JPH07110928B2 - Fluorine-modified wax composition, its manufacturing method, and resin modifier - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wax composition, a method for producing the same, and a resin modifier.

[0002]

2. Description of the Related Art As a wax composition used as a resin modifier, for example, polyethylene wax, polypropylene wax, carnauba wax, etc. have been known. When these are used in combination with a resin used in molded products, paints, printing inks, etc., they fulfill the functions of improving the dispersibility of pigments and fillers and improving the moldability of resins.

[0003]

However, the conventional one is
Although it functions as a wax as described above, there is a problem that it is insufficient when the resin to be used is required to have further improved water repellency, improved blocking resistance, improved abrasion resistance, and improved lubricity. It was

[0004]

As a result of intensive studies to solve these problems, the present inventors have found that a specific fluorine-modified wax composition can meet the above-mentioned requirements, and The invention was reached. That is, the present invention is
A fluorine-modified wax composition obtained by graft-polymerizing a vinyl compound (b) having a fluorine-containing alkyl group having 3 to 20 carbon atoms into the wax (a) and having a fluorine atom content of more than 5% and 70% or less. Thing; wax (a) has 3 carbon atoms
To 20 vinyl radical compound (b) having a fluorinated alkyl group in the presence of a polymerization initiator (c) at 50 to 250 ° C. by radical polymerization, and a method for producing a fluorine-modified wax composition; It is a resin modifier comprising a composition.

In the present invention, examples of the wax (a) include waxes having a number average molecular weight of usually 300 to 30,000, preferably 400 to 15,000.
Specific examples of (a) include the following. Two or more of the following may be used in combination. Synthetic wax a Synthetic hydrocarbon wax (Fisher / Tropsch wax, polyethylene wax, polypropylene wax, etc.). B. Hydrogenated wax (hardened castor oil, hardened castor oil derivative, etc.). Petroleum wax (paraffin wax, microcrystalline wax, petrolatum, etc.). Natural wax (i) Plant wax (carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, etc.). (B) Animal wax (beeswax, lanolin, whale wax, etc.) c Mineral wax (montan wax, ozokerite, ceresin, etc.). Is mentioned. Further, a modified wax obtained by further introducing a carboxyl group, a halogen group, an ester group, a hydroxyl group, an amide group, an amino group or the like into the above wax may be used. Among these, preferred are synthetic hydrocarbon wax, petroleum wax and carboxyl group-modified wax, and particularly preferred are synthetic hydrocarbon wax and carboxyl group-modified synthetic hydrocarbon wax.

