I) isocyanate group-containing (meth) acrylate ester,
(Ii) _{formula: H 2 C = C (R} 11) -A 1 -NCO
[R ¹¹ : H or a linear, branched or cyclic hydrocarbon group (for example, alkyl group) having 1 to 20 carbon atoms (for example, 1 to 10), A ¹ : a direct bond or carbonization having 1 to 20 carbon atoms Hydrogen group]
Or (iii) a compound having two isocyanate groups (iii-1) and a compound having a carbon-carbon double bond and active hydrogen (generally one carbon-carbon double bond and one It is a reaction product with a compound having an active hydrogen-containing group) (iii-2).

As the isocyanate group-containing (meth) acrylate ester (i),
^{_{H 2 C = C (R 12}} ) COO (CH 2 CH 2 O) n (CH 2) m -NCO
[R ^12: H or _{CH 3, n: 0~20, m} : 1~20]
(For example, 2-isocyanatoethyl (meth) acrylate)
Is mentioned.

As vinyl isocyanate (ii),
^{_{H 2 C = C (R 13}} ) -NCO
[R ^13: having 1 to 20 carbon atoms (e.g., 1 to 10) linear, branched or cyclic hydrocarbon group (e.g., an alkyl group or a cyclohexyl group)]
^{_{H 2 C = C (R 14}} ) - (CH 2) n -NCO
[R ^14: H or a carbon number from 1 to 20 (e.g., 1 to 10) linear, branched or cyclic hydrocarbon group (e.g., an alkyl group or a cyclohexyl group,), n: 2 to 20]
^{_{H 2 C = C (R 15}} ) -Ph-C (R 16) 2 -NCO
[R ^15: H or CH _3, R ^16: H or CH _3, Ph: a phenylene group]
Is mentioned.

  Examples of the compound (iii-1) having two isocyanate groups include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, and isophorone diisocyanate. .

As the compound (iii-2) having a carbon-carbon double bond and active hydrogen (hereinafter also referred to as “monomer having active hydrogen”),
Hydroxyethyl (meth) acrylate,
_{HO (CH 2 CH 2 O)} n COC (R 17) C = CH 2
[R ^17: H or CH _3, n = 2~20],
Aminoethyl (meth) acrylate is mentioned.

  The reaction between the compound (iii-1) having two isocyanate groups and the monomer (iii-2) having active hydrogen is carried out in a solvent (particularly an aprotic solvent such as an ester solvent), if necessary dibutyltin dilaurate. Or a catalyst such as In the reaction, the amount of the monomer (iii-2) having active hydrogen is 1.0 to 2.0 equivalents, preferably 1.0 to 1.7, relative to the compound (iii-1) having two isocyanate groups. It may be equivalent.

  The amount of the isocyanate group-containing vinyl monomer may be 1% by weight, for example 2% by weight, in particular 6% by weight, and the upper limit is 30% by weight, for example 20% by weight, in particular 10%, based on the backbone polymer. It may be weight percent.

  In addition to the isocyanate group-containing vinyl monomer, the backbone polymer includes at least one of a fluoroalkyl group-containing vinyl monomer or an oxyalkylene group-containing vinyl monomer (particularly, an oxyalkylene group-containing vinyl monomer) and, if necessary, other monomers (non-fluorine). Monomer and / or fluorine monomer).

  The branched polymer is composed of a chain transfer agent, at least one of a fluoroalkyl group-containing vinyl monomer or an oxyalkylene group-containing vinyl monomer (particularly, a fluoroalkyl group-containing vinyl monomer), and, if necessary, other monomers (non-fluorine monomer and / or fluorine monomer). Monomer).

The chain transfer agent may be a chain transfer agent having an active hydrogen group at both ends, for example, an alkylene thiol chain transfer agent having an active hydrogen group or an aryl chain transfer agent having an active hydrogen group. Examples of the active hydrogen group include OH, NH ₂ , SO ₃ H, NHOH, COOH, and SH. Carbon number of the alkylene group of alkylene thiol may be 1-20.

