WO2022004654A1

WO2022004654A1 - Thermoplastic resin composition, molded product, and production method for molded product

Info

Publication number: WO2022004654A1
Application number: PCT/JP2021/024354
Authority: WO
Inventors: 良治天野
Original assignee: Ａｇｃセイミケミカル株式会社
Priority date: 2020-06-30
Filing date: 2021-06-28
Publication date: 2022-01-06
Also published as: CN115698189A; JPWO2022004654A1

Abstract

The purpose of the present invention is to provide a thermoplastic resin composition for obtaining a molded product having good water repellency and lipophilicity. The present invention involves a thermoplastic resin composition that includes a thermoplastic resin and a fluorine-containing copolymer, wherein: the fluorine-containing copolymer includes repeating units based on a compound represented by a specific formula, repeating units based on a non-fluorine monomer, repeating units based on a (meth)acryloyl-based compound comprising silicone, and repeating units based on a compound having two or more mercapto groups per molecule; the thermal decomposition temperature of the fluorine-containing copolymer is at least 250°C; and the fluorine-containing copolymer content is not more than 10 mass% of the total content of the thermoplastic resin and the fluorine-containing copolymer.

Description

Thermoplastic Resin Compositions, Molds, and Methods for Manufacturing Molds

The present invention relates to a thermoplastic resin composition, a molded product, and a method for producing the molded product.

Techniques for applying a fluorine treatment to the surface of a molded product in order to impart water and oil repellency to the surface of the molded product have been conventionally known, and examples thereof include a dipping treatment and a coating treatment on the surface of the molded product.
However, the method of applying fluorine treatment to the surface of the molded product has a problem that the sustainability of the water-repellent and oil-repellent function is weak and the water- and oil-repellent function is deteriorated by repeated use.

To solve this problem, for example, Patent Document 1 describes a resin composition containing a thermoplastic resin and a specific fluorine-containing polymer, and a molded product obtained by molding the resin composition. .. The technique described in Patent Document 1 is to add a fluorine compound to a resin at a stage before molding and melt-knead it to segregate the fluorine component on the surface after molding to impart continuous water and oil repellency. It is something to do.

Japanese Unexamined Patent Publication No. 2006-037085

Antifouling property, mold releasability, water repellency, lipophilicity and the like may be required for the surface of such a molded product.
The present inventor has found that a molded product obtained by molding the resin composition described in Patent Document 1 may have poor lipophilicity.
On the other hand, silicone (polysiloxane resin) has many performances such as antifouling property, mold release property, water repellency, lipophilicity, etc., and is an industrially useful compound. If it can be given, it can be used for various purposes.
However, even if silicone is simply added to the resin and melt-mixed at the stage before the molding process, it is presumed that the benefits of silicone are unlikely to be exhibited unless a large amount of silicone is added.

Therefore, it is an object of the present invention to provide a thermoplastic resin composition capable of obtaining a molded product having good water repellency and lipophilicity.
Another object of the present invention is to provide a molded product having good water repellency and lipophilicity and a method for producing the same.

As a result of diligent studies to solve the above problems, the present inventor has a specific fluorine-containing copolymer having a thermoplastic resin and a repeating unit based on a (meth) acryloyl-based compound having silicone as a repeating unit. It has been found that a thermoplastic resin composition containing a polymer and having a fluorine-containing copolymer in a specific range can obtain a molded product having good water repellency and oil lipophilicity. Completed the invention.
That is, the present inventor has learned 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 includes a repeating unit based on the compound represented by the formula (1), a repeating unit based on a non-fluorine monomer, a repeating unit based on a (meth) acryloyl compound having silicone, and 1 Contains repeating units based on compounds having two or more mercapto groups in the molecule.
The thermal decomposition temperature of the fluorine-containing copolymer is 250 ° C. or higher, and the temperature is 250 ° C. or higher.
The content of the fluorine-containing copolymer is 10% by mass or less in the total content of the thermoplastic resin and the fluorine-containing copolymer.
Thermoplastic resin composition.
CH ₂ = CR ^1- CO-X-CR ² R ^3- (CH ₂ ) _n1- (COO) _n2- Q ^1- Rf ¹ (1)
In equation (1):
R ¹ represents a hydrogen atom or a methyl group;
X is, -O- or -NR ⁴ - represents a;
R ² , R ³ and R ⁴ 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 a 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 equation (r):
Q ² is a single bond or a divalent linking group;
Rf ² represents a polyfluoroalkyl group or a 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], wherein the non-fluorine monomer is a compound represented by the formula (2).
CH ₂ = CR ^5- Q ^3- [Q ^4- R ⁶ ] _k (2)
In equation (2):
R ⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Q ³ are a single bond, -COO -, - CONH-, or an -CON <;
Q ⁴ are, represents a single bond or 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, a cyclic ether group, or an aromatic ring; and
If Q ³ is a single bond, -COO-, or -CONH-, then k is 1, and if Q ³ is -CON <, then k is 2.
[3] The thermoplastic according to [1] or [2], wherein the compound having two or more mercapto groups in one molecule has two or more groups represented by the formula (3) in one molecule. Resin composition.
_{_{^{_{-OCO- (CH 2) a -CHR 7}}}} - (CH 2) b -SH (3)
In equation (3):
a represents an integer of 0 to 2;
b represents 0 or 1;
R ⁷ represents an alkyl group having 1 or 2 carbon atoms.
[4] The thermoplastic resin composition according to any one of [1] to [3], wherein the (meth) acryloyl compound having silicone is a compound represented by the following formula (4).
_{^{^{^{CH 2 = CR 8 -Q 5 -Q}}}} 6 - (SiR 9 2 -O-) n-SiR 10 3 (4)
In equation (4):
R ⁸ represents a hydrogen atom or a methyl group;
Q ⁵ represents -COO-, or -CONH-;
Q ⁶ represents a single bond or a divalent linking group;
R ⁹ and R ¹⁰ each independently represent a hydrocarbon group; and
n represents 2 or more.

[5] A molded product obtained by heat-molding the thermoplastic resin composition according to any one of [1] to [4].
[6] The molded product according to [5], which is heat-molded by any molding method selected from the group consisting of extrusion molding, injection molding and blow molding.

[7] A method for producing a molded product, comprising a step of heat-molding the thermoplastic resin composition according to any one of [1] to [4].
[8] The production method according to [7], wherein in the heat molding step, heat molding is performed by any molding method selected from the group consisting of extrusion molding, injection molding and blow molding.

According to the present invention, it is possible to provide a thermoplastic resin composition capable of obtaining a molded product having good water repellency and lipophilicity.
The present invention can also provide a molded product having good water repellency and lipophilicity and a method for producing the same.

[Range expressed using "~"]
In the present specification, the range represented by using "-" shall include both ends of "-" within the range. For example, the range represented by "A to B" includes "A" and "B".

