JP2006037067A - Resin composition having excellent alcohol repellency and molded product thereof - Google Patents

Abstract

To obtain a molded article excellent in alcohol repellency.
SOLUTION: (I) (I-1) 60 to 98% by weight of a first resin and (I-2) 2 to 40% by weight of a second resin having lower crystallinity or melting point than the first resin. that the resin 100 parts by weight of a mixture, and (II) a linear or branched fluoroalkyl or fluoroalkenyl group 4 to 21 carbon atoms or _{-C 3 F 6 O, -,} - C 2 F 4 O- and - Molded from a resin composition comprising 0.1 to 5 parts by weight of a fluoropolymer containing a fluoroether group having at least one repeating unit selected from the group consisting of CF ₂ O— in a total number of 1 to 200 Form the body.
[Selection figure] None

Description

  The present invention relates to a resin composition having excellent alcohol repellency and a molded product 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, and sanitary goods.

  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 plastic. 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.

  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. For this reason, it has been difficult to put it into practical use in general daily goods such as household goods, stationery, interior materials and sanitary goods.

  Therefore, as a result of repeated research to solve these problems, a compound containing two or more resins having different crystallinity or melting point is combined with a fluorine-containing compound, particularly a fluorine-containing polymer, and then molded. As a result, it was found that the fluorine compound effectively segregates on the surface, and the present invention has been completed.

The present invention
(I) (I-1) 60 to 98% by weight of the first resin, and (I-2) a resin mixture 100 composed of 2 to 40% by weight of the second resin having lower crystallinity or melting point than the first resin. parts, and (II) a linear or branched fluoroalkyl or fluoroalkenyl group 4 to 21 carbon atoms or _{-C 3 F 6 O, -,} - C 2 F 4 O- and _-CF 2 O- There is provided a resin composition comprising 0.1 to 5 parts by weight of a fluoropolymer containing a fluoroether group having at least one repeating unit selected from the group consisting of 1 to 200 in total.
The present invention also relates to a molded article molded from a resin composition.
In the present invention, (I) the first resin (I-1) having crystallinity or melting point and the second resin (I-2) having lower crystallinity or melting point than the first resin (I-1) In a molded product molded after melt-kneading the mixed resin and (II) the fluoropolymer, the fluoropolymer effectively segregates on the surface of the molded product, resulting in alcohol repellency on the molded product surface. Is granted.

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

BEST MODE FOR CARRYING OUT THE INVENTION

  The crystallinity referred to in the present invention is based on the structure based on the stereoregularity of the resin, and the information can be easily obtained by known literature, instrumental analysis, and the like. In addition, information on the melting point can be easily obtained by known literature, instrumental analysis, and the like. One of the crystallinity or melting point of the second resin (I-2) may be lower than that of the first resin (I-1), or both the crystallinity and melting point of the second resin (I-2) are It may be lower than that of the first resin (I-1).

  In the present invention, the first resin (I-1) has higher crystallinity or melting point than the second resin (I-2). The first resin (I-1) is preferably a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include polyolefin, polyester and polyamide. Specific examples of the thermoplastic resin include polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene and α-olefin copolymer, propylene-α-olefin copolymer, polybutadiene, ethylene-acrylate copolymer, ethylene- Methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, chlorinated polyethylene, chlorinated polypropylene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylonitrile-styrene copolymer, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 6 , 6 and the like. Examples of the thermosetting resin include melamine resin, urethane resin, epoxy resin, silicon resin, phenol resin and the like.

  The polyethylene includes high density polyethylene and low density polyethylene. The polypropylene includes isotactic polypropylene and syndiotactic polypropylene.

  Of these, isotactic polypropylene is preferred.

  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.

  In the present invention, the second resin (I-2) has a lower crystallinity or melting point than the first resin (I-1). The second resin (I-2) is preferably a thermoplastic resin or a thermosetting resin. When the second resin (I-2) is exemplified, examples of the thermoplastic resin include polyolefin, polyester and nylon. Specific examples of the thermoplastic resin include polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene α-olefin copolymer, propylene-α-olefin copolymer, polybutadiene, polybutylene, polyisoprene, and ethylene-acrylic acid ester. Copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylonitrile-styrene copolymer, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 6, 6, etc. Can be mentioned. Examples of the thermosetting resin include melamine resin, urethane resin, epoxy resin, silicon resin, and phenol resin. As the second resin, one or a combination of two or more resins can be selected.

  The polyethylene includes low density polyethylene and linear low density polyethylene. The polypropylene includes syndiotactic polypropylene, atactic polypropylene, and amorphous polypropylene.

