JP2006037085A - Resin composition and molded product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded product having excellent water repellency and oil repellency in relation to a resin composition and the molded product thereof. <P>SOLUTION: The resin composition comprises (A) a thermoplastic resin and (B) a fluorine-containing polymer composed of an acrylate ester as a constituent unit. Furthermore, the acrylate ester is represented by formula [wherein, X is a hydrogen atom or a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX<SP>1</SP>X<SP>2</SP>group (with the proviso that X<SP>1</SP>and X<SP>2</SP>are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a 1-21C linear or branched fluoroalkyl group, a substituted or an unsubstituted benzyl group or a substituted or an unsubstituted phenyl group; Y is a 1-10C aliphatic group or the like; and Rf is a 1-6C linear or branched fluoroalkyl group or fluoroalkenyl group]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin composition and a molded body thereof. The molded body is characterized in that the fluoropolymer is unevenly distributed on the surface of the molded body. The molded body can be used as household goods, stationery, interior materials, sanitary goods, medical supplies, and the like.

  In order to impart water and oil repellency to the surface of the molded body, a technique for subjecting the surface to fluorine treatment has been conventionally known. However, the method of performing the fluorine treatment after molding has a problem in that the water / oil repellent function is not durable and the water / oil repellent function is lowered by repeated use. In order to solve this problem, research has been conducted to impart water and oil repellency by segregating a fluorine component on the surface after molding by adding a fluorine compound into the resin and melt-kneading the resin before molding.

  For example, in Japanese Patent No. 2631911, in a composition in which an oily or gum-like perfluorinated polyether or perfluorinated polypropylene oxide is melt-kneaded in a thermoplastic resin, the amount of fluorine is different between the inside and the surface of the molded body. It is described that it is possible to produce a molded body in which more fluorine is segregated on the surface. However, the compatibility between the fluorine additive and the thermoplastic resin is considerably poor, and kneading in a high-efficiency, high-shear extruder is required. In Japanese Patent No. 2505536, water and oil repellency is imparted to a molded article by melt-kneading a monovalent or divalent alcohol, an ester of a compound having a perfluoroalkyl group and one carboxyl group, and a plastic, followed by molding. Is described. However, a large amount of fluorine additive is required as 5% by weight, which is disadvantageous in terms of product cost.

  In Japanese Patent No. 1574020, a polyfluoroalkyl ester compound, which is limited to be melted at a molding temperature, is kneaded with rubber and subjected to heat press primary vulcanization at 180 ° C. for 10 minutes and oven secondary vulcanization at 150 ° C. for 15 hours. It is described that, when vulcanized, the polyfluoroalkyl compound exudes (bleeds) to the surface to form a non-tacky surface, and it is possible to impart releasability and water / oil repellency. In Japanese Patent No. 2585904, 0.1 to 5% by weight of a perfluoroalkyl group-containing ester is blended with a thermoplastic resin, and after heat-kneading and molding at 70 to 130 ° C., a liquid detergent or the like is obtained. It describes that it exhibits liquid repellency with respect to a solution containing a surfactant. However, even if the molded body prepared by this method was evaluated, the desired alcohol repellency could not be obtained.

  US Pat. No. 6,380,289 discloses a thermoplastic composition obtained by adding a surface modifier having a fluorine-containing aliphatic group and a second thermoplastic polymer to a semicrystalline first thermoplastic polymer. ing. The fluorine-containing aliphatic group in the surface modifier has 8 carbon atoms as shown in the examples.

  The environmental issues of PFOA are explained below. From recent research results [EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)] Concerns about the environmental impact of PFOA (perfluorooctanoic acid), a type of fluoroalkyl compound, have become apparent, and on April 14, 2003, EPA (US Environmental Protection Agency) will strengthen scientific research on PFOA Announced.

  Meanwhile, Federal Register (FR Vol.68, No.73 / April 16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf) and EPA Environmental News FOR RELEASE : MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) and EPA OPPT FACT SHEET April 14, 2003 (http: // www. epa.gov/opptintr/pfoa/pfoafacts.pdf) publishes that telomers can produce PFOA by degradation or metabolism (telomers mean long chain fluoroalkyl groups). We also announced that telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. Yes.