[(Meta) acrylic]
Further, in the present specification, "(meth) acrylic" shall include "acrylic" and "methacrylic", and similarly, "(meth) acrylate" shall include "acrylate" and "methacrylate". .. "(Meta) acryloyl" shall include "acryloyl" and "methacryloyl".

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

[-COO-]
In the present invention, the divalent linking group (ester bond) represented by the following formula may be referred to as "-COO-". However, "*" in the following formula represents a bond 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 referred to as "-OCO-". However, "*" in the following formula represents a bond 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 referred to as "-N (R)-". However, in the following formula, "*" represents a bond point with another atom or an atomic group, and "R" represents a hydrogen atom or a monovalent group.

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

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

[-SO _2- ]
In the present invention, the divalent linking group (sulfonyl group) represented by the following chemical formula may be referred to _{as "-SO 2-".} However, "*" in the following formula represents a bond point with another atom or atomic group.

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

[-COS-]
In the present invention, the divalent linking group represented by the following formula may be referred to as "-COS-". However, "*" in the following formula represents a bond 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 formula, " _* " and " ^* " represent a bond point with another atom or an atomic group, and "R" represents a monovalent group.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention (the composition of the present invention) is
A thermoplastic resin composition containing a thermoplastic resin and a fluorine-containing copolymer.
The fluorine-containing copolymer includes a repeating unit based on the compound represented by the formula (1), a repeating unit based on a non-fluorine monomer, a repeating unit based on a (meth) acryloyl compound having silicone, and 1 Contains repeating units based on compounds having two or more mercapto groups in the molecule.
The thermal decomposition temperature of the fluorine-containing copolymer is 250 ° C. or higher.
It is a thermoplastic resin composition in which the content of the fluorine-containing copolymer is 10% by mass or less in the total content of the thermoplastic resin and the fluorine-containing copolymer.

The fluorine-containing copolymer contained in the composition of the present invention is a repeating unit based on the compound represented by the formula (1) as a repeating unit (the above repeating unit has a property of easily segregating on the surface of the molded product). , And a repeating unit based on a (meth) acryloyl compound having silicone (the above repeating unit has excellent water repellency and lipophilicity) and the like.
In the molded product of the present invention formed by using the composition of the present invention, the fluorine-containing copolymer is rapidly segregated on the surface of the molded product by the repeating unit based on the compound represented by the formula (1), and the above-mentioned It is considered that water repellency and lipophilicity are efficiently exhibited because the repeating unit based on the (meth) acryloyl compound having silicone incorporated in the fluoropolymer by segregation can also be present on the surface of the molded product.
Therefore, it is considered that the composition of the present invention can be expected to exhibit its effect at a lower concentration than the case of adding a silicone having no repeating unit based on the compound represented by the formula (1).

In the present specification, more excellent water repellency and / or lipophilicity of the obtained molded product may be referred to as "more excellent effect of the present invention".

Hereinafter, each component contained in the composition of the present invention will be described.
The thermoplastic resin composition of the present invention contains a thermoplastic resin and a fluorine-containing copolymer.

<Thermoplastic resin>
The thermoplastic resin is not particularly limited, but specific examples thereof include nylon resin, polyethylene resin, polypropylene resin, polycarbonate resin, polyvinyl chloride resin, polymethylmethacrylate resin, polyester resin, polyoxymethylene resin, polystyrene resin, and polyphenylene ether resin. , Urethane resin, acrylic nitrile / butadiene / styrene resin (ABS) and fluorine-containing resin (excluding the above-mentioned fluorine-containing copolymer).

Examples of the thermoplastic resin used in the thermoplastic resin composition of the present invention include nylon resin, polyethylene resin, polypropylene resin, polycarbonate resin, polyphenylene ether resin, acrylic nitrile butadiene styrene resin (ABS), and PET resin (PET resin). At least one thermoplastic resin selected from the group consisting of polyethylene terephthalate) is preferable, and at least one thermoplastic resin selected from the group consisting of polyethylene resin, polypropylene resin, and polycarbonate resin is more preferable.

In the thermoplastic resin composition of the present invention, one type of thermoplastic resin can be used alone or in combination of two or more types.

<Fluorine-containing copolymer>
The fluorine-containing copolymer includes a repeating unit based on the compound represented by the formula (1), a repeating unit based on a non-fluorine monomer, a repeating unit based on a (meth) acryloyl compound having silicone, and one molecule. It contains a repeating unit based on a compound having two or more mercapto groups.

<< Repeating unit based on the compound represented by the formula (1) >>
The compound represented by the formula (1) will be described.
CH ₂ = CR ^1- CO-X-CR ² R ^3- (CH ₂ ) _n1- (COO) _n2- Q ^1- Rf ¹ (1)
The meanings of the symbols in the formula (1) are as follows.

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

・ X
X is, -O- or -NR ⁴ - represents preferably an -O-.
・ R ² , R ³ , R ⁴
R ² , R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group represented by the following formula (r). The group represented by the formula (r) will be described later.

・ Q ¹
Q ¹ represents a single bond or a divalent linking group.
The divalent linking group includes 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 4 to 6 members. divalent alicyclic group ring, 5 or 6-membered heteroarylene ^{^{^{group, -X 1 -, - X 1}}} -X 2 -, - Z 1 -X 1 -, - X 1 -Z 1 -X 2 -, - Examples thereof include Z ^1- X ^1- X ^2- , -Z ^1- X ^1- ^{Z 2-} X ^2- , and a divalent group consisting of a combination of two or more of these. Here, in a divalent group consisting of a combination of a plurality of ring groups, two monocycles may be condensed.

The ^{^{^{^{-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 -Z ^² -X ² - in,
X ¹ and X ² : 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 Two or more monocycles consisting of a combination of two or more of a 6-membered heteroarylene group, a 6-membered arylene group, and a 4- to 6-membered divalent alicyclic group and a 5- or 6-membered heteroarylene group. Represents a divalent group selected from the group consisting of divalent groups that may be fused.
Z ¹ and Z ² : -O-, -S-, -CO-, -COO-, -OCO-, -COS-, -SCO-, -N (R ¹ )-, -SO _{2-, respectively.} , -PO (OR ¹ )-, -N (R ¹ ) -COO-, -COO-N (R ¹ )-, -N (R ¹ ) -CO-, -CO-N (R ¹ )-,- ^{_{_{^{N (R 1) -SO 2 -}}}} , - SO 2 -N (R 1) -, - N (R 1) -PO (oR 2) -, and ^{^{-PO (oR 2) -N (R}} 1) - from Represents a divalent group selected from the group, and in the above formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

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

・ Rf ¹
Rf ¹ represents a polyfluoroalkyl group or a polyfluoroether group having 1 to 6 carbon atoms, and may be linear or branched, but is 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 , -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 , and-(CF ₂ ) ₃ CF (CF ₃ ) ₂ , but not limited to these.
Rf ¹ is preferably − (CF ₂ ) ₃ CF ₃ or − (CF ₂ ) ₅ CF ₃ and more preferably − (CF ₂ ) ₅ CF ₃ .

