JPH0246604B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel methacrylimide-containing fluoroalkyl methacrylate polymer. [Prior art] In addition to heat resistance, corrosion resistance, and high-performance dielectric materials, fluorine-containing polymers have characteristic surface properties, optical properties,
Due to its radiation sensitivity, permselectivity, electrical properties, and properties as a medical material, it is being functionally applied in various fields, and its demand is increasing. However, it is currently expensive, and compared to general-purpose resins, its manufacturing and molding methods are not fully established. Among fluorine-containing polymers, fluoroalkyl methacrylate monomer resins are transparent, have low refraction, and have surface properties such as water and oil repellency, as well as radiation sensitivity based on the characteristic solubility of the polymer. It is positioned as a special resin with excellent properties such as hardness, hygroscopicity, and dimensional stability. One of these characteristics is that it has a low refractive index, and it is used to construct an optical transmission body as a sheath material for a core material such as polystyrene, polymethyl methacrylate, or polycarbonate resin. In addition, fluoroalkyl methacrylate polymers are used as resin molding materials. However, fluoroalkyl methacrylate polymers have inferior thermal decomposition resistance compared to corresponding alkyl methacrylate polymers, and are thermally decomposed during high-temperature molding processing to generate volatile matter. Therefore, defects such as jetting silver occur in the molded product, and it is difficult to say that the resin has excellent thermoplasticity. Also,
When compared with the corresponding alkyl methacrylate polymer, the double bond electron density that has radical polymerization ability is sparse, resulting in a molecular structure that is susceptible to radical depolymerization. Therefore, the properties imparted during production deteriorate as heat shaping is repeated during molding, the degree of polymerization decreases, and the properties significantly decrease due to the plasticizing effect of monomers produced by depolymerization. Regarding heat resistance, poly 2,2,2-trifluoroethyl methacrylate has the best heat resistance, but it still has a glass transition temperature of 83℃.
and polymethacrylic acid 2,2,2,2',2',
Even 2'-hexafluoroisopropyl has a low temperature of 95°C, which is inferior to polymethyl methacrylate's temperature of 100°C. On the other hand, fluorine-containing polymers, as typified by polytetrafluoroethylene, have surface properties derived from their molecular structure, such as water and oil repellency, and they do not get wet with water or oil. This is also an excellent feature of fluorine-containing polymers that are currently widely used as industrial materials. Furthermore, fluoroalkyl methacrylate polymers have excellent properties of being transparent with very little absorption and scattering. [Problems to be Solved by the Invention] The present invention provides a novel polymer that can improve heat resistance and thermal decomposition resistance while maintaining the above-mentioned excellent properties of fluorine-containing polymers, especially fluoroalkyl methacrylate polymers. This was done to provide integration. [Means for Solving the Problems] That is, the methacrylimide-containing fluoroalkyl methacrylate polymer of the present invention, which was discovered as a means for solving the above problems, has the following formula: (A) General formula [I] (In the formula, R is a hydrogen atom or a carbon number of 1 to 20
represents an aliphatic, aromatic or alicyclic hydrocarbon group. ) 2 to 98% by weight of methacrylimide structural units represented by (B) 98 to 2% by weight of structural units that can be formed from fluoroalkyl methacrylate monomers, and (C) fluoroalkyl methacrylate monomers of (B) It is characterized by comprising 0 to 50% by weight of structural units that can be formed from monomers that can be copolymerized with other polymers, and having an intrinsic viscosity of 0.01 to 3.0 dl/g. [Specific Description and Examples of the Invention] In the methacrylimide structural unit of (A),
R in the general formula [I] is a hydrogen atom, or a saturated to unsaturated (having a bond) hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group (these The hydrocarbon group represents a group selected from a halogen atom or a substituent other than a hydrocarbon group (which may have a substituent such as an organic group).
