JP7162523B2 - THERMOPLASTIC RESIN COMPOSITION, MOLDED PRODUCT, AND METHOD FOR MAKING MOLDED PRODUCT - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition, a molded article, and a method for producing a molded article.

In order to impart water and oil repellency to the surface of a molded article, techniques for applying fluorine treatment to the surface have been conventionally known.
However, in the method of applying fluorine treatment to the surface of the molded product, there is a problem that the durability of the water- and oil-repellent function is weak, and the water- and oil-repellent function deteriorates with repeated use.

To address this problem, for example, Patent Document 1 describes a resin composition containing a thermoplastic resin and a specific fluoropolymer, and a molded article obtained by molding the resin composition. . In the technique described in Patent Document 1, a fluorine compound is added to a resin before molding and melt-kneaded to segregate the fluorine component on the surface after molding, thereby imparting sustained water and oil repellency. It is something to do.

Japanese Patent Application Laid-Open No. 2006-037085

However, the present inventors have found that there is room for improvement in the water and oil repellency of the molded article obtained by molding the resin composition described in Patent Document 1.

Accordingly, an object of the present invention is to provide a thermoplastic resin composition from which a molded article having good water and oil repellency can be obtained.
Another object of the present invention is to provide a molded article having good water and oil repellency and a method for producing the same.

The inventor of the present invention has made intensive studies to solve the above problems, and found that a thermoplastic resin composition containing a thermoplastic resin and a specific fluorine-containing copolymer exhibits good water and oil repellency. The present inventors have completed the present invention by learning that a molded article having
That is, the inventors have found that the above problems can be solved by the following configuration.

[1] A thermoplastic resin composition containing a thermoplastic resin and a fluorine-containing copolymer,
The fluorine-containing copolymer has a repeating unit based on the compound represented by formula (1), a repeating unit based on a non-fluorine monomer, and a repeating unit based on a compound having two or more mercapto groups in one molecule. including units and
With respect to the total mass of the fluorine-containing copolymer, the content of the repeating unit based on the compound represented by the formula (1) is 15% by mass to 65% by mass, and the repeating unit based on the non-fluorine monomer The content of the unit is 20% by mass to 70% by mass, and the content of the repeating unit based on the compound having two or more mercapto groups in one molecule is 5% by mass to 20% by mass, provided that the above When the repeating unit based on the non-fluorinated monomer contains the repeating unit based on the chain alkyl group-containing monomer, the chain alkyl group-containing monomer is added to the total mass of the fluorine-containing copolymer. The content of the repeating unit based on is 20% by mass to 60% by mass,
In the fluorine-containing copolymer, the mass ratio of the repeating unit based on the compound represented by the formula (1) to the repeating unit based on the non-fluorine monomer [the repeating unit based on the compound represented by the formula (1) Total mass of / total mass of repeating units based on non-fluorine monomer] is 78.9 / 21.1 to 21.1 / 78.9,
The fluorine-containing copolymer has a thermal decomposition temperature of 250° C. or higher,
The total content of the fluorine-containing copolymer is 0.5% by mass to 10% by mass with respect to the total mass of the thermoplastic resin and the fluorine-containing copolymer, and
The total content of the thermoplastic resin and the fluorine-containing copolymer is 80% by mass or more with respect to the total mass of the thermoplastic resin composition.
A thermoplastic resin composition.
_CH2 =CR1-CO-X ^{- CR2R3-} ( ^CH2 ) _n1- (COO) _n2 - ^Q1 - _Rf1 ( ¹ )
In formula (1):
R ¹ represents a hydrogen atom or a methyl group;
X represents -O- or -NR ⁴ -;
R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group represented by the following formula (r);
Q ¹ represents a single bond or a divalent linking group;
Rf ¹ represents a polyfluoroalkyl group or polyfluoroether group having 1 to 6 carbon atoms;
n1 represents an integer from 0 to 4; and
n2 represents 0 or 1;
—(CH ₂ ) _m1 —(COO) _m2 —Q ² —Rf ² (r)
In formula (r):
Q ² represents a single bond or a divalent linking group;
Rf ² represents a polyfluoroalkyl group or polyfluoroether group having 1 to 6 carbon atoms;
m1 represents an integer from 0 to 4; and
m2 represents 0 or 1;
[2] The thermoplastic resin composition according to [1] above, wherein the non-fluorine monomer is a compound represented by formula (2).
_CH2 =CR5 ^{- Q3} - ^{Q4 -} R6 (2)
In formula (2):
R ⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Q ³ represents a single bond, -COO-, or -CONH-;
Q ⁴ represents a single bond or a divalent linking group; and
R ⁶ represents a hydrogen atom, an OH group, a chain alkyl group having 1 to 30 carbon atoms, a cyclic alkyl group, or an aromatic ring.
[3] The heat according to [1] or [2] above, wherein the compound having two or more mercapto groups in one molecule has two or more groups represented by formula (3) in one molecule. A plastic resin composition.
—OCO—(CH ₂ ) _a —CHR ⁷ —(CH ₂ ) _b —SH (3)
In formula (3):
a represents an integer from 0 to 2;
b represents 0 or 1;
^R7 represents an alkyl group having 1 or 2 carbon atoms.
[4] A molded product obtained by thermoforming the thermoplastic resin composition according to any one of [1] to [3] above.
[5] The molded article according to [4] above, which is heat-molded by any molding method selected from the group consisting of extrusion molding, injection molding and blow molding.
[6] A method for producing a molded product, comprising the step of thermally molding the thermoplastic resin composition according to any one of [1] to [3] above.
[7] The manufacturing method according to [6] above, wherein in the step of thermoforming, thermoforming is performed by any molding method selected from the group consisting of extrusion molding, injection molding and blow molding.

ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition from which the molding which has favorable water-repellent oil-repellent performance is obtained can be provided.
The present invention can also provide a molded article having good water and oil repellency and a method for producing the same.

In the molded article of the present invention, the segregation of the fluorine-containing copolymer on the surface of the molded article is thought to impart good water and oil repellency to the surface of the molded article.

[Range represented using "~"]
In this specification, the range represented by "-" shall include both ends of "-". For example, a range denoted "AB" includes "A" and "B."

[(Meth) acrylic]
In this specification, "(meth)acryl" shall include "acryl" and "methacryl", and similarly, "(meth)acrylate" shall include "acrylate" and "methacrylate". .

[-CO-]
In the present invention, the divalent linking group (carbonyl group) represented by the following formula may be expressed as "--CO--". However, "*" in the following formula represents a bonding point with another atom or atomic group.

[-COO-]
In the present invention, a divalent linking group (ester bond) represented by the following formula may be expressed as "--COO--". However, "*" in the following formula represents a bonding point with another atom or atomic group.

[-OCO-]
In the present invention, the divalent linking group (ester bond) represented by the following formula may be expressed as "--OCO--". However, "*" in the following formula represents a bonding point with another atom or atomic group.

[-N(R)-]
In the present invention, the divalent linking group (imino group) represented by the following formula may be expressed as "-N(R)-". However, "*" in the following formula represents a bonding point with another atom or atomic group, and "R" represents a hydrogen atom or a monovalent group.

[-CONH-]
In the present invention, a divalent linking group (amide bond) represented by the following formula may be expressed as "-CONH-". However, "*" in the following formula represents a bonding point with another atom or atomic group.

[-NHCO-]
In the present invention, a divalent linking group (amide bond) represented by the following formula may be expressed as "--NHCO--". However, "*" in the following formula represents a bonding point with another atom or atomic group.

[ _-SO2- ]
In the present invention, the divalent linking group (sulfonyl group) represented by the following chemical formula may be expressed as " _--SO.sub.2-- ". However, "*" in the following formula represents a bonding point with another atom or atomic group.

[-SCO-]
In the present invention, the divalent linking group represented by the following formula may be expressed as "-SCO-". However, "*" in the following formula represents a bonding point with another atom or atomic group.

[-COS-]
In the present invention, the divalent linking group represented by the following formula may be expressed as "--COS--". However, "*" in the following formula represents a bonding point with another atom or atomic group.

[-PO(OR)-,-P(=O)(OR)-]
In the present invention, the divalent linking group represented by the following formula may be expressed as "-PO(OR)-" or "-P(=O)(OR)-". However, in the following formulas, " _* " and " ^* " represent bonding points with other atoms or atomic groups, and "R" represents a monovalent group.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention contains a thermoplastic resin and a fluorine-containing copolymer.
In the thermoplastic resin composition of the present invention, the total content of the thermoplastic resin and the fluorine-containing copolymer is 80% by mass or more, 80% by mass to 100% by mass, based on the total mass of the thermoplastic resin composition. % is preferred. When the total content of the thermoplastic resin and the fluorine-containing copolymer is within this range, water and oil repellency can be effectively expressed on the surface of the thermoplastic resin composition. If the total content of the thermoplastic resin and the fluorine-containing copolymer is less than 80% by mass, the surface of the thermoplastic resin composition cannot be imparted with sustained water and oil repellency.

<Thermoplastic resin>
The thermoplastic resin is not particularly limited, but specific examples include nylon resin, polyethylene resin, polypropylene resin, polycarbonate resin, polyvinyl chloride resin, polymethyl methacrylate resin, polyester resin, polyoxymethylene resin, polystyrene resin, polyphenyl ether Examples include resins, urethane resins, and fluorine-containing resins.

The thermoplastic resin used in the thermoplastic resin composition of the present invention is selected from the group consisting of nylon resins, polypropylene resins, polycarbonate resins, and polyphenyl ether resins, since these resins are highly effective in improving water and oil repellency. is preferably at least one thermoplastic resin, more preferably polyethylene resin and/or polypropylene resin.

In the thermoplastic resin composition of the present invention, the thermoplastic resin can be used singly or in combination of two or more.

<Fluorine-containing copolymer>
The fluorine-containing copolymer has a repeating unit based on the compound represented by formula (1), a repeating unit based on a non-fluorinated monomer, and a repeating unit based on a compound having two or more mercapto groups in one molecule. including.