・ N1, n2
n1 represents an integer of 0 to 4.
n2 represents 0 or 1.

Hereinafter, the group represented by the formula (r) as ^{R 2} , R ³ or R ⁴ in the formula (1) will be described.
_{_{_{- (CH 2) m1 - (}}} COO) m2 -Q 2 -Rf 2 (r)
The meanings of the symbols in the formula (r) are as follows.

・ Q ²
Q ² is a single bond or a divalent linking unit.
The divalent linking group includes 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 4 to 6 members. divalent alicyclic group ring, 5 or 6-membered heteroarylene ^{^{^{group, -X 1 -, - X 1}}} -X 2 -, - Z 1 -X 1 -, - X 1 -Z 1 -X 2 -, - Examples thereof include Z ^1- X ^1- X ^2- , -Z ^1- X ^1- ^{Z 2-} X ^2- , and a divalent group consisting of a combination of two or more of these. Here, in a divalent group consisting of a combination of a plurality of ring groups, two monocycles may be condensed.

It said Q ² is preferably a divalent linking group, and more preferably an alkylene group having 1 to 10 carbon atoms.

・ Rf ²
Rf ² represents a polyfluoroalkyl group or a polyfluoroether group having 1 to 6 carbon atoms, and may be linear or branched, but is 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 and more preferably − (CF ₂ ) ₅ CF ₃ .

・ M1, m2
m1 represents an integer from 0 to 4.
m2 represents 0 or 1.

(Specific example of the compound represented by the formula (1))
Specific examples of the compound represented by the formula (1) are listed below, but are not limited thereto.
CH ₂ = CH-COO-CH _2- (CF ₂ ) ₅ CF ₃
CH ₂ = C (CH ₃ ) -COO-CH _2- (CF ₂ ) ₅ CF ₃
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) ₃ CF (CF ₃ ) ₂
CH ₂ = C (CH ₃ ) -COO- (CH ₂ ) _2- (CF ₂ ) ₃ CF ₃
CH ₂ = C (CH ₃ ) -COO-CH ₂ CH _2- (CF ₂ ) ₅ CF ₃
CH ₂ = CH-COO-CH ₂ CH _2- (CF ₂ ) ₅ CF ₃
CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) ₃ CF ₃
_{_{CH 2 = CH-COO- (CH}} 2) 2 -CF 2 CF 3

From the viewpoint that the compound represented by the formula (1) is superior to the effect of the present invention, C6FMA: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ and / or bis (3, 3). , 4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) = N-methacryloyl aspartate (ASP) is preferably contained, and C6FMA is more preferable. ..

<< Repeating unit based on non-fluorine monomer >>
The non-fluorine monomer will be described.
In the present invention, the non-fluorine monomer does not have a fluorine atom. Further, the non-fluorine monomer does not contain the (meth) acryloyl compound having silicone, which will be described later. Further, the non-fluorine monomer does not contain a compound having two or more mercapto groups in one molecule, which will be described later.

The non-fluorine monomer copolymerizes with the compound represented by the formula (1) and the like.
The non-fluorine monomer preferably has, for example, a group represented by the following formula (X) as a group for copolymerizing with the compound represented by the formula (1).
CH ₂ = CR ^51- (X)
The meanings of the symbols in the above formula (X) are as follows.

・ R ⁵¹
R ⁵¹ represents a hydrogen atom or a hydrocarbon group. It is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

The non-fluorine monomer is not particularly limited, but is preferably a compound represented by the formula (2).

CH ₂ = CR ^5- Q ^3- [Q ^4- R ⁶ ] _k (2)
The meanings of the symbols in the formula (2) are as follows.

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

・ Q ³
Q ³ are a single bond, -COO -, - CONH-, or -CON represents <is preferably -COO- or -CONH-, more preferably -COO-.

· ^{Q 4}
Q ⁴ are, it represents a single bond or a divalent linking group.
The divalent linking group includes 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 4 to 6 members. divalent alicyclic group ring, 5 or 6-membered heteroarylene ^{^{^{group, -X 1 -, - X 1}}} -X 2 -, - Z 1 -X 1 -, - X 1 -Z 1 -X 2 -, - Examples thereof include Z ^1- X ^1- X ^2- , -Z ^1- X ^1- ^{Z 2-} X ^2- , and a divalent group consisting of a combination of two or more of these. Here, in a divalent group consisting of a combination of a plurality of ring groups, two monocycles may be condensed.

The Q ⁴ are preferably a divalent linking group. More specifically, examples of the divalent linking group include a methylene group, _{an alkylene group such as −C 22} H ₄₄ −; and a polyoxyalkylene group.
The molecular weight of the fluorine-monomers when Q ⁴ is a polyoxyalkylene group (weight average molecular weight or number average molecular weight) can be measured by GPC (gel permeation chromatography).

・ R ⁶
R ⁶ represents a hydrogen atom, an OH group, a chain alkyl group having 1 to 30 carbon atoms, a cyclic alkyl group, a cyclic ether group, or an aromatic ring.
The chain alkyl group having 1 to 30 carbon atoms may be linear or branched.
Cyclic ether group refers to an ether group having a structure in which one or more carbons of a cyclic hydrocarbon are substituted with oxygen. Examples of the cyclic ether group include an ether group having a 3- to 6-membered ring. Specific examples thereof include an oxetane group, a tetrahydrofuran group, a tetrahydropyran group and the like.
In the present specification, the cyclic alkyl group, the cyclic ether group, and the aromatic ring may be collectively referred to as a “cyclic structure”.

・ K
If Q ³ is a single bond, -COO-, or -CONH-, then k is 1, and if Q ³ is -CON <, then k is 2. When Q ³ is -CON <, two- [Q ^4- R ⁶ ] are bonded to the nitrogen atom at -CON <, respectively. If k is 2, the two of Q ⁴ may be the same or different. R ⁶ is the same.