  In order to maintain the liquid repellency, it is necessary that the fluorine compound is segregated on the surface by melting and mixing the polymer and the fluorine compound. However, even if a molded body is prepared according to a known technique, in order to facilitate the segregation of the fluorine compound on the surface, a fluorine compound having poor compatibility with the thermoplastic resin has to be used under limited conditions. . Even if kneading is possible under normal conditions, there is a problem that it is necessary to increase the addition amount of the fluorine compound, which is not preferable in terms of cost and process.

  Therefore, as a result of repeated research to solve these problems, it was found that a fluorine compound is effectively segregated on the surface by melting and kneading a specific fluoropolymer into a thermoplastic resin and then forming a molded body. The headline and the present invention were completed.

［式中、Ｘは、水素原子またはメチル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ¹Ｘ²基（但し、Ｘ¹およびＸ²は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。）、シアノ基、炭素数１〜２１の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基、
Ｙは、炭素数１〜１０の脂肪族基、炭素数６〜１０の芳香族基または環状脂肪族基、−ＣＨ₂ＣＨ₂Ｎ(Ｒ¹)ＳＯ₂−基（但し、Ｒ¹は炭素数１〜４のアルキル基である。）または−ＣＨ₂ＣＨ(ＯＹ¹)ＣＨ₂−基（但し、Ｙ¹は水素原子またはアセチル基である。）、
Ｒｆは、炭素数１〜６の直鎖状または分岐状のフルオロアルキル基またはフルオロアルケニル基である。］
で示される含フッ素アクリレートエステルを構成単位とする含フッ素重合体
を含んでなる樹脂組成物を提供する。
本発明は、樹脂組成物から成形された成形体にも関する。成形体の形状は、繊維、フイルム、チューブなどである。 The present invention
(A) thermoplastic resin, and (B) formula:

[Wherein, X is a hydrogen atom or a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, a fluorine atom, a chlorine atom, bromine A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group,
Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms or a cyclic aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is the number of carbon atoms 1 to 4 alkyl groups) or —CH ₂ CH (OY ¹ ) CH ₂ — group (where Y ¹ is a hydrogen atom or an acetyl group),
Rf is a linear or branched fluoroalkyl group or fluoroalkenyl group having 1 to 6 carbon atoms. ]
A resin composition comprising a fluorine-containing polymer having a fluorine-containing acrylate ester represented by the structural unit as a structural unit.
The present invention also relates to a molded article molded from a resin composition. The shape of the molded body is a fiber, a film, a tube, or the like.

  According to the present invention, a molded article excellent in water and oil repellency (particularly alcohol repellency) can be obtained. This molded body is relatively inexpensive and can be used for products such as household items (for example, washbasins), stationery items (for example, ink bottles), interior materials, sanitary items, and medical items.

BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the thermoplastic resin (A) include polyamide resins (eg, nylon 6, nylon 12, nylon 66, aromatic nylon), polyester resins (eg, polyethylene terephthalate, polybutylene terephthalate), polyolefin resins (eg, polyethylene, polypropylene) , Copolymers of ethylene and propylene, copolymers of ethylene or propylene and C _{4 to} C ₂₀ α olefins, terpolymers of ethylene, propylene and C _{4 to} C ₂₀ α olefins, copolymers of ethylene and vinyl acetate, propylene and vinyl Copolymer with acetate, copolymer of styrene and α-olefin, polybutylene, polyisobutylene), polyether resin, polyether ester resin, polyacrylate resin, ethylene alkyl acrylate Resin, polydiene resin (for example, polybutadiene, copolymer of isobutylene and isoprene), polyurethane resin, polyether ether ketone resin, polyether imide resin, polyether sulfone resin, polyphenylene sulfide resin, polycarbonate resin and the like.

