JPH036210A - Fluoropolymer - Google Patents

Abstract

PURPOSE:To obtain a fluoropolymer excellent in oil and water repellency, flexibility, durability, adhesiveness, dispersion stability, etc., by graft-polymerizing fluoroalkyl (meth)acrylate onto a polymer comprising a specified monomer system. CONSTITUTION:A fluoroalkyl (meth)acrylate, e.g. CH2=CHCOOCH2C10F21, is graft-polymerized in the presence of a polymerization initiator, e.g. benzoyl peroxide, onto a polymer prepared from a system at least containing a monomer of formula I (wherein R<1> and R<2> are each H or CH3; X is halogen; (l), (m1), (m2) and (n) are each 1-10) or formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a fluorine-containing polymer, and more specifically, to water-repellent materials such as fibers, paper, plastic surfaces, metal surfaces, printing inks, electrophotographic toners, paints, etc. This invention relates to a fluorine-containing graft copolymer useful as an oil dispersant.

[Prior art]

Conventionally, fiber 1 paper, plastic surface, metal surface, paint,
Fluorine-containing acrylate copolymers, fluorine-containing polyether copolymers, fluorine-containing urethane oligomers, and the like are used as water- and oil-repellent treatment agents for printing inks and the like. However, although these are satisfactory in terms of water and oil repellency, they have other properties such as durability and flexibility (especially when used on textiles and paper).
, adhesion (related to durability), dispersion stability (particularly when used in paints and printing inks), etc.

A method in which organopolysiloxane is used as a softening component in combination with the above-mentioned fluorine-containing treatment agent or separately in a two-stage treatment for the purpose of improving durability and flexibility (Japanese Patent Application Laid-Open No. 59-157)
No. 380) has been proposed. However, although these methods have a satisfactory level of durability, they have not yet been sufficiently effective in terms of flexibility.

In addition, in an attempt to introduce softening ingredients into water and oil repellent treatment agents, we have developed fluorine-containing (meth)acrylate and siloxane-containing (meth)acrylate.
Method by copolymerization with acrylate (JP-A-60-13
0408), a method using a reaction product of a fluorine-containing urethane compound and a reactive organopolysiloxane (JP-A-60-81278), a method using an organopolysiloxane having a perfluoroalkyl group in the side chain (
Japanese Patent Publication No. 61-6187) is known, but processing agents with high flexibility tend to have low initial performance or durability, and processing agents with high durability tend to have poor texture.

As described above, although conventional water and oil repellent treatment agents can impart water and oil repellency, it is difficult to simultaneously satisfy durability, flexibility, adhesion, dispersion stability, etc. [Solved by the invention] [Objective] The present invention solves the above-mentioned deficiencies in conventional oil and water repellent treatment agents, and can simultaneously impart properties such as oil and water repellency, flexibility, durability, adhesion, and dispersion stability. The object of the present invention is to provide a fluorine-containing polymer (fluorine-containing graft copolymer).

[Means to solve the problem]

The fluorine-containing polymer of the present invention can be produced by monomer A represented by the following general formula (1) or by the general formula (
It is characterized in that it is obtained by graft polymerizing fluoroalkyl acrylate or fluoroalkyl methacrylate to a polymer polymerized from a system containing at least monomer A2 represented by If).

(However, R1 and R2 are -H or -CH3, X is a halogen, fi, +111.m, and n are integers of 1 to 20.

)1 CH2-C-C-0-CnH,,Q (I
I) (However, R1 and n are the same as in (1) above) Incidentally, in order to achieve the above object, the present inventors conducted various studies and found that a specific fluorine-containing polymer is water and oil repellent. It has been confirmed that it is extremely useful as a processing agent. The present invention has been achieved thereby.

The present invention will be explained in more detail below.

Briefly speaking, the fluorine-containing polymer of the present invention has a fluorine-containing backbone polymer containing monomer A represented by the general formula (r) or monomer A2 represented by the general formula (n) as a constituent unit. It consists of polymerized monomers.

Here, representative examples of monomer A and monomer A2 are as follows. In addition, A knee 1. A1-2o
. . . is an example of monomer A□, and A2-1°A, -21, . . . is an example of monomer A2.

