JPS59122512A - Fluoroalkyl polymer resin having multi-stage structure - Google Patents

Abstract

PURPOSE:To provide the titled resin having high elongation and composed of the innermost layer consisting of a polymer composed mainly of fluoroalkyl (meth)acrylate, an elastic layer having rubber elasticity, and an outermost layer, wherein said elastic layer and the outermost layer have respective specific glass transition temperature (Tg). CONSTITUTION:The objective resin is obtained as follows. The innermost polymer (A) composed mainly of a fluoroalkyl methacrylate (FM) is prepared preferably by emulsion polymerization of a fluoroalkyl (meth)acrylate, and if necessary a monomer having copolymerizable ethylenic double bond, a polyfunctional monomer, a graft crosslinking agent, etc. A polymer (B) having a Tg of <=0 deg.C, exhibiting rubber elasticity and composed mainly of a fluoroalkyl (meth)acrylate is prepared in the presence of the polymer (A) to obtain a polymer having double-layer structure. Finally, a polymer composed mainly of FM and having a Tg of >=50 deg.C is formed in the presence of the above polymer. EFFECT:Excellent heat resistance and weather resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fluorinated acrylic multi-stage structure copolymer resin which is excellent in weather resistance, solvent resistance, water and oil repellency, high elongation and transparency.

More specifically, it relates to a fluorinated acrylic multi-stage structure copolymer resin that has high resistance to elongation fracture in application-strain tests at room temperature, and has excellent weather resistance, solvent resistance, and water and oil repellency. be.

The multistage polymer resin 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, excellent transparency, and low refractive index. 1. Because it is water and oil repellent, it is also used as a fiber treatment agent, and recently it has been used as a 5R (Soil Release) treatment agent. -Among the Banbanka acrylic polymers,
In particular, lower fluorinated alkyl methacrylate homopolymers have the characteristics of being hard and brittle. Therefore, when used for special purposes, it is desirable to impart elasticity to them, and for this purpose, Various studies have been made.

As mentioned above, as a method of imparting elasticity to fluorinated acrylic resin, higher fluorinated alkyl methacrylate, for example 3,
3, 4, 4, 5, 5, 6.6, 7, 7, 81
8, 9, 9.

- or a copolymer with fluorinated alkyl methacrylate;
and/or (4, elastomeric polymers (vinylipone fluoride, vinylidene fluoride-tetrafluoroethylene, vinylidene fluoride-
A method of blending polymethyl methacrylate with hexafluoropropylene, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, etc. has been carried out.

The former, 17FMA, is a polymer whose main component is a methacrylate vinyl monomer with a long-chain fluorinated alkyl group in the side chain, and its homopolymer has a low refractive index, but at room temperature It is rubber-like and difficult to mold,
For this purpose, processability is improved and a low refractive index is maintained by copolymerizing methyl methacrylate with relatively high '1 or fluorinated alkyl methacrylate with relatively high T2. However, this method is difficult because higher fluorinated methacrylates are currently expensive on the market, and the resulting copolymer has unsatisfactory elongation at low temperatures due to the simple structure of the copolymer. There are drawbacks such as being

This elastic polymer is a rubber elastic body with a high degree of fluorination, and is a vinylidene fluoride derivative that exhibits extremely specific compatibility with polymethyl methacrylate or polyfluorinated alkyl methacrylate. and polymethyl methacrylate, a high range of blend component regions is possible and a transparent resin body with a low refractive index is obtained.

However, since the vinylidene fluoride derivative is a crystalline polymer, it has a major drawback in that its crystallinity increases when heated, resulting in a decrease in the transparency of the blended resin. Currently, it is used as a molding material such as injection molding material while retaining these defects. In other words, the heat resistance of the above blended resin is an extremely important property when used alone as a film or sheet or as a laminated material on a base material, and if heating causes softening or whitening due to crystallization. , its commercial value will drop significantly.

In view of the current situation, the present inventors have further studied in detail the structure of the polymer itself, and in order to obtain a multi-stage copolymer resin that is particularly excellent in high elongation, heat resistance, weather resistance, and low refractive index. As a result of quantitative studies, the present invention has been completed.

An object of the invention is to provide a fluorinated acrylic multi-stage copolymer resin that has excellent elongation, excellent heat resistance and weather resistance, and low refractive index.