The fluorine-containing alkyl group contained in the vinyl compound (b) usually has 3 to 20 carbon atoms, preferably 4 to 16 carbon atoms.
Is. The fluorine-containing alkyl group in (b) is usually 1 to 3
It is an individual. Specific examples of (b) include the following (a) to
Each compound of (i) is mentioned. (In each of the structural formulas below, Me
Represents a methyl group, Et represents an ethyl group, and Pr represents a propyl group. ) (A) Fluorine-containing alkyl ethylene: C ₄ F ₉ CH = CH ₂ , C ₆ F ₁₃ CH =
CH ₂ , C ₈ F ₁₇ CH = CH ₂ , C ₁₀ F ₂₁ CH = CH ₂ , C ₁₂ F ₂₅ CH = CH ₂ , C ₁₄ F
₂₉ CH = CH ₂ , C ₁₆ F ₂₇ CH = CH _2, etc. (B) Fluorine-containing alkylallyl: C ₄ F ₉ CH ₂ CH = CH ₂ , C ₆ F ₁₃ CH
₂ CH = CH ₂ , C ₈ F ₁₇ CH ₂ CH = CH ₂ , C ₁₀ F ₂₁ CH ₂ CH = CH _2, etc. (C) Compounds having a fluorine-containing alkyl group and a (meth) acryloyl group: C ₇ F ₁₅ CH ₂ OCOCH = CH ₂ , C ₇ F ₁₅ CH ₂ OCOC (Me) = CH
₂ , CF ₃ (CF ₂ ) ₂ CH ₂ OCOC (Me) = CH ₂ , C ₆ F ₁₃ (CH ₂ ) ₂ OCOCH = C
H ₂ , C ₈ F ₁₇ (CH ₂ ) ₂ OCOCH = CH ₂ , C ₁₀ F ₂₁ (CH ₂ ) ₂ OCOCH = CH ₂ , C
₇ F ₁₅ CH ₂ OCOC (Me) = CH ₂ , CF ₃ (CF ₂ ) ₂ CH ₂ OCOC (Me) = CH ₂ , C ₆ F
₁₃ (CH ₂ ) ₂ OCOC (Me) = CH ₂ , C ₈ F ₁₇ (CH ₂ ) ₂ OCOC (Me) = CH ₂ , C ₁₀
F ₂₁ (CH ₂ ) ₂ OCOC (Me) = CH ₂ , C ₁₂ F ₂₅ (CH ₂ ) ₂ OCOC (Me) = CH ₂ , C
₁₄ F ₂₉ (CH ₂ ) ₂ OCOC (Me) = CH ₂ , C ₁₆ F ₃₃ (CH ₂ ) ₂ OCOC (Me) = C
H ₂ , C ₈ F ₁₇ (CH ₂ ) ₁₁ OC OC (Me) = CH ₂ , C ₇ F ₁₅ CON (Et) (CH ₂ ) ₂ OC
OC (Me) = CH ₂ , C ₆ F ₁₃ SO ₂ N (Me) (CH ₂ ) ₂ OCOCH = CH ₂ , C ₈ F ₁₇ SO ₂
N (Pr) (CH ₂ ) ₂ OCOCH = CH ₂ , C ₈ F ₁₇ SO ₂ N (Me) (CH ₂ ) ₂ OCOC (Me) =
CH ₂ , C ₈ F ₁₇ SO ₂ N (Me) (CH ₂ ) ₁₀ OCOCH ₂ CH = CH ₂ , C ₈ F ₁₇ SO ₂ N
_{(CH 2 CH 2 OCOCH = CH} 2) 2, HCF 2 (CF 2) 7 CH 2 OCOC (Me) = CH 2.

[0007]

[Chemical 1]

[0008]

[Chemical 2]

[0009]

[Chemical 3]

[0010]

[Chemical 4]

(D) Maleic acid mono- or diester having a fluorine-containing alkyl group: C ₈ F ₁₇ (CH ₂ ) ₁₁ OCOCH = CHCOOM
e, C ₈ F ₁₇ (CH ₂ ) ₁₁ OCOCH = CHCOOCH ₂ C ₇ F _15, etc. (E) Vinyl ether or allyl ether having a fluorine-containing alkyl group: C ₇ F ₁₅ CH ₂ OCH = CH ₂ , C ₇ F ₁₅ CH ₂ OCH ₂ CH = CH
_2nd prize. (F) Compounds having a fluorine-containing alkyl group and a vinyl sulfone group: C ₈ F ₁₇ SO ₂ NHCH ₂ SO ₂ CH = CH _2, etc. (G) Amine having a fluorine-containing alkyl group [C ₈ F ₁₇ CH ₂ CH ₂ N
H ₂ , (C ₆ F ₁₃ CH ₂ CH ₂ ) ₂ NH, etc.], and a vinyl compound [Glycidyl (meth) acrylate] having a group reactive therewith,
(Meth) acrylic acid, (meth) acrylic acid isocyanate
Toethyl etc.] was reacted. (H) Alcohol having a fluorine-containing alkyl group (C ₈ F ₁₇ CH ₂
CH ₂ OH, etc.) is reacted with a vinyl compound having a reactive group with it [glycidyl (meth) acrylate, (meth) acrylic acid, isocyanatoethyl (meth) acrylate, etc.]. (I) Carboxylic acid having a fluorine-containing alkyl group (C ₈ F ₁₇ COO
H, etc.), a vinyl-based compound having a group reactive therewith [glycidyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (methylol) acrylamide, etc.] What reacted.

Of the compounds exemplified in (a) to (i), preferred are (a) and / or (c).

The composition of the present invention comprises (a) and (b) graft-polymerized. During this graft polymerization, another vinyl-based monomer (copolymerizable with (b) ( d)
You may use together. Specific examples of the monomer (d) include methyl (meth) acrylate, butyl (meth) acrylate, styrene, glucidyl (meth) acrylate,
Examples thereof include (meth) acrylic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and (methylol) acrylamide. The amount when (d) is used in combination is usually 0 to 1500 parts with respect to 100 parts by weight of (b).