Typical specific examples include hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-
Examples include butyl group, isobutyl group, tert-butyl group, phenyl group, substituted phenyl group, cyclohexyl group, bornyl group, and the like. Particularly preferred are a hydrogen atom, a methyl group, and a cyclohexyl group from the viewpoint of heat resistance, moldability, and the like. The methacrylimide-containing fluoroalkyl methacrylate polymer of the present invention may contain only one type of methacrylimide structural unit of the above (A), or may contain two or more types. Examples of the structural unit that can be formed from the fluoroalkyl methacrylate monomer (B) include structural units represented by the following general formula [] and general formula []. [Note] General formula [] (In the formula, x is 1 or 2, y is 0 or an integer from 1 to 10, and Z ₁ represents a hydrogen atom or a fluorine atom.) General formula [] (In the formula, l, m and n are each 0 or an integer of 1 to 10, and Z ₂ , Z ₃ and Z ₄ each represent a hydrogen atom or a fluorine atom. However, if l, m and n are 0 at the same time)
and Z ₂ , Z ₃ and Z ₄ do not represent hydrogen atoms at the same time. ) The methacrylimide-containing fluoroalkyl methacrylate polymer of the present invention has one of the structural units of (B) above.
It may contain only one species or two or more species. Representative specific examples of fluoroalkyl methacrylate monomers that can form these structural units include:
2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,3,
4,4-hexafluorobutyl methacrylate,
2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 2,2,3,3,4,4,
5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 9-
heptadecafluorononane methacrylate, 2,
Examples include 2,2,2',2',2'-hexafluoroisopropyl methacrylate and 2,2,2,2',2',2'-pentafluoroisopropyl methacrylate. The structural unit that can be formed from a vinyl monomer copolymerizable with the fluoroalkyl methacrylate monomer (B) in (C) above is preferably not present if only heat resistance is desired, but moldability Since it acts as a regulator, it is added as necessary in relation to the resin properties. Preferred vinyl monomers include acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, styrene and substituted styrene. Among these, acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, norbornyl acrylate, and 2-ethylhexyl acrylate. , benzyl acrylate, etc. can be used. Examples of methacrylate esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, norbornyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid. Benzyl and the like can be used. Among these vinyl monomers, methacrylic acid, methyl methacrylate and styrene are particularly preferred. Furthermore, the methacrylimide-containing fluoroalkyl methacrylate polymer of the present invention may contain only one type of structural unit that can be formed from these vinyl monomers, or may contain two or more types. In the methacrylimide-containing fluoroalkyl methacrylate polymer of the present invention, the structural unit (B) is an essential component for exhibiting the excellent properties of the fluorine-containing polymer. Therefore, in order to balance heat resistance and thermal decomposition resistance with these excellent properties, it is necessary to select the blending amount and molecular structure of the methacrylimide structural unit (A) and the structural unit (B). becomes. The intrinsic viscosity of the methacrylimide-containing fluoroalkyl methacrylate polymer of the present invention, as measured by the measuring method described below, is preferably in the range of 0.01 to 3.0 dl/g. If the intrinsic viscosity is less than 0.01, the mechanical strength will be poor, and if it exceeds 3.0, shaping will be difficult. The method for producing the methacrylimide-containing fluoroalkyl methacrylate polymer of the present invention includes:
A monomer that can form the methacrylimide structural unit of (A), a fluoroalkyl methacrylate monomer that can form the structural unit of (B), and optionally a structural unit of (C). Although it is possible to copolymerize the obtained vinyl monomer, the fluoroalkyl methacrylate monomer that can form the structural unit (B) and, if necessary, the vinyl monomer that can form the structural unit (C) Polymerization of monomers (homopolymerization or copolymerization)
The fluoroalkyl methacrylate-containing polymer _obtained by