The uninvented fluorinated acrylic multi-stage copolymer resin is formed so as to form a two-layer structure, with holes in the innermost polymer layer containing fluorinated alkyl methacrylate as the main polymerization component, and an outermost layer of the innermost layer. , fluorinated alkyl acrylate, and/or
fluorinated alkyl methacrylate as a polymerization component, and
A rubber elastic polymer layer CB) having a glass transition temperature ('rr) of 0° C. or lower, and an outermost polymer layer C) having a T2 of 50° C. or higher, containing fluorinated alkyl methacrylate as a polymerization component, It is characterized by being composed of.

Description of the Invention In the fluorinated acrylic multi-stage copolymer resin of the present invention, the polymer constituting the innermost polymer layer pores is a fluorinated alkyl methacrylate)(A+)i product, and if desired, fluorinated A monomer having an ethylenic double bond (A2), a polyfunctional monomer (A3), and a grafting agent (A4) copolymerizable with the alkyl methacrylate (A1). At least one of them may be copolymerized. It is necessary that the innermost polymer layer contains at least 50% or more of fluorinated alkyl methacrylate (A1) as a polymerization component.

Further, the rubber elastic polymer layer [F]) forming a double structure together with the innermost polymer layer (4) is made of fluorinated alkyl acrylate and/or fluorinated alkyl methacrylate) (Bl).
is the main polymerization component, and the glass transition temperature (Tri) is below 0℃.
It has the following. In this rubber elastic polymer layer (B), the fluorinated alkyl acrylate and/or the fluorinated alkyl methacrylate (B1) may be a monomer (B,
), polyfunctional monomer (Da), or graft cross-agent (
It may be copolymerized with at least one member selected from the group consisting of B4). It is necessary that the rubber elastic polymer layer (8) contains at least 50% of fluorinated alkyl acrylate and/or fluorinated alkyl methacrylate (Bl) as a polymerization component.

The outermost polymer layer C) is alkyl fluoride methacrylate) (C
I) as the main polymerization component, and its T1 is 50
℃ or higher. This fluorinated alkyl methacrylate) (CI
'> may be copolymerized with another monomer (C7) having an ethylenic double bond that can be copolymerized with it, if necessary. It is necessary that the outermost polymer layer (Q) contains at least 50% of fluorinated alkyl methacrylate (CI) as a polymerization component.

Moreover, in order to form a graft between the above-mentioned layer weights between 0 and 00, it is preferable to copolymerize a graft cross-agent in each layer.

In each of the above polymer layers (N to (C)), the monomer component copolymerized with the main polymerization component is effective for adjusting the TtO value of each layer, but the processability of the resulting resin is This is not necessarily necessary, as it may reduce the

In addition, in the innermost polymer layer and the rubber elastic polymer layer (B), the polyfunctional monomers (As, Bs) used as copolymerization components form a crosslinked rubber elastic polymer, and This has the effect of improving the rubber elasticity and elongation of the multistage polymer resin.

When a graft reaction between the outermost polymer layer having rubber elasticity and the rubber elastic polymer layer (B) and the outermost polymer layer (C) as described above is required, each of these layers is Grafting cross-agents can be used during formation, resulting in a multi-stage polymer resin having good rubber elasticity as well as good transparency and extensibility.

The innermost polymer layer (3) contains the grafting or mating agent component (A), and the rubber elastic polymer layer (81 contains the polyfunctional monomer component (A)).
When containing B8) and the grafting agent (B4), the obtained multistage polymer resin has high elongation, transparency, and good film formability, and has good film bending and whitening properties due to its rubber elasticity effect and grafting effect. It is something without.

In order to obtain a multistage polymer resin' with good rubber elasticity, it is necessary that T2 of the rubber elastic polymer layer tB) is 0° C. or lower. If T2 of layer (B) is higher than 0°C, the obtained multistage polymer resin does not exhibit rubber elasticity at room temperature.

Further, in order to obtain a multistage polymer resin with excellent mechanical properties, it is necessary that the outermost polymer layer (C) has a T2 of 50° C. or higher. When the Tf of the layer (C) is lower than 50°C, the resulting multi-stage polymer resin has poor film formability, extrusion formability, injection formability, etc. It becomes unsatisfactory. In the multistage polymer resin of the present invention,
The composition weight ratio of each layer is 1 to 25 parts, more preferably 5 parts of the innermost polymer layer (A).
~15 parts, rubber elastic polymer layer 13): 5 to 75 parts, more preferably 10 to 50 parts, outermost polymer layer (C): 19 to 93 parts, more preferably 35 to 80 parts. preferable.

