JP2001114932A - Synthetic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide synthetic resin compositions with much improved affinity of inorganic solids and the like for various synthetic resins and the like. SOLUTION: Synthetic resin compositions contain an inorganic solid or a solid silicone, at least part of the surface of which is covered with a polymer of an organopolysiloxane having (B) a poly(N-acylalkyleneimine) segment composed of repeating units represented by the formula (wherein R1 is a hydrogen atom or a 1-22C alkyl group; and n is 2 or 3) bonded to at least one silicon atom of (A) an organopolysiloxane segment through a hetero atom-containing alkylene group at a weight ratio [(A)/(B)] of organopolysiloxane segment (A) to poly(N-acylalkyleneimine) segment (B) of from 5/95 to less than 99/1 and having a weight average molecular weight of 10,000-5,000,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a synthetic resin composition.

[0002]

BACKGROUND OF THE INVENTION Silica, titanium oxide, alumina, calcium carbonate, aluminum hydroxide, carbon black, conductive metal powder, glass fiber, carbon fiber, clay mineral, pigment (metal oxide and Inorganic solids and solid silicones (hereinafter referred to as inorganic solids, etc.) for various purposes, as synthetic resins other than silicone resins or as blends of silicones (hereinafter referred to as synthetic resins), or function themselves. It is used as a conductive powder (for example, powder for cosmetics). In this case, the surface characteristics of the inorganic solid or the like greatly affect the physical properties of various compositions or functional powders, and often significantly suppress the realization of the intended function.

For example, in a synthetic resin or the like, if the affinity for the surface of an inorganic solid or the like is low, interface separation or aggregation of the inorganic solid or the like is caused, and not only the workability is greatly reduced, but also the material strength is greatly reduced. It causes fatal problems such as deterioration, weakening, hue deterioration, non-conductivity, and sedimentation and separation of pigment. In addition, the functional powder causes the formation of aggregates, the reduction of charging characteristics and fluidity, and the appearance of unpleasant feelings such as squeaky feeling. These problems occur when a large amount of an inorganic solid or the like is used or when a fine inorganic solid or the like is used. The interface between the medium (hereinafter, a medium that forms a continuous phase in the composition is referred to as a medium) and the inorganic solid is used. This is particularly noticeable when the total area is large, and significantly limits more effective use of inorganic solids and the like.

[0004] An object of the present invention is to provide a synthetic resin composition containing an inorganic solid or the like in which the affinity between the inorganic solid or the like and various synthetic resins and the like is remarkably improved.

[0005]

According to the present invention, at least one silicon atom of the organopolysiloxane segment has a general formula (1):

[0006]

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(Wherein, R ¹ is a hydrogen atom or a C ¹ -C 22)
Wherein n represents a number of 2 or 3), which is a poly (N-acylalkyleneimine) segment comprising a repeating unit represented by the following formula, wherein the organopolysiloxane segment ( The weight ratio ((A) / (B)) of A) to the poly (N-acylalkyleneimine) segment (B) is 5/95 or more and 99
/ Less than 1 and a weight average molecular weight of 10,000 to 5,000,000
(Hereinafter referred to as surfactant polymer (I))
Synthetic resin composition containing inorganic solid coated on at least part of its surface with surface active polymer (I)
A synthetic resin composition other than a silicone resin, containing a solid silicone coated on at least a part of the surface thereof, and a synthesis containing (b) an inorganic solid and / or silicone, and (c) a surfactant polymer (I). It is a resin composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION [1] Inorganic solid etc. The kind and form of the inorganic solid in the present invention are not limited. For example, (a) silica, titanium oxide, alumina, zirconium oxide, zinc oxide, ferrite oxide, cobalt-modified iron oxide, magnetite, α-Fe ₂ O ₃ , γ-Fe ₂ O ₃ , indium oxide-tin oxide (ITO) Metal oxides such as magnesium oxide, calcium oxide, etc .; (b) metal hydroxides such as sodium hydroxide, magnesium hydroxide, aluminum hydroxide; (c) sodium carbonate, sodium hydrogen carbonate, calcium carbonate, sodium sulfate, sulfuric acid Other metal salts such as barium, sodium chloride, potassium titanate, and talc; (d) non-oxide ceramics such as boron nitride, aluminum nitride, titanium nitride, and silicon carbide; (e) α-Fe powder, silver powder, and copper powder ,
Metal powders such as silicon powder, (f) carbon materials such as carbon black, graphite, carbon whiskers, (mica),
Clay minerals such as smectite (montmorillonite) and sericite; inorganic fiber materials such as (h) glass fiber and carbon fiber; Organic pigments containing metal ions such as phthalocyanine blue and dye lake (in the present invention, the organic pigments are also inorganic solids of the present invention if they contain metal ions) can be used. Two or more of these inorganic solids may be used as a mixture.