amine (hereinafter referred to as an imidizing agent) in the presence of a solvent at 100 to 350°C and in the presence of an inert gas to cause a condensation reaction between polymer side chains (hereinafter referred to as an imidizing agent). , a condensation reaction step) and then separating and removing volatile substances, mainly solvents, from the reaction product (hereinafter referred to as a separation step). The fluoroalkyl methacrylate-containing polymer used in this production method preferably has an intrinsic viscosity of 0.01 to 3.0 dl/g, as measured by the measuring method described below. The fluoroalkyl methacrylate-containing polymer is preferably a polymer using only one or more fluoroalkyl methacrylate monomers that can form the structural unit (B). In the condensation reaction step, the fluoroalkyl methacrylate-containing polymer is preferably dissolved in a solvent and reacted with the imidizing agent in this solution. The solvent used at this time is one that does not inhibit the imidization reaction, which is a condensation reaction between polymer side chains, and does not change the fluoroalkyl methacrylate or methacrylate ester segment in the case of a partial imidization reaction. It is necessary that The solvent to be used is not particularly limited as long as it does not impede the purpose of the present invention, but preferably the solubility parameter δ value (Polymer Handbook, Second
Ed., J.Brandrap, EHImmergut, John Wiley
& Sons, New York, 1975) is 14-19.5
(cal/cm ³ ) ^1/2 , and the solubility parameter δ value is 8.5 to 13.9 (cal/cm ³ ) ^{1/ 2} is preferably a mixed solvent with a solvent (hereinafter referred to as a good solvent) that can dissolve the fluoroalkyl methacrylate-containing polymer at room temperature. Examples of the poor solvent used in the present invention include methanol, ethylene glycol, and glycerol, with methanol being particularly preferred. Good solvents used in the present invention include alcohols such as ethyl alcohol, isopropyl alcohol, and butyl alcohol, aromatic hydrocarbon compounds such as benzene, toluene, and xylene, and ketones such as methyl ethyl ketone, glyme, diglyme, dioxane, and tetrahydrofuran. -ether compound, dimethylformamide,
Examples include dimethyl sulfoxide and dimethyl acetamide, but among these, those selected from benzene, toluene and dioxane are preferred. The above-mentioned solvent used in the present invention allows the imidizing agent to easily diffuse between the fluoroalkyl methacrylate-containing polymers to quickly perform a uniform imidizing reaction, and also has the effect of controlling heat generation and heat removal of the reaction, and the imidizing agent In order to bring about the dissolution effect and the viscosity adjustment effect of the dissolved polymer, it becomes possible to produce a methacrylimide-containing fluoroalkyl methacrylate polymer that is transparent, has a low refractive index, and has excellent heat resistance as a desired optical material. Regarding the amount of the solvent used in the method of the present invention, a small amount is preferable from the viewpoint of production, but if the amount is too small, the effect of the solvent described above will be reduced. The preferable range is 10 to 1000 parts by weight. In the method of the present invention, when a mixed solvent of a poor solvent and a good solvent is used, the quantitative ratio is not limited. Said general formula used in the method of the present invention: R-
Specific examples of imidizing agents represented by NH ₂ include:
Primary amines such as methylamine, ethylamine, propylamine, 1,3-dimethylurea, 1,
Examples include compounds that generate primary amines when heated, such as 3-diethylurea and 1,3-dipropylurea, ammonia, and urea. Further, examples of aromatic amines include aniline, toluidine, trifluoroaniline, and the like. Furthermore, examples of the alicyclic amine include cyclohexylamine and bornylamine. The amount of these compounds to be used cannot be absolutely limited depending on the amount to be imidized, but is 1 to 250 parts by weight per 100 parts by weight of the raw material, the fluoroalkyl methacrylate-containing polymer. If the amount is less than 1 part by weight, no obvious improvement in heat resistance can be expected. If it exceeds 250 parts by weight, it is unfavorable from an economic point of view. Furthermore, when aiming at a low refractive index, it is not preferable that the methacrylimide structural unit (A) accounts for a large proportion in the polymer. Therefore, the ratio of the methacrylimide structural unit (A) to the structural unit (B) is important. The reaction between the raw material fluoroalkyl methacrylate-containing polymer and the imidizing agent in the reactor is as follows:
The temperature is 100-350°C, preferably 150-300°C. If the reaction temperature is less than 100°C, the imidization reaction will be delayed, and if it exceeds 350°C, a decomposition reaction of the raw resin will occur simultaneously. The reaction time is not particularly limited, but from the viewpoint of productivity, the shorter the better, and is in the range of about 30 minutes to 5 hours. When a large amount of water is present in the reaction, the ester moiety, which is a fluoroalkyl methacrylate segment, undergoes hydrolysis with water as a side reaction during the imidization condensation reaction process, and as a result, methacrylic acid is produced, which is the object of the present invention. It becomes difficult to obtain a methacrylimide-containing polymer having a desired amount of imidization. Therefore, in this reaction, it is preferable to carry out the reaction under conditions substantially free of moisture, that is, under conditions where the moisture content is 1% by weight or less, preferably under anhydrous conditions. In addition, as for the atmosphere of the reaction system, it is preferable to carry out the reaction under an inert gas having a low oxygen content, such as nitrogen, helium, or argon gas, from the viewpoint of the colorability of the obtained polymer. The amount of imidization of the raw material resin in the present invention can be arbitrarily determined, but from the viewpoint of heat resistance and low refractive index, (A) 10 to 90% by weight of methacrylimide structural units, 10% by weight of (B) structural units ~90% by weight, (C)
