JPH0261968B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a fluorinated acrylic multi-stage structured copolymer resin which has excellent weather resistance, solvent resistance, water and oil repellency, high elongation and transparency. To explain in more detail, application at room temperature -
High resistance to elongation failure in strain tests,
The present invention also relates to a method for producing a fluorinated acrylic multi-stage copolymer resin having excellent weather resistance, solvent resistance, and water and oil repellency. The multistage polymer resin produced by the method of the present invention is useful as a weather-resistant film and a sheath material for optical fibers. Prior Art Fluorinated acrylic resins, particularly fluorinated alkyl methacrylate polymers, are used in optical materials that take advantage of their beautiful appearance, outstanding transparency, and low refractive index. Also, since it is water and oil repellent,
It is also used as a fiber treatment agent, and recently SR (Soil
Release) is used as a processing agent. On the other hand, among fluorinated acrylic polymers, lower fluorinated alkyl methacrylate homopolymers in particular have the characteristics of being hard and brittle, so when used for special purposes, it is difficult to impart elasticity to them. This is desirable, and various studies have been made for this purpose. As mentioned above, as a method of imparting elasticity to fluorinated acrylic resin, higher fluorinated alkyl methacrylate, such as 3,3,4,4,5,5,6,
6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate (hereinafter
17FMA), a copolymer of methyl methacrylate or fluorinated alkyl methacrylate, and/or an elastic polymer (polyvinylidene fluoride, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexane A method of blending fluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, etc. with polymethyl methacrylate has been carried out. A polymer whose main component is a long-chain fluorinated alkyl group, and the homopolymer has a low refractive index but is rubbery at room temperature and difficult to mold. For this purpose, processability is improved and a low refractive index is maintained by copolymerizing methyl methacrylate with a relatively high Tg or fluorinated alkyl methacrylate with a relatively high Tg.However, This method has the drawbacks that higher fluorinated methacrylates are currently expensive on the market and that the resulting copolymer has unsatisfactory elongation at low temperatures due to its simple structure. In the case of the latter elastomeric polymer, it is a rubber elastomer with a high degree of fluorination, and has a very specific compatibility with polymethyl methacrylate or polyfluorinated alkyl methacrylate. Since it is a vinylidene derivative, a blend of this elastomeric polymer and polymethyl methacrylate allows for a wide range of blend components and provides a transparent resin body with a low refractive index.However, vinylidene fluoride derivatives have high crystallinity. Since it is a molecule, it has the major drawback that its crystallinity increases when heated, resulting in a decrease in the transparency of the blended resin.At present, while maintaining this defect, It is used as a molding material such as an injection molding material.That is, the heat resistance of the blended resin is an extremely important property when used alone as a film or sheet or as a laminated material on other base materials. If heating causes softening or whitening due to crystallization, the commercial value of the polymer will be significantly reduced.In view of the current situation, the present inventors have further studied in detail the structure of the polymer itself, and have The present invention was completed as a result of intensive studies to obtain a multi-stage structured copolymer resin that has excellent elongation, heat resistance, weather resistance, and low refractive index.Objective and Summary of the Invention The present invention The object of the present invention is to provide a method for producing a fluorinated acrylic multistage copolymer resin that has excellent elongation, excellent heat resistance and weather resistance, and a low refractive index. The method for producing the fluorinated acrylic multi-stage copolymer resin of the present invention comprises 50 to 100% by weight of fluorinated alkyl methacrylate (A ₁ ) and 0 to 50% by weight of a monomer having an ethylenic double bond. (A ₂ ), and polyfunctional monomer (A ₃ ) and grafting agent (A ₄ )
a step of forming an innermost polymer layer (A) of 1 to 25 parts by weight by polymerizing at least one member selected from the group consisting of; in the presence of the polymer, 50-100% by weight of at least one member (B ₁ ) selected from the group consisting of fluorinated alkyl acrylates and fluorinated alkyl methacrylates and 0-50% by weight of ethylenic double bonds. by polymerizing with at least one member selected from the group consisting of another monomer (B ₂ ) having 0, a polyfunctional monomer (B ₃ ), and a grafting agent (B ₄ ),
a step of forming a rubber elastic polymer layer (B) of 5 to 75 parts by weight having a glass transition point (Tg) of ℃ or less on the outside of the innermost polymer layer (A), and the innermost polymer layer (A) 50-100% by weight of fluorinated alkyl methacrylate ( _C1 ) and 0-50% by weight of the polymer formed in the forming step;
Polymerizing at least one selected member consisting of a monomer (C ₂ ) having an ethylenic double bond and a grafting agent (C ₃ ) and having a glass transition point (Tg) of 50°C or higher, 19- forming an outermost polymer layer (C) of 93 parts by weight on the outside of the rubber elastic polymer layer (B), the monomer having an ethylenic double bond (A ₂ ,
B ₂ and C ₂ ) are lower alkyl (meth)acrylate, lower alkoxy (meth)acrylate,
Cyanoethyl (meth)acrylate, acrylamide, acrylic acid, methacrylic acid, styrene,
selected from the group consisting of alkyl-substituted styrene, acrylonitrile and methacrylonitrile, wherein the polyfunctional monomer (A ₃ and B ₃ ) having an ethylenic double bond is ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, _{divinylbenzene} , _{trivinylbenzene} and alkylene glycol diacrylate; ₃ ) but
It is characterized in that it is selected from the group consisting of allyl, methallyl and crotyl esters of α-, β-unsaturated carboxylic acids and dicarboxylic acids, triallyl cyanurate and triallyl isocyanurate. Description of the invention In the method for producing a fluorinated acrylic multi-stage copolymer resin of the present invention, the polymer constituting the innermost polymer layer (A) is fluorinated alkyl methacrylate (A ₁ ).