The form may be particulate or fibrous. When in the form of particles, the average particle size is 0.8 nm to 1 mm
Is preferably, more preferably 3 nm to 300 μm,
Particularly preferably, it is 5 nm to 10 μm. When it is fibrous, the average diameter of the cross section is preferably 0.8 nm to 1 mm, more preferably 3 nm to 300 μm, and particularly preferably 5 nm to 10 μm.

In the present invention, solid silicone can also be used as the object to be surface-modified. In the present invention, solid silicone is a concept including silicone rubber and silicone resin.

[2] Surfactant polymer (I) In the surfactant polymer (I), the weight ratio of the organopolysiloxane segment (A) to the poly (N-acylalkylenimine) segment (B) ((A) / ( B))
Is 5/95 or more and less than 99/1, preferably 20/80 or more and less than 96/4, more preferably 40/95 from the viewpoint of the affinity between the inorganic solid or solid silicone and the synthetic resin (hereinafter referred to as affinity). It is 60 or more and less than 96/4. The weight average molecular weight is 10,000 to 5,000,000 from the viewpoint of affinity, preferably 10,000 to 1,000,000, more preferably 50,000 to 50.
It is 0,000.

As an alkylene group containing a hetero atom intervening in the bond between the organopolysiloxane segment and the poly (N-acylalkyleneimine) segment,
Examples thereof include an alkylene group having 2 to 20 carbon atoms including a nitrogen atom, an oxygen atom and / or a sulfur atom, and preferably an alkylene group having 2 to 20 carbon atoms including 1 to 3 of these hetero atoms. Specifically, (a) a secondary amine or a tertiary amine, (ii) a carbon-carbon and / or terminal between alkylene chains.
Ammonium salts obtained by adding H ⁺ to secondary or tertiary amines, (c) quaternary ammonium salts,
(D) An alkylene group having 2 to 20 carbon atoms containing an oxygen atom and / or (e) a sulfur atom. Of these,
Specific examples of preferred ones include:

[0013]

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[0014] (wherein, X ^-. Is showing the counter ion of the ammonium salt) and the like. The carbon number of the alkyl group represented by R ¹ is preferably 1 to 3 when using a highly polar inorganic solid or a synthetic resin, preferably 4 to 22 when using a low-polarity synthetic resin, and more preferably 8 to 22. preferable.

The surfactant polymer (I) can be obtained, for example, by the method described in JP-A-7-133352, page 5, column 7, line 44 to page 6, column 9, line 33.

[3] Inorganic solid or the like surface-coated with surfactant polymer (I) By coating a part or all of the surface of the inorganic solid or the like with surfactant polymer (I), the affinity of the surface with silicone is improved. Inorganic solids and the like can be obtained. The coating method may be any of a wet mixing method and a dry mixing method.

When the surface of the inorganic solid or the like is coated with the surface active polymer (I), the amount of the surface active polymer (I) used depends on the specific surface area of the inorganic solid or the like, that is, the average particle size, porosity and the like. The surfactant is preferably 0.001 to 300 parts by weight, more preferably 0.05 to 100 parts by weight, per 100 parts by weight of the inorganic solid or the like.

The surfactant polymer (I) may be used alone or in combination of two or more. Further, known surface modifiers, dispersants, surfactants, coupling agents and the like can be used in combination.