(Specific example of non-fluorine monomer)
Examples of the non-fluorine monomer include (meth) acrylate compounds having a chain alkyl group such as stearyl (meth) acrylate, behenyl (meth) acrylate, and 2-decyl-1-tetradecanyl (meth) acrylate; cyclohexyl (meth). Compounds with a cyclic structure such as meta) acrylates, benzyl (meth) acrylates, tetrahydrofurfuryl (meth) acrylates; polyoxyalkylenediol mono (meth) acrylates such as polyethylene glycol monomethacrylates, methoxypolyethylene glycol methacrylates and the like. Alkoxypolyoxyalkylene diol mono (meth) acrylates; alkyl acrylamides such as N, N-diethylacrylamide can be mentioned. The alkylacrylamide includes N-alkylamide and N, N-dialkylamide.
The fluorine-free monomer, the effect of the present invention is more excellent from the viewpoint of excellent compatibility with the thermoplastic resin (e.g., polypropylene resin), preferably contains a compound wherein R ⁶ is a chain alkyl group, stearyl It is more preferable to contain at least one selected from the group consisting of (meth) acrylate, behenyl (meth) acrylate and 2-decyl-1-tetradecanyl (meth) acrylate.
The non-fluorine monomer is more excellent in the effect of the present invention, and is excellent in compatibility with a thermoplastic resin (for example, polypropylene resin, polycarbonate resin).
It is preferable that the compound in which R ⁶ is a chain alkyl group and / or the compound in which R ⁶ has a cyclic structure is contained (however, in the above case, ^{the compound in which R 6} is a chain alkyl group is represented by the formula (2). ) in - ^[Q 4 -R ^6] does not have a ring structure in)
The compound wherein R ⁶ is a chain alkyl group, and / or, more preferably comprising benzyl (meth) acrylate or tetrahydrofurfuryl (meth) acrylate,
It is more preferred to include a compound in which R ⁶ is a chain alkyl group and a benzyl (meth) acrylate or tetrahydrofurfuryl (meth) acrylate.

<< Repeating unit based on (meth) acryloyl compound with silicone >>
A (meth) acryloyl compound having silicone will be described.
The (meth) acryloyl compound having silicone has a skeleton due to a siloxane bond (silicon and oxygen are alternately bonded) and a (meth) acryloyl group (CH ₂ = CH-CO- or CH ₂ = CCH _{3-CO-) as silicone.} ) And.

-Silicone possessed by the (meth) acryloyl compound The (meth) acryloyl compound having silicone may preferably have one silicone and one (meth) acryloyl group.
The (meth) acryloyl-based compound having silicone copolymerizes with the compound represented by the above formula (1) or the like.

The silicone contained in the (meth) acryloyl compound is represented by, for example,-(Si—O) n—, and n can be 2 or more. The repeating unit n of the siloxane can be appropriately determined depending on the number average molecular weight and structure of the (meth) acryloyl compound having silicone, which will be described later (with the number of repeating units of (Si—O)). The same applies to a certain n).
Examples of the silicone include polyorganosiloxane. In the polyorganosiloxane, the hydrocarbon group bonded to the silicon atom is not particularly limited. For example, an aliphatic hydrocarbon group (linear, branched, or cyclic), an aromatic hydrocarbon group, or a combination thereof can be mentioned.
Examples of the polyorganosiloxane include polydialkylsiloxane. In the polydialkylsiloxane, the alkyl group bonded to the silicon atom is not particularly limited. Specific examples of the polyorganosiloxane include polydimethylsiloxane.

Examples of the silicone contained in the above (meth) acryloyl compound include, for example.
- include the structures represented by ^{_{(SiR 9 2 -O) n-}} SiR 10 3.
The ^- In _{(SiR 9 2 -O) n-} SiR 10 3, R 9, R 10 each independently represent a hydrocarbon radical, n is 2 or more. The hydrocarbon group is the same as the hydrocarbon group bonded to the silicon atom described in the above polyorganosiloxane.

In the (meth) acryloyl compound having silicone, the silicone and the (meth) acryloyl group can be bonded directly or via an organic group. The organic group is not particularly limited. For example, an alkylene group; a linking group formed by a combination of an oxygen atom or a nitrogen atom and an alkylene group can be mentioned.

The (meth) acryloyl compound having silicone is preferably a compound represented by the following formula (4) from the viewpoint that the effect of the present invention is more excellent.
_{^{^{^{CH 2 = CR 8 -Q 5 -Q}}}} 6 - (SiR 9 2 -O-) n-SiR 10 3 (4)

The meanings of the symbols in the formula (4) are as follows.
· ^{R 8}
R ⁸ represents a hydrogen atom or a methyl group.
· ^{Q 5}
Q ⁵ represents a -COO-, or -CONH-.
・ Q ⁶
Q ⁶ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group.

・ R ⁹ and R ¹⁰
R ⁹ and R ¹⁰ each independently represent a hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group (linear, branched, or cyclic), an aromatic hydrocarbon group, or a combination thereof. A preferred embodiment is that the hydrocarbon group is an alkyl group. R ⁹ and R ¹⁰ may all be the same or different.

・ N
n represents 2 or more. n is preferably 200 or less from the viewpoint that the effect of the present invention is more excellent.

(Number average molecular weight of (meth) acryloyl compound having silicone)
The number average molecular weight (Mn) of the (meth) acryloyl compound having silicone is preferably 500 to 20,000, more preferably 1,000 to 15,000, from the viewpoint of further improving the effect of the present invention. , 1,000 to 12,000 is more preferable, and 5,000 to 10,000 is even more preferable.
When a compound having a different Mn is used in combination with respect to the (meth) acryloyl compound having a silicone, the (meth) acryloyl compound having a silicone has a Mn of 500 to 3,000 from the viewpoint that the effect of the present invention is more excellent. It is preferable to use the compound and the compound having Mn of 4,000 to 12,000 in combination, and the compound having Mn of 500 to 3,000 and the compound having Mn of 4,000 to 10,000 are used in combination. Is more preferable.

In the present invention, the number average molecular weight can be measured by GPC (gel permeation chromatography).

<< Repeating unit based on a compound having two or more mercapto groups in one molecule >>
A compound having two or more mercapto groups in one molecule will be described.
A compound having two or more mercapto groups in one molecule can function as a monomer constituting a fluorine-containing copolymer. Further, a compound having two or more mercapto groups in one molecule may function as a chain transfer agent.
Further, in the present invention, one of the preferred embodiments is that the compound having two or more mercapto groups in one molecule does not have a (meth) acryloyl group.

The mercapto group contained in the compound having two or more mercapto groups in one molecule can be CH ₂ = CR ¹ − possessed by the compound represented by the formula (1), and the formula (X) can be possessed by the non-fluorinated compound. Can react with the group represented by or the (meth) acryloyl group of the (meth) acryloyl compound having silicone.
One of the preferred embodiments is that the fluorine-containing copolymer does not have a mercapto group.

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 the formula (3) in one molecule.

_{_{^{_{-OCO- (CH 2) a -CHR 7}}}} - (CH 2) b -SH (3)
The meanings of the symbols in the formula (3) are as follows.

・ A, b
a represents an integer of 0 to 2, preferably 1 or 2, and more preferably 1.
b represents 0 or 1, and is preferably 0.

・ R ⁷
R ⁷ represents an alkyl group having 1 or 2 carbon atoms, and is preferably a methyl group.