Examples of alkylene thiol chain transfer agents are as follows.
HS (CH ₂ ) _n OH [n is 1 to 20, especially 2, 4, 6, 11]
HSCH ₂ COOH
HSCH ₂ CH (CH ₃ ) COOH
HSCH ₂ CH ₂ SO ₃ Na
HSCH ₂ CH ₂ SO ₃ H

Examples of aryl chain transfer agents are:

The active hydrogen group of the chain transfer agent reacts with the isocyanate group of the trunk polymer to form a —NH—C (═O) — bond (amide bond). When the active hydrogen group is an OH group, a urethane bond (—NH—C (═O) —O—) is formed. When the active hydrogen group is an NH ₂ group, a urea bond (—NH—C (═O) —NH—) is formed. It is preferable that the amount of the isocyanate group of the trunk polymer is 1.0 to 2.5 equivalents, for example, 1.0 to 2.0 equivalents with respect to 1.0 equivalent of the chain transfer agent.

  The amount of chain transfer agent may be 0.05 to 0.7, preferably 0.1 to 0.6, in molar ratio to the amount of branch monomer. A chain transfer agent is bonded to one end of the branch polymer obtained by polymerizing the branch monomer. Chain transfer agents can adjust the chain length of the branched polymer. The degree of polymerization of the branched polymer may be a monomer of 3 to 25 molecules, preferably 4 to 20 molecules, per molecule of chain transfer agent.

  The method for producing the graft polymer of the present invention may be any method, but some examples are given.

As a synthesis method of the graft copolymer,
(1) A method using graft polymerization with a macromonomer,
(2) A branch having an active hydrogen group at one end polymerized by a chain transfer agent having an active hydrogen group on a trunk polymer having a group reactive with active hydrogen (for example, NCO group, glycidyl group, acid chloride group) A method of reacting a polymer,
(3) A method of generating a living radical with a metal halide catalyst in a trunk polymer having a halomethyl group as in the ATRP method (atomic transfer radical polymerization) and substituting the halogen atom with a branched polymer,
(4) A method of polymerizing a branch monomer using a chain transfer initiating species such as radical, cation active species, anion active species, hydroperoxide as the trunk polymer (see Japanese Patent Publication No. 61-50082) and the like.

  The graft polymerization method (1) using a macromonomer is a typical method in which a vinyl monomer is first radicalized in the presence of a mercaptan chain transfer agent having an active hydrogen group such as a hydroxyl group, a carboxyl group, an amino group, or a sulfonic acid group. Polymerize to obtain a polymer having an active hydrogen group at one end, and then react with an active hydrogen having a polymerizable double bond and a group reactive with active hydrogen such as NCO group, glycidyl group, and acid chloride group. A vinyl monomer having a group is reacted to obtain a macromonomer. This macromonomer is copolymerized with a vinyl monomer constituting the trunk polymer to obtain a graft polymer.

  The method (2) in which a trunk polymer having a group reactive with active hydrogen (NCO group, glycidyl group, acid chloride group) is reacted with a branched polymer polymerized with a chain transfer agent having an active hydrogen group is first active. A backbone polymer having a group that reacts with hydrogen and a vinyl monomer having a polymerizable double bond and a group that reacts with active hydrogen obtained by radical polymerization of the vinyl monomer is obtained. In addition, a vinyl polymer is radically polymerized in the presence of a mercaptan chain transfer agent having an active hydrogen group such as a hydroxyl group, a carboxyl group, an amino group, or a sulfonic acid group to form a branched polymer having an active hydrogen at one end. obtain. The graft polymer is obtained by reacting the active hydrogen of the branched polymer with a group that reacts with the active hydrogen of the trunk polymer.

For example,
(A) A method comprising forming a trunk polymer by copolymerizing a macromonomer obtained by reacting a vinyl monomer having reactivity with active hydrogen with a branch polymer and a copolymerizable monomer (trunk monomer). A method in which a trunk monomer is polymerized in the presence of a polymer), or (B) a branched polymer is reacted with a trunk polymer obtained by copolymerizing a monomer copolymerizable with a vinyl monomer reactive with active hydrogen. (Branching polymer and trunk polymer are separately polymerized)
May be used.

Method (A) consists of the following steps:
(A-1) A chain transfer agent which is a constituent component of a branch polymer and a vinyl monomer are polymerized to obtain a branch polymer;
(A-2) reacting the obtained branch polymer with a vinyl monomer reactive with active hydrogen to obtain a macromonomer;
(A-3) The macromonomer is polymerized with a copolymerizable monomer constituting the trunk polymer to obtain a graft polymer.