<<Content of fluorine-containing copolymer in thermoplastic resin composition>>
In the thermoplastic resin composition of the present invention, the total content of the fluorocopolymer is 0.5% by mass to 10% by mass with respect to the total mass of the thermoplastic resin and the fluorocopolymer. 0.5 mass % to 7.0 mass % is preferable, and 0.5 mass % to 5.0 mass % is more preferable. When the total content of the fluorocopolymer is within this range, the liquid repellency of the surface of the molded product obtained by thermoforming the thermoplastic resin composition is good, and the fluorocopolymer is heat resistant. It is easily mixed with plastic resins and does not reduce the strength of the thermoplastic resin composition. If the total content of the fluorine-containing copolymer is less than 0.5% by mass, the water- and oil-repellent performance cannot be effectively exhibited. is difficult, and it leads to an increase in the cost of the molded product.

<<Mass ratio of the repeating unit based on the compound represented by the formula (1) and the repeating unit based on the non-fluorine monomer>>
In the fluorine-containing copolymer, the mass ratio of the repeating unit based on the compound represented by formula (1) and the repeating unit based on the non-fluorine monomer [total mass of repeating units based on the compound represented by formula (1) /total mass of repeating units based on non-fluorine monomer] is 78.9/21.1 to 21.1/78.9. When the mass ratio of the repeating unit based on the compound represented by formula (1) and the repeating unit based on the non-fluorine monomer is within this range, the resin molding can be relatively inexpensive and can be imparted with liquid repellency. Also, if the mass ratio of the repeating unit based on the compound represented by formula (1) to the repeating unit based on the non-fluorine monomer is greater than 78.9/21.1, the cost becomes expensive. If it is smaller than 21.1/78.9, the liquid repellency cannot be exhibited sufficiently.

<<Thermal decomposition temperature of fluorine-containing copolymer>>
The thermal decomposition temperature of the fluorine-containing copolymer is 250° C. or higher, and is preferably 250° C. to 350° C. in consideration of shear heat generated during resin kneading.
However, the thermal decomposition temperature is obtained by measuring the change in mass of the fluorine-containing copolymer when the temperature of the fluorine-containing copolymer is increased from 50° C. to 450° C. at a rate of 5° C./min. , is the temperature at which the weight starts to decrease and the extrapolation point (generally called the extrapolation start temperature) of the point where the slope of the curve is greatest.

Since the thermosetting resin composition of the present invention has a thermal decomposition temperature of 250° C. or higher, the thermosetting resin composition of the present invention has heat resistance that can withstand the kneading and molding temperatures of thermoplastic resins.

<<Repeating Unit Based on Compound Represented by Formula (1)>>
The compound represented by formula (1) will be described.
_CH2 =CR1-CO-X ^{- CR2R3-} ( ^CH2 ) _n1- (COO) _n2 - ^Q1 - _Rf1 ( ¹ )
The symbols in formula (1) have the following meanings.

R ¹ represents a hydrogen atom or a methyl group, preferably a methyl group.

X represents -O- or -NR ⁴ -, preferably -O-.
R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group represented by formula (r) below.

Q ¹ represents a single bond or a divalent linking group.
Examples of the divalent linking group include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an oxyalkylene group having 1 to 10 carbon atoms, a 6-membered arylene group, and a 4- to 6-membered group. ring divalent alicyclic group, 5- or 6-membered heteroarylene group, -X ¹ -, -X ¹ -X ² -, -Z ¹ -X ¹ -, -X ¹ -Z ¹ -X ² -, - Z ¹ -X ¹ -X ² -, -Z ¹ -X ¹ -Z ² -X ² -, and divalent groups formed by combining two or more of these. Here, in the divalent group formed by combining a plurality of ring groups, two single rings may be condensed.

-X ¹ -, -X ¹ -X ² -, -Z ¹ -X ¹ -, -X ¹ -Z ¹ -X ² -, -Z ¹ -X ¹ -X ² - and -Z ¹ -X ¹ above -Z ² -X ² -,
X ¹ and X ² : each independently an alkylene group having 1 to 10 carbon atoms, an oxyalkylene group having 1 to 10 carbon atoms, a 6-membered arylene group, a 4- to 6-membered divalent alicyclic group, 5 or 6-membered heteroarylene groups, 6-membered arylene groups, and two or more monocyclic rings formed by combining two or more of 4- to 6-membered divalent alicyclic groups and 5- or 6-membered heteroarylene groups represents a divalent group selected from the group consisting of optionally condensed divalent groups,
Z ¹ and Z ² : each independently -O-, -S-, -CO-, -COO-, -OCO-, -COS-, -SCO-, -N(R ¹ )-, -SO ₂ - , -PO(OR ¹ )-, -N(R ¹ )-COO-, -COO-N(R ¹ )-, -N(R ¹ )-CO-, -CO-N(R ¹ )-,- from N(R ¹ )-SO ₂ -, -SO ₂ -N(R ¹ )-, -N(R ¹ )-PO(OR ² )-, and -PO(OR ² )-N(R ¹ )- represents a divalent group selected from the group consisting of: wherein R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;

Q ⁴ above is preferably a divalent linking group, more preferably an alkylene group having 1 to 10 carbon atoms.