The group represented by the above formula (3) can be bonded to an organic group. The organic group is not particularly limited. For example, a hydrocarbon group, an isocyanate ring, or a combination thereof can be mentioned.
Examples of the hydrocarbon group as the organic group include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof.
The group represented by the formula (3) can be bonded to the nitrogen atom of the isocyanurate ring as the organic group directly or via a hydrocarbon group.
The organic group may be divalent or higher, and the organic group can have a valence corresponding to the number of groups represented by the formula (3) contained in one molecule of the above compound.
One of the preferred embodiments is that the organic group does not have polysiloxane.

(Specific example of a compound 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), trimethylolpropanetris (3-mercaptobutyrate), and trimethylolethanetris (3-). Mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), 1,3,5-tris (3-mercaptobutylyloxyethyl) -1,3, 5-Triazine-2,4,6 (1H, 3H, 5H) -trione, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, and 1,4-bis (3-mercaptobutylyloxy). Butan can be mentioned.

Compounds having two or more mercapto groups in one molecule are described as pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropanthris (3-mercaptobutyrate), 1 from the viewpoint that the effect of the present invention is more excellent. , 3,5-Tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, and 1,4-bis (3-mercaptobuty) At least one selected from the group consisting of lyloxy) butane is preferred, with pentaerythritol tetrakis (3-mercaptobutyrate) and / or 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3. , 5-Triazine-2,4,6 (1H, 3H, 5H) -trione is more preferred, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2, 4,6 (1H, 3H, 5H) -trione is more preferred.

(Content of repeating unit based on the compound represented by the formula (1))
In the fluoropolymer, the content of the repeating unit based on the compound represented by the formula (1) is the formula (1) constituting the fluoropolymer from the viewpoint that the effect of the present invention is more excellent. 10-70 mol% is preferred, preferably 15-70 mol% of the total content of the repeating units based on the represented compounds, the repeating units based on the non-fluorinated monomer, and the repeating units based on the (meth) acryloyl-based compound having silicone. 65 mol% is more preferable.

-Contents of repeating units based on the compound represented by the formula (1) when the compound represented by the formula (1) does not have ^{Rf 2 The} compound represented by ^{the formula (1) has Rf 2} . ^{In the absence of, that is, when the compound represented by the formula (1) has only Rf 1} as a polyfluoroalkyl group or a polyfluoroether group having 1 to 6 carbon atoms, the compound represented by the formula (1) in the fluorine-containing copolymer. From the viewpoint that the effect of the present invention is more excellent, the content of the repeating unit based on the represented compound is a repeating unit based on the compound represented by the formula (1), which constitutes a fluorine-containing copolymer, and is a non-fluorocarbon simple substance. The total content of the repeating unit based on the polymer and the repeating unit based on the (meth) acryloyl compound having silicone is preferably 15 to 70 mol%, more preferably 20 to 65 mol%.

When the compound represented by the formula (1) is a compound represented by the content type of the repeating units based on a compound represented by the formula (1) when having Rf ² (1) has a Rf ^2, i.e. , When the compound represented by the formula (1) has Rf ¹ and Rf ² , the content of the repeating unit based on the compound represented by the formula (1) in the fluorine-containing copolymer has the effect of the present invention. From the viewpoint of superiority, a repeating unit based on the compound represented by the formula (1), a repeating unit based on a non-fluorinated monomer, and a (meth) acryloyl-based compound having silicone, which constitute a fluorine-containing copolymer. 10-40 mol%, more preferably 15-35 mol%, of the total content of the repeating unit based on.

(Content of repeating unit based on non-fluorine monomer)
In the fluorine-containing copolymer, the content of the repeating unit based on the non-fluorine-containing monomer is the repeating unit based on the compound represented by the formula (1) constituting the fluorine-containing copolymer, the non-fluorine monomer. 20-80 mol% of the total content of the repeating unit based on and the repeating unit based on the (meth) acryloyl-based compound having silicone is preferred.

(Content of repeating unit based on (meth) acryloyl compound having silicone)
In the fluoropolymer, the content of the repeating unit based on the (meth) acryloyl compound having silicone constitutes the fluoropolymer from the viewpoint that the effect of the present invention is more excellent, according to the formula (1). The total content of the repeating units based on the represented compound, the repeating unit based on the non-fluorinated monomer, and the repeating unit based on the (meth) acryloyl-based compound having silicone is preferably 1.0 to 15 mol%.

(Content of repeating unit based on a compound having two or more mercapto groups in one molecule)
In the fluoropolymer, the content of the repeating unit based on the compound having two or more mercapto groups in one molecule constitutes the fluoropolymer from the viewpoint that the effect of the present invention is more excellent. With respect to the total content (100 mol%) of the repeating unit based on the compound represented by (1), the repeating unit based on the non-fluorine monomer, and the repeating unit based on the (meth) acryloyl-based compound having silicone. , 1.0 to 25 mol% is preferable.

In the present invention, the amount of the compound represented by the formula (1) used in producing the fluorine-containing copolymer is the compound represented by the formula (1) constituting the fluorine-containing copolymer. It shall be reflected in the content of the repeating unit based on. The same applies to the amounts of the non-fluorine monomer, the (meth) acryloyl compound having silicone, and the compound having two or more mercapto groups in one molecule used in producing the fluorine-containing copolymer. Is.

<< Method for synthesizing fluorine-containing copolymer >>
The fluorine-containing copolymer can be synthesized by a known method. For example, a compound represented by the formula (1), a non-fluorine monomer, a (meth) acryloyl-based compound having silicone, and a compound having two or more mercapto groups in one molecule are solution-polymerized and suspended. A fluorine-containing copolymer can be synthesized by polymerizing using various polymerization methods such as turbid polymerization or emulsion polymerization.

(Polymerization initiator)
A polymerization initiator can be used for the above polymerization.
The polymerization initiator that can be used in producing the fluorine-containing copolymer is not particularly limited, and is, for example, 2,2'-azobis-2-methylbutyronitrile, dimethyl-2,2'-azobis-2-methylpro. Examples thereof include azo compounds such as pionate and 2,2'-azobisisobutyronitrile, and organic oxides such as lauroyl peroxide.

(solvent)
When producing the fluorine-containing copolymer, a solvent may be used.
As the solvent that can be used in producing the fluorine-containing copolymer, for example, general solvents such as methanol, ethanol, isopropyl alcohol, butyl alcohol, methyl acetate, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, and toluene (fluorine-based solvent). (Excluding solvents), fluorosolvents such as freon, hydrofluoroether, xylenehexafluorolide and the like can be mentioned.

<< Thermal decomposition temperature of fluorine-containing copolymer >>
In the present invention, the thermal decomposition temperature of the fluorine-containing copolymer is 250 ° C. or higher.
Since the thermosetting resin composition of the present invention has a pyrolysis temperature of 250 ° C. or higher for the fluoropolymer, it can have heat resistance to withstand mixing with a thermoplastic resin and molding temperature.

The thermal decomposition temperature of the fluorine-containing copolymer is preferably 250 ° C to 350 ° C in consideration of the shear heat generated during mixing with the thermoplastic resin.

