WO2012074051A1 - Fluorinated hyperbranched polymer and process for production thereof - Google Patents

Abstract

[Problem] To provide a novel compound which can keep satisfactory transparency, has high solubility in organic solvents and excellent mixing/dispersing properties in matrix resins, is not aggregated in matrix resins, and enables the production of a thin film or a molded article having excellent surface modification properties and high transparency. [Solution] A specific fluorinated hyperbranched polymer having a weight average molecular weight of 1,000 to 500,000 in terms of polystyrene content as measured by gel permeation chromatography; and a thin film comprising a fluorinated hyperbranched polymer. (In formula [1], R¹ represents a hydrogen atom or a methyl group; A¹ represents a structure represented by formula [2] or formula [3]; L represents -SC(=O)- or -O-; Rf's may be the same as or different from each other and independently represent a fluoroalkyl group having 2 to 12 carbon atoms; and n is the number of repeating unit structures and represents an integer of 2 to 3,000.) (In formulae [2] and [3], A² represents a linear, branched or cyclic alkylene group which may contain an ether bond or an ester bond; and Y¹-Y⁴ independently represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a hydroxy group, an amino group, a carboxyl group or a cyano group.)

Description

Fluorine-containing hyperbranched polymer and method for producing the same

The present invention relates to a fluorine-containing hyperbranched polymer, and more specifically, a hyperbranched polymer having a fluorinated alkyl group that can be used as a surface modifier for a resin, a resin composition containing the same, and a method for producing the hyperbranched polymer About.

Polymer (polymer) materials are increasingly used in many fields in recent years. Along with this, the characteristics of the surface and interface of the polymer as a matrix, as well as the properties of the polymer, have become important for each field. For example, by using a fluorine compound with a low surface energy as a surface modifier, water and oil repellency, antifouling properties, non-adhesiveness, peelability, release properties, slipperiness, wear resistance, antireflection properties, Various improvements relating to interface control such as chemical resistance are expected and various proposals have been made.

The disclosure regarding the surface modification of a thermoplastic resin using a fluorine-based polymer includes, for example, poly (4-methyl-1-pentene having improved releasability by blending a tetrafluoroethylene-ethylene copolymer (ETFE). ) (PMP) resin film (Patent Document 1) and fluorine-containing polyolefin (Patent Document 2) excellent in water and oil repellency have been proposed.
Moreover, as a disclosure regarding the surface modification of light and thermosetting transparent resin using a fluoropolymer, for example, a surface treatment agent for a thermosetting epoxy resin using a fluoropolymer having fluoropolyether (Patent Document 3) In addition, it is disclosed that a photocurable acrylic resin containing a fluorine-containing surfactant and / or a fluorine-based polymer having a cyclic structure is excellent in releasability and has been surface-modified ( Patent Document 4).

Further, as a fluorine compound having a multi-branched structure, an ether and / or ester derivative of a polyalcohol in which a specific fluorine-containing group is arranged in a multi-branched manner via an ether or ester bond on a polyalcohol skeleton is disclosed. (Patent Document 5).
However, the fluorine compound having the multi-branched structure is, for example, an ester derivative formed from glycerin 10-mer and hexafluoropropylene oxide trimer, which is a low-molecular weight compound, and a highly branched polymer. A method for modifying the surface of the used light and thermosetting transparent resin has not been proposed.

JP 2005-307059 A JP-A-1-289817 JP 2009-7488 A International Publication No. 2006/114958 Pamphlet Japanese Patent Laid-Open No. 2006-137689

Although the above-mentioned linear fluoropolymers can give a certain surface modification effect to some thermoplastic resins, they are generally poorly mixed and dispersible with the resin, and particularly represented by polymethyl methacrylate (PMMA). When dispersed in a thermoplastic transparent resin, phase separation may occur and the transparency of the transparent resin may be impaired.
In addition, these fluorine-based polymers have low solubility in organic solvents, and even if surface modification of light and thermosetting resins is performed using these polymers, the process for film formation using organic solvents is not possible. Application was difficult.
In addition, the fluorine compound having the above-mentioned multi-branched structure has been confirmed to have a solubility in water or propylene glycol monomethylol of only 1% by mass, and this is also applied to a process for forming a film using an organic solvent. It was difficult.
That is, a new compound that has sufficient transparency, has high solubility in an organic solvent, and also has a surface modification effect has been demanded.

As a result of intensive studies to achieve the above object, the present inventors have introduced a fluoroalkyl group into a hyperbranched polymer that has not been studied in the past, and the resulting fluorine-containing hyperbranched polymer is modified with a resin surface. By adopting it as an agent, it not only has excellent solubility in organic solvents, but also has excellent mixing and dispersibility in the matrix resin, does not cause aggregation in the matrix resin, and has excellent surface modification and high transparency. And it discovered that a molded object was obtained and completed this invention.

That is, this invention relates to the fluorine-containing hyperbranched polymer represented by Formula [1] whose weight average molecular weight Mw measured by polystyrene conversion by gel permeation chromatography is 1,000 to 500,000 as a 1st viewpoint. .

(Wherein R ¹ represents a hydrogen atom or a methyl group, A ¹ represents a structure represented by the formula [2] or [3], and L represents —SC (═O) — or —O—. Rf represents a fluoroalkyl group having 2 to 12 carbon atoms which may be the same or different, and n represents the number of repeating unit structures and represents an integer of 2 to 3,000.)

(In the formula, A ² is a linear alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, or a C 3 to 30 carbon atom which may contain an ether bond or an ester bond. Represents a branched alkylene group or a cyclic alkylene group having 3 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom. Represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxyl group, or a cyano group.
As a second aspect, the present invention relates to the fluorine-containing hyperbranched polymer according to the first aspect, wherein Rf represents a C2-C12 fluoroalkyl group in which a hydrogen atom and a fluorine atom are bonded to a main chain or a terminal carbon atom. .
As a third aspect, the present invention relates to the fluorine-containing hyperbranched polymer according to the second aspect, in which the fluoroalkyl group is a fluoroalkyl group having a difluoromethyl structure at its terminal.
As a fourth aspect, the present invention relates to the fluorine-containing hyperbranched polymer according to the first aspect, in which Rf represents a fluoroalkyl group having 2 to 12 carbon atoms represented by the formula [4].

(In the formula, X represents a hydrogen atom or a fluorine atom, k represents 1 or 2, and m represents an integer of 0 to 5).
As a fifth aspect, the present invention relates to the fluorine-containing hyperbranched polymer according to the fourth aspect, in which X represents a hydrogen atom.
As a sixth aspect, the present invention relates to a varnish containing the fluorine-containing hyperbranched polymer according to any one of the first aspect to the fifth aspect.
As a seventh aspect, the present invention relates to a thin film comprising the fluorine-containing hyperbranched polymer according to any one of the first aspect to the fifth aspect.
As an eighth aspect, the present invention relates to a resin composition containing (a) the fluorine-containing hyperbranched polymer according to any one of the first aspect to the fifth aspect, and (b) a thermoplastic resin or a curable resin.
As a 9th viewpoint, it is related with the resin molded product produced from the resin composition as described in an 8th viewpoint.
As a tenth aspect, a polymerizable composition comprising (a) the fluorine-containing hyperbranched polymer according to any one of the first aspect to the fifth aspect, (c) a polymerizable compound, and (d) a polymerization initiator. Related to things.
As an 11th viewpoint, it is related with the resin molded product produced by polymerizing the polymeric composition as described in a 10th viewpoint.
As a twelfth aspect, (A) a fluorine-containing hyperbranch represented by the formula [6] including a step of reacting a hyperbranched polymer represented by the formula [5] with a fluoroalkoxide having 2 to 12 carbon atoms. The present invention relates to a method for producing a polymer.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, A ¹ represents a structure represented by the formula [2] or [3], Hal represents a halogen atom, and Rf may be the same. And represents a fluoroalkyl group having 2 to 12 carbon atoms which may be different, and n is the number of repeating unit structures and represents an integer of 2 to 3,000.)