In the multi-stage polymer resin of the present invention, if the content of the innermost polymer layer is less than 1 part by weight, the film processability and resistance to film bending and whitening will be unsatisfactory. Increasing the amount by weight is not preferable because film processability deteriorates.

The higher the T2 of the innermost polymer layer, the better the film formability of the obtained multi-stage polymer resin, and the higher the resistance to film folding and whitening. In addition, if the Tf of the four layers is low and, for example, equal to Tli' of the rubber elastic polymer layer (B), the resulting resin will have unsatisfactory film formability and resistance to film bending whitening. . Therefore, T attributable to the innermost layer polymer? is preferably higher than T2 of the rubber elastic polymer layer CB+.

If the content of the rubber elastic polymer layer (B) is less than 5 parts by weight, high elongation cannot be obtained, and if it is more than 75 parts by weight,
Resin processability becomes unsatisfactory. If the content of the layer (B) is 5 N parts or more and is relatively small compared to the content of the outermost polymer layer (C), even if the T2 of the outermost polymer layer tc) is higher than 50°C, but even when the temperature is close to 50°C, the processability and elongation of the resulting multistage polymer resin are good.

In addition, the content of the CB) layer is 75 parts by weight or less, and (
C) When the content is relatively large compared to the content of the layer (C), the strength and elongation of the resulting multistage polymer resin are
There is a tendency that the higher the TS' above 0°C, the better the performance.

Polyfluorinated alkyl acrylate and polyfluorinated alkyl methacrylate forming the main polymeric components of the innermost layer polymer, the rubber elastic polymer layer (B), and the outermost polymer layer FC of the multistage polymer resin of the present invention has the following structural formula (1) or (II).

0 (CH2) (CF2) Xm
n or, however, in the above formula, m represents an integer of 1 to 5, and n is 1 to 10
represents an integer of , X represents an F or H atom, and 2 represents an H atom or a -CH's group.

Examples of fluorinated alkyl acrylate polymers or fluorinated methacrylates as described above include 2.2-difluoroethyl-methacrylate (2FM) and -acrylate, 2.2.2-)difluoroethyl-methacrylate (3F'') M) and -acrylate), 2.2.3
．． 3-tetrafluoropropyl-methacrylate (4F
IVI) and -acrylate, 2,2,3°3.3-
Pentafluoropropyl methacrylate (5FM) and -acrylate, 2,2,3,3,4.4-hexafluorobutyl methacrylate (6F\1) and -
Acrylate, 2,2, 3.3, 4,4, 5.5
-octafluoropentyl-methacrylate (8FIV
I) and -acrylate, 1.1-J<)lifluoromethyl)2,2.2-)lifluoroethyl-methacrylate (9FM) and -acrylate,2,2
, 3.3, 4゜4, 5,5, 6,6, 7.7
- Dozocafluorobenthyl methacrylate (12FM
) and -acrylate, 3.3, 4.4, 5
,5 ,6.6 ,7,7 ,8.8 ,9.9.10
Examples include 110.10-fluorodecanyl methacrylate (17F]Vl) and -acrylate.

In general, the fluorinated alkyl acrylate or fluorinated alkyl methacrylate used in the rubber elastic polymer layer fB) may have either a linear or branched side chain; Combined T? The lower the value, the better.

The ethylenic double-bond gold monomer (A2-B2, C2) copolymerizable with the above-mentioned fluorinated alkyl acrylate and/or fluorinated alkyl methacrylate includes lower alkyl (meth)acrylate, lower alkoxy (meth)acrylate Preferred are acrylic monomers such as , cyanoethyl (meth)acrylate, acrylamide, acrylic acid, and methacrylic acid. Furthermore, styrene, alkyl-substituted styrene, acrylonitrile, methacrylate trile, etc. can also be used. Such a copolymer component is effective in adjusting the T-g of the resulting polymer, but it also changes the refractive index of the polymer, so its content should be limited to 30% of the total amount of the polymer. The following is preferred, preferably as little as possible.