[4] Compositions such as synthetic resins As synthetic resins other than silicone resins, polyethylene,
Polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, polybutadiene, polycarbonate, polyacrylonitrile, ABS
Resin, AES resin, polyamide 6, polyamide 66, polyamide 12, polyetherimide, polyetheretherketone, polysulfone, polyallylamine, polyphenylene oxide, petroleum resin, polytetrafluoroethylene, polyvinyl fluoride, polydimethyl silicone, polydiphenyl silicone Thermoplastic resins such as thermoplastic resins and their derivatives, and copolymers containing them, epoxy resins, phenolic resins, polyimides, polyurethanes, melamine resins, urea resins, polyester resins, thermosetting resins such as unsaturated polyester resins and the like Are exemplified. In this case, based on 100 parts by weight of the synthetic resin, the inorganic solid or the like is preferably 0.01 to 500 parts by weight, more preferably
0.1 to 300 parts by weight is blended.

In this case, the surface of the inorganic solid or the like may be previously coated with the surface active polymer (I) and then mixed with the synthetic resin, or the mixture of the synthetic resin and the surface active polymer (I) may be mixed with the inorganic solid or the like. You may mix. Further, the surface active polymer (I) may be mixed with a mixture of a synthetic resin and an inorganic solid.

Further, silicone may be contained in place of the synthetic resin. In the present invention, silicone is a concept including silicone oil, silicone rubber and silicone resin.

Furthermore, in the synthetic resin composition of the present invention containing (b) an inorganic solid and / or silicone, and (c) a surfactant polymer (I), when the synthetic resin and the silicone are compatibilized with each other, Polymer (I) functions as a compatibilizer. In this case, silicone may be mixed with the mixture of the synthetic resin and the surfactant polymer (I), the surfactant polymer (I) may be mixed with the mixture of the synthetic resin and silicone, or the silicone and the surfactant may be mixed. A synthetic resin may be mixed with the mixture with the polymer (I). In this case, the content of the component (b) in the synthetic resin composition is preferably 1 to 50% by weight, and the content of the component (c) is preferably 0.01 to 10% by weight.

[0023]

EXAMPLES In the examples, the weight average molecular weight is a weight average molecular weight in terms of polystyrene determined by gel permeation type liquid chromatography using chloroform as a developing solvent.

Synthesis Example 1: Synthesis of surfactant polymer (I-1)

[0025]

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(X ₁ , x ₂ and x ₃ indicate the number of repeating units, and the ratio of the numbers is x ₁ / x ₂ / x ₃ = 1/330/30) 12.78 g (0.0829 mol) of diethyl sulfate 519 g of ethyl acetate obtained by dehydrating 281.4 g (2.488 mol) of 2-ethyl-2-oxazine
And heated under reflux for 15 hours under a nitrogen atmosphere to synthesize terminal-reactive poly (N-propionylpropyleneimine). Here, 1666.7 g of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight: 100,000, amine equivalent: 20,010)
A 33% solution of ethyl acetate (0.0829 mol as an amino group) was added all at once, and the mixture was heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to give an N-propionylpropyleneimine-dimethylsiloxane copolymer as a pale yellow solid (1907 g, yield 99%).
As obtained. The weight average molecular weight was 168,000. Further, as a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Synthesis Example 2: Synthesis of surfactant polymer (I-2)

[0028]

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(X ₄ , x ₅ , x ₆ and x ₇ indicate the number of repeating units, and the ratio of the numbers is x ₄ / x ₅ / x ₆ / x ₇ = 3/165/1
5.67 g (0.0497 mol) of diethyl sulfate and 2-octyl-2-
Ethyl acetate 5 obtained by dehydrating 45.51 g (0.249 mol) of oxazoline
The resultant was dissolved in 19 g and heated under reflux in a nitrogen atmosphere for 15 hours to synthesize terminal-reactive poly (N-perargonylethyleneimine). Here, 166.7 g of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight 30,000, amine equivalent 2010)
A 33% solution of ethyl acetate (0.0829 mol as an amino group) was added all at once, and the mixture was refluxed for 12 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-perargonylethyleneimine-dimethylsiloxane copolymer as a pale yellow solid (218 g, yield 99%). The weight average molecular weight was 154,000. Further, as a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that 40% of amino groups remained.