Rf ¹ represents a polyfluoroalkyl group or polyfluoroether group having 1 to 6 carbon atoms and may be linear or branched, preferably linear.
Examples of polyfluoroalkyl groups having 1 to 6 carbon atoms are -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF2CF( _CF3 ) ₂ , -C _{( CF3} ) ₃ , -( _CF2 ) _4CF3 , -( _CF2 ) _2CF ( _CF3 ) ₂ , _{-CF2C ( CF3} ) ₃ , but not limited to -CF(CF ₃ )CF ₂ CF ₂ CF ₃ , -(CF ₂ ) ₅ CF ₃ , and -(CF ₂ ) ₃ CF(CF ₃ ) ₂ ;
Rf ¹ is preferably -(CF ₂ ) ₃ CF ₃ or -(CF ₂ ) ₅ CF ₃ , more preferably -(CF ₂ ) ₅ CF ₃ .

n1 represents an integer of 0-4.
n2 represents 0 or 1;

—(CH ₂ ) _m1 —(COO) _m2 —Q ² —Rf ² (r)
The symbols in formula (r) have the following meanings.

^Q2 represents a single bond or a divalent coupler.
Examples of the divalent linking group include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an oxyalkylene group having 1 to 10 carbon atoms, a 6-membered arylene group, and a 4- to 6-membered group. ring divalent alicyclic group, 5- or 6-membered heteroarylene group, -X ¹ -, -X ¹ -X ² -, -Z ¹ -X ¹ -, -X ¹ -Z ¹ -X ² -, - Z ¹ -X ¹ -X ² -, -Z ¹ -X ¹ -Z ² -X ² -, and divalent groups formed by combining two or more of these. Here, in the divalent group formed by combining a plurality of ring groups, two single rings may be condensed.

-X ¹ -, -X ¹ -X ² -, -Z ¹ -X ¹ -, -X ¹ -Z ¹ -X ² -, -Z ¹ -X ¹ -X ² - and -Z ¹ -X ¹ above -Z ² -X ² -,
X ¹ and X ² : each independently an alkylene group having 1 to 10 carbon atoms, an oxyalkylene group having 1 to 10 carbon atoms, a 6-membered arylene group, a 4- to 6-membered divalent alicyclic group, 5 or 6-membered heteroarylene groups, 6-membered arylene groups, and two or more monocyclic rings formed by combining two or more of 4- to 6-membered divalent alicyclic groups and 5- or 6-membered heteroarylene groups represents a divalent group selected from the group consisting of optionally condensed divalent groups,
Z ¹ and Z ² : each independently -O-, -S-, -CO-, -COO-, -OCO-, -COS-, -SCO-, -N(R ¹ )-, -SO ₂ - , -PO(OR ¹ )-, -N(R ¹ )-COO-, -COO-N(R ¹ )-, -N(R ¹ )-CO-, -CO-N(R ¹ )-,- from N(R ¹ )-SO ₂ -, -SO ₂ -N(R ¹ )-, -N(R ¹ )-PO(OR ² )-, and -PO(OR ² )-N(R ¹ )- represents a divalent group selected from the group consisting of: wherein R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;

The above Q ² is preferably a divalent linking group, more preferably an alkylene group having 1 to 10 carbon atoms.

Rf ² represents a polyfluoroalkyl group or polyfluoroether group having 1 to 6 carbon atoms and may be linear or branched, preferably linear.
Examples of polyfluoroalkyl groups having 1 to 6 carbon atoms are as described for Rf ¹ .
Rf ² is preferably -(CF ₂ ) ₃ CF ₃ or -(CF ₂ ) ₅ CF ₃ , more preferably -(CF ₂ ) ₅ CF ₃ .

m1 represents an integer of 0 to 4;
m2 represents 0 or 1;

(Specific examples of compounds represented by formula (1))
Specific examples of the compound represented by Formula (1) are listed below, but are not limited thereto.
_CH2 =CH _- COO _- CH2- ₍ CF2) _5CF3
CH2 =C _{( CH3} )-COO _- CH2- ₍ CF2) _5CF3
CH2 =CH-COO-( _CH2 ) _2- ( _CF2 ) _3CF ( _CF3 ) _2
CH2 =C( _CH3 )-COO- _{( CH2} ) _{2- (} CF2) _3CF3
CH2 =CH- _COO- ( _CH2 ) _{2- (} CF2) _3CF3
CH2 =CH-COO-( _CH2 ) _{2 - CF2CF3}

(Content of repeating units based on the compound represented by formula (1))
The content of repeating units based on the compound represented by formula (1) is 15% by mass to 65% by mass with respect to the total mass of the fluorine-containing copolymer.

<<Repeating unit based on non-fluorine monomer>>
A non-fluorine monomer is demonstrated.
Although the non-fluorine monomer is not particularly limited, it is preferably a compound represented by formula (2).

_CH2 =CR5 ^{- Q3} - ^{Q4 -} R6 (2)
The symbols in formula (2) have the following meanings.

R ⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a methyl group.

^Q3 represents a single bond, -COO- or -CONH-, preferably -COO- or -CONH-, more preferably -COO-.