(In the formula, A ² is a linear alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, or a C 3 to 30 carbon atom which may contain an ether bond or an ester bond. Represents a branched alkylene group or a cyclic alkylene group having 3 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom. Represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxyl group, or a cyano group.
As a thirteenth aspect, (B) the fluorine-containing compound according to the twelfth aspect, further including the step of substituting the halogen atom with a halogen atom for the dithiocarbamate group at the molecular end of the hyperbranched polymer represented by the formula [7]. The present invention relates to a method for producing a hyperbranched polymer.

(In the formula, R ¹ , A ¹ and n are as defined in the formula [5], and R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms, the number of carbon atoms. It represents a 1 to 5 hydroxyalkyl group or an arylalkyl group having 7 to 12 carbon atoms, or R ² and R ³ may form a ring together with the nitrogen atom bonded thereto. .)
As a fourteenth aspect, (C) a step of converting the dithiocarbamate group at the molecular end of the hyperbranched polymer represented by the formula [7] into a thiol anion (—S ⁻ ) by treating with a base, and (D) The present invention relates to a method for producing a fluorine-containing hyperbranched polymer represented by the formula [9], comprising a step of reacting the thiol anion with a carboxylic acid derivative represented by the formula [8].

(Wherein R ¹ represents a hydrogen atom or a methyl group, A ¹ represents a structure represented by Formula [2] or Formula [3], and R ² and R ³ each independently represents 1 carbon atom. Represents an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms, or R ² and R ³ are combined with a nitrogen atom bonded thereto. A ring may be formed, and n is the number of repeating unit structures and represents an integer of 2 to 3,000, and Rf may be the same or different and has 2 to 12 carbon atoms. Z represents a hydroxy group, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.)

(In the formula, A ² is a linear alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, or a C 3 to 30 carbon atom which may contain an ether bond or an ester bond. Represents a branched alkylene group or a cyclic alkylene group having 3 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom. Represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxyl group, or a cyano group.

The fluorine-containing hyperbranched polymer of the present invention can form a thin-film structure as it is by a simple coating / drying operation by taking advantage of the characteristics of a polymer compound. Moreover, the fluorine-containing hyperbranched polymer of the present invention is soluble not only in N, N-dimethylformamide (DMF) and tetrahydrofuran (THF), but also in N-methyl-2-pyrrolidone (NMP), cyclohexanone, acetone, and the like. Since it exists, it can be set as the form of a varnish, without limiting a solvent, and a thin film can be formed. Further, since the fluorine-containing hyperbranched polymer can be dissolved in such a solvent at a high concentration, it can be used as a coating material.

In addition, the fluorine-containing hyperbranched polymer of the present invention has a molecular structure compared to the linear polymer because the conventional linear polymer generally has a string-like shape, but actively introduces a branched structure. There is little entanglement between them and it shows a fine particle behavior. That is, movement in the resin as a matrix is facilitated.
Therefore, when the fluorine-containing hyperbranched polymer of the present invention is blended with a polymerizable composition or a resin composition containing a thermoplastic resin or a thermosetting resin to form a resin molded product, it is easy at the interface (molded product surface). This can contribute to interface control and improve the surface modification of the resin.
Moreover, the fluorine-containing hyperbranched polymer of the present invention has a high mixing / dispersibility with the matrix resin, and can be mixed / dispersed without causing aggregation in the resin. Can be manufactured.

Further, the resin molded product of the present invention is not only a molded product having excellent transparency as described above, but can also be a surface-modified resin molded product. It is possible to obtain a molded product having excellent mold releasability or releasability from other resin molded products such as a film, water / oil repellency, and antifouling properties.

FIG. 1 is a diagram showing ¹ H NMR spectra of hyperbranched polymers: HPS-SC3F-1 to HPS-SC3F-4 produced in Examples 1 to 4. FIG. 2 shows the ¹ H NMR spectrum of the hyperbranched polymer: HPS-OC1F produced in Example 9. FIG. 3 is a diagram showing the ¹ H NMR spectrum of the hyperbranched polymer: HPS-OC4H produced in Example 10. FIG. 4 shows the ¹ H NMR spectrum of the hyperbranched polymer: HPS-OC6F produced in Example 11. FIG. 5 shows the ¹ H NMR spectrum of the hyperbranched polymer: HPS-OC6H produced in Example 12. 6 is a diagram showing a ¹ H NMR spectrum of hyperbranched polymer: HPS-OC7F produced in Example 13. FIG.

The fluorine-containing hyperbranched polymer of the present invention has a structure represented by the following formula [1].

In the formula [1], R ¹ represents a hydrogen atom or a methyl group. A ¹ represents a structure represented by the following formula [2] or formula [3]. L represents —SC (═O) — or —O—. Rf represents a fluoroalkyl group having 2 to 12 carbon atoms, which may be the same or different. N is the number of repeating unit structures and represents an integer of 2 to 3,000.

Preferably, Rf preferably represents a fluoroalkyl group having 2 to 12 carbon atoms in which a hydrogen atom and a fluorine atom are bonded to a main chain or a terminal carbon atom, and in particular, the fluoroalkyl group is A fluoroalkyl group having a difluoromethyl structure at the terminal is preferable.
Most preferably, Rf represents a fluoroalkyl group having 2 to 12 carbon atoms represented by the following formula [4].

In the above formula [4], X represents a hydrogen atom or a fluorine atom, k represents 1 or 2, and m represents an integer of 0 to 5.
In particular, X preferably represents a hydrogen atom.

Specific examples of Rf include —CH ₂ CF ₃ group, —CH ₂ CF ₂ CF ₃ group, —CH ₂ (CF ₂ ) ₂ CF ₃ group, —CH ₂ (CF ₂ ) ₃ CF ₃ group, —CH ₂ (CF ₂ ) ₄ CF ₃ group, —CH ₂ (CF ₂ ) ₅ CF ₃ group, —CH ₂ (CF ₂ ) ₆ CF ₃ group, —CH ₂ CF ₂ CHF ₂ group, —CH ₂ (CF ₂ ) ₃ CHF ₂ groups, —CH ₂ (CF ₂ ) ₅ CHF ₂ groups, —CH ₂ (CF ₂ ) ₇ CHF ₂ groups, —CH (CF ₃ ) CF ₃ groups, —CH ₂ CF ₂ CHFCF ₃ groups, —CH ₂ CF (CF ₃ ) CHF ₂ group, —CH ₂ CF ₂ CClF ₂ group, — (CH ₂ ) ₂ (CF ₂ ) ₃ CF ₃ group, — (CH ₂ ) ₂ (CF ₂ ) ₅ CF ₃ group, — (CH ₂ ) ₂ (CF ₂ ) ₇ CF ₃ group, — (CH ₂ ) ₂ (CF ₂ ) ₉ CF ₃ group, — (CH ₂ ) ₂ (CF ₂ ) ₂ CF (CF ₃ ) CF ₃ group, — (CH ₂ ) ₂ (CF ₂ ) ₄ C F (CF ₃ ) CF ₃ group, — (CH ₂ ) ₂ (CF ₂ ) ₆ CF (CF ₃ ) CF ₃ group, —CH ₂ CH (OH) CH ₂ (CF ₂ ) ₃ CF ₃ group, —CH ₂ CH (OH) CH ₂ (CF ₂ ) ₅ CF ₃ group, —CH ₂ CH (OH) CH ₂ (CF ₂ ) ₇ CF ₃ group, —CH ₂ CH (OH) CH ₂ (CF ₂ ) ₂ CF (CF ₃₎ CF _{3 group, -CH 2 CH (OH) CH} 2 (CF 2) 4 CF (CF 3) CF 3 _{group, -CH 2 CH (OH) CH} 2 (CF 2) 6 CF (CF 3) CF 3 Group, —CF ₂ CF ₃ group, — (CF ₂ ) ₂ CF ₃ group, — (CF ₂ ) ₅ CF ₃ group, —CF ₂ CHF ₂ group, — (CF ₂ ) ₂ CHF ₂ group, — (CF ₂ ) ₅ CHF ₂ group and the like.