A polymer comprising 0 to 50% by weight of structural units is more preferred. In the present invention, the reaction apparatus used to carry out the condensation reaction step is not particularly limited as long as it does not impede the purpose of the present invention, but may include a plug flow type reaction apparatus, a screw extrusion type reaction apparatus, and a columnar reaction apparatus. , a tubular reactor, a duct-like reactor, a tank-type reactor, etc., but in order to perform imidization uniformly and obtain a uniform methacrylimide-containing polymer, it is necessary to provide a supply port and a discharge port. It is preferable to use a tank-type reactor equipped with a stirring device such as 100 ml of water, which has a mixing function throughout the inside of the reactor. In the volatile substance separation step, most of the volatile substances are separated and removed from the reaction product containing the intermolecular condensation reaction product by the reaction between the fluoroalkyl methacrylate-containing polymer and the imidizing agent. The content of residual volatile substances in the final polymer should be less than 1% by weight, preferably less than 0.1% by weight. Volatile substances can be removed using a general vent extruder, devolatizer, etc., or
Other methods can be used, such as diluting the reaction product with a solvent, precipitating it in a large amount of insoluble medium, filtering and drying. The methacrylimide-containing fluoroalkyl methacrylate polymer obtained by the above method has excellent transparency, low refractive index, and heat resistance with little color discoloration, but it develops discoloration during repeated molding processes. There are things that come to mind. For this purpose, an antioxidant can also be added to the obtained polymer in the present invention. Examples of the hindered phenol antioxidant that can be added include 2,6-di-tert-butyl-p-cresol. In addition, as a phosphite antioxidant, tetrakis (2,4-di-tert-butylphenol)
Examples include 4,4'biphenylene phosphoonite. Examples of thioether antioxidants include dilaurylthiodipropionate. The amount of the antioxidant used is 0.01 to 5 parts by weight per 100 parts by weight of the methacrylimide-containing fluoroalkyl methacrylate polymer. Furthermore, depending on performance requirements, other additives such as plasticizers, lubricants, ultraviolet absorbers, colorants, and pigments may also be added. In the present invention, the fluoroalkyl methacrylate-containing polymer can be produced either continuously or batchwise. In the polymerization of the fluoroalkyl methacrylate-containing polymer, which is the raw material resin in the present invention, an ordinary radical polymerization initiator can be used as a polymerization catalyst, such as di-tert
-butyl peroxide, dicumyl peroxide,
Organic peroxides such as methyl ethyl ketone peroxide are
Examples include azo compounds such as 2,2'-azobisisobutyronitrile. As a chain transfer agent during polymerization, an alkyl mercaptan, which is usually used as a polymerization degree regulator, is used. Polymerization methods include emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization, but bulk polymerization is preferred in order to obtain a highly pure polymer. The present invention will be explained in more detail with reference to Examples below. All parts and percentages used in the examples are by weight. In these Examples, the following method was used to measure the properties of the polymer. (1) The infrared absorption spectrum was measured by the KBγ disk method using an infrared spectrophotometer (manufactured by Hitachi, Model 285). (2) The intrinsic viscosity of a polymer is determined by measuring the flow time (ts) of a dimethylformamide solution with a sample polymer concentration of 0.5% by weight and the flow time (to) of dimethylformamide using a Deereax-Bishoff viscometer at a temperature of 25%. Measured at ℃±0.1℃,
Find the relative viscosity η _rel of the polymer from the ts/to value,
The value was then calculated using the following formula. Intrinsic viscosity = (lnη _rel )/C (dl/g) (In the formula, C represents the number of grams of polymer per 100 ml of solvent.) (3) The heat distortion temperature is determined according to the American Materials Testing Standard ASTM.