^Q4 represents a single bond or a divalent linking group.
Examples of the divalent linking group include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an oxyalkylene group having 1 to 10 carbon atoms, a 6-membered arylene group, and a 4- to 6-membered group. ring divalent alicyclic group, 5- or 6-membered heteroarylene group, -X ¹ -, -X ¹ -X ² -, -Z ¹ -X ¹ -, -X ¹ -Z ¹ -X ² -, - Z ¹ -X ¹ -X ² -, -Z ¹ -X ¹ -Z ² -X ² -, and divalent groups formed by combining two or more of these. Here, in the divalent group formed by combining a plurality of ring groups, two single rings may be condensed.

-X ¹ -, -X ¹ -X ² -, -Z ¹ -X ¹ -, -X ¹ -Z ¹ -X ² -, -Z ¹ -X ¹ -X ² - and -Z ¹ -X ¹ above -Z ² -X ² -,
X ¹ and X ² : each independently an alkylene group having 1 to 10 carbon atoms, an oxyalkylene group having 1 to 10 carbon atoms, a 6-membered arylene group, a 4- to 6-membered divalent alicyclic group, 5 or 6-membered heteroarylene groups, 6-membered arylene groups, and two or more monocyclic rings formed by combining two or more of 4- to 6-membered divalent alicyclic groups and 5- or 6-membered heteroarylene groups represents a divalent group selected from the group consisting of optionally condensed divalent groups,
Z ¹ and Z ² : each independently -O-, -S-, -CO-, -COO-, -OCO-, -COS-, -SCO-, -N(R ¹ )-, -SO ₂ - , -PO(OR ¹ )-, -N(R ¹ )-COO-, -COO-N(R ¹ )-, -N(R ¹ )-CO-, -CO-N(R ¹ )-,- from N(R ¹ )-SO ₂ -, -SO ₂ -N(R ¹ )-, -N(R ¹ )-PO(OR ² )-, and -PO(OR ² )-N(R ¹ )- represents a divalent group selected from the group consisting of: wherein R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;

^Q4 above is preferably a divalent linking group.

R ⁶ represents a hydrogen atom, an OH group, a chain alkyl group having 1 to 30 carbon atoms, a cyclic alkyl group, or an aromatic ring.

(Specific examples of non-fluorine monomers)
Specific examples of non-fluorine monomers include n-stearyl methacrylate, cyclohexyl methacrylate, stearyl acrylate, and behenyl methacrylate.
The non-fluorine monomer is preferably at least one selected from the group consisting of n-stearyl methacrylate, stearyl acrylate and behenyl methacrylate, wherein R ⁶ is a chain alkyl group.

(Content of repeating units based on non-fluorinated monomers)
The content of repeating units based on non-fluorine monomers is 20% by mass to 70% by mass with respect to the total mass of the fluorine-containing copolymer.
However, when the repeating unit based on the non-fluorinated monomer contains the repeating unit based on the chain alkyl group-containing monomer, the chain alkyl group-containing monomer with respect to the total mass of the fluorine-containing copolymer The content of the repeating unit based on is 20% by mass to 60% by mass.

<<Repeating Unit Based on Compound Having Two or More Mercapto Groups in One Molecule>>
A compound having two or more mercapto groups in one molecule will be described.
The compound having two or more mercapto groups in one molecule is not particularly limited, but is preferably a compound having two or more groups represented by formula (3) in one molecule.

—OCO—(CH ₂ ) _a —CHR ⁷ —(CH ₂ ) _b —SH (3)
The symbols in formula (3) have the following meanings.

a represents an integer of 0 to 2, preferably 1;
b represents 0 or 1, preferably 0;

^R7 represents an alkyl group having 1 or 2 carbon atoms, preferably a methyl group.

(Specific examples of compounds having two or more mercapto groups in one molecule)
Specific examples of compounds having two or more mercapto groups in one molecule include ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3- mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3, 5-triazine-2,4,6(1H,3H,5H)-trione, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, and 1,4-bis(3-mercaptobutyryloxy) Butane is mentioned.

Examples of compounds having two or more mercapto groups in one molecule include pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5- At least one selected from the group consisting of triazine-2,4,6(1H,3H,5H)-trione and 1,4-bis(3-mercaptobutyryloxy)butane is preferred.

(Content of repeating units based on compounds having two or more mercapto groups in one molecule)
The content of repeating units based on compounds having two or more mercapto groups in one molecule is 5% to 20% by mass, and 6% to 19% by mass, based on the total mass of the fluorine-containing copolymer. %, more preferably 7% by mass to 18% by mass.

<<Method for synthesizing fluorine-containing copolymer>>
A fluorine-containing copolymer can be synthesized by a known method. For example, a compound represented by formula (1), a non-fluorine monomer, and a compound having two or more mercapto groups in one molecule are subjected to various polymerizations such as solution polymerization, suspension polymerization, or emulsion polymerization. A fluorine-containing copolymer can be synthesized by polymerizing using the method.

<Other ingredients>
The thermoplastic resin composition of the present invention contains, in addition to the thermoplastic resin and the fluorine-containing copolymer, a polymerization initiator, a solvent, and within a range that does not impair the effects of the present invention, such as a pigment and an antistatic agent. It is also possible to add additives.

(Polymerization initiator)
The polymerization initiator is not particularly limited, and examples thereof include 2,2'-azobis-2-methylbutyronitrile, dimethyl-2,2'-azobis-2-methylpropionate, 2,2'-azobisisobutyl Examples include azo compounds such as lonitrile and organic peroxides such as lauroyl peroxide.