The content of fluorine atoms in the fluorine-modified wax composition of the present invention is usually more than 5% and 70% or less.
When it is at most 5%, good water repellency, abrasion resistance and lubricity will not be exhibited as a resin modifier. If it exceeds 70%,
The composition has tackiness and the blocking resistance becomes extremely poor as a modifier for resin.

The softening point of the fluorine-modified wax composition is usually 40 to 200 ° C, preferably 60 to 170 ° C.

The composition of the invention is obtained by the method of the invention. To further explain the method of the present invention, a fluorine-modified wax composition is obtained by heating and melting (a) under an inert gas atmosphere, adding (b), and using a polymerization initiator (c) to carry out graft polymerization. To be At this time, instead of heating and melting (a), graft polymerization may be performed in the same manner as described above except that (a) is dissolved or dispersed using the solvent (e).

In the method of the present invention, the polymerization initiator (c) is a peroxide (benzoyl peroxide,
Dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,4-bis (t-
Butylpa-oxyisopropyl) benzene, lauroylperoxide, t-butylperoxide, t-butylperoxybenzoate, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3,2,5 -Dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl 2,5-di (t-butylperoxy) hexane, t-butylper-benzoate, t-butylper- Phenylacetate, t-butylper-isobutyrate, t-butylper-sec-octoate, t-butylperpivalate, cumylperpivalate, t-butylperdiethylacetate, etc.); and azo series Examples thereof include compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.). Among these, preferred is peroxide.

The amount of the polymerization initiator (c) added to the total weight of (a), (b) and (d) is (a), (b),
It can be varied within a wide range depending on the type of (d), reaction temperature and the like. The preferred range is 0.01 to 0.01 parts by weight of the polymerization initiator (c) based on 100 parts by weight of the total of (a), (b) and (d).
40 parts by weight, particularly preferably 0.03 to 10 parts by weight.

As the solvent (e), aromatic hydrocarbons (toluene, xylene, ethylbenzene etc.), aliphatic hydrocarbons (hexane, heptane, cyclohexane etc.), aliphatic esters (ethyl acetate, n-butyl acetate etc.) , Aliphatic ketones (acetone, methyl ethyl ketone,
Methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.), aliphatic ethers (dioxane, tetrahydrofuran, etc.), alcohols (isopropanol, n-butanol, etc.), cellosolve (ethyl cellosolve, n-butyl cellosolve, cellosolve acetate, etc.), halogenated Hydrocarbons (carbon tetrachloride, ethylene dichloride, etc.) and the like, and mixtures of two or more thereof are included. Preferred are aromatic hydrocarbons, aliphatic esters, aliphatic ketones, aliphatic hydrocarbons alone or as a mixture of two or more thereof.

When the solvent (e) is used, the weight ratio of the solvent (e) to the total of (a), (b) and (d) can be arbitrarily selected, but is usually 1/10 to 10/0, preferably Is 1/2
~ 5/1. In the graft polymerization, (b) may be mixed with (a) from the beginning or added at any time, but the polymerization initiator (c) is preferably added at any time.

The conditions for the graft polymerization are the polymerization initiator (c)
The reaction temperature is usually 50 to 250 ° C., preferably 70 to 200 ° C., and the reaction time is usually 1 to
8 hours. After the reaction, the solvent is removed from the product if necessary. The end point of the reaction can be checked by infrared analysis when the absorption of the double bond disappears.

The fluorine-modified wax composition of the present invention usually contains an unreacted substance of (a) in addition to the fluorine-modified wax.

The properties of the fluorine-modified wax composition of the present invention are different from the mixture of the wax (a) and the homopolymer of the vinyl compound (b). For example, the fluorine-modified wax composition of the present invention is dissolved or uniformly dispersed in heated xylene, but in the case of a mixture of a homopolymer of the wax (a) and the vinyl compound (b), separation is non-uniform and separation occurs. Occur.

When the fluorine-modified wax composition of the present invention is used as a resin modifier, the resin of interest is vinyl chloride resin, polyolefin resin (polyethylene, polypropylene, etc.), polystyrene resin (polystyrene, AS resin). , ABS resin, MBS resin, etc., polyester resin (polyethylene terephthalate, polybutylene terephthalate, polycarbonate, etc.), polyamide resin (6 nylon, 6,6 nylon, 11 nylon, 12)
Nylon etc.), aromatic polyether resins (polyphenylene ether etc.) and the like.

