JPH0578528A - Thermoplastic resin composition excellent in liquid repellency - Google Patents

Abstract

PURPOSE:To prepare an olefin resin compsn. exhibiting an excellent liq. repellency for a long time even to a solvent such as acetone or methyl ethyl ketone by compounding an olefin resin with a specific graft copolymer. CONSTITUTION:An olefin resin is compounded with a graft copolymer which is obtd. by grafting a monomer mixture consisting of a polyfluoroalkylated (meth)acrylic ester and a vinyl or vinylidene monomer onto an unsatd. copolymer resin obtd. by copolymerizing at least one 2-12C alpha-olefin with at least one nonconjugated diene of the formula (wherein R<1>, R<2>, R<3>, R<4>, and R<5> are each independently H or 1-8C alkyl; and (n) is an integer of 1-10).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing a polyfluoroalkyl group-containing (meth) acrylic acid ester and having excellent liquid repellency.

[0002]

2. Description of the Related Art Liquid repellents composed of a polymer containing a polyfluoroalkyl group or a copolymer of a monomer containing a polyfluoroalkyl group and another monomer have been conventionally known. (JP-A-58-59277, etc.), a method for producing a liquid-repellent molding by melting and kneading such a liquid-repellent agent with an olefin resin has also been proposed (JP-A-3-7745). ). However, although the resins obtained by these methods are excellent in liquid repellency, they are not always satisfactory in that they retain liquid repellency for a long time with respect to solvents such as acetone and methyl ethyl ketone.

Other means for making the surface of the resin lyophobic include (i) coating the surface of the molded article with a compound having a low surface tension, and (ii) a compound having a low surface tension on the surface of the molded article. There is a method such as graft addition using a method such as plasma treatment, but these are somewhat complicated because the molded product is further processed, and regarding (i), the liquid repellent layer Is easily peeled off due to friction and the like, and the liquid repellency is reduced in a short time. Regarding (ii), there are disadvantages such that a special machine is required.

[0004]

In view of the above-mentioned drawbacks, an object of the present invention is to provide an olefin resin composition which exhibits excellent liquid repellency for a long time even in a solvent such as acetone or methyl ethyl ketone. Is.

[0005]

Therefore, as a result of intensive studies, the present inventors have found that (a) an olefin resin, and (b) at least one of an α-olefin having 2 to 12 carbon atoms and the following general formula: (I):

[0006]

[Chemical 2]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 10). An unsaturated copolymer resin composed of at least one of the non-conjugated dienes represented is a polyfluoroalkyl group-containing (meth) acrylic acid ester, or a polyfluoroalkyl group-containing (meth) acrylic acid ester and vinyl or vinylidene. A resin composition containing a graft-modified copolymer obtained by subjecting the monomer to radical polymerization conditions, is excellent in liquid repellency, has high durability of liquid repellency, and is suitable for solvents such as acetone and methyl ethyl ketone. On the other hand, it was found that a thermoplastic resin molding having a high liquid repellency is provided, and the present invention has been completed.

[Detailed Description of the Invention] 1. Olefin-based resin (component (a)) Examples of the olefin-based resin include polyethylene, polypropylene, ethylene-propylene random copolymer,
Examples thereof include copolymers of polybutadiene, polyisoprene, ethylene or propylene in an amount of 50 mol% or more with monomers such as acrylic acid ester, acrylonitrile, styrene, vinyl acetate and vinyl chloride which can be copolymerized therewith. Among them, preferred resins are polyethylene, polypropylene, propylene / ethylene copolymer,
Propylene-4-methylpentene copolymer and the like. These resins have an MFR of 0.5 to 100 g /
10 minutes is preferable in terms of moldability.

2. Graft Modified Copolymer (Component (b)) The graft modified copolymer comprises at least one α-olefin (i) having 2 to 12 carbon atoms and a non-conjugated diene represented by the general formula (I) (ii). An unsaturated copolymer resin (iii) containing at least one of (1), a polyfluoroalkyl group-containing (meth) acrylic acid ester (iv), or a polyfluoroalkyl group-containing (meth) acrylic acid ester and vinyl or vinylidene. It is obtained by subjecting the monomer (v) to radical polymerization conditions.