Of these, polyolefin resins are preferred. As the polyolefin resin, polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, and polybutylene can be used.
Polyethylene includes high density polyethylene and low density polyethylene. Polypropylene includes isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, and amorphous polypropylene.

The isotactic polypropylene is a highly crystalline polypropylene mainly composed of isotactic polypropylene produced by a Zigler-Natta catalyst or a metallocene catalyst. For injection molding, extrusion molding, film use, and fiber use. It is possible to select and obtain from commercially available molding polypropylenes.
The amorphous polypropylene is propylene having extremely low crystallinity prepared using a metallocene catalyst. Amorphous polypropylene may be a mixture of very low crystallinity polypropylene (eg, at least 50% by weight of the total amount of the mixture) made with a metallocene catalyst and other propylene. Amorphous polypropylene is available, for example, as Tough Selenium T-3512, T-3522, etc. manufactured by Sumitomo Chemical Co., Ltd.

  In the present invention, the thermoplastic resin (A) may be a mixture of two or more thermoplastic resins. As thermoplastic resin (A), you may use the resin mixture of 1st resin and 2nd resin whose crystallinity or melting | fusing point is lower than 1st resin. One of the crystallinity or melting point of the second resin may be lower than that of the first resin, or both the crystallinity and melting point of the second resin may be lower than those of the first resin. The second resin may be a mixture of at least two resins.

Preferred first resin / second resin combinations are polypropylene / polyethylene, polypropylene / polybutylene, polypropylene / polypropylene, polypropylene / propylene-alpha olefin copolymer, polypropylene / ethylene-alpha olefin copolymer. In the polypropylene / polypropylene combination, the first resin is preferably isotactic propylene (crystalline propylene) and the second resin is preferably amorphous propylene.
In the resin mixture of the first resin and the second resin, the amount of the second resin is 1 to 60% by weight, for example 2 to 40% by weight, in particular 3 to 30% by weight, especially 5 to 20% by weight. Good.

  Crystallinity means the amount of crystallization heat measured by DSC (Differential Scanning Calorimetry). It refers to the amount of heat of the exothermic peak that appears when the temperature is lowered from 20 ° C to 200 ° C and then cooled to 20 ° C. The crystallization heat amount of the second resin is 1 J / g or more, preferably 5 J / g or more, more preferably 10 J / g or more, for example, 15 J / g or more, particularly 20 J / g or more lower than the crystallization heat amount of the first resin. You can.

  The melting point can be measured by DTA (differential thermal analysis). The endothermic peak temperature that appears when heated from room temperature (10 ° C. to 30 ° C.). The melting point of the second resin may be lower than the melting point of the first resin by 10 ° C. or more, preferably 15 ° C. or more, such as 20 ° C. or more, particularly 25 ° C. or more.

  The degree of segregation on the surface of the fluorine compound can be confirmed by a method of analyzing the surface fluorine by XPS (X-ray photoelectron spectroscopy). From the surface fluorine concentration value obtained by this method, the degree of segregation of the fluorine compound on the surface can be compared.

  The fluorine-containing polymer (B) is a homopolymer of a fluorine-containing polymerizable compound or a copolymer with a polymerizable compound (particularly a non-fluorine polymerizable compound) copolymerizable with the fluorine-containing polymerizable compound. Are preferred, and compounds prepared by known techniques can be used.

［式中、Ｘは、水素原子またはメチル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ¹Ｘ²基（但し、Ｘ¹およびＸ²は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。）、シアノ基、炭素数１〜２１の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基、
Ｙは、炭素数１〜１０の脂肪族基、炭素数６〜１０の芳香族基または環状脂肪族基、−ＣＨ₂ＣＨ₂Ｎ(Ｒ¹)ＳＯ₂−基（但し、Ｒ¹は炭素数１〜４のアルキル基である。）または−ＣＨ₂ＣＨ(ＯＹ¹)ＣＨ₂−基（但し、Ｙ¹は水素原子またはアセチル基である。）、
Ｒｆは、炭素数１〜６の直鎖状または分岐状のフルオロアルキル基またはフルオロアルケニル基である。］
で示される含フッ素アクリレートエステルである。 The fluorine-containing polymerizable compound has the formula:

[Wherein, X is a hydrogen atom or a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, a fluorine atom, a chlorine atom, bromine A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group,
Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms or a cyclic aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is the number of carbon atoms 1 to 4 alkyl groups) or —CH ₂ CH (OY ¹ ) CH ₂ — group (where Y ¹ is a hydrogen atom or an acetyl group),
Rf is a linear or branched fluoroalkyl group or fluoroalkenyl group having 1 to 6 carbon atoms. ]
It is a fluorine-containing acrylate ester shown by these.

  In the fluorine-containing acrylate ester, X is preferably a hydrogen atom or a methyl group.

In the formula (I), the Rf group is preferably a perfluoroalkyl group or a perfluoroalkenyl group. The carbon number of the fluoroalkyl group or fluoroalkenyl group is 1-6, for example 1-4.
Examples of fluoroalkyl _{group, -CF 3, -CF 2 CF 3} , -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3 ) ₂ , —C (CF ₃ ) ₃ , — (CF ₂ ) ₄ CF ₃ , — (CF ₂ ) ₂ CF (CF ₃ ) ₂ , —CF ₂ C (CF ₃ ) ₃ , —CF (CF ₃ ) CF ₂ CF ₂ CF ₃ , — (CF ₂ ) ₅ CF ₃ , — (CF ₂ ) ₃ CF (CF ₃ ) _2, etc.
Examples of fluoro-alkenyl _{groups, -CF = CF 2, -CF 2} CF = CF 2, - (CF 2) 2 CF = CF 2, -CF 2 C (CF 3) = CF 2, -CF (CF 3) _{CF = CF 2, - (CF} 2) 3 CF = CF 2, -C (CF 3) 2 CF = CF 2, - (CF 2) 2 C (CF 3) = CF 2, - (CF 2) 4 CF _{= CF 2, - (CF 2} ) 4 CF = CF 2, - (CF 2) 3 C (CF 3) = CF 2, and so on.

Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms or a cyclic aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is the number of carbon atoms 1 to 4 alkyl groups) or —CH ₂ CH (OY ¹ ) CH ₂ — group (where Y ¹ represents a hydrogen atom or an acetyl group). The aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, such as 1 or 2). The aromatic group and the cycloaliphatic group may be either substituted or unsubstituted.

As an example of a fluorine-containing polymerizable compound, the formula:

[Wherein Rf is a C 1-6 perfluoroalkyl group R ¹ is hydrogen or an alkyl group having 1-10 carbon atoms,
R ² is an alkylene group having 1 to 10 carbon atoms,
R ³ represents a hydrogen atom or a methyl group,
Ar is an aryl group which may have a substituent,
n represents an integer of 1 to 10. ]
The fluorine-containing acrylate ester shown by these can be mentioned.

Specific examples of the fluorine-containing polymerizable compound are as follows:
CF ₃ (CF ₂ ) ₅ (CH ₂ ) OCOCH═CH ₂ ,
CF ₃ (CF ₂ ) ₅ (CH ₂ ) OCOC (CH ₃ ) ═CH ₂ ,
(CF ₃ ) ₂ CF (CF ₂ ) ₃ (CH ₂ ) ₂ OCOCH═CH ₂ ,
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ OCOC (CH ₃ ) ═CH ₂ ,
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ OCOCH═CH ₂ ,
CF ₃ CF ₂ (CH ₂ ) ₂ OCOCH═CH ₂ ,
CF ₃ (CF ₂ ) ₃ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOCH═CH ₂ ,
_{CF 3 (CF 2) 3 SO} 2 N (C 2 H 5) (CH 2) 2 OCOC (CH 3) = CH 2,
_{(CF 3) 2 CF (CF} 2) 3 CH 2 CH (OCOCH 3) CH 2 OCOC (CH 3) = CH 2,
(CF ₃ ) ₂ CF (CF ₂ ) ₃ CH ₂ CH (OH) CH ₂ OCOCH═CH ₂
Can be illustrated.