Method (B) consists of the following steps:
(B-1) A monomer copolymerizable with a vinyl monomer having reactivity with active hydrogen which is a constituent component of the trunk polymer is polymerized to obtain a trunk polymer having reactivity with active hydrogen;
(B-2) A separately synthesized branch polymer is grafted to the obtained trunk polymer to obtain a graft polymer.

  The polymerization step (A-1) of the branched polymer and the polymerization steps (A-3) and (B-1) of the trunk polymer may be performed in a solvent at a temperature of 70 to 80 ° C. using a polymerization initiator. . The polymerization time is generally 2 to 12 hours.

  As the polymerization initiator, azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxide pivalate, diisopropyl peroxydicarbonate, etc. are used. . The polymerization initiator is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the monomer.

The polymerization solvent may be any of a polar solvent, a hydrocarbon solvent, and a mixed solvent thereof. When a group reactive with active hydrogen is present in the reaction system (that is, in steps (A-2), (B-1) and (B-2)), a proton having an active hydrogen group such as an alcohol solvent. Volatile solvents cannot be used.
The polar solvent is a solvent having a polar group in the molecule. The polar group is a hydroxyl group, a carboxyl group, an ester group, an acyl group, an ether oxygen group or the like. Examples of the polar solvent include alcohol solvents, glycol solvents, ester solvents, and ketone solvents.

  The hydrocarbon solvent may be a solvent composed only of carbon and hydrogen. The hydrocarbon solvent may be an aliphatic hydrocarbon. Examples of hydrocarbon solvents are n-heptane, n-hexane, n-octane, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, methylpentane, 2-ethylpentane, isoparaffin hydrocarbons, liquid paraffin, decane, undecane , Dodecane, mineral spirits, mineral terpenes, etc. In some cases, an aromatic hydrocarbon solvent may be used.

  Examples of alcohol solvents are butyl alcohol, isopropyl alcohol, and the like. Examples of the glycol solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and acetates thereof. Examples of ester solvents include monobasic acid esters such as methyl acetate, ethyl acetate, and butyl acetate, and dibasic acid esters such as diethyl succinate, diethyl adipate, dibutyl phthalate, and dioctyl phthalate. Examples of ketone solvents are methyl isobutyl ketone (MIBK), methyl ethyl ketone, acetone and the like.

  A mixture of a hydrocarbon solvent and a polar solvent may be used. The weight ratio of the hydrocarbon solvent to the polar solvent may be 100: 0 to 0: 100, for example, 5:95 to 95: 5.

  The reaction steps (A-2) and (B-2) of the active hydrogen group of the chain transfer agent constituting the branched polymer and the group reactive with the active hydrogen contained in the monomer constituting the trunk polymer, You may carry out at the temperature of 30-130 degreeC in a solvent. The reaction time is generally 2 to 24 hours. When the reaction temperature is 50 ° C. or higher, it is necessary to add a polymerization inhibitor, but when it is 50 ° C. or lower, a polymerization inhibitor may or may not be added.

The solvent may be the polymerization solvent described above, but a protic solvent having an active hydrogen group such as an alcohol solvent cannot be used.
The graft polymer of the present invention functions as an agricultural fluorine-containing additive that retains fog prevention ability and transparency.

The fluorine-containing polymer of the present invention may be a fluorine-containing block polymer (II). The repeating unit having a fluoroalkyl group may be derived from an epoxy compound, and the oxyalkylene repeating unit may be derived from an alkylene oxide or an alkylene glycol.
The fluorine-containing block polymer (II) may be a compound represented by the following formula, for example.

ｋは、１〜１０の数、
ｌ、ｍ、ｎが同時に０とならないという条件の下、ｌ、ｍおよびｎは０〜１００の数である。
（但し、Rfは炭素数１〜８のフルオロアルキル基、
Ｘは、-CH₂-，-OCH₂CH₂-または-N(R¹)SO₂-（ここで、R¹は炭素数１〜４０の直鎖または分枝鎖のアルキル基である。）、
Ｚは、水酸基、炭素数１〜４０の直鎖または分枝鎖のアルキル基、CH₂Cl、CH₂OR³（ここで、R³は炭素数１〜４０の直鎖または分枝鎖のアルキル基、置換基を有しても良いフェニル基）である。）、
重合体において、複数の繰り返し単位Ｋが隣接してブロックを形成しており、Ｌ、ＭおよびＮは、ランダム状またはブロック状、好ましくはブロック状であり、フルオロアルキル基を有する繰り返し単位からなるブロックの数は、少なくとも１以上であり、オキシアルキレン繰り返し単位からなるブロックの数は、少なくとも１以上である。］
A ¹ -K _k -L _l -M _m -N _n -A ²
[Where:
A ¹ and A ² are a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, an optionally substituted phenyl group, a linear or branched chain group having 1 to 40 carbon atoms. alkylene ether group, a fluoroalkyl group having 1 to 8 carbon atoms or ^{C (= O) -R 2 (} R 2 is a straight or branched chain alkyl Le group 1 to 40 carbon atoms, substituted Is also a good phenyl group.),