(I) α-Olefin As the α-olefin having 2 to 12 carbon atoms which is a raw material for producing the unsaturated copolymer resin (iii), ethylene, propylene, butene-1, pentene-1, Hexene-1, octene-1,3-methyl-butene 1,3-methyl-pentene-1,4-methyl-pentene-1,3,3
-Dimethyl-butene-1,4,4-dimethyl-pentene-1,3-methylhexene-1,4-methyl-hexene-1,4,4-dimethyl-hexene-1,5-methyl-
Hexene-1, allylcyclopentane, allylcyclohexane, styrene, allylbenzene, 3-cyclohexylbutene-1, vinylcyclopropane, vinylcyclopentane, vinylcyclohexane, 2-vinylbicyclo [2,2,1] -heptane and the like. be able to.
Among these, preferable examples are ethylene, propylene, butene-1, 3-methyl-butene-1, 4-methyl-pentene-1, styrene and the like, and particularly preferable examples are ethylene and propylene. Two or more kinds of these α-olefins may be used.

(Ii) Non-Conjugated Dienes The other raw material for producing the unsaturated copolymer resin, the non-conjugated dienes, is a compound represented by the following general formula (I).

[0012]

[Chemical 3]

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 10).

Examples of the non-conjugated dienes represented by the above general formula (I) include 1,4-hexadiene and 4-methyl-diene.
1,4 such as 1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,4-heptadiene
-Dienes; 1,5-heptadiene, 5-methyl-1,
1,5-dienes such as 5-heptadiene, 6-methyl-1,5-heptadiene, 1,5-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene; 1, 6-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 7-ethyl-1,6-octadiene, 1,6-
1,6-dienes such as nonadiene, 7-methyl-1,6-nonadiene, 4-methyl-1,6-nonadiene;
1,7-Dienes such as 1,7-nonadiene and 8-methyl-1,7-nonadiene; 1,9-decadiene, 1,1
Various non-conjugated dienes such as 3-tetradecadiene; and the like. Two or more kinds of these non-conjugated dienes can be mixed and used.

(Iii) Unsaturated Copolymer Resin The above α-olefins (i) and non-conjugated dienes (ii)
The unsaturated copolymer resin can be produced by subjecting and to block and / or random copolymerization using a known Ziegler catalyst and a known method and apparatus similar to those for the α-olefin polymer. To produce the unsaturated copolymer resin, JP-B-64-2127, JP-B-64-2128, JP-B-64-9326, JP-A-59-155416,
The methods described in JP-A-62-115008 and JP-A-2-311507 can be adopted.

The unsaturated copolymer resin used in the present invention has a content of non-conjugated dienes of 0.1 to 30 mol%, preferably 0.5 to 20 mol%. If it is less than 0.1 mol%, there is a drawback that it is difficult to increase the desired graft ratio because the unsaturated copolymer resin has a small amount of unsaturated groups. On the other hand, if it exceeds 30 mol%, the copolymerization rate is slow during the production of the unsaturated copolymer resin, and in the case of slurry polymerization, the solvent-soluble by-product polymer increases and the viscosity of the polymerization system increases, resulting in poor productivity. However, there are drawbacks such that the resulting unsaturated copolymer becomes sticky and the resinous state is not maintained.

The molecular weight of the unsaturated copolymer resin is not particularly limited as long as it maintains the above-mentioned resin state. For example, when the α-olefin is mainly propylene, JIS-
The melt flow rate (MFR) measured according to K-6758 is usually 0.001 to 3000 g / 10 minutes, preferably 0.01 to 2000 g / 10 minutes, and particularly preferably 0.05 to 1000 g / 10 minutes. Those of comparable molecular weight are preferred. Further, this unsaturated copolymer resin is
The elastic modulus according to IS-K-7203 is 500 to 50,000.
It is preferably 0 kg / cm ² . For example, when the α-olefin mainly consists of propylene, the elastic modulus is 1,
It is preferably 000 to 20,000 kg / cm ² .