In the above formulas [2] and [3], A ² may contain an ether bond or an ester bond and may contain a C 1-30 linear alkylene group, an ether bond or an ester bond. A branched alkylene group having 3 to 30 carbon atoms or a cyclic alkylene group having 3 to 20 carbon atoms which may contain an ether bond or an ester bond is represented.
Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, Represents a carboxyl group or a cyano group

Specific examples of the linear alkylene group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, and an n-hexylene group. Specific examples of the branched alkylene group include isopropylene group, isobutylene group and 2-methylpropylene group.
Examples of the cyclic alkylene group include alicyclic aliphatic groups having a cyclic structure of 3 to 30 carbon atoms, such as monocyclic, polycyclic and bridged cyclic structures. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, or pentacyclo structure having 4 or more carbon atoms. The structural examples (a) to (s) of the alicyclic moiety in the alicyclic aliphatic group are shown below.

Examples of the alkyl group having 1 to 20 carbon atoms in Y ¹ , Y ² , Y ³ and Y ⁴ include a methyl group, an ethyl group, an isopropyl group, an n-pentyl group and a cyclohexyl group.
Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, isopropoxy group, n-pentyloxy group and cyclohexyloxy group.
Y ¹ , Y ² , Y ³ and Y ⁴ are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

The weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography of the fluorine-containing hyperbranched polymer of the present invention is 1,000 to 500,000, preferably 2,000 to 500,000, most preferably. 3,000 to 200,000.
The degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, or 1.1 to 6.0, or 1.2 to 5.0. is there.

<Method for producing fluorine-containing hyperbranched polymer represented by formula [1]>
Next, regarding the method for producing a fluorine-containing hyperbranched polymer represented by the formula [1], when L represents —O—, that is, the fluorine-containing hyperbranched polymer represented by the following formula [6]

And L represents —SC (═O) —, that is, a fluorine-containing hyperbranched polymer represented by the following formula [9]

Each will be described in detail.
(In the above formulas [6] and [9], R ¹ , A ¹ , Rf and n represent the same as defined in formula [1].)

(1) Fluorine-containing hyperbranched polymer in which L represents —O— In the formula [1], when L represents —O—, that is, the fluorine-containing hyperbranched polymer represented by the formula [6]
(A) a step of reacting a hyperbranched polymer having a halogen atom at the molecular end represented by the formula [5] with a fluoroalkoxide having 2 to 12 carbon atoms,
Is manufactured.

In the above formula [5], R ¹ , A ¹ , Rf and n represent the same as defined in formula [1], and Hal represents a halogen atom.
Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

(A) Process: Reaction process of the hyperbranched polymer represented by Formula [5] and a fluoroalkoxide [fluoroalkoxide]
As the fluoroalkoxide having 2 to 12 carbon atoms used in this step, specifically, an alkali metal fluoroalkoxide is used. Examples of the alkali metal include lithium, sodium, potassium, and the like. Among them, those using sodium as the alkali metal are preferable.
In particular, as the fluoroalkoxide having 2 to 12 carbon atoms used in this step, an alkali metal fluoroalkoxide represented by NaO—Rf (Rf is the same as defined in the formula [1]) is preferable. preferable.
The fluoroalkoxide can be produced from the corresponding fluoroalkyl alcohol Rf—OH (Rf is the same as defined in the formula [1]) by a known method.

[solvent]
This step is usually performed in a solvent.
The solvent used in this step is not particularly limited, and among various solvents used for general organic synthesis, those that do not affect the above step can be appropriately selected and used.
Specific examples include amide compounds such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc); nitrile compounds such as acetonitrile, propionitrile and butyronitrile; methyl acetate, ethyl acetate, butyl acetate, Ester compounds such as methyl propionate; ketone compounds such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone; aliphatic hydrocarbon compounds such as pentane, hexane, cyclohexane, octane, decane, decalin, petroleum ether; benzene, Aromatic hydrocarbon compounds such as toluene and xylene; diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane , Diethylene glycol dimethyl ether, ether compounds such as cyclopentyl methyl ether; dimethyl sulfoxide (DMSO), tetramethylurea, sulfolane, N, and other aprotic polar organic solvents such as N- dimethyl-imidazolidinone. These solvents may be used alone or in combination of two or more.
Among the above solvents, it is most preferable to use at least one solvent selected from an ether compound or an aprotic polar organic solvent, particularly THF, DMSO, from the viewpoint of high solubility of the fluoroalkoxide and the halogen atom-containing compound. .
When a mixed solvent of THF and DMSO is used, the mixing ratio of DMSO when THF is set to 1 is preferably 0.5 or less.

[Reaction temperature]
This step can be carried out at any temperature below the boiling point of the solvent, and is preferably carried out at 30 to 150 ° C., more preferably 40 to 120 ° C. from the viewpoint of obtaining the desired product in a high yield in a short time. Is done.

[Reaction time]
The reaction time of the hyperbranched polymer having a halogen atom at the molecular terminal and the fluoroalkoxide varies depending on the type of the hyperbranched polymer, the type of the fluoroalkoxide, the type of base, the solvent used, the reaction temperature to be applied, etc. However, it is usually about 1 to 24 hours.

Although this step can be performed under air, it is preferable to perform under a nitrogen atmosphere.
Moreover, since it is not desirable to mix water into the reaction system, the use of a dehydrated solvent is preferred.
After the completion of this step, the crude product can be separated by a known method such as evaporation of the solvent, filtration, reprecipitation, etc., and the crude product is distilled, silica gel column chromatography, recrystallization, etc. And can be purified.

The hyperbranched polymer having a halogen atom at the molecular end represented by the above formula [5] is a halogenating agent for (B) the dithiocarbamate group at the molecular end of the hyperbranched polymer represented by the following formula [7]. Substituting with a halogen atom at
Is manufactured.

In the above formula, R ¹ , A ¹ and n represent the same as defined in the formula [5].
R ² and R ³ each independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms, or R ² and R ³ may form a ring together with the nitrogen atom bonded thereto.

Examples of the alkyl group having 1 to 5 carbon atoms in R ² and R ³ include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an n-pentyl group, and a cyclopentyl group.
Examples of the hydroxyalkyl group having 1 to 5 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
Examples of the arylalkyl group having 7 to 12 carbon atoms include a benzyl group and a phenethyl group.
Examples of the ring formed by R ² and R ³ together with the nitrogen atom bonded to them include 4- to 8-membered rings. Examples of the ring include a ring containing 4 to 6 methylene groups. Moreover, the ring containing an oxygen atom or a sulfur atom and 4 to 6 methylene groups as a ring is also mentioned. Specific examples of the ring formed by R ² and R ³ together with the nitrogen atom bonded thereto include a piperidine ring, a pyrrolidine ring, a morpholine ring, a thiomorpholine ring, and a homopiperidine ring.

The hyperbranched polymer having a dithiocarbamate group at the molecular end represented by the formula [7] has a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography of 500 to 5,000,000, preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and most preferably 3,000 to 200,000.
The degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, or 1.1 to 6.0, or 1.2 to 5.0. is there.

Hyperbranched polymers having a dithiocarbamate group at the molecular end represented by the above formula [7] are, for example, Koji Ishizu, Akihide Mori, Polymer International 50, 906-910 (2001), Koji Ishizu, TakeshiPhiMiyaPhiMhiPhiMhiPhiMakiPhi International 51, 424-428 (2002), Koji Ishizu, Yoshihiro Ohta, Journal of Materials Science Letters, 22 (9), 647-650 (2003).