k is a number from 1 to 10,
l, m, and n are numbers from 0 to 100 under the condition that l, m, and n are not 0 simultaneously.
(However, Rf is a C1-C8 fluoroalkyl group,
X _{is, -CH 2 -, - OCH 2} CH 2 - or _{^{-N (R 1) SO 2 -}} ( wherein, R ¹ is alkyl Le group straight or branched chain 1 to 40 carbon atoms. ),
Z represents a hydroxyl group, a straight or branched chain alkyl Le group having a carbon number of _{1~40, CH 2 Cl, CH 2} OR 3 ( wherein, R ³ is a straight or branched chain 1 to 40 carbon atoms alkyl group, a phenyl group) which may have a substituent. ),
In the polymer, a plurality of repeating units K are adjacent to form a block, and L, M and N are random or block, preferably block, and are composed of repeating units having a fluoroalkyl group Is at least 1 and the number of blocks composed of oxyalkylene repeating units is at least 1 or more. ]

  The above compound can be produced by a ring-opening addition reaction of an epoxy compound to an alcohol compound.

(Production method 1)
A method for ring-opening polymerization of an Rf epoxy compound using a hydroxyl group of alkylene glycol as an initiating group:

(Production method 2)
Method for reacting Rf epoxy compound with hydroxyl group of ring-opening polymer and glycidyl compound

The said reaction is performed by using a solvent according to reaction and stirring at the temperature of 20-150 degreeC, Preferably it is 30-100 degreeC. Suitable catalysts include ZnCl ₂ , AlCl ₃ , SnCl, SbCl ₃ , FeCl ₃ , etc. Periodic Table Group II to Group V and Group VII metal halides and BF ₃ (usually ether and alcohol Complex), sulfuric acid, NaSO _{4 and} other known acid catalysts can be used. Among these, the BF ₃ complex is very reactive and advantageous in that it has few by-products. The usage-amount of a catalyst is about 0.001-1 mol normally with respect to 1 mol of epoxy compounds.

Examples of R in the alkylene glycol represented by the R—H group are as follows.
_{H (CH 2) m - (} CH 2 CH 2 O) n - (m is 1 to 40, n is 1 to 100)
H- (CH ₂ CH ₂ O) _n- (n is 1 to 100)
_{H- (CH 2) m- (CH} 2 CH (CH 3) O) n - (m is 1 to 40, n is 1 to 100)
H- (CH ₂ CH (CH ₃ ) O) _n- (n is 1 to 100)
_{H- (CH 2) m - (} CH 2 CH (CH 3) O) n - (CH 2 CH 2 O) o - (m is 1 to 40, n is 1 to 100, o is 1 to 100)
_{H- (CH 2 CH (CH 3} ) O) n- (CH 2 CH 2 O) o- (n is 1 to 100, o is 1 to 100)

（ｍは１〜４０、ｎは１〜１００）

(M is 1-40, n is 1-100)

The alkylene moiety may be a block copolymer or a random copolymer.
The fluoroalkyl (Rf) group has 1 to 8 carbon atoms, such as 1 to 7, in particular 1 to 4, carbon atoms. Examples of fluoroalkyl groups are F (CF ₂ ) n-, H (CF ₂ ) n-, (CF ₃ ) ₂ CF (CF ₂ ) n-, CF ₃ CF ₂ CF ₂ -O- (CF ₂ CF ₂ CF ₂ —O) n—, F (CF ₂ ) ₃ O—CF (CF ₃ ) CF ₂ O— and the like. The Rf group is preferably a perfluoroalkyl group. As for the number of carbon atoms of the fluoroalkyl group (particularly perfluoroalkyl group), the fluoroalkyl group (Rf group) is particularly preferably C ₄ F ₉ .
In the fluorinated block polymer (II), the weight ratio of the repeating unit having a fluoroalkyl group to the oxyalkylene repeating unit is from 1: 0.01 to 1: 200, for example from 1: 0.1 to 1: 100, particularly 1 : 0.1 to 1:50.