In the present invention, the thermal decomposition temperature of the fluorine-containing copolymer is determined by conducting a thermal decomposition test in which the fluoropolymer is heated from 50 ° C. to 450 ° C. at a rate of 5 ° C./min. The change in mass is measured, and it refers to the temperature when the mass of the fluoropolymer is reduced by 5% by mass from the start of the thermal decomposition test.

<Other ingredients>
In addition to the thermoplastic resin and the fluoropolymer, the thermoplastic resin composition of the present invention may further contain additives such as a solvent, a pigment, and an antistatic agent as long as the effects of the present invention are not impaired. good. The type and content of each of the above additives can be appropriately selected. Examples of the solvent include the same solvents as those that can be used in producing the above-mentioned fluorine-containing copolymer.

≪Contents of fluorine-containing copolymer≫
In the thermoplastic resin composition of the present invention, the content of the fluorine-containing copolymer is 10% by mass or less of the total content of the thermoplastic resin and the fluorine-containing copolymer.
When the content of the fluorine-containing copolymer is within the above range, the obtained molded product has excellent lipophilicity. In addition, the fluorine-containing copolymer is easily mixed with the thermoplastic resin, the obtained molded product has excellent water repellency, and the strength of the obtained molded product can be maintained.
Regarding the content of the fluorine-containing copolymer, the effect of the present invention is more excellent, the fluorine-containing copolymer is easily mixed with the thermoplastic resin, the obtained molded product has excellent water repellency, and the strength of the obtained molded product can be maintained. From this point of view, 0.01 to 10% by mass, more preferably 0.5% by mass to 7.0% by mass, and 0.5% by mass in the total content of the thermoplastic resin and the fluoropolymer. % To 5.0% by mass is even more preferable.

≪Total content of thermoplastic resin and fluorine-containing copolymer≫
The total content of the thermoplastic resin and the fluoropolymer is in the total mass of the thermoplastic resin composition of the present invention from the viewpoint that the effect of the present invention can be better exhibited while maintaining the physical characteristics of the thermoplastic resin. It is preferably 80% by mass to 100% by mass.

<Manufacturing method of thermoplastic resin composition>
The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing a thermoplastic resin and a fluorine-containing copolymer.
The method for mixing the thermoplastic resin and the fluorine-containing copolymer is not particularly limited, and examples thereof include a method using a single-screw extruder, a twin-screw extruder, or a kneader.
The temperature at which the thermoplastic resin and the fluorine-containing copolymer are mixed can be appropriately selected depending on the type of the thermoplastic resin. When the thermoplastic resin contains a polypropylene resin, the mixing temperature can be set to, for example, 180 to 220 ° C.
A molded product can be obtained by molding a mixture obtained by heating and mixing a thermoplastic resin and a fluorine-containing copolymer.

[Molded product and manufacturing method of molded product]
The molded product of the present invention is obtained by heat-molding the above-mentioned thermoplastic resin composition.
That is, the molded product of the present invention can be produced by the method for producing a molded product including the step of heat-molding the thermoplastic resin composition described above.
The thermoplastic resin composition used in the method for producing a molded product of the present invention is not particularly limited as long as it is the thermoplastic resin composition of the present invention (the composition of the present invention).
The method for heat-molding the composition of the present invention or the method for heat-molding the thermoplastic resin composition in the production method of the present invention is not particularly limited, but is selected from the group consisting of extrusion molding, injection molding and blow molding. It is preferable to use any of the molding methods.

In the method for producing a molded product of the present invention, after the step of heat-molding the thermoplastic resin composition, the molded product is, for example, from 80 ° C. for the purpose of promoting the transfer of the fluorine-containing copolymer to the surface of the molded product. It may further have a step of heat-treating at a temperature of 120 ° C.

In the method for producing a molded product of the present invention, in the step of heat-molding the thermoplastic resin composition, the composition of the present invention (for example, simply in a mixed state or separately added from the thermoplastic resin and the fluorine-containing copolymer) is added. ) May be heated and mixed to form a heated mixture. The method for manufacturing a molded product of the present invention can be the same as the process or equipment in a general manufacturing process for a molded product. That is, it is not necessary to provide a process or equipment for immersing the molded product in the thermoplastic resin composition, applying the thermoplastic resin composition to the molded product, and the like, and the productivity is excellent.

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

[Fluorine-containing monomer: ASP synthesis]
2-Perfluorohexylethyl alcohol (110.3 g), L-aspartic acid (16.65 g), cyclohexane (62.4 g), and p-toluenesulfonic acid monohydrate (28) in a 300 mL four-necked flask. .46 g) was charged, and reflux was performed for 20 hours while removing the generated water. The reaction solution was cooled to 60 ° C. or lower, and the precipitated solid was washed with acetone and isopropyl alcohol (IPA) and filtered under reduced pressure. The obtained solid was vacuum dried to obtain 88.5 g of a white solid.
The obtained 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. Hydroquinone (0.01 g) was added thereto, and the mixture was washed twice with water, the lower layer was recovered and concentrated under reduced pressure to obtain 46.2 g of a pale yellow solid. Ethyl acetate and hexane were added thereto to dissolve them by heating, and then ice-cooled to precipitate crystals.
The obtained crystals are collected by filtration and dried under reduced pressure to form a 20.0 g pale yellow solid compound represented by the following formula (bis (3,3,4,4,5,5,6,6,7). , 7,8,8,8-Tridecafluorooctyl) = N-methacryloyl aspartate) was obtained. The compound synthesized as described above may be referred to as "ASP".

[Synthesis of Fluorine-Containing Copolymer]
<Synthesis Examples 1 to 14><Comparative Synthesis Examples 1 to 4>
A compound represented by the formula (1) (hereinafter, may be referred to as “monomer A”) and a non-fluorine monomer (hereinafter, “monomer”) shown in the “monomer composition” column of Table 1 in a 100 mL duran bottle. (Sometimes referred to as "body B"), a silicone-containing monomer (hereinafter sometimes referred to as "monomer C"), and a compound having a mercapto group (hereinafter sometimes referred to as "monomer D"). Charged in the amount (unit: mol%) shown in Table 1 (monomer mixture), and further, an azo-based polymerization initiator (dimethyl-2,2'-azobis (2-methylpropionate); V-601, Fujifilm. Wako Junyaku Co., Ltd.) is used in an amount of 1 mol% of the total of monomers A, B, and C, and the solvent (ethyl acetate, Fujifilm Wako Junyaku Co., Ltd.) is used in the monomers A, B, C, and D. The mixture was charged in an amount twice the total weight of the above, the inside of the system was replaced with monomer, the lid was closed, and the mixture was stirred at a water temperature of 75 ° C. for 15 hours or more.
After cooling to room temperature, the solvent was distilled off to obtain the desired product.
Each of the fluorine-containing copolymers obtained in Synthesis Examples 1 to 14 is referred to as fluorine-containing copolymers 1 to 14.
Each of the fluorine-containing copolymers obtained in Comparative Synthesis Examples 1 to 4 is referred to as comparative fluorine-containing copolymers 1 to 4.
In the "monomer composition" column of Table 1, the content of the monomer A is the content in 100 mol% of the total of the monomer A, the monomer B and the monomer C. The contents of the monomer B and the monomer C are also the same. Monomer C was not used in Comparative Synthesis Examples 1 to 4.
The content of the monomer D is the content (mol%) of the monomer D with respect to the total of 100 mol% of the monomer A, the monomer B and the monomer C.