as a main component, and optionally a fluorinated alkyl methacrylate (A ₁ ), a monomer having an ethylenic double bond (A ₂ ) copolymerizable with it, a polyfunctional monomer (A ₃ ), and a graft cross-agent (A ₄ ). The innermost polymer layer (A) needs to contain 50 to 100% by weight of fluorinated alkyl methacrylate (A ₁ ) as a polymerization component. In addition, the innermost polymer layer (rubber elastic polymer layer (B) forming a double structure with A has fluorinated alkyl acrylate and/or fluorinated alkyl methacrylate (B ₁ ) as a polymeric main component, and has a temperature below 0°C. In this rubber elastic polymer layer (B), fluorinated alkyl acrylate and/or fluorinated alkyl methacrylate (B ₁ ) can be copolymerized with it, if necessary copolymerized with at least one selected from the group consisting of a monomer (B ₂ ) having an ethylenic double bond, a polyfunctional monomer (B ₃ ), or a graft cross-agent (B ₄ ). Rubber elastic polymer layer (B)
It is necessary that 50 to 100% by weight of fluorinated alkyl acrylate and/or fluorinated alkyl methacrylate (B ₁ ) be contained therein as a polymerization component. The outermost polymer layer (C) has fluorinated alkyl methacrylate (C ₁ ) as a main polymerization component, and has a Tg of 50° C. or higher. This fluorinated alkyl methacrylate (C ₁ ) may optionally be copolymerized with other monomers (C ₂ ) having an ethylenic double bond and/or graft cross-agents (C ₃ ).
Obtained by copolymerizing with. The outermost polymer layer (C) needs to contain 50 to 100% by weight of fluorinated alkyl methacrylate (C ₁ ) as a polymerization component. Moreover, in order to form a graft between each of the layers (A) to (C), it is preferable to copolymerize a graft cross-agent (A ₄ , B ₄ , C ₃ ) in each layer. In each of the above polymer layers (A) to (C),
The monomer component copolymerized with the main polymerization component is
Although it is effective for adjusting the Tg value,
This is not absolutely necessary as it may reduce the processability of the resulting resin. In addition, in the innermost polymer layer (A) and the rubber elastic polymer layer (B), the polyfunctional monomers (A ₃ , B ₃ ) used as copolymerization components are crosslinked rubber elastic polymers. It has the effect of improving the rubber elasticity and elongation of the multistage polymer resin obtained. When a graft reaction between the outermost polymer layer (A) having rubber elasticity as described above, the rubber elastic polymer layer (B), and the outermost polymer layer (C) is required, each of these layers Graft cross-agents (A ₄ , B ₄ , C ₃ ) can be used when forming . In this way, a multistage polymer resin having good rubber elasticity as well as good transparency and extensibility can be obtained. The innermost polymer layer (A) contains a graft cross-agent component (A ₄ ), and the rubber elastic polymer layer (B) contains a polyfunctional monomer component (B ₃ ) and a graft cross-agent (B ₄ ). When it is contained, the resulting multistage polymer resin has high elongation, transparency, and good film formability due to its rubber elasticity effect and grafting effect, and has no whitening property when the film is folded. In order to obtain a multistage polymer resin with good rubber elasticity, it is necessary that the Tg of the rubber elastic polymer layer (B) is 0° C. or less. If the Tg of layer (B) is 0
When higher than ℃, the obtained multistage polymer resin is
It does not exhibit rubber elasticity at room temperature. In addition, in order to obtain a multistage polymer resin with excellent mechanical properties, the Tg of the outermost polymer layer (C) must be 50
The temperature must be above ℃. (C) The Tg of the layer is
When the temperature is lower than 50°C, processing properties such as film moldability, extrusion moldability, and injection moldability of the resulting multistage polymer resin become unsatisfactory. In the multistage polymer resin of the present invention, the constituent weight ratios of each layer are as follows: Innermost polymer layer (A): 1 to 25 parts, more preferably 5 to 15 parts, Rubber elastic polymer layer (B): 5 to 75 parts. outermost polymer layer (C): 19 to 93 parts, more preferably 35 to 80 parts. In the multi-stage polymer resin of the present invention, when the content of the innermost polymer layer (A) is less than 1 part by weight, the film processability and resistance to whitening upon folding of the film become unsatisfactory; It is not preferable to increase the amount because the processability of the film deteriorates. The higher the Tg of the innermost polymer layer (A), the better the film moldability of the resulting multistage polymer resin, and
Resistance to film folding and whitening also increases.