The synthetic resin coating material of the present invention comprises a synthetic resin and a fluorine-containing additive.
In the present invention, a thermoplastic resin and a thermosetting resin can be used as the synthetic resin. Thermoplastic resins include polyvinyl chloride resin (PVC), polyvinyl acetate, low density polyethylene resin (LD-PE), high density polyethylene resin (HD-PE), and chained low density polyethylene resin (L-LE-PE). ), Ethylene vinyl acetate copolymer (EVA), ethylene ethyl acrylate copolymer (EEA), polypropylene (PP), polystyrene (PS), acrylonitrile-styrene resin (AS), acrylonitrile-acrylate-styrene resin (AAS), acrylonitrile-butadiene- Styrene resin (ABS), acrylonitrile-chlorinated polyethylene-styrene resin (ABS), methacrylic resin (PMMA), polyphenylene ether resin (PPO, PPE), polyether ether ketone resin (PEEK), polysulfone resin (PSU), polyether Sulphone resin (PES), polyacetal (POM), polybutylene tele Talate (PBT), polyethylene terephthalate (PET), polycarbonate (PC), polyarylate (PAR), polyphenylene sulfide (PPS), polyamide (PA), methylpentene polymer (TPX), polybutadiene resin, thermoplastic polyurethane (TPU), etc. Is mentioned. Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, furan resin, epoxy resin, unsaturated polyester resin, silicone resin, polyurethane resin, and acrylic resin.

  Agricultural coating materials with good film-forming ability, such as vinyl chloride, vinyl acetate, ethylene, propylene, (meth) acrylic acid, vinylidene chloride, or copolymers of each other, polyester resins, polyamide resins , Fluorine-containing resins or blends of these synthetic resins. Of these, vinyl chloride resins and ethylene resins are particularly preferred from the viewpoint of weather resistance, strength, light transmittance, and economy. As the polyvinyl chloride resin, a vinyl chloride homopolymer and a copolymer with vinyl acetate, ethylene, propylene, alkyl vinyl ether and the like can be used.

The synthetic resin coating material of the present invention may contain a drip-proofing agent, a plasticizer, a stabilizer, a lubricant, a filler, an ultraviolet absorber, an antistatic agent, an antioxidant, and the like as appropriate.
The amount of the fluorine-containing additive of the present invention is usually 0.01 to 2.0 parts by weight, preferably 0.05 to 1.0 parts by weight, particularly 0.1 to 0. It may be 5.

The fluorine-containing additive is, for example, a method of directly adding to a thermosetting resin before curing, for example, a thermosetting resin for mold curing, a method of adding directly to a solution of a synthetic resin, or kneading into a synthetic resin in a molten state. It can mix | blend with a synthetic resin by the method. Subsequently, it can be formed into a film or the like by a conventional method to obtain a synthetic resin coating material.
Synthetic resin coatings can be used as agricultural coatings, especially greenhouse coatings.

  Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but it is needless to say that the present invention is not limited to these examples.

Production Example 1
Production of graft copolymer (I) (compound (1)):
Production of FA Macromonomer The following was put into a 1000 ml glass polymerization sample and reacted for 8 hours at 75 ° C. with shaking in a nitrogen atmosphere to obtain a branched polymer solution.
Mercaptoethanol 5.5g
CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ OCOCH = CH ₂ (FA) 90g
(Daikin Fine Chemical Laboratory)
Azoisobutyronitrile 0.28g
143.1 g of ethyl acetate
After the reaction, the monomer consumption rate by gas chromatography was 100%. According to NMR, the composition ratio (molar ratio) of each component in the polymer was mercaptoethanol: FA = 1.0: 4.2.
Next, the temperature was lowered to 55 to 60 ° C., and in an air atmosphere, a solution prepared by dissolving 13.2 g of 2-isocyanatoethyl methacrylate in 19.8 g of ethyl acetate and 0.13 g of dibutyltin dilaurate were added and shaken. The mixture was reacted at 55 ° C. to 60 ° C. for 6 hours to obtain an FA macromonomer solution. After the reaction, the absorption peak of the NCO group in the IR spectrum almost disappeared.