Details of Monomer A, Monomer B, Monomer C, and Monomer D in Table 1 are as follows.
In addition, in calculating the number of moles of each monomer used in this Example, in this specification, the molecular weight of each monomer is tentatively calculated or based on some catalog values and the like. , Set as follows. The weight average molecular weight or the number average molecular weight of the polymer compound is assumed to be a provisional value.

(Monomer A)
C6FMA: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ (C6FMA, manufactured by AGC) Molecular weight 432.2
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) Molecular weight 892.4
C6SFA: CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ (C6SFA, manufactured by Daikin Industries, Ltd.) Molecular weight 418.2

(Monomer B)
LE BZ: Benzyl methacrylate (light ester BZ, manufactured by Kyoeisha Chemical Co., Ltd.) Molecular weight 176.2
PME-1000: Methoxypolyethylene glycol methacrylate (Blemmer ^(R) PME-1000, manufactured by _{NOF CORPORATION) CH 2} = CHCH _3- COO- (C ₂ H ₄ O) n-CH ₃ (n ≈ 23) Weight average molecular weight 1113 .3
PE-200: Polyethylene glycol monomethacrylate (Blemmer ^(R) PE-200, manufactured by _{NOF CORPORATION) CH 2} = CHCH _3- COO- (C ₂ H ₄ O) n-H (n ≈ 4.5) Weight average molecular weight 284.3
VMA-70: _{Behenyl methacrylate (C 22} : 70%; Blemmer ^(R) VMA-70, manufactured by NOF CORPORATION) Has a chain alkyl group. Molecular weight 394.7
LE THF: Tetrahydrofurfuryl methacrylate (light ester THF (1000), manufactured by Kyoeisha Chemical Co., Ltd., structure below) molecular weight 170.2

LE DTD-MA:.. 2--decyl-1-tetradecanyl methacrylate (Light Ester DTD-MA, manufactured by Kyoeisha Chemical Co., Ltd. following structural Incidentally, _CH 3 _(CH 2 to ^{C *} in the following _{structure) 9} - binds .) Molecular weight 422.7
CH ₃ (CH ₂ ) _11- C ^* HCH ₂ O-CO-CCH ₃ = CH ₂
DEAA: N, N-diethylacrylamide. Made by KJ Chemicals. Molecular weight 127.19
BZA: Benzyl acrylate. (Funkril FA-BZA, manufactured by Hitachi Kasei Co., Ltd.) Molecular weight 162.19

(Monomer C)
FM-0711: α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane (Silaplane ^(R) FM-0711, manufactured by JNC Corporation. Structure below) Number average molecular weight 1,000

FM-0721: α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane (Silaplane ^(R) FM-0721, manufactured by JNC Corporation. Structure below) Number average molecular weight 5,000

X-22-2426: Acrylic-modified organopolysiloxane (X-22-2426, manufactured by Shin-Etsu Chemical Co., Ltd. The following structure. The introduced organic groups are also shown.) Functional group equivalent 12,000 g / mol to number average molecular weight Was set to 12,000.

(Monomer D)
MT-PE1: Pentaerythritol tetrakis (3-mercaptobutyrate) (Carens MT ^(R) PE1, manufactured by Showa Denko KK. The following structure.) Molecular weight 544.8

MT-NR1: 1,3,5-Tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione (Karens MT ^(R) NR1 , Made by Showa Denko. The following structure.) Molecular weight 567.7

MT-BD1: 1,4-bis (3-mercaptobutyryloxy) butane (Calens MT ^(R) BD1, manufactured by Showa Denko KK. The following structure.) Molecular weight 294.4

MT-TPMB: Trimethylolpropane Tris (3-mercaptobutyrate) (Carens MT ^(R) TPMB, manufactured by Showa Denko KK. Structure below.) Molecular weight 440.6

[Evaluation of heat resistance of fluorine-containing copolymer (measurement of thermal decomposition temperature)]
The pyrolysis temperature of the fluorine-containing copolymers 1 to 14 synthesized in Synthesis Examples 1 to 14 was measured using a differential thermal thermogravimetric simultaneous measuring device (STA7300, manufactured by Hitachi High-Tech Science Co., Ltd.).
The same applies to Comparative Synthesis Examples 1 to 4.

A pyrolysis test was conducted in which the fluorine-containing copolymer was heated from 50 ° C. to 450 ° C. at a rate of 5 ° C./min to measure the change in the mass of the fluorine-containing copolymer. From the start of the pyrolysis test, the temperature when the temperature was reduced by 5% by mass was obtained.
The temperature when the mass of the fluorine-containing copolymer was reduced by 5% by mass was defined as the thermal decomposition temperature when the mass of the fluorine-containing copolymer was reduced by 5% by mass, and the results obtained as described above were shown in Table 1 ". It is shown in the column of "5% decrease temperature" of "heat resistance of a fluorine-containing copolymer".

-Pyrolysis temperature of the fluorine-containing copolymer The heat resistance of the fluorine-containing copolymer can be evaluated at the above-mentioned thermal decomposition temperature of the fluorine-containing copolymer.
In the present invention, when the decomposition amount of the fluorine-containing copolymer at 250 ° C. is 5% by mass or less, the heat resistance of the fluorine-containing copolymer is considered to be excellent.
On the other hand, when the decomposition amount of the fluorine-containing copolymer at 250 ° C. exceeds 5% by mass, the heat resistance of the fluorine-containing copolymer is considered to be poor.

(Results of heat resistance evaluation of fluorine-containing copolymer)
As shown in the “5% decrease temperature” column of Table 1, the thermal decomposition temperature (5% decrease temperature) of the fluorine-containing copolymers of Synthesis Examples 1 to 14 was 250 ° C. or higher. Further, it was confirmed that the fluorine-containing copolymers of Synthesis Examples 1 to 14 did not cause a steep weight loss at less than 250 ° C. and had excellent heat resistance.