  Among these, polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, and polybutylene are preferable, and amorphous polypropylene is more preferable among the 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 65% by weight of the total amount of the mixture) made with a metallocene catalyst and other propylene. Amorphous polypropylene is available as Sumitomo Chemical's Tough Selenium T-3512, T-3522, and the like.

  The same resin is included in the examples of the first resin (I-1) and the second resin (I-2), but the second resin (I-2) is the first resin (I-1). This is because it defines that the crystallinity or the melting point is low. Depending on the resin combination method, the same resin may be the first resin (I-1) or the second resin (I-2).

  Crystallinity means the amount of crystallization heat measured by DSC (Differential Scanning Calorimetry). When the molded body was measured by DSC, (A) the amount of crystallization heat of the mixed resin of the first resin (I-1) having high crystallinity and the second resin (I-2) having low crystallinity was (B ) Lower than the amount of crystallization heat of only the first resin (I-1) having high crystallinity. The amount of heat of crystallization is the amount of heat generated when the molten resin is crystallized. When the crystallization heat quantity of (A) is 5 kJ / kg or more lower than the crystallization heat quantity of (B), the fluoropolymer (II) effectively segregates on the surface and makes the molded article surface alcohol-repellent. It can be given well. Further, when the crystallization heat amount of (A) is 10 kJ / kg or more, for example, 15 kJ / kg or more, particularly 20 kJ / kg or more, lower than the crystallization heat amount of (B), the amount of crystallization on the surface of the fluoropolymer (II) is reduced. Segregation becomes prominent.

  The melting point can be measured by DSC. In the mixed resin of the first resin (I-1) and the second resin (I-2), when the compatibility between the first resin (I-1) and the second resin (I-2) is good, the two melting points One peak is detected between the two, and when the compatibility between the first resin (I-1) and the second resin (I-2) is not good, two peaks are detected. When the difference in melting point between the first resin (I-1) and the second resin (I-2) is 10 ° C. or more, the fluoropolymer (II) is effectively segregated on the surface, whereby the surface of the molded body Alcohol repellency can be imparted satisfactorily. Further, when the difference in melting point is 15 ° C. or higher, for example, 20 ° C. or higher, particularly 25 ° C. or higher, segregation on the surface of the fluoropolymer (II) becomes remarkable.

  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 (II) 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. The fluorine-containing polymerizable compound is preferably a fluorine-containing acrylate. The fluorine-containing acrylate may be substituted with hydrogen at the α-position. Examples of the substituent at the α-position are methyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² are hydrogen atom, fluorine atom, chlorine atom, bromine atom) Or a iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.

［式中、Ｘは、水素原子、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４〜２１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、あるいは−Ｃ_３Ｆ_６Ｏ−、−Ｃ_２Ｆ_４Ｏ−および−ＣＦ_２Ｏ−からなる群から選択された少なくとも一種の繰り返し単位を合計数１〜２００で有するフルオロエーテル基である。］
で示される含フッ素アクリレートエステルであることが好ましい。 The fluorine-containing polymerizable compound has the 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 or fluoroalkenyl group 4 to 21 carbon atoms or _{-C 3 F 6 O, -,} - from C _{2 F} 4 O- and _-CF 2 group consisting of O- It is a fluoroether group having at least one selected repeating unit in a total number of 1 to 200. ]
It is preferable that it is a fluorine-containing acrylate ester shown by these.

  In the present invention, a fluorine-containing polymerizable compound in which X is a hydrogen atom or a methyl group gives better performance than a fluorine-containing polymerizable compound in which X is chlorine.

In the formula (I), when the Rf group is a fluoroalkyl group or a fluoroalkenyl group, it is preferably a perfluoroalkyl group or a perfluoroalkenyl group. The carbon number of the fluoroalkyl group or fluoroalkenyl group is 4-21, typically 4-18, especially 4-16. Examples of fluoroalkyl _{group, -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 ,-(CF ₂ ) ₄ CF (CF ₃ ) ₂ ,-(CF ₂ ) ₇ CF ₃ ,-(CF ₂ ) ₅ CF (CF ₃ ) ₂ ,-(CF ₂ ) ₆ CF (CF ₃ ) ₂ , - a (CF _{2) 9} CF ₃ and the like.

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.