In addition, a polyfunctional monomer (
Preferred examples of A41, Bs) include alkylene glycol dimethacrylates such as ethylene glycol some methacrylate), 1,3-butylene glycol some methacrylate, 1,4-butylene glycol some methacrylate, and 3-butylene glycol some methacrylate. ,
It is also possible to use sovinylpene centrivinylbenzene and alkylene glycol diacrylates. 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 it is not used, a crosslinking bond between the layers can be formed by using a Graph) 35 polymer, 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.

Further, as the grafting cross-agent used with the fluorinated alkyl acrylate and the fluorinated alkyl acrylate and the fluorinated alkyl methacrylate, copolymerizable allyl methallyl or crotyl ester of an α-β unsaturated carboxylic acid or socarboxylic acid is used, and preferably Allyl esters of acrylic acid, methacrylic acid, maleic acid, and fumaric acid are used, and allyl methacrylate exhibits particularly excellent effects. Other effective examples include triallyl cyanurate and triallyl isocyanurate. Such a graft cross-agent mainly has a conjugated unsaturated bond in its ester structure that bonds with an allyl group, methallyl group, or crotyl group of other polymeric components, and the substantial kana part is connected to the adjacent layer. It effectively bonds with the above group in the polymer of , and provides a graft bond between two adjacent layers.

The amount of the graft cross-agent used is important for adjusting the properties of the resulting resin, and it is particularly preferably used in a range of 10 parts by weight or less based on the rubber elastic polymer layer tD) and the intermediate polymer layer tD). , is preferably used 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 M (combined material) is produced by polymerizing specified monomer components in the presence of a catalyst at a temperature of 30°C to 100°C for 5 to 122 minutes. Although it may be carried out by any legal method, it is generally preferable to use an emulsion polymerization method.

A normal lasocal polymerization catalyst is used as a polymerization catalyst,
Specifically, cumene hydroperoxide (CHP), 7-tert-bunalperoxide, zucumyl peroxide, methyl ether ketone peroxide, te
rt-butyl perphthalate, tert-butyl perbenzoate, methyl isobutyl ketone peroxide, lauroyl peroxide, cyclohexyl peroxide,
Organic peroxides such as 2.5-J methyl, 2.5-so-tert-butyl peroxyhexane, tert-butyl peroctanoate, tert-butyl perisobutyrate, tert-butyl peroxy isoderovir carbonate; , methyl 2,2'-azobisisobutyrate, 1
．． 1'-Azobiscyclohexane, 2-
Phenylazo-2,4--/methyl-4-methoxyvaleronitrile, 2-carpamoylazobisinobuteronitrile, 2,2'-azobis2,4-trimethylvaleronitrile, 2,2'-azobisiso Examples include azo compounds such as butyronitrile. As the chain transfer agent, alkyl mercaptan, which is usually used as a polymerization degree regulator, is used. The amount used is from 0.01% by weight to 5% by weight based on the amount of monomer.
It is preferable to use it within a range of % by weight.

Next, in the presence of the outermost polymer layer, a predetermined monomer is added at a temperature of 30°C to 100°C in the presence of a catalyst.
Polymerize for 120 minutes. Although this polymerization operation may be carried out by any polymerization method, 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 presence of the double structure type coalescence obtained in the above step,
Predetermined monomers are polymerized in the presence of a catalyst to form an outermost polymer layer. The polymerization method, conditions and catalyst at this time can be selected from those mentioned above.

The obtained multistage polymer resin can be isolated, washed and dried to obtain powdered qn(jii).

The fluorinated acrylic multi-stage polymer resin of the present invention can be used by mixing with other thermoplastic resins, if necessary, and can also contain other additives, such as antioxidants, ultraviolet May be mixed with leg absorbents, fillers, pigments, antistatic agents, etc.

The fluorinated acrylic multi-stage polymer resin of the present invention can be used to form weather-resistant films or as sheath materials for plastic or quartz-based optical fibers.

The present invention will be further explained below with reference to Examples.