Furthermore, if the Tg of the upper (A) layer is low and, for example, approximately equal to the Tg of the rubber elastic polymer layer (B), the resulting resin may have unsatisfactory film formability and resistance to film folding and whitening. Become.
Therefore, the Tg of the innermost polymer layer (A) is preferably higher than the Tg of the rubber elastic polymer layer (B). When the content of the rubber elastic polymer layer (B) is less than 5 parts by weight, high elongation cannot be obtained, and when it is more than 75 parts by weight, resin processability becomes unsatisfactory.
If the content of the layer (B) is 5 parts by weight or more and is relatively small compared to the content of the outermost polymer layer (C), even if the content of the outermost polymer layer (C) is
If Tg is higher than 50℃ but close to 50℃,
The processability and elongation of the resulting multistage polymer resin are as follows:
In good condition. Further, the content of the layer (B) is 75 parts by weight or less,
And when the content is relatively large compared to the content of the (C) layer, the processability and elongation of the resulting multistage polymer resin tend to be better as the Tg of the (C) layer is higher at 50°C or higher. be. Polyfluorinated alkyl acrylate and polyfluorinated polyfluorinated alkyl acrylate that constitute the main polymeric components of the innermost polymer layer (A), rubber elastic polymer layer (B), and outermost polymer layer (C) of the multistage polymer resin of the present invention The alkyl methacrylate has the following structural formula () or (). Or However, in the above formula, m represents an integer of 1 to 5, and n
represents an integer from 1 to 10, X represents an F or H atom, and Z represents an H atom or a _-CH3 group. Examples of the above-mentioned fluorinated alkyl acrylate polymers or fluorinated alkyl methacrylates include:
2,2-difluoroethyl-methacrylate (2FM) and -acrylate (2FA), 2,2,
2-trifluoroethyl-methacrylate (3MF) and -acrylate (3FA), 2,2,
3,3-tetrafluoropropyl-methacrylate (4FM) and -acrylate (4FA), 2,
2,3,3,3-pentafluoropropyl-methacrylate (5FM) and -acrylate (5FA), 2,2,3,3,4,4-hexafluorobutyl-methacrylate (6FM) and -acrylate (6FA), 2, 2, 3, 3, 4, 4,
5,5-octafluoropentyl-methacrylate (8FM) and -acrylate (8FA), 1,
1-di(trifluoromethyl)2,2,2-trifluoroethyl-methacrylate (9FM) and acrylate (9FA), 2,2,3,3,4,
4,5,5,6,6,7,7-dodecafluoropentyl-methacrylate (12FM) and -acrylate (12FA), 3,3,4,4,5,5,
6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-
Examples include peptadecafluorodecanyl methacrylate (17FM) and -acrylate (17FA). In general, the fluorinated alkyl acrylate or fluorinated alkyl methacrylate used in the rubber elastic polymer layer (B) may have either a linear or a branched side chain; The lower the Tg of the polymer, the better. The ethylenic double bond-containing monomers (A ₂ , B ₂ , C ₂ ) copolymerizable with the above-mentioned fluorinated alkyl acrylate and/or fluorinated alkyl methacrylate include lower alkyl (meth)acrylate, lower alkoxy (meth) ) Acrylic monomers such as acrylate, cyanoethyl (meth)acrylate, acrylamide, acrylic acid, and methacrylic acid are preferred. Furthermore, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, etc. can also be used. Such copolymerization components are used in the resulting polymer.