The fluorine-modified wax composition of the present invention can be added to a resin together with other resin additives according to various uses. Examples of other resin additives include heat stabilizers, antioxidants, ultraviolet absorbers, pigments and fillers, plasticizers and antistatic agents.

When the fluorine-modified wax composition of the present invention is added to the resin, it may be added to the total amount of the resin together with other resin additives (as exemplified above) used for various purposes, Alternatively, the wax composition of the present invention may be dispersed in a resin in a high concentration in advance to form a master batch, and the master batch may be mixed with a resin or another resin additive.

As a mixer for mixing the fluorine-modified wax composition of the present invention with a resin, known mixers such as a Henschel mixer, an extruder, a Brabender, and a kneader are used.
And a Banbury mixer. These mixers can be similarly used in the case of the above master-batch and in the case of mixing with other resin additives.

The fluorine-modified wax composition of the present invention is useful as a modifier for resins and an additive for products containing various resins. That is, as a moldability improver for various resins, an additive for paints, a dispersant for pigments and fillers, a printing ink additive, a floor wax additive, a surface modifier, a fiber treating agent, a paper treating agent, etc. Can be used. When used in such applications, the addition amount of the fluorine-modified wax composition of the present invention is usually 0.001 to 5 with respect to 100 parts by weight of the target resin.
It is 0 part by weight, preferably 0.01 to 30 parts by weight.

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Parts and% in production examples and examples are based on weight.

Example 1 70 parts of Fischer-Tropsch wax [Sasol Wax H2, manufactured by Sazol Co.] were put in a Kolben, and 16 parts were added.
The mixture was heated to 0 ° C. and melted, and then perfluoroalkylethylene [Fluowe] was added under a nitrogen atmosphere and stirring conditions.
t V3196-612 Hoechst Co., Ltd.] 30 parts and 5.0 parts of di-t-butylperoxide were added dropwise over 1 hour and then the reaction was continued under the same conditions for 1 hour to give the fluorine-modified wax of the present invention. A composition A ¹ was obtained. The IR (infrared absorption spectrum) of A ¹ shows 1648 due to the carbon-carbon double bond.
There was no absorption of cm ^-1 .

Example 2 Polyethylene wax [Polywax 10 was added to Kolben.
00, manufactured by Petrolite Co., Ltd.] was added and heated to 170 ° C. and melted. Under a nitrogen atmosphere and stirring conditions, perfluoroalkyl methacrylate [NOXGUARD was used.
FAMAC-M, manufactured by Nippon Mektron Ltd.] 23 parts, maleic anhydride 2 parts, and dicumylperoxide 6.
A solution prepared by dissolving 0 parts in 6.0 parts of xylene was added dropwise over 1 hour, and then a solution prepared by dissolving 3.0 parts of dicumylperoxide in 3.0 parts of xylene was added dropwise over 0.5 hours, and thereafter. The reaction was continued under the same conditions for 1 hour. Xylene is removed from the reaction product to obtain the fluorine-modified wax composition A of the present invention.
Got ² The IR (infrared absorption spectrum) of A ² did not show absorption at 1648 cm ⁻¹ due to the carbon-carbon double bond.

Example 3 100 parts of xylene to Kolben, maleic acid-modified low molecular weight polyethylene [MPX-2000, Sanyo Chemical Industry Co., Ltd.
Manufactured] and heated to 140 ° C. and dissolved therein, and under a nitrogen atmosphere and stirring conditions, 20 parts of perfluoroalkyl methacrylate [NOXGUARD FAMAC-M, manufactured by Nippon Mektron Co., Ltd.], Di-t-butylper
After dropwise adding 4.0 parts of oxide over 1 hour, di-t-
2.0 parts of butylperoxide was added dropwise over 0.5 hour, and the reaction was continued for 1 hour under the same conditions to remove the solvent from the reaction product to obtain a fluorine-modified wax composition A ³ of the present invention. .