Measured based on D648. (4) The melt index of the polymer is based on the American Materials Testing Standard ASTM D1238 (grams per 10 minutes at 230°C and a load of 3.8 kg). (5) The amount of imidization (%) of the polymer is measured using the elemental analysis value ( Nitrogen content and proton NMR using measuring device CHN coder (MT-3, manufactured by Yanagimoto Seisakusho)
JNM-FX-100 (JEOL) spectrometer
Measured at 100MHz. (6) Evaluation of thermal decomposition The obtained polymer was heated at 270° C. in an air atmosphere for 120 minutes to obtain a heating loss value (%), which was used as a thermal decomposition evaluation result. (7) Evaluation of transparency A plate with a thickness of 3 mm was formed and the transparency was evaluated by total transparency value according to ASTM D1003. Example 1 80 parts of 2,2,3,3,3-pentafluoropropyl methacrylate, 20 parts of methyl methacrylate, 1 part of methacrylic acid, 0.05 part of polymerization initiator 2,2'-azobisisobutyronitrile, n - After mixing and dissolving 0.1 part of dodecyl mercaptan, the autoclave for bulk polymerization (2) was charged, followed by repeated deaeration and nitrogen replacement, and then sealed. After reacting at a reaction temperature of 50°C for 10 hours and further heating and polymerizing at 70°C for 5 hours, the peak due to the exothermic polymerization was completed, and the polymerization was completed to obtain a transparent polymer. The polymerization conversion rate was 99%. The obtained polymer was crushed using a crusher and fractionated into 16 mesh passes and 32 meshes according to JIS Z8801 standard. The obtained polymer had a refractive index of 1.415 and an intrinsic viscosity of 0.75 dl/g. After washing 100 parts of the obtained sufficiently dried polymer with sulfuric acid, water and drying with calcium chloride, a raw material consisting of 90 parts of toluene purified by distillation and 10 parts of methanol purified by distillation after dehydration and drying was mixed with a stirrer. After charging the autoclave and replacing it with nitrogen,
The mixture was dissolved and stirred at a stirring speed of 90 rpm. Thereafter, 4.6 parts of dried methylamine was added, and the reaction vessel was heated and stirred at 230° C. for 2 hours.
The internal pressure became 45 Kg/cm ² G, and the lower valve of the reaction tank was opened to obtain a produced polymer. A white powder polymer was obtained by heating and vacuum drying the resulting polymer at 100°C. The infrared absorption spectrum of the polymer thus obtained was measured at 1663 cm ^-1 and 750 cm ^-1
Absorption peculiar to N-methylmethacrylimide polymer was observed. (See Figure 1) In the nuclear magnetic resonance spectrum, a signal indicating a methacrylimide ring structure was confirmed, and the imidization rate was determined from the signal intensity.
It was 22%. (See Figure 2) (Solvent D benzene 5
Weight%, measurement temperature 70℃, internal standard tetramethylsilane) Nitrogen content of 2.15% from elemental analysis value, 15.9
% of fluorine content. It was a methacrylic acid 2,2,3,3,3-pentafluoropropylmethyl methacrylate copolymer containing methacrylic imide with an imidization rate of 22%. The refractive index (n ²⁵ _D ) was 1.476. Further, when the physical properties of this polymer were evaluated, the following values were shown.

[Table] When this polymer was subjected to a heating test at 270°C for 120 minutes in an air atmosphere, the loss on heating was 0.52%. thickness 3
After making a molded specimen of mm in diameter, we evaluated the transparency and found that it was 93% transparent when evaluated according to ASTM D1003.
%, indicating good transparency. Example 2 After mixing and dissolving 100 parts of 2,2,3,3,3-pentafluoropropyl methacrylate, 0.05 part of polymerization initiator 2,2'-azobisisobutyronitrile, and 0.1 part of n-dodecylmercaptan, The autoclave for bulk polymerization described in No. 2 was charged and the mixture was repeatedly degassed and replaced with nitrogen, and then sealed. After reacting at a reaction temperature of 50°C for 10 hours and further heating and polymerizing at 70°C for 5 hours, the peak due to the exothermic polymerization was completed, and the polymerization was completed to obtain a transparent polymer. The polymerization conversion rate was 99%. The obtained polymer was crushed using a crusher and separated into JIS Z8801 standard 16 mesh passes and 32 mesh passes. The obtained polymer had a refractive index of 1.405 and an intrinsic viscosity of 0.51.