(solvent)
The solvent is not particularly limited as long as it can dissolve the thermoplastic resin and the fluorine-containing copolymer. Examples of solvents include common solvents such as methanol, ethanol, isopropyl alcohol, butyl alcohol, methyl acetate, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, and toluene, as well as Freon, hydrofluoroether, xylene hexafluoride, and the like. A fluorine-based solvent or the like may also be used.

<Method for producing thermoplastic resin composition>
A method for producing the thermoplastic resin composition of the present invention is not particularly limited, but an example thereof includes a method of kneading a thermoplastic resin and a fluorine-containing copolymer.
The method of kneading the thermoplastic resin and the fluorine-containing copolymer is not particularly limited, but examples thereof include methods using a single-screw extruder, twin-screw extruder, or kneader.

[Molded product and method for manufacturing molded product]
The molded article of the present invention is obtained by heat-molding the thermoplastic resin composition described above.
That is, the molded product of the present invention can be manufactured by the method for manufacturing a molded product including the step of heat-molding the thermoplastic resin composition described above.
The method of thermoforming is not particularly limited, but any molding method selected from the group consisting of extrusion molding, injection molding and blow molding is preferred.

Heat treatment may be performed at a temperature of 80° C. to 120° C. in order to exhibit the liquid repellency of the molded product.

Although details will be described below with reference to examples, the present invention is not limited only to these examples. In the examples and comparative examples, the unit is % by mass unless otherwise specified.

[Synthesis of fluorine-containing monomer]
2-perfluorohexylethyl alcohol (110.3 g), L-aspartic acid (16.65 g), cyclohexane (62.4 g), p-toluenesulfonic acid monohydrate (28 .46 g) was charged and refluxed for 20 hours while removing the water produced. The reaction solution was cooled to 60° C. or lower, and filtered under reduced pressure while washing the precipitated solid with acetone and isopropyl alcohol (IPA). The obtained solid was vacuum dried to obtain 88.5 g of a white solid.
The resulting solid (79.78 g), methylene chloride (199.44 g), and triethylamine (17.8 g) were placed in a 300 mL four-necked flask and cooled to 0.3° C. with ice water. Methacrylic acid chloride (8.69 g) was slowly added dropwise thereto. After stirring at room temperature for 2 hours, the mixture was filtered. After adding hydroquinone (0.01 g) thereto, the mixture was washed twice with water, and the lower layer was collected and concentrated under reduced pressure to obtain 46.2 g of a pale yellow solid. Ethyl acetate and hexane were added thereto and dissolved by heating, followed by cooling with ice to precipitate crystals.
The resulting crystals were collected by filtration and dried under reduced pressure to obtain 20.0 g of a pale yellow solid of a compound represented by the following formula (bis(3,3,4,4,5,5,5,6,6,7 ,7,8,8,8-tridecafluorooctyl)=N-methacryloylaspartate).

[Synthesis of fluorine-containing copolymer]
<Synthesis Examples 1 to 25>
In a 100 mL Duran bottle, a fluorine-containing monomer (hereinafter sometimes referred to as "monomer A"), a non-fluorine monomer (hereinafter sometimes referred to as "monomer B"), and a mercapto group-containing monomer A monomer (hereinafter sometimes referred to as "monomer C") is charged in an amount (unit: mass %) shown in Table 1 (monomer mixture), and further, with respect to 100 g of the monomer mixture, azo 0.069 g to 0.070 g of a polymerization initiator (dimethyl-2,2'-azobis (2-methylpropionate); V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and a solvent (ethyl acetate, Fujifilm Wako Pure Chemical Industries, Ltd.) was charged with 2% by mass of the total mass of the monomers A and B, and the inside of the system was replaced with nitrogen.
After cooling to room temperature, 50 g of methanol was put into a Duran bottle, reprecipitated, filtered and dried, or the solvent was distilled off to obtain the desired product.

Monomer A, monomer B, and monomer C in Table 1 are as follows.
(monomer A)
C6FMA: _{CH2 =} C( _CH3 ) _{COOCH2CH2 (} CF2) _{5CF3 (} C6FMA, manufactured by AGC)
C6SFA: _{CH2 = CHCOOCH2CH2 (} CF2) _{5CF3 (} C6SFA, manufactured by Daikin Industries, Ltd.)
ASP: Compound synthesized in "Synthesis of fluorine-containing monomer" (bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) = N-methacryloyl aspartate)

(monomer B)
LE S: n-stearyl methacrylate (Light Ester S, manufactured by Kyoeisha Chemical Co., Ltd.)
LA SA: Stearyl acrylate (Light acrylate SA, manufactured by Kyoeisha Chemical Co., Ltd.)
VMA-70: behenyl methacrylate ₍ C22: 70%; Blemmer ^(R) VMA-70, manufactured by NOF Corporation;)
LE CH: Cyclohexyl methacrylate (Light ester CH, manufactured by Kyoeisha Chemical Co., Ltd.)
LE BZ: benzyl methacrylate (light ester BZ, manufactured by Kyoeisha Chemical Co., Ltd.)
BZAA: benzyl acrylate (FA-BZA, manufactured by Hitachi Chemical Co., Ltd.)
LE PO: phenoxyethyl methacrylate (light ester PO, manufactured by Kyoeisha Chemical Co., Ltd.)
2-HEMA: 2-hydroxyethyl methacrylate
PE-350: Polyethylene glycol monomethacrylate (Blemmer ^(R) PE-350, manufactured by NOF Corporation)
DEAA: Diethylacrylamide (manufactured by KJ Chemicals)