Step (B): Step of substituting the dithiocarbamate group of the hyperbranched polymer represented by the following formula [7] with a halogen atom [halogenating agent]
The method for halogenating the dithiocarbamate group at the molecular end of the hyperbranched polymer represented by the following formula [7] is not particularly limited as long as it can convert the dithiocarbamate group to a halogen atom.
Examples of the halogenating agent that can be used in this reaction include chlorine, N-chlorosuccinimide, chlorinated isocyanuric acid, sulfuryl chloride, tert-butyl hypochloride, phosphorus trichloride, phosphorus pentachloride, triphenylphosphine dichloride, and secondary chloride. Chlorinating agents such as copper and antimony pentachloride, bromine, N-bromosuccinimide, N-bromoglutarimide, N, N ′, N ″ -tribromoisocyanuric acid, sodium N, N′-dibromoisocyanurate, N, N'-bromoisocyanuric acid potassium, N, N'-dibromoisocyanuric acid, sodium N-bromoisocyanurate, N, N'-dibromohydantoin, N-bromohydantoin potassium, N, N'-bromohydantoin sodium, N-bromo -N'-methylhydantoin, 1,3-dibromo-5,5'-dimethylhy Tontoin, 3-bromo-5,5'-dimethylhydantoin, 1-bromo-5,5'-dimethylhydantoin sodium, 1-bromo-5,5'-dimethylhydantoin potassium, 3-bromo-5,5'-dimethyl Brominating agents such as sodium hydantoin, potassium 3-bromo-5,5′-dimethylhydantoin, and iodinating agents such as iodine, N-iodosuccinimide, potassium iodate, potassium periodate, periodic acid, iodic acid, etc. Can be used.
The amount of the halogenating agent used may be 1 to 20 times molar equivalent, preferably 1.5 to 15 times molar equivalent, more preferably 2 to 10 times molar equivalent to the number of dithiocarbamate groups in the hyperbranched polymer. That's fine.

The reaction for substituting the dithiocarbamate group at the molecular end with a halogen atom is preferably carried out in water or an organic solvent. The solvent used is preferably a solvent capable of dissolving the hyperbranched polymer having a dithiocarbamate group and the halogenating agent. In addition, it is preferable that the solvent is the same as the solvent used when producing the hyperbranched polymer having a dithiocarbamate group because the reaction operation is simplified.

The halogenation method is preferably a reaction carried out by heating and refluxing using a halogenating agent such as bromine in an organic solvent solution.
Any organic solvent may be used as long as it does not significantly inhibit the progress of this reaction, such as an organic acid compound such as acetic acid, an aromatic hydrocarbon compound such as benzene, toluene, xylene, ethylbenzene, 1,2-dichlorobenzene, tetrahydrofuran, Used ether compounds such as diethyl ether, ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aliphatic hydrocarbon compounds such as chloroform, dichloromethane, 1,2-dichloroethane, n-heptane, n-hexane, cyclohexane, etc. it can. These solvents may be used alone or in combination of two or more.
The mass of the hyperbranched polymer having a dithiocarbamate group at the molecular end is 0.2 to 1,000 times, preferably 1 to 500 times, more preferably 5 to 100 times, most preferably 10 to It is preferable to use 50 times mass organic solvent.
In this reaction, it is necessary to sufficiently remove oxygen in the reaction system before the start of the reaction, and the inside of the system may be replaced with an inert gas such as nitrogen or argon. The reaction conditions are appropriately selected from a reaction time of 0.01 to 100 hours and a reaction temperature of 0 to 300 ° C. The reaction time is preferably 0.1 to 10 hours and the reaction temperature is 20 to 150 ° C.

After the reaction, it is desirable to decompose the halogenating agent remaining in the system. In this case, an aqueous solution of a reducing agent such as sodium thiosulfate and sodium sulfite, or sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. An alkaline aqueous solution can be used. Moreover, you may make it react with the compound containing unsaturated bonds, such as ethylene, propylene, butene, and cyclohexene. The amount used may be 0.1 to 50 equivalents, preferably 0.5 to 10 equivalents, more preferably 1 to 3 equivalents, relative to the halogenating agent used. The hyperbranched polymer having a halogen atom at the molecular end of the present invention obtained by the reaction as described above can be separated from the solvent from the reaction solution by solvent distillation or solid-liquid separation. Moreover, the hyperbranched polymer which has a halogen atom in the molecular terminal of this invention can be precipitated by adding a reaction solution in a poor solvent, and it can also collect | recover as powder.
In the hyperbranched polymer containing a halogen atom at the molecular end of the present invention, a part of the molecular end may remain as a dithiocarbamate group, but preferably most of them are substituted with halogen atoms. preferable.

(2) Fluorine-containing hyperbranched polymer in which L represents —SC (═O) — In the formula [1], when L represents —SC (═O) —, that is, the compound represented by the formula [9] Fluorine hyperbranched polymer
(C) a step of converting the dithiocarbamate group at the molecular end of the hyperbranched polymer represented by the above formula [7] into a thiol anion (—S ⁻ ) by treating with a base, and (D) the thiol anion. And a carboxylic acid derivative represented by the formula [8].

In the above formula [8], Rf represents the same as defined in the formula [1].
In the above formula [8], Z represents a hydroxy group, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.
Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, and n-pentoxy group. , Isopentoxy group, neopentoxy group, tert-pentoxy group and the like.
Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

Step (C): Conversion step of dithiocarbamate group to thiol anion (—S ⁻ ) [base]
In step (C), the base used for conversion of the dithiocarbamate group to a thiol anion includes alkali metal inorganic acid salt, alkali metal hydroxide, alkali metal hydride, alkali metal alkoxide, aliphatic amine, alicyclic An amine, an aromatic amine, etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types.

Examples of the alkali metal inorganic acid salt include sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, and potassium phosphate.
Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.
Examples of the alkali metal hydride include lithium hydride, sodium hydride, potassium hydride and the like.
Alkali metal alkoxides include lithium methoxide, lithium ethoxide, lithium butoxide, lithium tert-butoxide, sodium methoxide, sodium ethoxide, sodium butoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium butoxide, potassium Examples thereof include tert-butoxide.

Examples of the aliphatic amine include trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, triisopropylamine, triisobutylamine and the like.
Examples of the alicyclic amine include 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,5-diazabicyclo [4.3.0] nonene.
Aromatic amines include pyridine, 5-ethyl-2-methylpyridine, 2-phenylpyridine and the like.

Among the above bases, alkali metal inorganic acid salts, alkali metal hydroxides or alkali metal alkoxides are preferable from the viewpoint of high conversion ratio of dithiocarbamate groups to thiol anions, and it is particularly preferable that the base is selected from alkali metal alkoxides. .
Among the alkali metal alkoxides, those using potassium as the alkali metal, particularly potassium methoxide, potassium ethoxide, and potassium tert-butoxide are more preferable.

The amount of the base used is not particularly limited, but it is usually 1 to 10 molar equivalents, preferably 1 to 5 molar equivalents, most preferably 1 to 3 molar equivalents relative to the dithiocarbamate group.
When used in an amount less than the above numerical range, a part of the dithiocarbamate group-containing compound is converted to thiol, and in particular, when the dithiocarbamate-containing compound is a polymer compound, a plurality or many dithiocarbamate groups are present in the molecule. Will be partly converted.
When used in an amount larger than the above numerical range, the conversion of the dithiocarbamate group into thiol itself is not affected, but the carboxylic acid derivative (required) that the unreacted base is introduced in the subsequent step (step (D)). The economy becomes worse, for example, it reacts with the electronic agent).

[solvent]
Both the conversion step of a dithiocarbamate group into a thiol and the reaction step with a carboxylic acid derivative described later are performed in a solvent.
The solvent used in this step is not particularly limited, and among various solvents used for general organic synthesis, those that do not affect the above step can be appropriately selected and used.
Specific examples include amide compounds such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc); nitrile compounds such as acetonitrile, propionitrile and butyronitrile; methyl acetate, ethyl acetate, butyl acetate, Ester compounds such as methyl propionate; ketone compounds such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone; aliphatic hydrocarbon compounds such as pentane, hexane, cyclohexane, octane, decane, decalin, petroleum ether; benzene, Aromatic hydrocarbon compounds such as toluene and xylene; diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane , Diethylene glycol dimethyl ether, ether compounds such as cyclopentyl methyl ether; dimethyl sulfoxide, tetramethylurea, sulfolane, N, and other aprotic polar organic solvents such as N- dimethyl-imidazolidinone. These solvents may be used alone or in combination of two or more.