Examples of the unsaturated copolymer resin include the non-conjugated dienes and various combinations of block copolymers and random copolymers selected from the α-olefins. Among them, the following are preferable. [Here, methyl-1,4-hexadiene represents a mixture of 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, and the mixing ratio thereof is 95: 5 to 5:95. Refers to a range. ] Ethylene / methyl-1,4-hexadiene random copolymer Ethylene / 7-methyl-1,6-octadiene random copolymer Propylene / methyl-1,4-hexadiene random copolymer Propylene / 7-methyl-1 , 6-octadiene random copolymer propylene / 1,9-decadiene random copolymer propylene / ethylene / methyl-1,4-hexadiene random copolymer propylene / ethylene / 7-methyl-1,6-octadiene Random copolymer propylene / ethylene / methyl-1,4-hexadiene block copolymer propylene, / ethylene / 7-methyl-1,6-octadiene block copolymer and the like.

(Iv) Polyfluoroalkyl group-containing (meth) acrylic acid ester The polyfluoroalkyl group-containing (meth) acrylic acid ester used as a graft monomer in the graft-modified copolymer of the component (b) is, for example, _{CF 3 (CF 2) 7 CH} 2 CH 2 OCOCH = CH 2 CF 3 (CF 2) 7 CH 2 CH 2 OCOC (CH 3) = CH 2 CF 3 (CF 3) CF (CF 2) 6 CH 2 CH 2 OCOCH =
_{CH 2 CF 3 (CF 3)} CF (CF 2) 6 CH 2 CH 2 OCOC (C
_{H 3) = CH 2 CF 3} (CF 2) 6 CH 2 CH 2 OCOCH = CH 2 CF 3 (CF 2) 6 CH 2 CH 2 OCOC (CH 3) = CH 2 CF 3 (CF 2) 4 CH 2 CH _{2 OCOCH = CH 2 CF 3 (} CF 2) 4 CH 2 CH 2 OCOC (CH 3) = CH 2 CF 3 (CF 2) 7 OCOCH = CH 2 CF 3 (CF 2) 7 OCOC (CH 3) = CH 2 Etc.

(V) Vinyl or vinylidene monomer As the vinyl or vinylidene monomer which is optionally used together with the above-mentioned ester as a graft monomer, for example, a styrene-based monomer such as styrene or a nucleus is used. Substituted styrene such as methyl styrene, dimethyl styrene, ethyl styrene, isopropyl styrene, chlorostyrene, α-substituted styrene such as α-methyl styrene, α-ethyl styrene, acrylic acid ester (particularly C ₁ -C ₇ alkyl ester), methacrylic acid Ester (particularly C ₁ -C ₇ alkyl ester), vinyl halide or vinylidene (particularly vinyl chloride, vinylidene chloride), acrylonitrile, methacrylonitrile, vinylnaphthalene, vinylcarbazole, acrylamide,
Methacrylamide may be used, and these may be used alone or in combination.

(Vi) Production of Graft-Modified Copolymer The graft-modified copolymer is the above unsaturated copolymer resin (ii
i) can be produced by subjecting the above-mentioned monomers (iv, v) to conventionally known radical graft polymerization conditions. For example, in the coexistence of the unsaturated copolymer resin and the monomer, γ-ray, a method of irradiating with radiation such as an electron beam, a method of irradiating the unsaturated copolymer resin with radiation and then allowing the monomer to coexist, Any method such as coexistence of an unsaturated copolymer resin and a monomer in a solution state, a molten state or a dispersed state, and graft polymerization in the presence or absence of a radical polymerization catalyst can be adopted in the present invention. Of these, the method of performing graft polymerization in a solution or molten state is preferable.

Radical polymerization catalysts include benzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, t-butyl hydroperoxide, t-butyl peroxyacetate, diisopropyl peroxydicarbonate and 2,2-bis. There are organic and inorganic peroxides such as (t-butylperoxy) octane, methyl ethyl ketone peroxide, potassium peroxide and hydrogen peroxide, and azo compounds such as α, α′-azobisisobutyronitrile. The peroxide can be used as a redox system in combination with a reducing agent. For example, there is a combination of hydrogen peroxide and a ferrous salt. These radical polymerization catalysts are appropriately selected in relation to the type of monomer and the polymerization method, and one kind or two or more kinds may be used in combination.

The temperature of the radical graft polymerization reaction is usually 30 ° C. to 350 ° C., preferably 50 ° C. to 300 ° C., and the polymerization time is 30 seconds to 50 hours, preferably 1
The range is from minutes to 24 hours. The amount of the radical polymerization catalyst used is 0 with respect to 100 parts by weight of the unsaturated copolymer resin.
To 100 parts by weight, preferably 0 to 30 parts by weight. When it is necessary to adjust the molecular weight of the polymerized portion of the monomer, a molecular weight adjusting method that is usually used in radical polymerization can be used. For example, polymerization temperature, amount of radical polymerization catalyst added, amount of monomer used, mercaptans, 2,
The purpose can be achieved by adding a molecular weight regulator such as 4-diphenyl-4-methyl-1-pentene.