[Manufacturing of molded product] (Manufacturing of test piece for measurement)
(Examples 1 to 14, Comparative Examples 1 to 4)

The thermoplastic resin (polypropylene powder; PPW-5J, manufactured by Seishin Enterprise Co., Ltd.) and each fluorine-containing copolymer or comparative fluorine-containing copolymer are mixed with a thermoplastic resin in an amount of 99.0% by mass, each fluorine-containing copolymer or Each comparative fluoropolymer was prepared at a ratio of 1.0% by mass.
The thermoplastic resin is placed in a stainless petri dish, heated and melted on a hot plate at 200 ° C., and then each fluorine-containing copolymer or each comparative fluorine-containing copolymer is added in the above proportions, and these are added using a spatula. The mixture was stirred and mixed so as to be uniform.
Next, after returning the stainless steel petri dish to room temperature, a molded product (thermoplastic resin-fluorine-containing copolymer mixture. The molded product is disk-shaped, and its size is 48 mm in diameter × 0.4 mm in thickness. ) Was taken out (the above is the step of heat-molding the thermoplastic resin composition).
Each molded product obtained as described above was used as a test piece for measuring the contact angle on the surface of the molded product.

[Evaluation of liquid repellency on the surface of the molded product (measurement of contact angle)]
1. 1. Measurement of Contact Angle Using each test piece prepared as described above, the contact angle of deionized water (DIW) or normal hexadecane (n-HD) was measured under the condition of 23 ° C. A contact angle meter DMo-501 (manufactured by Kyowa Interface Science Co., Ltd.) was used for the measurement.
With the above measuring device, the contact angle 30 seconds (30 s) after the drip of each of the above liquid samples was measured at five different points for the same liquid sample, and each of the contact angles 30 seconds after the drip was obtained. The average value was used as the measurement result of the contact angle (30 s).
The measurement results of the contact angle are shown in the "contact angle evaluation" column (Examples 1 to 14 and comparative examples 1 to 4) of the "molded article" in Table 1.
A molded product was formed in the same manner as in the step of heat-molding the thermoplastic resin composition using only the thermoplastic resin, and the contact angle of the surface of the molded product containing only the thermoplastic resin was measured in the same manner as described above. The results are shown in "PP blank" in Table 1.

<Evaluation criteria for lipophilicity of molded products>
In the present invention, the lipophilicity of the molded product was evaluated by the average value of the contact angles 30 seconds after the normal hexadecane as the liquid sample was dropped (in the "contact angle evaluation" of the "molded product" in Table 1). "N-HD (30s)" column).
In the present invention, when the contact angle (average value) 30 seconds after the normal hexadecane was dropped was 50 ° or less, it was evaluated that the lipophilicity of the molded product was excellent.
It was evaluated that the smaller the contact angle was, the better the lipophilicity of the molded product.
On the other hand, when the contact angle exceeded 50 °, it was evaluated that the lipophilicity of the molded product was poor.

<Evaluation criteria for water repellency of molded products>
The water repellency of the molded product was evaluated by the average value of the contact angles 30 seconds after the deionized water as a liquid sample was dropped (DIW (DIW (DIW) in "Contact angle evaluation" of "Molded product" in Table 1). 30s) ”column).
In the present invention, when the contact angle (average value) 30 seconds after the deionized water was dropped was 110 ° or more, it was evaluated that the water repellency of the molded product was excellent.
It was evaluated that the larger the contact angle was 110 °, the better the water repellency of the molded product.
On the other hand, when the contact angle was less than 110 °, it was evaluated that the water repellency of the molded product was poor.

From the results shown in Table 1, Comparative Examples 1 to 4 containing the comparative fluorine-containing copolymers 1 to 4 having no structural unit based on the (meth) acryloyl compound having silicone had poor lipophilicity of the molded product. rice field.
On the other hand, the molded product of the present invention was excellent in water repellency and lipophilicity.

Examples of the molded product obtained from the composition of the present invention include containers (industrial containers, chemical containers, cosmetic containers, etc.), household products, flooring materials, stationery, and the like.
Since the molded product of the present invention is formed from the composition of the present invention containing a fluorine-containing copolymer having a repeating unit based on a (meth) acryloyl compound having silicone, in addition to water repellency and lipophilicity, It can have the performance of silicone (for example, antifouling property, mold releasability, etc.).

Claims

A thermoplastic resin composition containing a thermoplastic resin and a fluorine-containing copolymer.
The fluorine-containing copolymer includes a repeating unit based on the compound represented by the formula (1), a repeating unit based on a non-fluorine monomer, a repeating unit based on a (meth) acryloyl compound having silicone, and 1 Contains repeating units based on compounds having two or more mercapto groups in the molecule.
The thermal decomposition temperature of the fluorine-containing copolymer is 250 ° C. or higher, and the temperature is 250 ° C. or higher.
The content of the fluorine-containing copolymer is 10% by mass or less in the total content of the thermoplastic resin and the fluorine-containing copolymer.
Thermoplastic resin composition.
CH 2 = CR 1- CO-X-CR 2 R 3- (CH 2 ) n1- (COO) n2- Q 1- Rf 1 (1)
In equation (1):
R 1 represents a hydrogen atom or a methyl group;
X is, -O- or -NR 4 - represents a;
R 2 , R 3 and R 4 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 a 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 equation (r):
Q 2 is a single bond or a divalent linking group;
Rf 2 represents a polyfluoroalkyl group or a 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 the formula (2).
CH 2 = CR 5- Q 3- [Q 4- R 6 ] k (2)
In equation (2):
R 5 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Q 3 are a single bond, -COO -, - CONH-, or an -CON <;
Q 4 are, represents a single bond or 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, a cyclic ether group, or an aromatic ring; and
If Q 3 is a single bond, -COO-, or -CONH-, then k is 1, and if Q 3 is -CON <, then k is 2.
The thermoplastic resin composition according to claim 1 or 2, wherein the compound having two or more mercapto groups in one molecule has two or more groups represented by the formula (3) in one molecule.
-OCO- (CH 2) a -CHR 7 - (CH 2) b -SH (3)
In equation (3):
a represents an integer of 0 to 2;
b represents 0 or 1;
R 7 represents an alkyl group having 1 or 2 carbon atoms.
The thermoplastic resin composition according to any one of claims 1 to 3, wherein the (meth) acryloyl compound having silicone is a compound represented by the following formula (4).
CH 2 = CR 8 -Q 5 -Q 6 - (SiR 9 2 -O-) n-SiR 10 3 (4)
In equation (4):
R 8 represents a hydrogen atom or a methyl group;
Q 5 represents -COO-, or -CONH-;
Q 6 represents a single bond or a divalent linking group;
R 9 and R 10 each independently represent a hydrocarbon group; and
n represents 2 or more.
A molded product obtained by heat-molding the thermoplastic resin composition according to any one of claims 1 to 4.
The molded product according to claim 5, 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 product, comprising a step of heat-molding the thermoplastic resin composition according to any one of claims 1 to 4.
The manufacturing method according to claim 7, wherein in the heat molding step, heat molding is performed by any molding method selected from the group consisting of extrusion molding, injection molding and blow molding.