Among the above solvents, it is most preferable to use at least one solvent selected from a nitrile compound or an ether compound, particularly THF, dioxane, acetonitrile, particularly THF, from the viewpoint of high solubility of the dithiocarbamate group-containing compound. .
When using a mixed solvent of THF and acetonitrile, the mixing ratio of acetonitrile when THF is 1 is preferably 0.5 or less.

[Reaction temperature]
This step can be carried out at any temperature below the boiling point of the solvent, and is preferably carried out at 40 to 70 ° C., more preferably 50 to 60 ° C. from the viewpoint of obtaining the desired product in a high yield in a short time. Is done.
Even if it exceeds the said temperature range, if it is the temperature below a boiling point, it can implement, but since the reaction process with the below-mentioned electrophile becomes disadvantageous at high temperature and cooling operation is needed, it is not economical.

[Reaction time]
The reaction time of the dithiocarbamate group-containing compound and the base varies depending on the type of dithiocarbamate group-containing compound, the type of base, the type of solvent used, the reaction temperature to be applied, etc., but is usually about 1 to 24 hours. .

In this step, it is necessary to sufficiently remove oxygen in the reaction system before the start of the reaction, and the system may be replaced with an inert gas such as nitrogen or argon.
After completion of this step, the solvent can be separated and collected in the form of a thiol salt by a known method such as distillation, filtration, reprecipitation, etc., but the obtained reaction solution can be used as it is in step (D). it can.

Step (D): Reaction step between thiol anion and carboxylic acid derivative [solvent, reaction temperature, reaction time]
As the solvent used in this step, the same solvent as used in the above-mentioned step (C) can be used.
This step is preferably carried out at a reaction temperature of room temperature (approximately 25 ° C.) to 60 ° C. Accordingly, when the steps (C) and (D) are continuously performed, it is preferable to perform the steps at a temperature of 50 to 60 ° C.
In addition, the reaction time of the thiol anion (containing compound) and the carboxylic acid derivative varies depending on the type of thiol anion (containing compound), the type of electrophile, the type of solvent used, the reaction temperature to be applied, etc. Usually about 1 to 24 hours.

After the completion of this step, the crude product can be separated by a known method such as evaporation of the solvent, filtration, reprecipitation, etc., and the crude product is distilled, silica gel column chromatography, recrystallization, etc. And can be purified.

<Method for producing varnish and thin film>
As a specific method for forming a thin film comprising the fluorine-containing hyperbranched polymer of the present invention, first, a fluorine-containing hyperbranched polymer is dissolved or dispersed in a solvent to form a varnish (film forming material). It is applied on the material by cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, ink jet method, printing method (letter plate, intaglio plate, planographic plate, screen printing, etc.) Thereafter, the film is dried by a hot plate or an oven to form a film.
Among these coating methods, the spin coating method is preferable. In the case of using the spin coating method, since it can be applied in a single time, even a highly volatile solution can be used, and there is an advantage that highly uniform application can be performed.

The solvent used in the form of the varnish may be any solvent that dissolves the fluorine-containing hyperbranched polymer, such as benzene, toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether. Acetate (PGMEA), diisopropyl ether (IPE), cyclopentyl methyl ether (cPME), tetrahydrofuran (THF), 1,4-dioxane, acetone, ethyl methyl ketone (MEK), isobutyl methyl ketone (MIBK), cyclohexanone (CHN), Ethyl acetate, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), chloroform, 1,2-dichloroethane (EDC), o Todichlorobenzene (ODB), N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), trichloromethane, propylene glycol monoethyl ether, ethyl lactate, diethylene glycol monoethyl ether, butyl cellosolve, γ-butyrolactone, etc. Is mentioned. These solvents may be used alone, or two or more kinds of solvents may be mixed.
The concentration in which the solvent is dissolved or dispersed is arbitrary, but the concentration of the fluorine-containing hyperbranched polymer is 0.001 to 90% by mass with respect to the total mass (total mass) of the fluorine-containing hyperbranched polymer and the solvent. The content is preferably 0.002 to 80% by mass, more preferably 0.005 to 70% by mass.
The thickness of the thin film formed of the fluorine-containing hyperbranched polymer is not particularly limited, but is usually 0.01 μm to 50 μm, preferably 0.05 μm to 20 μm.

<Resin composition and molded product produced therefrom>
The present invention also relates to a resin composition containing (a) the fluorine-containing hyperbranched polymer, (b) a thermoplastic resin or a thermosetting resin.

The thermoplastic resin is not particularly limited. For example, a polyolefin resin such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer); Polystyrene resins such as PS (polystyrene), HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer) Polycarbonate resin; polyamide resin; polyimide resin; (meth) acrylic resin such as PMMA (polymethyl methacrylate); PET (polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate Polybutylene naphthalate, PLA (polylactic acid), poly-3-hydroxybutyric acid, polycaprolactone, polybutylene succinate, polyethylene succinate / adipate and other polyester resins; polyphenylene ether resins; modified polyphenylene ether resins; polyacetal resins; polysulfone resins Polyphenylene sulfide resin; polyvinyl alcohol resin; polyglycolic acid; modified starch; cellulose acetate, cellulose triacetate; chitin, chitosan; lignin and the like.
Of these, polymethyl methacrylate resin or polylactic acid resin is preferable.
Moreover, it is although it does not specifically limit as said thermosetting resin, For example, a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, a polyurethane resin, an epoxy resin etc. are mentioned.

In the above resin composition, the blending amount of (a) the fluorine-containing hyperbranched polymer with respect to (b) the thermoplastic resin or the thermosetting resin is preferably 0.01% by mass to 20% by mass, and particularly 0.1% by mass. % To 20% by mass is preferable.

In the resin composition, additives generally added together with a thermoplastic resin or a thermosetting resin, for example, an antistatic agent, a lubricant, a heat stabilizer, an antioxidant, a light stabilizer, a fluorescent agent, a processing aid, You may use together a crosslinking agent, a dispersing agent, a foaming agent, a flame retardant, an antifoamer, a reinforcing agent, a pigment, etc.

The resin composition of the present invention can obtain a resin molded product such as a film, a sheet, or a molded product by any molding method such as injection molding, extrusion molding, press molding, blow molding and the like.

<Polymerizable composition and molded product produced therefrom>
The present invention also relates to a polymerizable composition containing (a) the fluorine-containing hyperbranched polymer, (c) a polymerizable compound, and (d) a polymerization initiator.

The polymerizable compound (c) is not particularly limited as long as it is a compound having one or more, preferably one to six, polymerizable sites that are polymerized by the action of a polymerization initiator.
In addition, the meaning of the polymerizable compound in the present invention is a compound that is not a so-called polymer substance, and not only a monomer compound (monomer) in a narrow sense but also a dimer, trimer, oligomer, and reactive polymer. Is also included.

Examples of the polymerizable moiety include an ethylenically unsaturated bond that is a radical polymerizable moiety, or a vinyl ether structure, a vinyl thioether structure that is a cationic polymerizable moiety, and a cyclic ether structure such as an epoxy ring or an oxetane ring. . Accordingly, examples of the polymerizable compound include a compound having an ethylenically unsaturated bond which is a radically polymerizable site, or a compound having a vinyl ether structure, an epoxy ring or an oxetane ring which is a cationically polymerizable site.

Among the polymerizable compounds, a polyfunctional (meth) acrylate compound having two or more (meth) acrylic groups having an ethylenically unsaturated bond site is preferable.
Examples of such polymerizable compounds include the following (meth) acrylic acid esters and vinyl compounds having a polyalkylene glycol chain. In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.
・ (Meth) acrylic acid ester:
Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkoxy titanium tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-methyl- 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trisic [5.2.1.0 ^2,6] decanedimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxy-propane, 2-hydroxy-1, 3-di (meth) acryloyloxypropane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, undecylenoxyethylene glycol di (meth) acrylate, bis [4- (meth ) Acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantanediol di (meth) acrylate, 1,3-adamantanedimethanol di (meth) acrylate, ethoxylated bisphenol A ( (Meth) acrylate and the like.
-Vinyl compounds having a polyalkylene glycol chain:
Polyethylene glycol (molecular weight 300) di (meth) acrylate, polypropylene glycol (molecular weight 500) di (meth) acrylate, and the like.