Although it is advantageous for adjusting Tg, it also changes the refractive index of the polymer, so its content is preferably below (30% of the total amount of polymer) and as small as possible. In addition, examples of polyfunctional monomers (A ₃ , B ₃ ) copolymerizable with fluorinated alkyl acrylate and/or fluorinated alkyl methacrylate include ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1 , 4-butylene glycol dimethacrylate and propylene glycol dimethacrylate are preferred, and divinylbenzene, trivinylbenzene, alkylene glycol diacrylate and the like can also be used. These polyfunctional monomers are effective in cross-linking the polymer in which they are contained, but they are not effective in interlayer cross-linking with other layers. Even if a grafting agent is not used, crosslinking between the layers is formed and a highly stable multi-stage polymer resin can be obtained. However, although polyfunctional monomers are effectively used when the resulting resin is required to have excellent hot strength and elongation, the amount used is preferably 10 parts by weight or less. Furthermore, as the graft cross-agent (A ₄ , B ₄ , C ₃ ) used with the fluorinated alkyl acrylate and/or the fluorinated alkyl methacrylate, allylmethallyl or copolymerizable α-β unsaturated carboxylic acid or dicarboxylic acid can be used. Crotyl esters are used, preferably allyl esters of acrylic acid, methacrylic acid, maleic acid, and fumaric acid, with allyl methacrylate being particularly effective. Other effective examples include triallyl cyanurate and triallyl isocyanurate. Such graft cross-agents mainly have conjugated unsaturated bonds in their ester structures that bond with allyl groups, methallyl groups, or crotyl groups of other polymeric components, and a substantial portion of these bonds are bonded to adjacent layers. It effectively bonds with the above group in the polymer and provides a graft bond between two adjacent layers. The amount of grafting agent used is important for adjusting the properties of the resulting resin, and each polymer layer (A),
It is particularly preferably used in an amount of 10 parts by weight or less based on (B) or (C), and more preferably in a range of 0.01 to 5 parts. The multistage polymer resin of the present invention is produced by the following method. First, the innermost layer polymer (A) is heated with predetermined monomer components at a temperature of 30°C to 100°C for 5 to 120°C in the presence of a catalyst.
Produced by polymerizing for minutes. This polymerization may be carried out by any polymerization method, but it is generally preferable to use an emulsion polymerization method. Usual radical polymerization catalysts are used as polymerization catalysts, specifically cumene hydroperoxide (CHP), di-tert-butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, tert-butyl perphthalate, and tert-butyl perbenzoate. , methyl isobutyl ketone peroxide, lauroyl peroxide, cyclohexyl peroxide, 2,5-dimethyl, or 2,5-di-tert-butyl-peroxyhexane, tert-butyl peroctanoate, tert-butyl perisobutyrate, tert- Organic peroxides such as butyl peroxyisopropyl carbonate, methyl 2,2'-azobisisobutyrate,
1,1'-azobiscyclohexanecarbonitrile, 2-phenylazo-2,4-dimethyl-4-
Examples include azo compounds such as methoxyvaleronitrile, 2-carbamoyl-azobisisobutyronitrile, 2,2'-azobis2,4-dimethylvaleronitrile, and 2,2'-azobisisobutyronitrile. The amount used is 0.01% by weight based on the amount of monomer.