In the examples, "part" and "%" are ! Unless you tell the samurai otherwise, it will be a portion by weight or a sweet by weight. In addition, T of each polymer used in the examples
7, for example from the Polymer Handbook (John Wil
It was calculated from the value of T7 described in ``Ley & 5or1s Publishing Company'' using the commonly known formula: FO)<. In addition, when the T7 of the polymer was unknown, the T1 was determined from the DSC (differential thermal measurement) measurement value of the polymer. Total light transmittance is ASTM D-1
Measurement was carried out using an integrating sphere haze meter in accordance with 003-61. The tear strength was measured by the Elmendorf method with cut 2II+++1 in accordance with JIS-P=811.6. The resistance to whitening on bending of the film sheet was expressed as follows based on the whitening state when the film sheet was bent by 180°.

◎ - No whitening at all ■ - Very slight whitening △ - Whitening is observed ・ × - Severe whitening XX - Severe whitening and breakage Water repellency was evaluated. (Kyowa Conductangle Meter Model CA-P was used.) Processability was evaluated by film molding processability by T-Di'e of 100 lp using 25 mm φ extrusion.

X Poor △ Moderate ○ Good Refractive index 'rJ', , 50 tt was formed into a film of about jw, and its refractive index was measured using an Atsube refractometer.

Example 1 In a polymerization vessel with a cooling type, 250 parts of ionized water, perfluoroalkyl sulfonate (Megafac F-11)
0, Inu-Nichi Ink Chemical Co., Ltd.) 1 part, 2 and Sosoum Walmaldehyde Sulfoxylate 0. (15 parts were charged, and after stirring at room temperature in a nitrogen atmosphere, 2.2.
2-) Lifluoroethyl methacrylate (3FM) 4
1 part of methyl methacrylate (MMA), 0.25 parts of 1,3-butylene dimethacrylate (B1. The mixture consisting of 1.5 parts was added and mixed. After heating this mixture to 70°C,
The temperature was maintained at this temperature for 0 minutes to complete the polymerization of the innermost layer polymer (g). Subsequently, 2,2.2
= 35 parts of trifluoroethyl acrylate (3FA),
2.5 parts of 1,3-butylene methacrylate (BD),
0.7 part of allyl methacrylate (AMA), and
A mixture consisting of 0.25 parts of cumene hydroperoxide (eHP) was added dropwise over 60 minutes, and the resulting mixture was maintained at a temperature of 70°C for 60 minutes with stirring to complete the polymerization of the rubber elastic polymer (B). did.

Furthermore, 50% of 2.2.2-trifluoroethyl methacrylate (3Fiv'I) was added to the resulting polymerization mixture.
10 parts of methyl methacrylate (MMA), 10 parts of n-octermel methacrylate (n-C++H87SH) 0.
5 parts and kilomene hydroperoxide (CI(P)
0.5 m of the mixed solution was added dropwise over 60 minutes, and the mixture was maintained at a temperature of 70° C. for 60 minutes while stirring to complete polymerization of the outermost layer polymer. The obtained polymer was in a water-dispersed latex state and had a polymerization conversion rate of 99. The latex particle size was 990A. 5 parts of calcium chloride was added to 100 parts of the polymer emulsion thus obtained, and the multi-stage structural electropolymer 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 the dry powder of this resin was processed into pellets using a 25wn extruder, 100 parts of T-Di were made from the pellets.
It was molded into a film using e. As a result, the multi-stage structure polymer resin exhibited good film processability, and a film with a thickness of 50 μm and excellent transparency and flexibility was obtained. The refractive index of the film is 1.4210 (25°C, N and D = 589.3 parts m
(measured with Atsube refractometer), the advancing contact angle with water is 75,
It was 5°.

In addition, the film has good resistance to whitening after bending and does not cause whitening. Furthermore, when measuring the viscoelastic behavior of the multistage polymer resin, the peak of the E' (dyne/cril) loss modulus showed a gentle dispersion in the range of 20°C to 75°C, and the tan δ decreased at a temperature of 80°C. It showed a peak.

The total light transmittance of the film was 92%, the haze was 2%, and the film had good transparency. Further, 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, T strength, etc. of each component polymer were consistent with those shown in Table 1, and the test results were consistent with those 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, T2, etc.
The test results were as shown in Table 2, and the test results were as shown in Table 2.

In Comparative Example 1, the T2 of the outermost layer polymer C) was 0° C. or less, and the film formability of the obtained polymer resin and the film's bending whitening resistance were extremely poor.