(monomer C)
MT-PE1: Pentaerythritol tetrakis (3-mercaptobutyrate) (Kalenz MT ^(R) PE1, manufactured by Showa Denko)
MT-NR1: 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Karens MT ^(R) NR1 , manufactured by Showa Denko)
MT-BD1: 1,4-bis(3-mercaptobutyryloxy)butane (Karens MT ^(R) BD1, manufactured by Showa Denko)

[Synthesis of Comparative Copolymer]
<Comparative Synthesis Examples 1 to 8>
A fluorine-containing monomer (monomer A), a non-fluorine monomer (monomer B), and a mercapto group-containing monomer (monomer C) were added to a 100 ml Duran bottle in the amounts shown in Table 2 (unit :% by mass) charged (monomer mixture), and 0.069 g to 0.070 g of an azo polymerization initiator (V-601) and a solvent (ethyl acetate) are added to 100 g of the monomer mixture. After 2% by weight of the total mass of the monomers A and B was charged, the system was replaced with nitrogen, the lid was closed, and the reaction was carried out at a water temperature of 75° C. for 15 hours or more.
After cooling to room temperature, 50 g of methanol was put into a Duran bottle, reprecipitated, filtered and dried, or the solvent was distilled off to obtain the desired product.

Monomer A, monomer B, and monomer C in Table 2 are the same as in Table 1.

[Heat resistance evaluation of copolymer (measurement of thermal decomposition temperature)]
<Fluorine-containing copolymers 1 to 25, comparative copolymers 1 to 8>
The thermal decomposition temperatures of the fluorine-containing copolymers 1 to 25 synthesized in Synthesis Examples 1 to 25 and the comparative copolymers 1 to 8 synthesized in Comparative Synthesis Examples 1 to 8 were measured using a simultaneous differential thermogravimetric measurement device (TG/DTA6300 , manufactured by Seiko Instruments Inc.).

The thermal decomposition temperature is the change in mass of the fluorocopolymer or comparative copolymer when the temperature of the fluorocopolymer or comparative copolymer is increased from 50°C to 450°C at a rate of 5°C/min. is the temperature at the extrapolation point between the point where the weight starts to decrease and the point where the slope of the curve is the largest in the obtained graph.

The measurement results are shown in Table 3 (fluorocopolymers 1 to 25) and Table 4 (comparative copolymers 1 to 8).

(Heat resistance evaluation result of copolymer)
The fluorine-containing copolymers of Synthesis Examples 1 to 25 had a thermal decomposition temperature of 250° C. or higher and were excellent in heat resistance. On the other hand, the thermal decomposition temperature of Comparative Copolymers 4 and 5 was less than 250° C., indicating poor heat resistance.

[Evaluation of liquid repellency of molding surface (measurement of contact angle)]
1. Preparation of measurement samples (Examples 1 to 8)
Thermoplastic resin (polypropylene; Novatec PP EA9, manufactured by Nippon Polypropylene Co., Ltd.) and fluorine-containing copolymers 1 to 8 synthesized in Synthesis Examples 1 to 8 were mixed with 99.0% by mass of thermoplastic resin and fluorine-containing copolymer 1. After mixing at a rate of .0 mass%, melt-kneading at 190 ° C. using a composite kneading extruder (IMC-1A75 type, manufactured by Imoto Seisakusho Co., Ltd.), screw type vertical injection molding machine (TS-5- DV8-SE, manufactured by Tabata Kikai Kogyo Co., Ltd.) was used to prepare a plate (plate size: 70 mm×30 mm×1 to 3 mm; with steps) for measuring the contact angle.

(Examples 9 to 25)
Thermoplastic resin (polypropylene powder; PPW-5J, manufactured by Seishin Enterprise Co., Ltd.) and fluorine-containing copolymers 9 to 25 synthesized in Synthesis Examples 9 to 25 were mixed with 99.0% by mass of thermoplastic resin and fluorine-containing copolymer 1. After mixing at a rate of .0% by mass, put it in a stainless petri dish, melt and stir it using a spatula on a hot plate heated to 200 ° C., cool it in a freezer, remove it from the stainless petri dish, and measure the contact angle. A plate (plate size (diameter 48 mm×thickness 0.4 mm; no step)) was prepared.

(Comparative Examples 1 to 8)
Thermoplastic resin (polypropylene; Novatec PP EA9, manufactured by Nippon Polypropylene Co., Ltd.) and comparative copolymers 1 to 8 synthesized in Comparative Synthesis Examples 1 to 8 were mixed with 99.0% by mass of thermoplastic resin, fluorine-containing copolymer 1 After mixing at a rate of .0% by mass, melt-kneading at 190 ° C. using a composite kneading extruder (IMC-1A75 type, manufactured by Imoto Seisakusho), screw type vertical injection molding machine (TS-5-DV8- SE manufactured by Tabata Kikai Kogyo Co., Ltd.) was used to prepare a plate (plate size: 70 mm × 30 mm × 1 to 3 mm; stepped) for measuring the contact angle.