）、
アミン基（例えば、H₂N-）、カルボン酸基（例えば、HOOC-）、酸ハライド基（例えば、F(O=)C-）、クロロメチル基（ClH₂C-）である。フルオロエーテル基は、オキシパーフルオロアルキレン繰り返し単位および末端基に加えて、炭素数１〜１０のフルオロアルキレン基、特にパーフルオロアルキレン基を有していてもよい。炭素数１〜１０のフルオロアルキレン基の例は、-CF₂-および-CF₂CF₂-である。 The fluoroether group has at least one repeating unit (oxyperfluoroalkylene group) selected from the group consisting of —C ₃ F ₆ O—, —C ₂ F ₄ O—, and —CF ₂ O—. -C ₃ F ₆ O- is -CF ₂ CF ₂ CF ₂ O- or -CF ₂ C (CF ₃₎ is fo-. -C ₂ F ₄ O- is generally _-CF 2 _CF 2 O- are. The total number of oxyperfluoroalkylene repeating units is 1 to 200, for example 1 to 100, in particular 5 to 50. The fluoroether group has a terminal group that is directly bonded to the oxyperfluoroalkylene repeat unit. Examples of the terminal group include a hydrogen atom, a halogen atom (for example, a fluorine atom), an alcohol group (for example, HOCH ₂ —), an epoxy group (for example,

),
An amine group (for example, H ₂ N-), a carboxylic acid group (for example, HOOC-), an acid halide group (for example, F (O =) C-), and a chloromethyl group (ClH ₂ C-). The fluoroether group may have a fluoroalkylene group having 1 to 10 carbon atoms, particularly a perfluoroalkylene group, in addition to the oxyperfluoroalkylene repeating unit and the terminal group. Examples of the fluoroalkylene group having 1 to 10 carbon atoms are —CF ₂ — and —CF ₂ CF ₂ —.

Examples of fluoroether groups (particularly perfluoroether groups) that are examples of Rf groups are as follows.
F- (CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF _2- (n is 1 to 200)
F- (CF ₂ C (CF ₃ ) FO) _n -CF ₂ CF _2- (n is 1 to 200)
F- (CF ₂ C (CF ₃ ) FO) _n- (CF ₂ O) _m -CF ₂ CF _2- (total of n and m is 1 to 200)
F- (CF ₂ CF ₂ O) _n- (CF ₂ O) _m -CF ₂ CF _2- (total of n and m is 1 to 200)

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

Wherein, Rf is a perfluoroalkyl group R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms from 4 to 21 carbon atoms,
R ² is an alkylene group having 1 to 10 carbon atoms,
R ³ is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom) Atom)), 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,
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 ) ₇ (CH ₂ ) OCOCH═CH ₂ ,
CF ₃ (CF ₂ ) ₆ (CH ₂ ) OCOC (CH ₃ ) ═CH ₂ ,
(CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH═CH ₂ ,
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OCOC (CH ₃ ) ═CH ₂ ,
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OCOCH═CH ₂ ,
CF ₃ CF ₂ (CH ₂ ) ₂ OCOCH═CH ₂ ,
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ OCOCH═CH ₂ ,
CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOCH═CH ₂ ,
_{CF 3 (CF 2) 7 SO} 2 N (C 2 H 5) (CH 2) 2 OCOC (CH 3) = CH 2,
_{(CF 3) 2 CF (CF} 2) 6 CH 2 CH (OCOCH 3) CH 2 OCOC (CH 3) = CH 2,
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCOCH═CH ₂ ,

を例示することができる。

Can be illustrated.

  In the α-substituted acrylic acid group of the fluorine-containing polymerizable compound, examples of the α substituent are a halogen atom, an alkyl group (for example, monofluoromethyl) having a hydrogen atom substituted with a halogen atom (for example, having 1 to 21 carbon atoms). Group and difluoromethyl group), a cyano group, and an aromatic group (for example, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group).

Specific examples of the fluorine-containing polymerizable compound having an α-substituted acrylic acid group are as follows.

［式中、Ｒｆは炭素数４〜２１の直鎖状または分岐状のパーフルオロアルキル基である。］

[Wherein, Rf represents a linear or branched perfluoroalkyl group having 4 to 21 carbon atoms. ]

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.
The molecular weight of the fluorine-containing polymer may generally be 1,000 to 1,000,000, particularly 1,000 to 100,000 (for example, polystyrene conversion as measured by GPC).

  The amount of the second resin (I-2) in the resin mixture is 2 to 40% by weight. When the amount of the second resin (I-2) is less than 2% by weight, the fluorine compound cannot effectively segregate on the surface of the molded body. Further, when the amount of the second resin (I-2) exceeds 40% by weight, the performance of the first resin (I-1) which is the basic resin may be deteriorated, which may adversely affect the original target performance of the molded body. There is. The amount of the second resin (I-2) is preferably 3 to 30% by weight, particularly 5 to 20% by weight.