In Comparative Example 2, the formation of the innermost polymer layer (4) was omitted,
The obtained polymer resin film had poor bending whitening resistance and elongation.

In Comparative Example 3, the production of the outermost polymer layer C) was omitted,
For this reason, the film formability of the obtained multistage polymer resin was extremely poor, and a power film for testing could not be obtained.

The following margin is Example 8 The sword obtained in Example 3 using a core-sheath spinneret? Composite spinning was carried out at 230°C using reamer as the cladding component and polymethyl methacrylate as the core component.
It was wound up at a speed of m/m. The obtained filament had a concentric cross-sectional shape with an outer diameter of 0.5+m and a core diameter of 0.48 ran, and the surface of the filament was smooth.

The optical transmission loss of this filament was 310 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 cladding portion.

The fluorinated acrylic multi-stage polymer resin having the specific composition of the present invention has satisfactory light transmittance, haze, and refractive index, moderate and excellent elongation at break, resistance to film folding whitening, and weather resistance. Therefore, it is extremely useful as a weather-resistant film and optical fiber sheath material.

Procedural Amendment (Spontaneous March 1980) Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the Case, 1982 Patent Application No. 2274792, Name of the Invention: Fluorinated Acrylic Multi-Structure Polymer Resin (New Name) 3. Relationship with the case of the person making the amendment Patent applicant name + jF (60 Phantom Mitsubishi Rayon Co., Ltd. 4, agent (2 others) 5. Subject of amendment A. "Title of the invention" column in the specification , "Claims" column of the specification distortion /・, "Detailed Description of the Invention" column 6 of the specification 1 = Contents of the amendment 0 Title of the invention is corrected as "alkyl fluoride multi-stage structure polymer".

As per the attached document, (1) On page 3, line 8 of the specification, "vinylidene fluoride" is amended to "polyvinylidene fluoride."

(2) Page 3, line 9, [Tetrafluoroethylene J
is corrected as "lr tetrafluoroethylene copolymer".

(3) Page 3, line 10 of the same page, amended to read "Hexafluoropropylene JkF hexafluoropropylene copolymer."

(4) On page 5, line 5, "commercial value is" is amended to "commercial value."

(5) On page 5, line 19, "polymer (4)" is corrected to "polymer factor."

(6) In the second, fourth, and tenth lines of page 6, the words "generated component" are corrected to "principal component."

(7) On page 17, lines 15-16, "2,5-dimethyl, 2,5-di-tert-butylperoxyhexane" is replaced with [2,5-dimethyl-1 or 2,5-tert-butylperoxyhexane].
ert-butyl peroxyhexane".

(8) Delete "... is used as the chain transfer agent." from lines 6 to 8 on page 18 of the same document.

7. Amended list of attached documents Claims 1 copy 2. Claim 1: An innermost polymer layer (A) containing fluorinated alkyl methacrylate as a main polymeric component; and the innermost polymer layer (4). A rubber elastic polymer formed to form a two-layer structure on the outside, containing fluorinated alkyl acrylate and/or fluorinated alkyl methacrylate as a main polymeric component, and having a glass transition temperature (T2) of 0° C. or lower A fluorinated acrylic multi-stage structure polymer resin comprising a layer (B) and an outermost polymer layer (C) which has a fluorinated alkyl methacrylate as a main polymerization component and has a Tf of 50° C. or higher.

2. The fluorinated acrylic multi-stage polymer resin according to claim 1, wherein the innermost layer polymer 1 has a higher Tf than the rubber isopolymer layer (B).

Claims (1)

[Scope of Claims] 1. An innermost polymer layer (5) containing fluorinated alkyl methacrylate as a main polymerization component, and a two-layer structure formed on the outside of the innermost polymer layer (3), A rubber elastic polymer layer CB) containing fluorinated alkyl acrylate and/or fluorinated alkyl methacrylate as a main polymerization component and having a glass transition temperature (T2) of 0° C. or lower, and fluorinated alkyl methacrylate.
A fluorinated acrylic multi-layer structure polymer resin comprising an outermost polymer layer C) having a T1 of 50° C. or higher and having a T1 as a main component. 2 T2 of the innermost layer polymer is Tf of the rubber layer polymer
The fluorinated acrylic multi-stage polymer resin according to claim 1, which has a higher strength.