Production of FA Graft Polymer The following was added to a predetermined amount of the obtained FA macromonomer solution and reacted at 75 ° C. for 8 hours while shaking in a nitrogen atmosphere to obtain a graft polymer.
FA macromonomer solution 15.0g
8.7 g of polypropylene glycol methacrylate
_{(HO- (C 3 H 6 O} ) n -COC (CH 3) = CH 2 n: about 13, manufactured by NOF Corporation, Blemmer PP-800)
Methoxypolyethylene glycol methacrylate 11.0g
(CH ₃ O— (C ₂ H ₄ O) _n —COC (CH ₃ ) ═CH ₂ n: about 9, manufactured by NOF Corporation, Blemmer PME-400)
0.88 g of n-butyl methacrylate (Nippon Yushi Co., Ltd., Blemmer BMA)
Mercaptoethanol 0.13g
Azoisobutyronitrile 0.15g
Ethyl acetate 71.2g
After the reaction, the monomer consumption rate by gas chromatography was 95%. The number average molecular weight by GPC of the obtained polymer was 14,000. The monomer composition in the polymer matched the charged monomer composition.

（FE）
で表される含フッ素エポキシ化合物（ダイキンファインケミカル研究所製）をポリオキシエチレンアルキルエーテルに対し、３．０当量の５６．１g(０．２０mol)を、無溶媒下で２時間かけて滴下した。反応液を当量のアセトンに溶解し、アセトンのピーク面積を基準にガスクロマトグラフィーにより反応を追跡した。６時間後、エポキシ化合物が１００％消費されていることを確認し、反応容器から取り出した。
仕込みモノマー組成に一致する重合体が生成されていることを、プロトンＮＭＲのスペクトルにより確認した。このプロトンＮＭＲのスペクトルを図１に示す。この重合体は、ポリオキシエチレンアルキルエーテル繰り返し単位のブロックおよび含フッ素エポキシ化合物繰り返し単位のブロックを有するブロック重合体であった。 Production Example 2
Production of fluorinated block polymer (II) (compound (2)):
Polyoxyethylene alkyl ether [HO- (CH ₂ CH ₂ O) _a- (CH ₂ ) _b -H dissolved in advance at 60 ° C in a 500 mL four-necked round bottom flask equipped with a condenser, thermometer, and dropping funnel Weigh 143.9 g (0.67 mol) (average of a is about 40, average of b is about 16, hydroxyl value is 26.4, manufactured by Nikko Chemicals, BC40-TX), and the stirring blade is rotated at 65 ° C. 0.4 g (0.0028 mol) of BF ₃ · Et ₂ O was added while being (300 rpm). There formula:

(FE)
In a polyoxyethylene alkyl ether, 56.1 g (0.20 mol) of 3.0 equivalents of a fluorine-containing epoxy compound represented by the formula (manufactured by Daikin Fine Chemical Laboratory) was added dropwise over 2 hours in the absence of a solvent. The reaction solution was dissolved in an equivalent amount of acetone, and the reaction was followed by gas chromatography based on the peak area of acetone. After 6 hours, it was confirmed that 100% of the epoxy compound was consumed, and the epoxy compound was taken out from the reaction vessel.
It was confirmed by proton NMR spectrum that a polymer corresponding to the charged monomer composition was produced. The proton NMR spectrum is shown in FIG. This polymer was a block polymer having a block of polyoxyethylene alkyl ether repeating units and a block of fluorine-containing epoxy compound repeating units.

Comparative production example 1
Production of FA random copolymer (compound (3)):
2.92 g of 2-isocyanatoethyl methacrylate and 1.47 g of 1.0 equivalent of mercaptoethanol were reacted at 50 ° C. for 12 hours in the presence of 0.01 g of dibutyltin dilaurate.
Next, to the obtained reaction product (reaction product of isocyanate group-containing vinyl monomer and mercaptoethanol) 4.39 g, the following was added, and the mixture was reacted at 75 ° C. for 8 hours while shaking in a nitrogen atmosphere. Obtained.

CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ OCOCH = CH ₂ (FA) 20.0g
(Daikin Fine Chemical Laboratory)
Polypropylene glycol methacrylate 27.3g
_{(HO- (C 3 H 6 O} ) n -COC (CH 3) = CH 2 n: about 13, manufactured by NOF Corporation, Blemmer PP-800)
Methoxypolyethylene glycol methacrylate 52.0g
(CH ₃ O— (C ₂ H ₄ O) _n —COC (CH ₃ ) ═CH ₂ n: about 9, manufactured by NOF Corporation, Blemmer PME-400)
n-Butyl methacrylate (Nippon Yushi Co., Bremer BMA) 3.5g
Mercaptoethanol 0.3g
Azoisobutyronitrile 0.6g
Ethyl acetate 322.7g
Almost 100% of the monomer was polymerized. The polymer obtained was not a graft polymer. According to GPC, the number average molecular weight of the obtained polymer was 21,000.

Example 1
Polyvinyl chloride (degree of polymerization 1300) 100 parts by weight Dioctyl phthalate 45 parts by weight Tricresyl phosphate 5 parts by weight Epoxy resin 2 parts by weight
Ba-Zn liquid stabilizer 2 parts by weight
Ba-Zn powder stabilizer 1 part by weight Benzophenone UV absorber 0.1 part by weight Sorbitan monopalmitate 2 parts by weight with respect to the above basic composition as shown in Table 1 (100% by weight of vinyl chloride resin) Parts by weight relative to parts) was added and blended, and calendered to produce a film having a thickness of 0.1 mm.

Test Examples The films obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were spread on a tunnel-shaped greenhouse (house) having a frontage of 4.8 m, a height of 4.8 m, and a depth of 25 m to prevent fog and anti-fogging. And film transparency were evaluated. The results are shown in Table 2.

(Anti-fog evaluation)
Evaluation was made by observing with the naked eye twelve times a day every hour from 7 am to 6 pm. The evaluation criteria are as follows:
1: No mist is observed in the house or only slightly in the vicinity of the manifestation in the film.
2: Although fog is generated in the entire house, the interior of the house 25 m ahead is clearly identified.
3: Fog is slightly dark throughout the house, and the interior of the house 25 meters away cannot be clearly identified.
4: Fog is generated in the whole house, and the depth of the house 25m ahead cannot be identified at all.

(Anti-fogging evaluation)
Evaluation was made with the naked eye. Evaluation criteria are as follows:
1: Water adheres in a thin film, and no water droplets are observed.
2: Water is attached in a thin film, but slightly large water droplets are observed.
3: Although water adheres in a thin film shape, large water droplets are partially observed.
4: Adhesion of fine water droplets is observed partially.

(Transparency evaluation)
Evaluation was made with the naked eye. Evaluation criteria are as follows:
1: Transparent and no change in appearance 2: Very slight whitening or slight brown spots.
3: Small whitening or brown spots are seen in some places.
4: Some whitening or many brown spots are observed.

化合物(４)：CF₃CF₂(CF₂CF₂)_nCH₂(OH)CHCH₂O-(CH2CH₂O)_１４-CH₃ 平均n=３．２

Compound (4): CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ (OH) CHCH ₂ O— (CH ₂ CH ₂ O) ₁₄ —CH ₃ average n = 3.2

6 is a proton NMR spectrum of the polymer produced in Production Example 2.

Claims (12)

A fluorine- containing internal additive comprising a fluorine-containing polymer which is a fluorine-containing graft polymer or a fluorine-containing block polymer,
(I) When the fluorine-containing polymer is a fluorine-containing graft polymer, the fluorine-containing polymer is
formula:
^{Rf-A 2 -OC (= O} ) CR 3 = CH 2
[Wherein Rf is a linear or branched fluoroalkyl group having 1 to 8 carbon atoms,
R ³ is hydrogen, F atom, Cl atom, CF ₃ group, CF ₂ H group, CFH ₂ group or methyl group,
A ² is a divalent organic group. ]
Is obtained by copolymerizing a macromonomer obtained from a fluoroalkyl group-containing acrylate represented by the formula (1) and a polyoxyalkylene unit-containing (meth) acrylate monomer, and at least one of the branch polymer and the trunk polymer has 1 to 1 carbon atoms. A fluorine-containing graft polymer having a block composed of repeating units having 8 fluoroalkyl groups and the other having a repeating unit having an oxyalkylene group;
(II) When the fluorine-containing polymer is a fluorine-containing block polymer, the fluorine-containing polymer is
(A) Formula:

[Wherein Rf is a fluoroalkyl group having 1 to 8 carbon atoms,
X _{is, -CH 2 -, - OCH 2} CH 2 - or _{^{-N (R 1) SO 2 -}} ( wherein, R ¹ is alkyl Le group straight or branched chain 1 to 40 carbon atoms. ). ]
A block having a repeating unit having a fluoroalkyl group having 1 to 8 carbon atoms, represented by formula (B):

[Wherein, Z is hydrogen, a hydroxyl group, a linear or branched alkyl group having 1 to 40 carbon atoms, CH ₂ Cl, CH ₂ OR ³ (wherein R ³ is a linear chain having 1 to 40 carbon atoms) Or a branched alkyl group or a phenyl group which may have a substituent. ]
A fluorine- containing internal additive, which is a fluorine-containing block polymer having a block having a repeating unit having an oxyalkylene group, represented by The fluorine- containing internal additive according to claim 1, wherein the fluorine-containing graft polymer (I) is a graft polymer in which a branch polymer having a block composed of a repeating unit having a fluoroalkyl group is bonded to a trunk polymer. The fluorine- containing internal additive according to claim 1, wherein in the fluorine-containing graft polymer (I), the branch polymer has a block composed of a repeating unit having a fluoroalkyl group, and the trunk polymer has a repeating unit having an oxyalkylene group. . The fluorine- containing internal additive according to claim 1, wherein in the fluorine-containing block polymer (II), the repeating unit having a fluoroalkyl group is derived from an epoxy compound, and the oxyalkylene repeating unit is derived from an alkylene oxide. Fluorine-containing block polymer (II)
A ¹ -K _k -L _l -M _m -N _n -A ²
[Where:
A ¹ and A ² are a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, an optionally substituted phenyl group, a linear or branched chain group having 1 to 40 carbon atoms. alkylene ether group, a fluoroalkyl group having 1 to 8 carbon atoms or ^{C (= O) -R 2 (} R 2 is a straight or branched chain alkyl Le group 1 to 40 carbon atoms, substituted Is also a good phenyl group.),

k is a number from 1 to 10,
l, m, and n are numbers from 0 to 100 under the condition that l, m, and n are not 0 simultaneously.
(However, Rf is a C1-C8 fluoroalkyl group,
X _{is, -CH 2 -, - OCH 2} CH 2 - or _{^{-N (R 1) SO 2 -}} ( wherein, R ¹ is alkyl Le group straight or branched chain 1 to 40 carbon atoms. ),
Z is a hydroxyl group, a linear or branched alkyl group having 1 to 40 carbon atoms, CH ₂ Cl, CH ₂ OR ³ (wherein R ³ is a linear or branched alkyl group having 1 to 40 carbon atoms) Group, a phenyl group which may have a substituent. ),
In the polymer, a plurality of repeating units K are adjacent to form a block, L, M and N are random or block-shaped, and the number of blocks composed of repeating units having a fluoroalkyl group is at least The number of the block consisting of one or more oxyalkylene repeating units is at least one. ]
The fluorine-containing internal additive according to claim 1, which is a polymer represented by the formula: The fluorine-containing internal additive according to any one of claims 1 to 5, wherein the fluoroalkyl group is a perfluoroalkyl group having 1 to 6 carbon atoms. Fluorinated internal additive according to any one of claims 1 to 6 fluoroalkyl group is a C ₄ F _9. The graft polymer in which the fluorinated graft polymer (I) has a branched polymer having a block composed of a repeating unit having a fluoroalkyl group bonded to a trunk polymer through a bond having a —C (═O) NH— group. The fluorine-containing internal additive according to claim 1, which is a coalescence. In the fluorine-containing graft polymer (I), a bonding group containing a -C (= O) NH- group is contained in the active hydrogen group of the chain transfer agent constituting the branch polymer and the monomer constituting the trunk polymer. The fluorine-containing internal additive according to claim 1, which is a graft polymer formed by a reaction with an isocyanate group. A synthetic resin film comprising a synthetic resin and the fluorine-containing internal additive according to claim 1. The synthetic resin film according to claim 10, wherein the synthetic resin is a polyvinyl chloride resin. 2. The fluorine-containing graft polymer (I), wherein the amount of non-fluorinated monomers including a vinyl monomer having a polyoxyalkylene group is 40 to 99% by weight based on the trunk polymer and the branch polymer. Fluorine-containing internal additive.

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