Among these, tricyclo [5.2.1.0 ^2,6 ] decanedimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dioxane glycol di (meth) acrylate, 9,9-bis [4- (2- (Meth) acryloyloxyethoxy) phenyl] fluorene, ethoxylated bisphenol A (meth) acrylate, and the like are preferable, and tricyclo [5.2.1.0 ^2,6 ] decanedimethanol di (meth) acrylate is particularly preferable.

As the above (d) polymerization initiator, known ones can be used. For example, benzoins; benzophenones; benzyl ketals; α-hydroxy ketones; α-amino ketones; acyl phosphine oxides; Class; iodonium salt; or sulfonium salt. Specifically, for example, Irgacure (registered trademark) 184, 369, 500, 651, 784, 907, 819, 1000, 1300, manufactured by BASF Japan Ltd. (hereinafter, trade name) 1700, 1800, 1850, 2959, Darocur (registered trademark) 1173 manufactured by the same company, and the like, but are not limited thereto. Such a polymerization initiator can also be used in combination of multiple types.

In the polymerizable composition, the blending amounts of (a) a fluorine-containing hyperbranched polymer, (c) a polymerizable compound, and (d) a polymerization initiator are as follows.
That is, (a) the fluorine-containing hyperbranched polymer is preferably 0.01% by mass to 20% by mass, and particularly preferably 0.1% by mass to 20% by mass with respect to (c) the polymerizable compound. .
Further, (d) the polymerization initiator is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to 10% by mass with respect to (c) the polymerizable compound. Within the above range, the polymerizable compound (c) can be polymerized without lowering the transmittance.

Additives generally added as necessary to the polymerizable composition, for example, sensitizers, polymerization inhibitors, polymerization initiators, leveling agents, surfactants, as long as the effects of the present invention are not impaired. Adhesion imparting agents, plasticizers, ultraviolet absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes and the like may be appropriately blended.

The polymerizable composition of the present invention can form a molded product such as a cured film or a laminate by being coated on a substrate and polymerized (cured).
Examples of the substrate include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate, and the like. Can be mentioned. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.
As the coating method of the polymerizable composition of the present invention, various coating methods described above in <Method for producing varnish and thin film> can be used. It is preferable that the polymerizable composition is filtered in advance using a filter having a pore diameter of about 0.2 μm in advance and then used for coating.
After coating, it is preferably followed by preliminary drying with a hot plate or oven, followed by photocuring by irradiating with actinic rays such as ultraviolet rays. Examples of actinic rays include ultraviolet rays, electron beams, and X-rays. As a light source used for ultraviolet irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like can be used.
Thereafter, post-baking is performed, and specifically, the polymerization can be completed by heating using a hot plate, an oven or the like.
The thickness of the film formed by coating is usually 0.01 μm to 50 μm, preferably 0.05 μm to 20 μm after drying and curing.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

(1) Gel permeation chromatography (GPC)
Equipment: HLC-8220 GPC manufactured by Tosoh Corporation
Column: Shodex (registered trademark) KF-804L + KF-803L
Column temperature: 40 ° C
Solvent: THF
Detector: UV (254 nm), RI
(2) ¹ H NMR spectrum apparatus: JNM-LA (Lambda) 600 (600 MHz) manufactured by JEOL Ltd.
Solvent: CDCl ₃
Internal standard: CHCl ₃ (δ 7.26 ppm)
(3) Spin coater: MS-A100 manufactured by Mikasa Co., Ltd.
(4) Haze meter (turbidity measurement)
Device: NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.
(5) Ellipsometry (refractive index and film thickness measurement)
Apparatus: J.M. A. EC-400 manufactured by Woollam
(6) Contact angle measurement device: VCA Optima manufactured by AST Products
Measurement temperature: 20 ° C
(7) Glass transition temperature (Tg) measurement device: DSC8230, manufactured by Rigaku Corporation
Measurement conditions: Under nitrogen atmosphere Temperature rising rate: 5 ° C / min (25 to 160 ° C)
(8) 5% weight loss temperature (Td _5% ) measurement device: TG8120 manufactured by Rigaku Corporation
Measurement conditions: In air atmosphere Temperature rising rate: 10 ° C / min (25-500 ° C)

Abbreviations represent the following meanings.
HPS: Hyperbranched polystyrene [Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd.]
THF: Tetrahydrofuran IPA: Isopropanol NMP: N-methyl-2-pyrrolidone DMSO: Dimethyl sulfoxide PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate IPE: Diisopropyl ether cPME: Cyclopentyl methyl ether CHN: Cyclohexanone DMAc: N, N- Dimethylacetamide DMF: N, N-dimethylformamide EDC: 1,2-dichloroethane

[Example 1] Synthesis of HPS-SC3F-1

In a 100 mL two-neck reaction flask, HPS 1.3 g (5 mmol) and potassium methoxide [manufactured by Aldrich] 74 mg (1 mmol, 20 mol% with respect to HPS) were charged, and the atmosphere in the flask was replaced with nitrogen. Thereto was added 35 mL of a THF / acetonitrile (volume ratio 4: 1) mixed solution, and the mixture was stirred at 60 ° C. for 16 hours. Furthermore, perfluorobutyryl chloride [manufactured by Tokyo Chemical Industry Co., Ltd.] 0.35 g (1.5 mmol, 30 mol% with respect to HPS) was added to 15 mL of a THF / acetonitrile (volume ratio 4: 1) mixed solution. The dissolved solution was dropped with a syringe and further stirred at 60 ° C. for 6 hours.
Next, this reaction solution was added to 300 mL of IPA / water (volume ratio 4: 1) to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and dried under reduced pressure to obtain 1.3 g of the desired product (HPS-SC3F-1) as a white solid (yield 92%).
A ¹ H NMR spectrum of the obtained target product is shown in FIG. The introduction rate of the fluoroalkyl group calculated from the NMR spectrum was 8%. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 35,000, and dispersion degree: Mw (weight average molecular weight) / Mn (number average molecular weight) was 4.2.

[Example 2] Synthesis of HPS-SC3F-2 Except that the amount of potassium methoxide used was changed to 0.15 g (2 mmol) and the amount of perfluorobutyryl chloride was changed to 0.70 g (3 mmol), respectively. The same operation as in Example 1 was performed to obtain 1.3 g of the target product (HPS-SC3F-2) as a white solid (yield 90%).
The ¹ H NMR spectrum of the obtained target product is also shown in FIG. The introduction rate of the fluoroalkyl group calculated from the NMR spectrum was 28%. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 46,000, and dispersion degree: Mw / Mn was 5.2.

Example 3 Synthesis of HPS-SC3F-3 Except that the amount of potassium methoxide used was changed to 0.22 g (3 mmol) and the amount of perfluorobutyryl chloride was changed to 1.1 g (4.5 mmol). In the same manner as in Example 1, 1.4 g of the white solid target product (HPS-SC3F-3) was obtained (yield: 90%).
The ¹ H NMR spectrum of the obtained target product is also shown in FIG. The introduction rate of the fluoroalkyl group calculated from the NMR spectrum was 41%. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 63,000, and dispersion degree: Mw / Mn was 5.5.

Example 4 Synthesis of HPS-SC3F-4 Except that the amount of potassium methoxide used was changed to 0.29 g (4 mmol) and the amount of perfluorobutyryl chloride was changed to 1.4 g (6 mmol), respectively. The same operation as in Example 1 was carried out to obtain 1.3 g of the desired product (HPS-SC3F-4) as a white solid (yield 85%).
The ¹ H NMR spectrum of the obtained target product is also shown in FIG. The introduction rate of the fluoroalkyl group calculated from the NMR spectrum was 50%. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 74,000, and dispersion degree: Mw / Mn was 5.3.