It was hot. The sufficiently dried polymer thus obtained
After washing 100 parts with sulfuric acid, washing with water, and drying over calcium chloride, a raw material consisting of 90 parts of toluene purified by distillation and 10 parts of methanol purified by distillation after dehydration and drying was charged into an autoclave equipped with a stirrer. After purging with nitrogen, the mixture was dissolved and stirred at a stirring speed of 90 rpm. Then dry methylamine
After adding 3.6 parts, the inside of the reaction tank was heated at 230°C for 2 hours for reaction. The internal pressure became 45 Kg/cm ² , and the lower part of the reaction tank was opened to obtain a produced polymer. Polymer produced at 100℃
A white powdery polymer was obtained by heating and vacuum drying. The infrared absorption spectrum of the polymer thus obtained was measured at 1663 cm ^-1 and 750 cm ^-1
Absorption characteristic of methyl methacrylimide polymer was observed. Further, in the nuclear magnetic resonance spectrum, a signal indicating a methacrylimide ring structure was confirmed, and the imidization rate was 51% based on the signal intensity. From the elemental analysis values, the nitrogen content was 3.7% and the fluorine content was 24.3%. Methacrylic acid 2,2,3,3,3 containing methacrylimide with imidization rate of 51%
- It was a pentafluoropropyl polymer. The refractive index (n ²⁵ _D ) was 1.443. When the physical properties of this polymer were evaluated, the following values were obtained. Intrinsic viscosity: 0.50 dl/g Melt index: 8.5 g/10 minutes Heat distortion temperature: 120°C When this polymer was subjected to a heating test at 270°C for 120 minutes in an air atmosphere, the loss on heating was 0.72%. A molded specimen with a thickness of 3 mm was prepared, and its transparency was evaluated according to ASTM D1003, and the total transparency was 93%, indicating good transparency. Examples 3 to 15 Methacrylimide-containing fluoroalkyl methacrylate polymers were produced and evaluated using the same formulations as in Examples 1 and 2. The results are summarized in Table-1. Comparative Examples 1 to 3 Monomers listed in Table 1 were used. Comparative Example 1 When the raw material polymer used in Example 2 was evaluated, the heat deformation temperature was 70°C, and the 2-hour heating loss at 270°C was 93.
%, the raw material polymer was extremely easy to thermally decompose. Comparative Example 2 The raw material polymer used in Example 3 was evaluated. The results are shown in Table-1. Comparative Example 3 The raw material polymer used in Example 4 was evaluated. The results are shown in Table-1.

【table】

[Summary of the invention]

According to the present invention, the methacrylimide-containing fluoroalkyl methacrylate polymer, which maintains and exhibits the excellent properties of fluorine-containing polymers such as conventional fluoroalkyl methacrylate polymers, and has excellent heat resistance and thermal decomposition resistance. Coalescing can be provided.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum curve diagram of the methacrylimide-containing fluoroalkyl methacrylate polymer of the present invention synthesized in "Example". FIG. 2 is a nuclear magnetic resonance spectrum curve diagram of this polymer.

Claims (1)

[Claims] 1 (A) General formula [I] (In the formula, R is a hydrogen atom or a carbon number of 1 to 20
represents an aliphatic, aromatic or alicyclic hydrocarbon group. ) 2 to 98% by weight of methacrylimide structural units represented by (B) 98 to 2% by weight of structural units that can be formed from a fluoroalkyl methacrylate monomer, and (C) (B) a fluoroalkyl methacrylate monomer 1. A methacrylimide-containing fluoroalkyl methacrylate polymer comprising 0 to 50% by weight of a structural unit that can be formed from a vinyl monomer copolymerizable with methacrylic acid and having an intrinsic viscosity of 0.01 to 3.0 dl/g. 2 R in general formula [I] is a hydrogen atom, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n
The methacrylimide-containing fluoroalkyl methacrylate polymer according to claim 1, which is a -butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a substituted phenyl group, a cyclohexyl group, or a bornyl group. 3. The methacrylate according to claim 1 or 2, wherein the structural unit that can be formed from the fluoroalkyl methacrylate monomer of (B) is represented by the following general formula [] or general formula []. Imide-containing fluoroalkyl methacrylate polymer. General formula [] (In the formula, x is 1 or 2, y is 0 or an integer from 1 to 10, and Z ₁ represents a hydrogen atom or a fluorine atom.) General formula [] (In the formula, l, m and n are each 0 or an integer of 1 to 10, and Z ₂ , Z ₃ and Z ₄ each represent a hydrogen atom or a fluorine atom. However, if l, m and n are 0 at the same time)
and Z ₂ , Z ₃ and Z ₄ do not represent hydrogen atoms at the same time. ) 4 (c) monomer is acrylic acid, methacrylic acid,
One or two selected from acrylic esters, methacrylic esters, styrene, and substituted styrenes
The methacrylimide-containing fluoroalkyl methacrylate polymer according to any one of claims 1 to 3, which is one or more monomers.