The copolymerizable polymerizable compound may be a non-fluorine polymerizable compound.
The fluorine-containing polymer may contain a chlorine-containing polymerizable compound as a structural repeating unit. The chlorine-containing polymerizable compound is a compound having chlorine and a carbon-carbon double bond. Examples of the chlorine-containing polymerizable compound are vinyl chloride, vinylidene chloride, α-chloroacrylate (for example, alkyl (C1-30) ester) and 3-chloro-2-hydroxypropyl methacrylate.

The non-fluorine polymerizable compound may be, for example, a non-fluorine alkyl (meth) acrylate.
Non-fluorinated alkyl (meth) acrylates generally have the formula:
_{^{X 1 -CX 2 = CH 2 (}} i)
[Wherein, X ¹ is an alkylcarboxylate group (alkyl group having 1 to 18 carbon atoms), and X ² is a hydrogen atom or a methyl group. ]
It is a compound shown by these. The fluorine-containing polymer may not contain non-fluorine alkyl (meth) acrylate.

There are various other copolymerizable polymerizable compounds. For example,
(1) Acrylic acid and methacrylic acid and their methyl, ethyl, butyl, isobutyl, t-butyl, propyl, 2-ethylhexyl, hexyl, decyl, lauryl, stearyl, isobornyl, β-hydroxyethyl, glycidyl ester, phenyl, benzyl 4-cyanophenyl esters,
(2) Vinyl esters of fatty acids such as acetic acid, propionic acid, caprylic acid, lauric acid, stearic acid,
(3) Styrene compounds such as styrene, α-methylstyrene, p-methylstyrene,
(4) Vinyl halides or vinylidene compounds (excluding chloride) such as vinyl fluoride, vinyl bromide and vinylidene fluoride,
(5) Aliphatic allyl esters such as allyl heptanoate, allyl caprylate and allyl caproate,
(6) Vinyl alkyl ketones such as vinyl methyl ketone and vinyl ethyl ketone,
(7) acrylamides such as N-methylacrylamide and N-methylolmethacrylamide;
(8) Examples include dienes such as 2,3-dichloro-1,3-butadiene and isoprene.

In the fluorine-containing polymer as a co-weight, the amount of the fluorine-containing polymerizable compound may be 10% by weight or more, for example, 20 to 80% by weight, particularly 30 to 60% by weight. In the fluorine-containing polymer, the amount of the chlorine-containing polymerizable compound may be 50% by weight or less, for example, 0 to 30% by weight, particularly 0.5 to 25% by weight.
The molecular weight of the fluorine-containing polymer may generally be 1,000 to 1,000,000, particularly 3,000 to 50,000 (for example, in terms of polystyrene as measured by GPC).

The amount of the fluoropolymer (B) is 0.1 to 10 parts by weight, for example 0.1 to 5 parts by weight, particularly 0.5 to 3 parts by weight, based on 100 parts by weight of the thermoplastic resin (A). It's okay.
The resin composition may contain additives (ie, auxiliary agents), for example, dyes, pigments, antistatic agents, antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, nucleating agents, epoxies as necessary. You may contain a stabilizer, a lubricant, an antibacterial agent, a flame retardant, a plasticizer, etc.

  The resin composition of the present invention can be obtained by kneading (for example, melt-kneading) the thermoplastic resin (A) and the fluoropolymer (B). Generally, the thermoplastic resin (A) and the fluoropolymer (B) are compatible in the molten state. The kneading can be performed by a conventionally known method such as a single screw extruder, a twin screw extruder, or a roll. The resin composition thus obtained can be molded by a known method such as extrusion molding, injection molding, compression molding, or film formation by pressing. The resin composition may be formed into various shaped bodies, for example, shaped bodies such as fibers, films and tubes. About the obtained molded object, you may heat-process in oven, a drying furnace, etc. after shaping | molding according to a well-known technique. In the fiber, the diameter may be 0.2 to 2000 microns, such as 0.5 to 50 microns, and the length may be 0.2 mm to 200 mm, such as 2 to 30 mm.