The copolymerization ratio between the polyfluoroalkyl group-containing (meth) acrylic acid ester and the vinyl or vinylidene monomer in the graft modified copolymer is such that the ratio of the polyfluoroalkyl group-containing (meth) acrylic acid ester decreases. Since the liquid repellency decreases, 1: 0 to 1: 9 is preferable. Further, the compounding ratio of the unsaturated copolymer and the polyfluoroalkyl group-containing (meth) acrylic acid ester is 1 because the liquid repellency is lowered when the ratio of the polyfluoroalkyl group-containing (meth) acrylic acid ester is decreased. : 20 to 20: 1 is preferable.

Incidentally, the graft copolymerization is generally equivalent to polymerizing a monomer which should give a "branch" polymer in the presence of the "stem" polymer, and thus, an ideal backbone-branched structure polymer is obtained. In addition to coalescence, it is often observed that a polymer of this monomer itself that does not "branch" is by-produced. Therefore, also in the present invention, the "graft-modified copolymer" includes a mixture containing such a by-product.

3. Resin Composition The resin composition of the present invention is substantially composed of the olefin resin (a) and the graft-modified copolymer (b). However, other components may be added without departing from the objects and effects of the present invention. For example, plasticizers or fluidity improvers such as paraffin oil; softeners such as olefin liquid rubber and conjugated diene liquid rubber; coloring agents; antioxidants; neutralizing agents; light stabilizers UV absorbers; Antistatic agents; Lubricants; Dispersing aids; Molecular weight modifiers; Crosslinking agents; Nucleating agents; Flame retardants, etc. and fillers, fillers, polytetrafluoroethylene, etc. May be.

The composition is a graft-modified copolymer (b).
If the amount of oleoresin used is reduced, the liquid repellency is lowered, and if it is increased, the liquid repellency is saturated and it is economically disadvantageous. It is preferably added, and particularly preferably 1 to 30 parts by weight. The resin composition of the present invention can be produced by melt-kneading the olefin resin (a) and the graft-modified copolymer (b), and at that time, any method can be adopted, Examples include rolls and extruders. On a small scale, there is Bravenda-Plastograph.

[0028]

EFFECTS OF THE INVENTION The resin composition of the present invention can maintain liquid repellency for a long period of time not only against water and alcohol but also against acetone, methyl ethyl ketone and the like. The reason for this is that the unsaturated copolymer, which is the trunk portion of the graft-modified copolymer, has compatibility with the olefin resin (a), and therefore exerts a strong anchoring effect and is essentially liquid repellent. Containing polyfluoroalkyl group (meta) which is the emitting part
It is considered that this is because the acrylic ester (co) polymer part can be firmly fixed to the olefin resin (a).

[0029]

EXAMPLES Next, the present invention will be described in more detail by way of examples. Synthesis of graft modification copolymer A In a separable flask, propylene and 7-methyl-1,
100 parts by weight of an unsaturated copolymer resin with 6-octadiene (7-methyl-1,6-octadiene content 2.8 mol%) and perfluorooctylethyl methacrylate 20
Parts by weight, 20 parts by weight of styrene, 2 parts by weight of t-butylperoxybenzoate, and 1000 parts by weight of toluene were supplied, and the reaction was carried out at 120 ° C. for 6 hours. The obtained reaction product was poured into a large amount of cold methanol to precipitate a polymer, which was washed by filtration and then dried under reduced pressure to obtain a graft-modified copolymer A. Infrared absorption spectrum analysis of this graft-modified copolymer A showed absorption near 1730 cm ⁻¹ by carbonyl group of perfluorooctylethyl methacrylate.

Synthesis of Graft-Modified Copolymer B As the unsaturated copolymer resin, a copolymer of propylene and 1,9-decadiene (1,9-decadiene content: 1,2 mol%) is used. A reaction was carried out in the same manner as in the case of the copolymer A to obtain a copolymer B. Synthesis of Graft-Modified Copolymer C In the synthesis of the above-mentioned copolymer A, a propylene homopolymer (MFR 3.5 g / MFR is used instead of the unsaturated copolymer resin).
Copolymer C was obtained by carrying out the reaction in the same manner as in Copolymer A except that 10 minutes) was used.