  The amount of the fluoropolymer (II) is 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin mixture. When the addition amount of the fluoropolymer (II) is less than 0.1 parts by weight, it is difficult to impart alcohol repellency to the surface of the molded body, and when it exceeds 5 parts by weight, the cost increases, and an inexpensive product can be obtained. The purpose of providing cannot be achieved. The addition amount of the fluoropolymer is more preferably 0.5 to 3 parts by weight.

  The resin composition is obtained by melt-kneading the first resin (I-1), the second resin (I-2) and the fluoropolymer (II). Melt kneading is to perform kneading at a temperature equal to or higher than the melting point of the resin. 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.

  In the resin composition, other additives such as dyes, pigments, antistatic agents and the like may be added as necessary during melt kneading. Moreover, about the obtained molded object, you may heat-process in oven, a drying furnace, etc. after shaping | molding according to a well-known technique.

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

Example 1
90 parts by weight of polypropylene PP-3155 (manufactured by Exxon Mobil) as the first resin (I-1) with high crystallinity, and Tufselen T, which is amorphous polypropylene as the second resin (I-2) with low crystallinity -3512 10 amounts portion (manufactured by Sumitomo chemical Co., Ltd.), the average _{C n F 2n + 1 CH 2} CH 2 OCOCH = CH 2 (n = 6,8,10,12,14 (n as fluoropolymer (II) 8) a mixture of compounds) (fluorine-containing monomer, hereinafter referred to as “FA”) and stearyl acrylate (hereinafter referred to as “StA”), and composition of FA / StA = 40/60 (weight ratio) After melt-kneading 1 part by weight of a polymer having a temperature of 180 ° C. with a twin screw extruder, 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 an IPA / ion exchange water = 70/30 (volume ratio) mixed solution and ion exchange 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. Regarding the heat of crystallization, the first resin (I-1) having high crystallinity and the second resin (I-2) having low crystallinity were melt-mixed, and then the molded article was DSC- manufactured by Shimadzu Corporation. Analysis was performed according to 50.

Example 2
Example 1 except that 90 parts by weight of polypropylene J-2000GP (manufactured by Idemitsu Petrochemical Co., Ltd.) as the first resin and 10 parts by weight of polybutylene DP-8911 (manufactured by Shell) as the second resin (I-2) were used. A film was prepared by the method and evaluated.

Example 3
The amount of the first resin (I-1) is 80 parts by weight, the second resin (I-2) is 20 parts by weight of Tuffmer A-35050 (made by Mitsui Chemicals), which is an ethylene-α-olefin copolymer, and a fluoropolymer. A film was prepared and evaluated in the same manner as in Example 1 except that the amount of (II) was 0.5 parts by weight.

Example 4
Example 1 except that the amount of the first resin (I-1) was 95 parts by weight, the amount of the second resin (I-2) was 5 parts by weight, and the amount of the fluorine-containing compound (II) was 3 parts by weight. A film was prepared by the same method and evaluated.

Comparative Example 1
A film was prepared and evaluated in the same manner as in Example 1 except that the amount of the first resin (I-1) was 100 parts by weight and the amount of the second resin (I-2) was 0 parts by weight. It was.

Comparative Example 2
A film was prepared and evaluated in the same manner as in Example 1 except that the amount of the first resin (I-1) was 99 parts by weight and the amount of the second resin (I-2) was 1 part by weight. It was.

Comparative Example 3
A film was prepared and evaluated in the same manner as in Example 1 except that the amount of the fluoropolymer (II) was 0.05 parts by weight.

Example 5
90 parts by weight of PP-3155 (manufactured by Exxon Mobil) as the first resin (I-1) having a high melting point, 10 parts by weight of polyethylene J1019 (manufactured by Ube Industries) as the second resin (I-2) having a low melting point, As the fluoropolymer (II), 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 “ 1 part by weight of a polymer having a composition of FA / StA = 40/60 (weight ratio) in a twin-screw extruder. After melt-kneading at 180 ° C., 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 an IPA / ion exchange water = 70/30 (volume ratio) mixed solution and ion exchange 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. About melting | fusing point, after melt-mixing 1st resin (I-1) and 2nd resin (I-2), the molded object was analyzed by DSC-50 by Shimadzu Corporation.

Example 6
As the first resin (I-1), 90 parts by weight of Sun Allomer PM600M (manufactured by Sun Allomer), the second resin (I-2) as 10 parts by weight of polybutylene DP-8911 (manufactured by Shell), as the fluoropolymer (II) This is a copolymer of C ₆ F ₁₃ CH ₂ CH ₂ OCOCH═CH ₂ (fluorinated monomer, hereinafter referred to as “13FA”) and StA, and has a composition of 13FA / StA = 40/60 (weight ratio). A film was prepared and evaluated in the same manner as in Example 5 except that it was combined.