The resin composition of the present invention may be made into a nonwoven fabric. The nonwoven fabric can be obtained by a card method, an airlaid method, a papermaking method, a melt blown method or a spun bond method in which a nonwoven fabric is obtained directly from melt extrusion. In the melt extrusion, it is preferable to use a temperature at which both the thermoplastic resin (A) and the fluoropolymer (B) are melted. The basis weight of the nonwoven fabric is not particularly limited, but may be 0.1 to 1000 g / m ² . Basis weight of the nonwoven fabric, depending on the nonwoven applications such, 5 to 60 g / m ² in the surface material or the like of the liquid absorbent article, the absorbent in the goods and a wiper such as 10 to 500 g / m ^2, in filter 8～1000G / m ² is preferred.

  Details will be described below with reference to examples, but the present invention is not limited to these examples.

Comparative Example 1
PP-3155 (manufactured by Exxon Mobil) (first resin) (isotactic polypropylene) 90 parts by weight, polyethylene J1019 (manufactured by Ube Industries) (second resin) (low density polyethylene) 10 parts by weight, C _n F _{2n + 1} CH ₂ CH ₂ OCOCH═CH ₂ (mixture of compounds of n = 6, 8, 10, 12, 14 (average of n is 8)) (fluorinated monomer, hereinafter referred to as “FA”) and stearyl acrylate (hereinafter “ 1 part by weight of a polymer (fluorinated polymer) having a composition of FA / StA = 40/60 (weight ratio) at 180 ° C. in a twin-screw extruder. Then, the film was obtained by molding with a heat press.

  In order to confirm the alcohol repellency of this film, the contact angle was measured with a mixed liquid of IPA / water = 70/30 (volume ratio) and water. Regarding the degree of segregation of the fluorine compound on the surface, the fluorine component on the film surface was analyzed using ESCA-3400 manufactured by Shimadzu Corporation. The melting point of the resin was analyzed by RTG220 manufactured by SII Nano Technology. Further, the heat of crystallization of the resin was analyzed with a DSC 822e manufactured by METTLER TOLEDO.

Example 1
The second resin is 10 parts by weight of polybutylene DP-8911 (manufactured by Shell), C ₆ F ₁₃ CH ₂ CH ₂ OCOCH═CH ₂ (fluorinated monomer, hereinafter referred to as “13FA”) and StA as the fluoropolymer. A film was prepared and evaluated in the same manner as in Comparative Example 1 except that the polymer was a polymer having a composition of 13FA / StA = 40/60 (weight ratio).

Example 2
A copolymer of _{C 6 F 13 CH 2 CH 2} OCOC (CH 3) = CH 2 as a fluorine-containing polymer (fluorine-containing monomer, hereinafter referred to as "13FMA") and StA, 13FMA / StA = 40/ 60 A film was prepared and evaluated in the same manner as in Example 1 except that the polymer had a composition of (weight ratio).

Example 3
Polyethylene J5019 (manufactured by Ube Industries) (low density polyethylene) as the second resin, C ₄ F ₉ CH ₂ CH ₂ OCOCH═CH ₂ (fluorinated monomer, hereinafter referred to as “9FA”) as the fluoropolymer A film was prepared in the same manner as in Comparative Example 1 except that the polymer having a composition of 9FA / StA = 40/60 (weight ratio) was 1 part by weight. went.

Example 4
A copolymer of _{C 4 F 9 CH 2 CH 2} OCO (CH 3) = CH 2 as a fluorine-containing polymer (fluorine-containing monomer, hereinafter referred to as "9FMA") and StA, 9FMA / StA = 40/ 60 A film was prepared and evaluated in the same manner as in Comparative Example 1 except that the polymer having the composition of (weight ratio) was 1 part by weight.