Example 1 100 parts by weight of polypropylene (MA4 manufactured by Mitsubishi Petrochemical Co., Ltd.) and 10 parts by weight of the above copolymer A were melt-kneaded for 5 minutes at 230 ° C. and 60 rpm using a Brabender Plastograph to obtain a resin composition. Obtained. This is 190 ℃, pressure 100kg / cm ²
And pressed for 5 minutes to form a sheet of 100 × 100 × 1 mm. Example 2 A sheet was prepared in the same manner as in Example 1 except that the copolymer B was used instead of the copolymer A.

Example 3 100 parts by weight of polyethylene (YK30 manufactured by Mitsubishi Petrochemical Co., Ltd.) and 10 parts by weight of the copolymer A were melt-kneaded at 180 ° C. and 60 rpm for 5 minutes using a Brabender Plastograph to prepare a resin composition. Got Then this is 160 ℃, pressure 1
Press at 00kg / cm ^{2 for} 5 minutes, 100 × 100 × 1
mm sheets were molded. Example 4 A sheet was produced in the same manner as in Example 3, except that the copolymer B was used instead of the copolymer A. Comparative Example 1 In Example 1, instead of the copolymer A, the copolymer C1
A sheet was prepared in the same manner as in Example 1 except that 0 part was used.

[Evaluation Test Example] Using the sheets obtained in Examples 1 to 4 and Comparative Example 1, the contact angle was measured with ion-exchanged water. Further, as a sustainability evaluation, the contact angle was measured with ion-exchanged water after immersion in 23 ° C. acetone for 1 to 24 hours and immersion in 79.5 ° C. methyl ethyl ketone for 1 hour. The results are shown in Table-1.

[0034]

[Table 1] Table-1 No contact angle treatment Acetone (23 ° C) Acetone (23 ° C) Methyl ethyl ketone Immersion 1 hour After immersion 24 hours (79.5 ° C) Immersion 1 hour After Example 1 112 112 111 111 110 Example 2 111 110 110 110 Example 3 109 109 109 108 107 Example 4 110 110 110 108 108 Comparative Example 1 110 107 107 104 98

As is clear from the results shown in Table 1, when the unsaturated copolymer is used as the trunk polymer (Examples 1 to 1)
In 4), although the contact angle was slightly reduced, that is, the water repellency was only slightly reduced, even if the propylene homopolymer (Comparative Example 1) was used as the trunk polymer, the acetone was slightly It can be seen that the contact angle is considerably lowered, that is, the water repellency is considerably lowered by the immersion in the water. This is because in the case of an unsaturated copolymer resin, the unsaturated portion and the polyfluoroalkyl group-containing (meth) acrylic acid ester polymer portion in the resin are firmly fixed by a graft reaction, Even when treated with acetone or methyl ethyl ketone, which are good solvents for the contained (meth) acrylic acid ester polymer, the polyfluoroalkyl group-containing (meth) acrylic acid ester polymer is less likely to be released from the surface of the sheet, and therefore the water repellency is reduced. It is considered to be difficult. On the other hand, in the case of propylene homopolymer, since the propylene homopolymer generally has no unsaturated part, the graft reaction between the polyfluoroalkyl group-containing (meth) acrylate polymer part and the propylene homopolymer Is less likely to occur, and when treated with acetone or the like, the polyfluoroalkyl group-containing (meth) acrylic acid ester polymer is likely to be liberated from the surface of the sheet, which is considered to reduce the contact angle, that is, the water repellency. ..

Claims (1)

[Claims] 1. An olefin resin (a) and at least one of α-olefins having 2 to 12 carbon atoms and the following general formula (I): (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n is 1 to
An unsaturated copolymer resin composed of at least one of non-conjugated dienes represented by the formula (10) is used as a polyfluoroalkyl group-containing (meth) acrylic acid ester or a polyfluoroalkyl group-containing (meth) A thermoplastic resin composition having excellent liquid repellency, which comprises a graft-modified copolymer (b) obtained by subjecting an acrylic ester and a vinyl or vinylidene monomer to radical polymerization conditions.