(A, -1) co, =c++coocu, cH,
o (3 (A, -2) CH,=C(CH,)CO
OCH, CH2 $ (At-3) CH2 shrimp cutting F12
CH2C1l □ mouth (A, '-4) cH, -c (
co,)coocu,cH,co2co2cH,Qfu(
A, -5) CH2-C) l-Coo (numb u, ], o
-1q mouth (A, -6) C112-C (CH,)C
CO(C12CH2), $(A2-7) Coz<u
coo(CH,C)+2>1oe(A,-11)
CH,=C'(CH3)-Coo(CH2Cl,)G-
伽(A, -9) cH2-c++-coo(co2
cH2), -勺(A2-10) CH,=C(C
H,)-COO(C12CH,), -d In the present invention, in order to further improve durability, adhesiveness, dispersion stability, etc., the axial polymer constituting the fluorine-containing graft copolymer is (1) or (n) structural unit and general formula (III
) "(Ct(, -9+ (■) [However, R1 is the same as general formula (1), Z is -COOCnL n
+, or -0C0CnHz n+z (n is an integer from 6 to 20).

The fluorine-containing graft copolymer of the present invention is produced by combining the above-mentioned axial polymer containing the structural unit (I) or (II) with a fluorine-containing monomer in a non-aqueous solvent in the presence of a 5-polymerization catalyst, if necessary. It can be produced by heating reaction.

Here, the axial polymer may be a homogeneous polymer having the above-mentioned -Momona (1) or (II) as a constituent unit, or it may be a homogeneous polymer having the above-mentioned -Momona (1) or (II) as one of the constituent units. It may be a copolymer containing In the case of homogeneous polymers, the general formula (
By polymerizing a monomer corresponding to 1) or (II) (hereinafter sometimes simply referred to as "monomer A") by a conventional method, or in the case of a copolymer, containing this general formula (1) or (II) It can be obtained by copolymerizing monomer A with another polymer monomer, particularly a monomer corresponding to the structural unit of the above-mentioned -mono (m) (hereinafter sometimes referred to as "r monomer B") by a conventional method.

Examples of other polymerizable monomers include monomers with polar groups (hereinafter sometimes referred to as "monomer C") and lower vinyl monomers (hereinafter referred to as "monomer D").
) can be used.

In addition, in order to improve dispersion stability, especially for axial polymers,
An olefin polymer or copolymer skeleton can be introduced.

Monomer A containing general formula (1) or (II) is a monomer that provides grafting points to the axial polymer, and is
The larger the number of 7mers in 1) or (II), the more graft points can be formed, but if there are too many, crosslinking reactions occur within or between molecules, making it difficult to obtain stable dispersion. Therefore, in the present invention, it is preferable to use a copolymer as the axial polymer. In this case, -
The polymerization ratio of the pattern (1) or (II)-containing monomer A/other polymerizable monomer is preferably 0.1 to 50,150 to 90.

Next, Shitsummer B, which corresponds to general formula (m), is used to further improve durability, adhesiveness, and dispersion stability. Specific examples include lauryl acrylate, lauryl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, dodecyl methacrylate, dodecyl acrylate, hexyl methacrylate, hexyl acrylate, octyl acrylate, octyl methacrylate, cetyl methacrylate, cetyl acrylate, vinyl laurate,
Vinyl stearate, nonyl methacrylate, nonyl acrylate, decyl methacrylate, decyl acrylate, cyclohexyl methacrylate.

Examples include cyclohexyl acrylate.

Monomer C having a polar group (carboxyl group, glycidyl group, hydroxyl group, etc.) is a monomer that, like monomer B, contributes to improving adhesiveness, flexibility, dispersion stability, etc. Specific examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid. Examples of monomers having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, glycidylpropyl methacrylate, glycidylpropyl acrylate, and glycidylbutyl. Examples include acrylate, glycidyl butyl methacrylate, hydroxyethyl methacrylate, and hydroxyethyl acrylate.

In addition, the lower vinyl monomer C is a monomer for improving film-forming properties and adhesive properties, and its specific examples include methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl methacrylate,
Propyl acrylate, n-butyl methacrylate, 1
so-butyl methacrylate, vinyl acetate, vinyltoluene, styrene, p-chlorostyrene, divinylbenzene, diethylene glycol dimethacrylate, trimethylolpropyne trimethacrylate, dimethylaminoethyl methacrylate, acrylonitrile, vinylpyrrolidone, vinylpyridine, dimethylaminomethyl methacrylate, etc. can be mentioned.

In addition, an olefin polymer or copolymer can be introduced into the backbone of the axial polymer, particularly for improving dispersion stability. Such olefin polymers or olefin copolymers include polyethylene (especially what is called polyethylene wax), polypropylene (especially what is called polypropylene wax), and ethylene-propylene copolymers.

Ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-acrylic acid copolymer, ethylene-vinyl acetate-acrylic acid copolymer, ethylene-propylene-maleic vinegar copolymer, propylene-ethyl acrylate copolymer, ethylene-ethyl acrylate Examples include glycidyl methacrylate copolymer, propylene-maleic anhydride copolymer, and the like. In addition, by adding these to one reaction system during the production of the axial polymer, a skeleton of a polymer or copolymer of these olefins can be imparted to the axial polymer obtained.

On the other hand, examples of fluorine-containing monomers to be graft-polymerized onto the above-mentioned axial polymer include fluoroalkyl acrylate (
The fluoroalkyl moiety is =CH, CF.

-CH,C,F,, -CH,C3F,, -CHtCJ*
,-CB,,C,F,,,-C)I,C,Fl=CH
,C,lF□7+ -CHlC,F Engineering,,, -CH2
C1,F.

), fluoroalkyl methacrylate (the fluoroalkyl moiety is -C)I, CF, , -C)l, (CF2C
F, ), H, -C) I2CH, C, F7. -(C1,)
GC, F Engineering 7, C) I, (CF2CF, ), Hl
-CH.

(CF o CF2) 4H1-(CHz )z (CFz
)t CFs , -CHz Cz. F, □, etc.).

In the production of the fluorine-containing graft copolymer of the present invention, the polymerization ratio of the axial polymer and the fluorine-containing monomer is usually 50 to 9971.
-50, preferably 70-90/10-30.

In addition, the polymerization catalyst used in the production of this fluorine-containing graft copolymer is azobisisobutyronitrile (AI
BN), benzoyl peroxide (BPO), phenylazotriphenylmethane, lauryl peroxide, di-t-butyl peroxide, t-butyl peroxide, cumene hydroperoxide, and the like.

Non-aqueous solvents include petroleum aliphatic hydrocarbons such as kerosene, ligroin, n-hexane, n-hebutane, n-octane, and i-dodecane (commercially available products include Isopar H, G, and Naphtha manufactured by Efsan); &6; Tsurpets 10
Examples include halogenated aliphatic hydrocarbons, such as carbon tetrachloride and perfluoroethylene. A small amount of an aromatic solvent such as toluene or xylene can also be added to these aliphatic hydrocarbon solvents.

The fluorine-containing graft copolymer obtained as described above has a particle size of about 0.1 to 51A, has good dispersion stability, and has intermolecular adhesive strength, so it is particularly suitable as a material for paints, printing inks, and toners. There is.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 In a flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping funnel, 100 g of lauryl methacrylate and the compound (A
Add 3g of monomer of 1-1) and BPOIg, and heat to 80°C.
In the first step, a polymerization reaction was carried out for 4 hours, in which CH2=
CHC00CH, C engineering a Fz 15g and BPO0,2
g was added dropwise through the dropping funnel over a period of 91 hours, and graft polymerization was carried out at 80°C. The polymerization rate was 97%, and the contact angle of the obtained fluorine-containing graft polymer was 27° with water and 30" with kerosene.
Met.

For comparison, 100 g of lauryl methacrylate, 10 g of monomer A of compound Nci (A1-1), and CH2=C
HCH,C.

In the case of a comparative copolymer obtained by reacting 5 g of F2□ and 1.2 g of BPO at 80°C for 1 hour, the contact angle was 11° with water and 15° with kerosene, and the contact angle of the product of the present invention was 11° with water and 15° with kerosene. was found to have high water and oil repellency.

Example 2 100g of kerosene was taken into the same flask as in Example 1, and 9
Heated to 0°C. While stirring, 90 g of 2-ethylhexyl methacrylate, monomer Log of the compound (A1-3) and 2 g of BPo were added, and a polymerization reaction was carried out for 6 hours. Next, CH2=C(CH3)COOCH
, CH, C3F, 10 g and 0.5 g of BPO were added and graft polymerized at 80°C for 5 hours. The polymerization rate was 93.
The contact angle of the resulting fluorine-containing graft copolymer was 40'' with water and 52° with kerosene.First, a cloth was impregnated with the fluorine-containing graft copolymer of the present invention for surface treatment. I washed this in the washing machine 10 times, and the contact angle with water was 40'.
Considerable durability was observed. Flexibility was also good.

Example 3 400 g of Isopar G was placed in a flask similar to Example 1, heated to 90°C, and while stirring, 200 g of cyclohexyl acrylate, tog monomer of the above compound (80-6), 5 g of methacrylic acid, and glycidyl methacrylate were added. A 7-mer solution consisting of 10 g of BPo and 3 g of BPo was added thereto, and the polymerization reaction was carried out at the above temperature for 4 hours. Thereto was added 1 g of vinylpyridine O, and the polymerization reaction was carried out at 80° C. for 10 hours. Next, in this, CH2=C(Cl(3)COO
CH.