2. Measurement of contact angle After heat-treating the prepared plate in an oven heated to 120 ° C. for 30 minutes, using an automatic contact angle measuring device (OCA20, manufactured by Eiko Seiki Co., Ltd.), deionized water (DIW), normal hexadecane (n -HD), and isopropyl alcohol (IPA) were measured.
The measurement results are shown in Table 5 (Examples 1-25) and Table 6 (Comparative Examples 1-8).

(Evaluation result of liquid repellency on molded article surface)
The moldings of Examples 1 to 25 had good liquid repellency against all of deionized water (DIW), isopropyl alcohol (IPA), and normal hexadecane (n-HD).

Since molded articles obtained from the resin composition of the present invention can be produced at relatively low cost, they can be used for products such as industrial chemical containers, household goods, flooring materials, stationery, and cosmetic containers.
In addition, since it can be applied to textiles, it can also be used for clothing.

Claims (7)

A thermoplastic resin composition containing a thermoplastic resin and a fluorine-containing copolymer,
The fluorine-containing copolymer has a repeating unit based on the compound represented by formula (1), a repeating unit based on a non-fluorine monomer, and a repeating unit based on a compound having two or more mercapto groups in one molecule. including units and
With respect to the total mass of the fluorine-containing copolymer, the content of the repeating unit based on the compound represented by the formula (1) is 15% by mass to 65% by mass, and the repeating unit based on the non-fluorine monomer The content of the unit is 20% by mass to 70% by mass, and the content of the repeating unit based on the compound having two or more mercapto groups in one molecule is 5% by mass to 20% by mass, provided that the above When the repeating unit based on the non-fluorinated monomer contains the repeating unit based on the chain alkyl group-containing monomer, the chain alkyl group-containing monomer is added to the total mass of the fluorine-containing copolymer. The content of the repeating unit based on is 20% by mass to 60% by mass,
In the fluorine-containing copolymer, the mass ratio of the repeating unit based on the compound represented by the formula (1) to the repeating unit based on the non-fluorine monomer [the repeating unit based on the compound represented by the formula (1) Total mass of / total mass of repeating units based on non-fluorine monomer] is 78.9 / 21.1 to 21.1 / 78.9,
The fluorine-containing copolymer has a thermal decomposition temperature of 250° C. or higher,
The total content of the fluorine-containing copolymer is 0.5% by mass to 10% by mass with respect to the total mass of the thermoplastic resin and the fluorine-containing copolymer, and
The total content of the thermoplastic resin and the fluorine-containing copolymer is 80% by mass or more with respect to the total mass of the thermoplastic resin composition.
A thermoplastic resin composition.
_CH2 =CR1-CO-X ^{- CR2R3-} ( ^CH2 ) _n1- (COO) _n2 - ^Q1 - _Rf1 ( ¹ )
In formula (1):
R ¹ represents a hydrogen atom or a methyl group;
X represents -O- or -NR ⁴ -;
R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group represented by the following formula (r);
Q ¹ represents a single bond or a divalent linking group;
Rf ¹ represents a polyfluoroalkyl group or polyfluoroether group having 1 to 6 carbon atoms;
n1 represents an integer from 0 to 4; and
n2 represents 0 or 1;
—(CH ₂ ) _m1 —(COO) _m2 —Q ² —Rf ² (r)
In formula (r):
Q ² represents a single bond or a divalent linking group;
Rf ² represents a polyfluoroalkyl group or polyfluoroether group having 1 to 6 carbon atoms;
m1 represents an integer from 0 to 4; and
m2 represents 0 or 1; The thermoplastic resin composition according to claim 1, wherein the non-fluorine monomer is a compound represented by formula (2).
_CH2 =CR5 ^{- Q3} - ^{Q4 -} R6 (2)
In formula (2):
R ⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Q ³ represents a single bond, -COO-, or -CONH-;
Q ⁴ represents a single bond or a divalent linking group; and
R ⁶ represents a hydrogen atom, an OH group, a chain alkyl group having 1 to 30 carbon atoms, a cyclic alkyl group, or an aromatic ring. 3. The thermoplastic resin composition according to claim 1, wherein the compound having two or more mercapto groups in one molecule has two or more groups represented by formula (3) in one molecule.
—OCO—(CH ₂ ) _a —CHR ⁷ —(CH ₂ ) _b —SH (3)
In formula (3):
a represents an integer from 0 to 2;
b represents 0 or 1;
^R7 represents an alkyl group having 1 or 2 carbon atoms. A molded product obtained by thermoforming the thermoplastic resin composition according to any one of claims 1 to 3. 5. The molded article according to claim 4, which is heat-molded by any molding method selected from the group consisting of extrusion molding, injection molding and blow molding. A method for producing a molded article, comprising a step of thermally molding the thermoplastic resin composition according to any one of claims 1 to 3. 7. The manufacturing method according to claim 6, wherein in the thermoforming step, thermoforming is performed by any molding method selected from the group consisting of extrusion molding, injection molding and blow molding.