Example 7
Second resin (I-2) 10 parts by weight of polyethylene J5019 (manufactured by Ube Industries), and C ₄ F ₉ CH ₂ CH ₂ OCOCH═CH ₂ (fluorinated monomer, hereinafter referred to as “9FA”) as fluoropolymer (II) The film was prepared in the same manner as in Example 5 except that 1 part by weight of the polymer having a composition of 9FA / StA = 40/60 (weight ratio) was prepared. And evaluated.

Comparative Example 4
A film was prepared and evaluated in the same manner as in Example 5 except that the amount of the first resin (I-1) was 99 parts by weight and the amount of the second resin (I-2) was 1 part by weight. .

Comparative Example 5
A film was prepared and evaluated in the same manner as in Example 5 except that the amount of the fluoropolymer (II) was 0.05 parts by weight.

Tables of Examples and Comparative Examples are shown in Tables 1 and 2, and contact angles and analysis results are shown in Tables 3 and 4.

表１、表２の略称について
ＰＰ ： ポリプロピレン
ＰＥ ： ポリエチレン
ＰＢ ： ポリブチレン

Abbreviations in Tables 1 and 2 PP: Polypropylene PE: Polyethylene PB: Polybutylene

表４で融点が２つ記載されているものは、２つのピークが検出されたことを示す。

Those having two melting points in Table 4 indicate that two peaks were detected.

From the results of Table 4, when the carbon number of the Rf group in the fluorine-containing polymerizable compound is 4 (Example 7) and 6 (Example 6), the case where the carbon number is 8 (Example 5) In comparison, it can be seen that the performance is equivalent or better.

Claims (14)

(I) (I-1) 60 to 98% by weight of the first resin, and (I-2) a resin mixture 100 composed of 2 to 40% by weight of the second resin having lower crystallinity or melting point than the first resin. parts, and (II) a linear or branched fluoroalkyl or fluoroalkenyl group 4 to 21 carbon atoms or _{-C 3 F 6 O, -,} - C 2 F 4 O- and _-CF 2 O- A resin composition comprising 0.1 to 5 parts by weight of a fluoropolymer containing a fluoroether group having at least one repeating unit selected from the group consisting of 1 to 200 in total.   The resin composition according to claim 1, wherein each of the first resin (I-1) and the second resin (I-2) is a thermoplastic resin or a thermosetting resin.   The resin composition according to claim 1 or 2, wherein each of the first resin (I-1) and the second resin (I-2) is polyolefin, polyester, or nylon.   The resin composition according to claim 1 or 2, wherein the first resin (I-1) comprises polypropylene.   The resin composition according to claim 1 or 2, wherein the second resin (I-2) comprises polyethylene, polypropylene, or polybutylene.   The crystallization heat amount (measured by DSC) of the mixed resin of the first resin (I-1) and the second resin (I-2) is 5 kJ / kg than the crystallization heat amount of the first resin (I-1) alone. The resin composition according to claim 1, which is lower than the above.   The crystallization heat amount (measured by DSC) of the mixed resin of the first resin (I-1) and the second resin (I-2) is 10 kJ / kg than the crystallization heat amount of the first resin (I-1) alone. The resin composition according to claim 1, which is lower than the above.   The resin composition according to claim 1, wherein the melting point of the second resin (I-2) is 10 ° C. or more lower than the melting point of the first resin (I-1).   The resin composition according to claim 1, wherein the melting point of the second resin (I-2) is 20 ° C or lower than the melting point of the first resin (I-1).   The resin composition according to claim 1, wherein the fluorinated polymer (II) is a homopolymer or a copolymer having a fluorinated acrylate ester as a structural unit. The fluoropolymer has the 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 or fluoroalkenyl group 4 to 21 carbon atoms or _{-C 3 F 6 O, -,} - from C _{2 F} 4 O- and _-CF 2 group consisting of O- It is a fluoroether group having at least one selected repeating unit in a total number of 1 to 200. ]
The resin composition according to claim 10, which is a fluorine-containing acrylate ester represented by:   The resin composition of Claim 1 obtained by melt-mixing 1st resin (I-1), 2nd resin (I-2), and fluoropolymer (II).   The molded object formed by shape | molding the resin composition in any one of Claims 1-12. The molded article according to claim 13, which is used as a household article, stationery, interior material, or sanitary article.