(CF, CF,), 050g, add AIBN3g,
Graft polymerization was carried out at the above temperature for 1 hour. As a result, the polymerization rate was 97%, the contact angle of the obtained fluorine-containing graft copolymer was 25" with water, and 231 with kerosene.

Note that the dispersion containing this fluorine-containing graft copolymer did not sediment even if it was left at room temperature for more than 6 months.

Example 4 Polyethylene wax (AC polyethylene 1l103 manufactured by Allied Chemical Co., Ltd.) 50% was added to the flask used in Example 1.
was taken and heated and dissolved at 90°C. A 7-mer solution consisting of 100 g of methyl methacrylate, 20 g of the monomer of the compound (AL-9), 1 g of acrylic acid, 8 g of glycidyl acrylate, and AIBNlog was added dropwise to this solution over a period of 2 hours using a dropping funnel, and the mixture was stirred at the above temperature for 6 hours.
The polymerization reaction was carried out for a period of time. Next, methyl methacrylate 10
0g, C)12=C(CH3)COOC82G2°F
Add 50g of 4m and 5g of t-butyl peroxide,
Further, the graft polymerization reaction was carried out at 130° C. for 6 hours with stirring, and the zero polymerization rate was 98.5″M, and the contact angle of the obtained fluorine-containing graft copolymer was 30″ with water and 40″ with kerosene.

Furthermore, when this fluorine-containing graft copolymer was hot-melt bonded to a polyethylene phrephthalate film, both adhesiveness and flexibility were good.

Example 5 A graft polymer was obtained in exactly the same manner as in Example 1 except that the compound (A, -1) was used instead of the compound (A-nee 1). The 0 polymerization rate was 93%, and the obtained content was The contact angle of the fluorine graft copolymer is 25.8' with water and 29' with kerosene.
．． It was 3”.

For comparison, 100 g of lauryl methacrylate, 10 g of the monomer A of the compound Nα(A□-1), and CH,=
CHCH2cooc,. Fzz5g and BPO1,2
In the case of the comparative copolymer obtained by reacting at 80°C for 1 hour in the presence of
6, indicating that the product of the present invention has greater water and oil repellency.

Example 6 A graft polymer was obtained in exactly the same manner as in Example 2 except that the compound (A2-3) was used instead of the compound (Ai-3). The 1 polymerization rate was 94.0%. The contact angle of the fluorine-containing graft copolymer is 38° with water and 51' with kerosene.
Met. Next, a cloth was impregnated with the fluorine-containing graft copolymer of the present invention and surface-treated. This was washed in the washing machine 10 times, and the contact angle with water was 37.8', indicating considerable durability. Flexibility was also good.

Example 7 A graft polymer was obtained in exactly the same manner as in Example 3, except that the compound (A, -6) was used instead of the compound (A1-S). As a result, the polymerization rate was 97%, the contact angle of the obtained fluorine-containing graft copolymer was 27° with water, and 2
It was 2″.

Note that the dispersion containing this fluorine-containing plant copolymer did not settle even if it was left at room temperature for more than 6 months.

Example 8 A graft polymer was obtained in exactly the same manner as in Example 4, except that the compound (Am-7) was used instead of the compound (A, -9). The polymerization rate was 97%, and the contact angle of the obtained fluorine-containing graft copolymer was 31° with water and 43'' with kerosene.

Next, when this fluorine-containing graft copolymer was hot-melt bonded to a polyethylene terephthalate film, both adhesiveness and flexibility were good.

〔Effect of the invention〕

The fluorine-containing graft copolymer of the present invention not only has sufficient water and oil repellency effects, but also has durability, flexibility, and adhesive properties.

Since it satisfies other properties such as dispersion stability, it is suitable as a water and oil repellent for paints, printing inks, electrophotographic toners, fiber paper, plastic surfaces, metal surfaces, etc.

Claims (1)

[Claims] (1) In the presence of a polymerization initiator, a fluoroalkyl acrylate or a fluoroalkyl A fluorine-containing polymer characterized by being obtained by graft polymerizing methacrylate. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, R^1 and R^2 are -H or -CH_3, X is halogen, and l, m_1, m_2 and n are integers from 1 to 20. )
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [However, R^1 and n are the same as in (I) above] (2) The monomer copolymerized with the above monomer A_1 or monomer A_2 has the following general formula (III ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) [However, R_1 is -H or -CH_3, Z is -C00C
qH_2q_+_1 (q is an integer from 1 to 20). ] The fluorine-containing polymer according to claim 1, which is a monomer represented by the following.