[Solvent solubility of HPS-SC3F]
About each hyperbranched polymer obtained in Example 1 thru | or Example 4, the solubility with respect to each solvent shown in Table 1 was evaluated. In the test, each hyperbranched polymer was mixed with each solvent so as to have a concentration of 5% by mass, stirred at 25 ° C. for 1 hour, and then visually evaluated according to the following criteria. The results are also shown in Table 1.
◯: Transparent solution that dissolves well △: Dissolves but remains undissolved ×: Precipitates are insoluble

[Examples 5 to 8] Preparation and evaluation of HPS-SC3F thin films 0.1 g of each hyperbranched polymer obtained in Examples 1 to 4 was dissolved in 10 g of NMP to prepare varnishes. The obtained varnishes were each spin-coated (1,000 rpm × 30 seconds) on a glass substrate and dried by heating on a 130 ° C. hot plate for 30 minutes to form a film.
About each obtained thin film, the HAZE value, the refractive index in wavelength 633nm, and the film thickness were measured. The results are also shown in Table 2.

[Synthesis Example 1] Synthesis of HPS-Br

According to a known method (for example, WO 2008/29688 pamphlet: Example 1), HPS was brominated with bromine to obtain the target HPS-Br.
The obtained HPS-Br had a weight average molecular weight Mw of 6,600 and a dispersity Mw / Mn of 2.2 as measured by GPC using polystyrene conversion.

[Example 9] Synthesis of HPS-OC1F

In a 300 mL two-neck reaction flask, 0.43 g (10.8 mmol) of 60% sodium hydride [manufactured by Kanto Chemical Co., Ltd.] was charged, and the atmosphere in the flask was replaced with nitrogen. Hexane was added thereto, and the mixture was stirred and allowed to stand, and the sodium hydride was washed by removing the supernatant by decantation. To this, 15 mL of anhydrous THF and 0.5 mL of anhydrous DMSO were added, and then 0.78 g (7.8 mmol) of 2,2,2-trifluoroethanol [manufactured by Tokyo Chemical Industry Co., Ltd.] was added, and room temperature (approximately 25 ° C.) For 15 hours. Subsequently, a solution in which 1.4 g (7.1 mmol) of HPS-Br synthesized according to Synthesis Example 1 was dissolved in 10 mL of THF was added dropwise to the reaction solution. The reaction solution was stirred at room temperature (approximately 25 ° C.) for 30 minutes, and further stirred at 50 ° C. for 4 hours.
Next, this reaction solution was added to 60 mL of IPA / water (volume ratio 4: 1) to precipitate the polymer. The precipitated polymer was filtered through a membrane filter and dried under reduced pressure to obtain 1.1 g of the desired product (HPS-OC1F) (yield 71%).
The ¹ H NMR spectrum of the obtained target product is shown in FIG. The target product had a Tg (glass transition temperature) of 91.0 ° C. and a Td _5% (5% weight loss temperature) of 194.0 ° C. In addition, the solubility to the GPC solvent of the obtained target object was low, and the molecular weight measurement by GPC was not able to be performed.

[Example 10] Synthesis of HPS-OC4H

In a 300 mL two-necked reaction flask, 0.48 g (12 mmol) of 60% sodium hydride [manufactured by Kanto Chemical Co., Ltd.] was charged, and the atmosphere in the flask was replaced with nitrogen. Thereto was added 100 mL of THF, and then 3.5 g (15 mmol) of 2,2,3,3,4,4,5,5-octafluoropentanol [manufactured by Tokyo Chemical Industry Co., Ltd.] was added to room temperature (approximately 25 At 30 ° C.) for 30 minutes. Subsequently, a solution prepared by dissolving 2.0 g (10 mmol) of HPS-Br synthesized according to Synthesis Example 1 in 50 mL of THF was added dropwise to the reaction solution. The reaction solution was stirred at room temperature (approximately 25 ° C.) for 30 minutes, and further stirred at 50 ° C. for 6 hours.
Next, the reaction solution was filtered through Celite, and the filtrate was added to 400 mL of hexane to precipitate the polymer as a viscous material. The supernatant was removed by decantation, and the remaining viscous material was further washed twice with 20 mL of hexane. The obtained solid was dried under reduced pressure to obtain 1.9 g of the desired product (HPS-OC4H) (yield: 55%).
The ¹ H NMR spectrum of the obtained target product is shown in FIG. The obtained target product had a Tg of 92.0 ° C., a Td _5% of 279.5 ° C., a weight average molecular weight Mw measured in terms of polystyrene by GPC of 29,000, and a degree of dispersion: Mw / Mn of 2. It was 5.

[Solvent solubility of HPS-OC4H]
Regarding the HPS-OC4H obtained in Example 10, the solubility in each solvent shown in Table 3 was evaluated. In the test, HPS-OC4H was mixed with each solvent so that the concentration was 10% by mass, stirred at 25 ° C. for 1 hour, and then visually evaluated according to the following criteria. The results are also shown in Table 3.
◯: Transparent solution that dissolves well △: Dissolves but remains undissolved ×: Precipitates are insoluble

[Example 11] Synthesis of HPS-OC6F

To a 300 mL two-necked reaction flask, 0.30 g (7.5 mmol) of 60% sodium hydride [manufactured by Kanto Chemical Co., Ltd.] was charged, and the atmosphere in the flask was replaced with nitrogen. Hexane was added thereto, and the mixture was stirred and allowed to stand, and the sodium hydride was washed by removing the supernatant by decantation. To this, 10 mL of anhydrous THF and 0.5 mL of anhydrous DMSO were added, and then 1.3 g (3.6 mmol) of 1H, 1H-tridecafluoro-1-heptanol [manufactured by Tokyo Chemical Industry Co., Ltd.] was added, and room temperature (approximately 25 At 30 ° C.) for 30 minutes. Subsequently, a solution obtained by dissolving 0.59 g (3.6 mmol) of HPS-Br synthesized according to Synthesis Example 1 in 5 mL of THF was added dropwise to the reaction solution. The reaction solution was stirred at room temperature (approximately 25 ° C.) for 30 minutes, and further stirred at 50 ° C. for 15 hours.
Next, this reaction solution was added to 60 mL of IPA / water (volume ratio 4: 1) to precipitate the polymer. The precipitated polymer was filtered through a membrane filter and dried under reduced pressure to obtain 1.2 g of the desired product (HPS-OC6F) (yield 83%).
The ¹ H NMR spectrum of the obtained target product is shown in FIG. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained target object was 27,000, and dispersion degree: Mw / Mn was 2.2. In addition, Tg and Td _5% of the obtained object were not observed as clear peaks.

[Example 12] Synthesis of HPS-OC6H

To a 300 mL two-necked reaction flask, 0.30 g (7.5 mmol) of 60% sodium hydride [manufactured by Kanto Chemical Co., Ltd.] was charged, and the atmosphere in the flask was replaced with nitrogen. Hexane was added thereto, and the mixture was stirred and allowed to stand, and the sodium hydride was washed by removing the supernatant by decantation. To this, 10 mL of anhydrous THF and 0.5 mL of anhydrous DMSO were added, and then 1.2 g (3.6 mmol) of 1H, 1H, 7H-dodecafluoro-1-heptanol [manufactured by Tokyo Chemical Industry Co., Ltd.] was added, and room temperature (approximately (25 ° C.) for 30 minutes. Subsequently, a solution obtained by dissolving 0.59 g (3.6 mmol) of HPS-Br synthesized according to Synthesis Example 1 in 5 mL of THF was added dropwise to the reaction solution. The reaction solution was stirred at room temperature (approximately 25 ° C.) for 30 minutes, and further stirred at 50 ° C. for 15 hours.
Next, this reaction solution was added to 60 mL of IPA / water (volume ratio 4: 1) to precipitate the polymer. The precipitated polymer was filtered through a membrane filter and dried under reduced pressure to obtain 1.2 g of the desired product (HPS-OC6F) (yield 85%).
The ¹ H NMR spectrum of the obtained target product is shown in FIG. The target product had a Tg of 96.7 ° C. and a Td _5% of 257.8 ° C. In addition, the solubility to the GPC solvent of the obtained target object was low, and the molecular weight measurement by GPC was not able to be performed.