Example 5
This is a copolymer of C ₄ F ₉ CH ₂ CH ₂ OCOCCl═CH ₂ (fluorinated monomer, hereinafter referred to as “9FC1A”) and StA as the fluoropolymer, and 9FC1A / StA = 40/60 (weight ratio). A film was prepared and evaluated in the same manner as in Comparative Example 1 except that 1 part by weight of the polymer having the above composition was used.

Example 6
A film was prepared and evaluated in the same manner as in Example 3 except that only 100 parts by weight of polyethylene J1019 (manufactured by Ube Industries) was used as the thermoplastic resin.

Example 7
The second resin is 10 parts by weight of Tough Selenium T-3512 (manufactured by Sumitomo Chemical Co., Ltd.) (amorphous propylene), and C ₄ F ₉ CH ₂ CH ₂ OCOCH═CH ₂ (fluorinated monomer, hereinafter referred to as “9FA”) as the fluoropolymer. Comparative Example 1 except that 1 part by weight of a polymer having a composition of 9FA / StMA = 40/60 (weight ratio) is a copolymer of stearyl methacrylate (hereinafter referred to as “StMA”). A film was prepared and evaluated in the same manner.

  Table 1 shows the components of Examples and Comparative Examples, and Table 2 shows the contact angle and each analysis result.

ＰＰ ： ポリプロピレン
ＰＥ ： ポリエチレン
ＰＢ ： ポリブチレン

PP: Polypropylene PE: Polyethylene PB: Polybutylene

  From the results of Table 2, when the carbon number of the Rf group in the fluorine-containing polymerizable compound is 4 (Examples 3 to 7) and 6 (Examples 1 and 2), the carbon number is 8 (comparison) Compared to Example 1), it can be seen that the performance is equivalent or better.

Claims (13)

(A) thermoplastic resin, and (B) formula:

[Wherein, X represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² represent a hydrogen atom, a fluorine atom, a chlorine atom, bromine A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group,
Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms or a cyclic aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is the number of carbon atoms 1 to 4 alkyl groups) or —CH ₂ CH (OY ¹ ) CH ₂ — group (where Y ¹ is a hydrogen atom or an acetyl group),
Rf is a linear or branched fluoroalkyl group or fluoroalkenyl group having 1 to 6 carbon atoms. ]
A resin composition comprising a fluorine-containing polymer having a fluorine-containing acrylate ester represented by the structural unit as a constituent unit.   The resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyolefin resin, a polyester resin or a polyamide resin.   The resin composition according to claim 1, wherein the thermoplastic resin (A) is a mixture of at least two thermoplastic resins.   The thermoplastic resin is composed of the first resin (I-1) and the second resin (I-2), and the crystallinity or melting point of the first resin (I-1) is the crystallinity of the second resin (I-2). Or the resin composition of Claim 3 higher than melting | fusing point.   The resin composition according to claim 1, wherein the fluoropolymer (B) is a homopolymer or a copolymer having a fluoroacrylate ester as a structural unit.   The resin composition according to claim 5, wherein in the formula (I) of the fluorine-containing acrylate ester, X is a hydrogen atom or a methyl group.   The resin composition according to claim 5, wherein the fluorine-containing polymer (B) is a copolymer of a fluorine-containing acrylate ester and a non-fluorine polymerizable compound.   The resin composition according to claim 7, wherein the non-fluorine polymerizable compound is a non-fluorine alkyl (meth) acrylate. The non-fluorinated alkyl (meth) acrylate has the formula:
_{^{X 1 -CX 2 = CH 2 (}} i)
[Wherein, X ¹ is an alkylcarboxylate group (alkyl group having 1 to 18 carbon atoms), and X ² is a hydrogen atom or a methyl group. ]
The resin composition of Claim 8 which is a compound shown by these.   The resin composition of Claim 1 obtained by melt-mixing a thermoplastic resin (A) and a fluorine-containing polymer (B).   The molded object formed by shape | molding the resin composition in any one of Claims 1-10.   The molded article according to claim 11, which is used as a household article, stationery, interior material, sanitary article, or medical article. The nonwoven fabric formed from the fiber which consists of a resin composition in any one of Claims 1-10.