It is preferable to use it in a range of 5% by weight. Next, in the rubber elastic polymer layer (B) forming step, in the presence of the innermost layer polymer (A), a predetermined monomer is added at a temperature of 30°C to 100°C in the presence of a catalyst. Polymerize for 120 minutes. This polymerization operation also
Although any polymerization method may be used, it is generally preferable to use an emulsion polymerization method. The type and amount of catalyst used are the same as in the case of polymerization of the innermost layer polymer. Furthermore, in the outermost polymer layer (C) forming step, in the presence of the double structure polymer obtained in the above step, a predetermined monomer is polymerized in the presence of a catalyst to form an outermost polymer layer. form a layer. The polymerization method, conditions and catalyst at this time can be selected from those mentioned above. The resulting multistage polymer resin can be isolated, washed, and dried to obtain a powdered resin. The fluorinated acrylic multi-stage polymer resin obtained by the method of the present invention can be used by mixing with other thermoplastic resins, if necessary, and can also be used with other additives, such as antioxidants. It may be mixed with agents, ultraviolet absorbers, fillers, pigments, antistatic agents, etc. The fluorinated acrylic multi-stage polymer resin obtained by the method of the present invention is used to form weather-resistant films, and is also useful as a sheath material for plastic or quartz-based chemical fibers. The present invention will be further explained below with reference to Examples. In the examples, "parts" and "%" are by weight unless otherwise specified. In addition, the Tg of each polymer used in the examples is determined by the Fox formula, which is generally known from the Tg value described in the Polymer Handbook (published by John Willey & Sons): 1/Tg=a ₁ /Tg ₁ + a ₂ /Tg ₂ (a ₁ and a ₂ are each weight fraction). Also, polymer
When the Tg was unknown, the Tg was determined from the DSC (differential thermal measurement) measurement value of the polymer. The total light transmittance was measured using an integrating sphere haze meter in accordance with ASTM D-1003-61. Tear strength is JIS-
Measurement was performed using the Elmendorf method with a cut depth of 2 mm in accordance with P-8116. The resistance to whitening by folding the film sheet was expressed as shown below based on the whitening state when the film sheet was bent by 180°. ◎-No whitening 〇-Very slight whitening △-Whitening observed ×-Severe whitening ××-Severe whitening and breakage The contact angle is calculated by calculating the advancing contact angle (θ) with water. , water repellency was evaluated. (A Kyowa Conduct Tangle Meter model CA-P was used.) Processability was evaluated by forming a film using a 100 mm wide T-Die using a 25 mmφ extruder. × Poor △ Moderate 〇 Good The refractive index was measured using an Atsube refractometer after molding into a film of about 50μ. Example 1 250 parts of ion-exchanged water in a polymerization vessel with a cooler,
1 part of perfluoroalkyl sulfonate (Megafac F-110, manufactured by Dainippon Ink Chemical) and 0.05 part of sodium formaldehyde sulfoxylate were charged, and after stirring at room temperature in a nitrogen atmosphere, 2, 4 parts of 2,2-trifluoroethyl acrylate (3FA), 1 part of 2,2,2-trifluoroethyl methacrylate (3FM),
1,3-butylene dimethacrylate (BD) 0.25
0.05 parts of allyl methacrylate (AMA), and 0.05 parts of cumene hydroperoxide (CHP) were added and mixed. This mixture was heated to 70° C. and maintained at this temperature for 60 minutes to complete polymerization of the innermost layer polymer (A). Subsequently, 35 parts of 2,2,2-trifluoroethyl acrylate (3FA), 2.5 parts of 1,3-butylene dimethacrylate (BD), 0.7 parts of allyl methacrylate (AMA), and cumene hydroperoxide were added to the resulting polymerization mixture. A mixture consisting of 0.25 parts of (CHP) was added dropwise over 60 minutes, and the resulting mixture was maintained at a temperature of 70° C. for 60 minutes while stirring to complete polymerization of the rubber elastic polymer (B). Further, in the resulting polymerization mixture, 50 parts of 2,2,2-trifluoroethyl methacrylate (3FM), 10 parts of methyl methacrylate (MMA), and n-octyl mercaptan (n
A mixture of 0.5 parts of -C ₈ H ₁₇ SH) and 0.5 parts of kilomene hydroperoxide (CHP) was added dropwise over 60 minutes, and the mixture was heated to 70°C while stirring.
The polymerization of the outermost layer was completed by holding for 60 minutes.
The obtained polymer was in the state of a water-dispersed latex, and the polymerization conversion rate was 99%. The latex particle size is
It was 980Å. 5 parts of calcium chloride was added to 100 parts of the polymer emulsion thus obtained, and the multi-stage structure polymer resin was salted out, washed, dried and subjected to extrusion molding. The residual amount of calcium in the obtained multistage polymer resin composition was 250 ppm. After processing this dry resin powder into pellets using a 25 mm extrusion molding machine, 100 mm
It was formed into a film using T-Die. As a result, the multi-stage structure polymer resin showed good film processability, and a film with a thickness of 50 μm with excellent transparency and flexibility was obtained. The refractive index of the film is 1.4209 (25℃,
The advancing contact angle with water was 75.5°. Furthermore, the film had good resistance to whitening upon bending and was not accompanied by whitening. Furthermore, when measuring the viscoelastic behavior of the multistage polymer resin, the peak of the loss modulus of E″ (dyne/cm ² ) is
It shows a gentle dispersion in the range of 20℃ to 75℃, and tanδ
showed a peak at a temperature of 78°C. The total light transmittance of the film was 92%, the haze was 2%, and the film had good transparency. Also,
The tensile elongation at break of the film was 25%. The composition and test results of each component polymer are shown in Tables 1 and 2, respectively. Examples 2-7 In each of Examples 2-7, the same operations as in Example 1 were performed. However, the composition of each component polymer,
The Tg etc. were as shown in Table 1, and the test results were as shown in Table 2. Comparative Examples 1 to 3 In each of Comparative Examples 1 to 3, the same operations as in Example 1 were performed. However, the composition of each component polymer,
The Tg etc. were as shown in Table 1, and the test results were as shown in Table 2. In Comparative Example 1, the outermost layer polymer (C) has a Tg of 0.