[Solvent solubility of HPS-OC6F and HPS-OC6H]
The solubility of each of the HPS-OC6F and HPS-OC6H obtained in Examples 11 to 12 in each solvent shown in Table 4 was evaluated. In the test, HPS-OC6F or HPS-OC6H was mixed with each solvent so that the concentration was 10% by mass, stirred at 25 ° C. for 1 hour, and then visually evaluated according to the following criteria. The results are also shown in Table 4.
◯: Transparent solution that dissolves well △: Dissolves but remains undissolved ×: Precipitates are insoluble

[Example 13] Synthesis of HPS-OC7F

A 300 mL two-neck reaction flask was charged with 0.28 g (7.0 mmol) of 60% sodium hydride [manufactured by Kanto Chemical Co., Ltd.], and the atmosphere in the flask was replaced with nitrogen. Hexane was added thereto, and the mixture was stirred and allowed to stand, and the sodium hydride was washed by removing the supernatant by decantation. To this, 10 mL of anhydrous THF and 0.5 mL of anhydrous DMSO were added, and the mixture was stirred at room temperature (approximately 25 ° C.) for 30 minutes. Next, a solution of 1.4 g (3.5 mmol) of 1H, 1H-pentadecafluoro-1-octanol (manufactured by Tokyo Chemical Industry Co., Ltd.) in 4 mL of benzotrifluoride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. And stirred at room temperature (approximately 25 ° C.) for 1.5 hours. Subsequently, a solution obtained by dissolving 0.70 g (3.6 mmol) of HPS-Br synthesized according to Synthesis Example 1 in 5 mL of THF was added dropwise to the reaction solution. The reaction solution was stirred at room temperature (approximately 25 ° C.) for 30 minutes, and further stirred at 50 ° C. for 4 hours.
Next, this reaction solution was added to 60 mL of IPA / water (volume ratio 4: 1) to precipitate the polymer. The precipitated polymer was filtered through a membrane filter and dried under reduced pressure to obtain 1.8 g of the desired product (HPS-OC7F) (yield: 66%).
The ¹ H NMR spectrum of the obtained target product is shown in FIG. The target product had a Tg of 97.0 ° C. and a Td _5% of 258.0 ° C. In addition, the solubility to the GPC solvent of the obtained target object was low, and the molecular weight measurement by GPC was not able to be performed.

[Examples 14 to 18] Production and Evaluation of Hyperbranched Polymer Thin Films Each hyperbranched polymer obtained in Examples 9 to 13 was dissolved in perfluorobenzene [manufactured by Tokyo Chemical Industry Co., Ltd.]. A 10% by weight varnish was prepared. The obtained varnishes were each spin-coated (500 rpm × 20 seconds) on a glass substrate and dried by heating on a hot plate at 100 ° C. for 30 minutes to form a film.
About each obtained thin film, the refractive index in wavelength 589nm, a film thickness, and the contact angle of water and diiodomethane were measured. Moreover, the surface free energy of each thin film was computed from the contact angle of the obtained water and diiodomethane. The results are also shown in Table 5. In addition, the contact angle measured the contact angle 10 seconds after dripping a measuring liquid on each thin film surface.

Claims (14)

1. A fluorine-containing hyperbranched polymer represented by the formula [1], wherein the weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography is 1,000 to 500,000.
   

   

   (Wherein R ¹ represents a hydrogen atom or a methyl group, A ¹ represents a structure represented by the formula [2] or [3], and L represents —SC (═O) — or —O—. Rf represents a fluoroalkyl group having 2 to 12 carbon atoms which may be the same or different, and n represents the number of repeating unit structures and represents an integer of 2 to 3,000.)
   

   

   (In the formula, A ² is a linear alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, or a C 3 to 30 carbon atom which may contain an ether bond or an ester bond. Represents a branched alkylene group or a cyclic alkylene group having 3 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom. Represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxyl group, or a cyano group.
2. The fluorine-containing hyperbranched polymer according to claim 1, wherein Rf represents a fluoroalkyl group having 2 to 12 carbon atoms in which a hydrogen atom and a fluorine atom are bonded to a main chain or a terminal carbon atom.
3. The fluorine-containing hyperbranched polymer according to claim 2, wherein the fluoroalkyl group is a fluoroalkyl group having a difluoromethyl structure at a terminal thereof.
4. The fluorine-containing hyperbranched polymer according to claim 1, wherein Rf represents a fluoroalkyl group having 2 to 12 carbon atoms represented by the formula [4].
   

   

   (In the formula, X represents a hydrogen atom or a fluorine atom, k represents 1 or 2, and m represents an integer of 0 to 5).
5. The fluorine-containing hyperbranched polymer according to claim 4, wherein X represents a hydrogen atom.
6. A varnish containing the fluorine-containing hyperbranched polymer according to any one of claims 1 to 5.
7. A thin film comprising the fluorine-containing hyperbranched polymer according to any one of claims 1 to 5.
8. (A) A resin composition comprising the fluorine-containing hyperbranched polymer according to any one of claims 1 to 5 and (b) a thermoplastic resin or a curable resin.
9. A resin molded product produced from the resin composition according to claim 8.
10. (A) A polymerizable composition comprising the fluorine-containing hyperbranched polymer according to any one of claims 1 to 5, (c) a polymerizable compound, and (d) a polymerization initiator.
11. A resin molded product produced by polymerizing the polymerizable composition according to claim 10.
12. (A) The manufacturing method of the fluorine-containing hyperbranched polymer represented by Formula [6] including the process with which the hyperbranched polymer represented by Formula [5] and the C2-C12 fluoroalkoxide are made to react.
    

    

    (In the formula, R ¹ represents a hydrogen atom or a methyl group, A ¹ represents a structure represented by the formula [2] or [3], Hal represents a halogen atom, and Rf may be the same. And represents a fluoroalkyl group having 2 to 12 carbon atoms which may be different, and n is the number of repeating unit structures and represents an integer of 2 to 3,000.)
    

    

    (In the formula, A ² is a linear alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, or a C 3 to 30 carbon atom which may contain an ether bond or an ester bond. Represents a branched alkylene group or a cyclic alkylene group having 3 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom. Represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxyl group, or a cyano group.
13. (B) The production of the fluorinated hyperbranched polymer according to claim 12, further comprising a step of substituting a halogen atom with a halogen atom for the dithiocarbamate group at the molecular end of the hyperbranched polymer represented by the formula [7]. Method.
    

    

    (In the formula, R ¹ , A ¹ and n are as defined in the formula [5], and R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms, the number of carbon atoms. It represents a 1 to 5 hydroxyalkyl group or an arylalkyl group having 7 to 12 carbon atoms, or R ² and R ³ may form a ring together with the nitrogen atom bonded thereto. .)
14. (C) a step of converting the dithiocarbamate group at the molecular end of the hyperbranched polymer represented by the formula [7] into a thiol anion (—S ⁻ ) by treating with a base, and (D) the thiol anion and the formula The manufacturing method of the fluorine-containing hyperbranched polymer represented by Formula [9] including the process with which the carboxylic acid derivative represented by [8] is made to react.
    

    

    (Wherein R ¹ represents a hydrogen atom or a methyl group, A ¹ represents a structure represented by Formula [2] or Formula [3], and R ² and R ³ each independently represents 1 carbon atom. Represents an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms, or R ² and R ³ are combined with a nitrogen atom bonded thereto. A ring may be formed, and n is the number of repeating unit structures and represents an integer of 2 to 3,000, and Rf may be the same or different and has 2 to 12 carbon atoms. Z represents a hydroxy group, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.)
    

    

    (In the formula, A ² is a linear alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, or a C 3 to 30 carbon atom which may contain an ether bond or an ester bond. Represents a branched alkylene group or a cyclic alkylene group having 3 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom. Represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxyl group, or a cyano group.

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