Example 4 100 parts of xylene in Kolben, polyethylene wax [Sun Wax 151P, manufactured by Sanyo Chemical Industry Co., Ltd.] 75
Parts and perfluoroalkyl methacrylate [NOXG
UARD FAMAC-M, manufactured by Nippon Mektron Ltd.]
25 parts was added, the temperature was raised to 140 ° C. and dissolved, 6.0 parts of di-t-butylperoxide was added dropwise over 1.5 hours under a nitrogen atmosphere and stirring conditions, and then under the same conditions for 1 hour. The reaction was continued at. Xylene was removed from the reaction product to obtain the fluorine-modified wax composition A ⁴ of the present invention. The IR (infrared absorption spectrum) of A ⁴ did not show absorption at 1648 cm ⁻¹ due to the carbon-carbon double bond.

Examples 5 to 8 and Comparative Example 1 Performance Test A performance test as an additive for vinyl chloride resin was conducted using the fluorine-modified wax compositions A ^{1 to} A ⁴ . As a comparative example, polyethylene wax [Sun Wax LEL-40
0P, manufactured by Sanyo Chemical Industry Co., Ltd.] was used to perform the same performance test.

The composition of each vinyl chloride resin compound, the kneading conditions of the compound, and the evaluation items are as follows. Further, Table 1 shows the fluorine-modified wax compositions or sun waxes used in Examples 5 to 8 and Comparative Example 1, respectively. The performance test results are shown in Table 1.

[Vinyl chloride resin composition] Vinyl chloride resin [Kaneka Vinyl S1001, manufactured by Kaneka Corporation] 100 parts by weight Calcium stearate 2.5 parts by weight Zinc stearate 1.0 part by weight Octyl tin maleate polymer 0.5 parts by weight Each fluorine-modified wax composition or sun wax 0.5 parts by weight

[Kneading conditions of compound] Kneader Plastomill Temperature 180 ° C Rotor speed 50 rpm Mixing head volume 60 ml Input sample amount 72 g Preheating time 3 minutes

[Evaluation Items] Water repellency: The contact angle of water at 20 ° C. of the film obtained by pressing was measured. (Unit: degree) Blocking resistance: 1 to the film obtained by pressing.
A heat panel at 00 ° C was applied for 30 seconds, and the surface condition of the film was observed. (○: No abnormality, ×: Fused to heat panel) Abrasion resistance: A film obtained by a pressure press is subjected to an abrasion test with a taper type abrasion tester to measure the abrasion amount per 1 cm ^2. did. (Unit: g, H22, load: 1000 gf, number of rotations: 5000) Lubricity: The dynamic friction coefficient of the film obtained by a pressure press was measured. (0.83 kgf · cm ^-2 , 6.2 cm / se
c, 20 ° C, 60% RH)

[0039]

[Table 1]

[0040]

The fluorine-modified wax composition of the present invention is a wax having a fluorine-containing alkyl group introduced into the wax.
Therefore, by using it as a modifier for various resins, the functions of the conventional wax such as improving the dispersibility of pigments and fillers and improving the moldability of the resin can be maintained and improved, and the functions unique to fluorine-modified products can be obtained. It also plays a role of improving water repellency, improving blocking resistance, improving abrasion resistance, improving lubricity, and the like. Because of the above effects, the fluorine-modified wax composition of the present invention is useful as a resin modifier and an additive for products containing various resins. Used as molding processability improver for various resins, paint additives, pigment and filler dispersants, printing ink additives, floor wax additives, surface modifiers, fiber treatment agents, paper treatment agents, etc. it can.

Claims (5)

[Claims] 1. A wax compound comprising a wax compound (a) and a vinyl compound (b) having a fluorine-containing alkyl group having 3 to 20 carbon atoms, which is graft-polymerized, wherein the content of fluorine atoms exceeds 5%.
% Or less of a fluorine-modified wax composition. 2. (a) is selected from synthetic hydrocarbon wax, petroleum wax, and carboxyl group-modified wax.
The composition of claim 1 which is more than one species. 3. A wax (a) is radically polymerized at 50 to 250 ° C. with a vinyl compound (b) having a fluorine-containing alkyl group having 3 to 20 carbon atoms in the presence of a polymerization initiator (c). And a method for producing a fluorine-modified wax composition. 4. Polymerization in the molten state of (a).
The manufacturing method described. 5. A resin modifier comprising the composition according to claim 1 or 2.