℃ or less, and the film formability and whitening resistance of the obtained polymer resin were extremely poor. In Comparative Example 2, the formation of the innermost polymer layer (A) was omitted, and the resulting polymer resin film had poor bending whitening resistance and elongation. In Comparative Example 3, the production of the outermost polymer layer (C) was omitted, and as a result, the film formability of the obtained multi-stage polymer resin was extremely poor, and a film to be used for testing could not be obtained. Ta.

【table】

[Table] Example 8 Using a core-sheath spinneret, composite spinning was carried out at 230°C using the polymer obtained in Example 3 as the clad component and polymethyl methacrylate as the core component, and the spinning was performed at 30 m/min. I wound it up at high speed. The obtained filament has an outer diameter of 0.5 mm and a core diameter of
The filament had a concentric cross-sectional shape of 0.48 mm, and the surface of the filament was smooth. The optical transmission loss of this filament was 325 dB/Km, which was excellent. Furthermore, even when this filament was wound around a mandrel with a diameter of 2 mm and observed under magnification under a microscope, no cracks were observed in the clad portion. Effects of the Invention The fluorinated acrylic multi-stage polymer resin having a specific structure obtained by the method of the present invention has a satisfactory light transmittance,
It not only has a high haze and refractive index, but also has excellent elongation at break, resistance to whitening when film is folded, and weather resistance, making it extremely useful as a weather-resistant film and optical fiber sheath material. be.

Claims (1)

[Claims] 1 50 to 100% by weight of fluorinated alkyl methacrylate (A ₁ ), 0 to 50% by weight of a monomer having an ethylenic double bond (A ₂ ), and a polyfunctional monomer (A ₃ ) and at least one member selected from the group consisting of a grafting agent (A ₄ ),
-25 parts by weight of forming an innermost polymer layer (A), and in the presence of the polymer formed in the innermost polymer layer (A) forming step, 50 to 100 parts by weight of fluorination. At least one member selected from the group consisting of alkyl acrylates and fluorinated alkyl methacrylates (B ₁ ), and 0 to 50% by weight of other monomers having an ethylenic double bond (B ₂ ) and polyfunctional monomers. polymerization agent (B ₃ ) and at least one member selected from the group consisting of a grafting agent (B ₄ ) to obtain 0
a step of forming a rubber elastic polymer layer (B) of 5 to 75 parts by weight having a glass transition point (Tg) of ℃ or less on the outside of the innermost polymer layer (A), and the innermost polymer layer (A) 50-100% by weight of fluorinated alkyl methacrylate ( _C1 ) and 0-50% by weight of the polymer formed in the forming step;
Other monomers with ethylenic double bonds (C ₂ )
and a graft cross-agent (C ₃ ) to form an outermost polymer layer (C) having a glass transition point (Tg) of 50° C. or higher and having an amount of 19 to 93 parts by weight, The rubber elastic polymer layer (B)
forming the monomer having an ethylenic double bond (A ₂ ,
B ₂ and C ₂ ) are lower alkyl (meth)acrylate, lower alkoxy (meth)acrylate,
Cyanoethyl (meth)acrylate, acrylamide, acrylic acid, methacrylic acid, styrene,
selected from the group consisting of alkyl-substituted styrene, acrylonitrile and methacrylonitrile, wherein the polyfunctional monomer (A ₃ and B ₃ ) having an ethylenic double bond is ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, divinylbenzene, _{trivinylbenzene} and alkylene glycol _{diacrylate ;} )but,
A fluorinated acrylic multistage structural polymer selected from the group consisting of allyl, methallyl, and crotyl esters of α-, β-unsaturated carboxylic acids, and dicarboxylic acids, triallyl cyanurate, and triallyl isocyanurate. Method of manufacturing resin.