Synthesis Example 3: Synthesis of surfactant polymer (I-3)

[0031]

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(X ₈ , x ₉ and x ₁₀ represent the number of repeating units, and the ratio of the numbers is x ₈ / x ₉ / x ₁₀ = 1/68/75) 5.16 g (0.0335 mol) of diethyl sulfate 508 g of ethyl acetate obtained by dehydrating 249 g (2.51 mol) of 2-ethyl-2-oxazoline
And heated under reflux in a nitrogen atmosphere for 15 hours to synthesize terminal-reactive poly (N-propionylethyleneimine).
To this, a 33% ethyl acetate solution of 166.7 g (0.0335 mol as an amino group) of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight: 40,000, amine equivalent: 4980) was added all at once, followed by heating under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow solid (409 g, yield 97%). The weight average molecular weight was 101,000. Further, as a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Example 1 Ultrafine anhydrous silica (Aerosil 20 manufactured by Nippon Aerosil Co., Ltd.)
0; average particle size: 12 nm, BET specific surface area: 200 ± 25 m ² /
g) 10 g was mixed with a 500 g ethyl acetate solution in which 0.1 g of the surfactant polymer (I-1) was dissolved in a Henschel mixer for 5 minutes, dried, and then ultrafine silica particles surface-modified with the surfactant polymer were obtained. Was. 90 g of polybutylene terephthalate (Novadur 5010, manufactured by Mitsubishi Chemical Corporation)
Was added and melt-kneaded at a temperature of 200 to 240 ° C. by an axle screw extruder and molded to obtain a polyester containing ultrafine silica particles.

Example 2 Instead of the surfactant polymer (I-1), the surfactant polymer (I-
3) Ultrafine silica-containing polyester whose surface was modified in the same manner as in Example 1 was obtained using 0.1 g.

Test Example 1 The ultrafine silica-containing polyester obtained in Examples 1 and 2, melted and kneaded with 10 g of untreated Aerosil 200 and 90 g of the above polybutylene terephthalate as Comparative Example 1 were molded under a polarizing microscope. Observed. Although coarse aggregates of silica were not observed in the polyesters obtained in Examples 1 and 2, many coarse aggregates of silica were observed in the polyester of Comparative Example 1.

Example 3 Silicone oil (KF-96A manufactured by Shin-Etsu Chemical Co., Ltd .; 6 cs) 10
g, 0.01 g of surface-active polymer (I-1) and 0.5 g of ultrafine titanium oxide (TTO-55, manufactured by Ishihara Sangyo Co., Ltd.) are added, heated and stirred at 50 ° C., and further subjected to ultrasonic immersion for 15 minutes. Process,
An ultrafine titanium oxide-dispersed silicone oil composition was obtained. When the composition was allowed to stand, the titanium oxide particles were uniformly dispersed without settling even after 12 hours. Observation of this composition under a polarizing microscope revealed no coarse particles of titanium oxide having a size of 2 μm or more.

COMPARATIVE EXAMPLE 2 10 g of silicone oil was used without using a surfactant polymer.
Ultrafine titanium dioxide dispersed silicone treated in the same manner as in Example 3 except that 0.5 g of ultrafine titanium oxide surface-treated with 0.05 g of tridecafluoro-1,1,1,2,2-tetrahydrooctyl) triethoxysilane was added in advance. An oil composition was obtained. When this composition was allowed to stand, all of the titanium oxide particles settled out within 5 minutes. Observation of this composition under a polarizing microscope revealed that titanium oxide had formed coarse aggregates of several tens of μm or more.

Example 4 0.1 g of a surfactant polymer (I-2) was mixed with 10 g of a silicone resin (Trefil R-925 manufactured by Dow Corning Toray Co., Ltd.), and polybutylene terephthalate (manufactured by Mitsubishi Kasei Corp.,
90 g of Novadur 5010) was added thereto, and the mixture was melt-kneaded at a temperature of 200 to 240 ° C. by a single screw extruder and molded to obtain a silicone resin-containing polyester. When the cross section of the molded article was observed under a polarizing microscope, no aggregated particles of the silicone resin were observed.

Comparative Example 3 A silicone resin-containing polyester was obtained in the same manner as in Example 4 without using a surfactant polymer. Observation of the cross section of the molded product under a polarizing microscope revealed that the silicone resin had formed aggregates.

Example 5 Silicone resin (SH805 manufactured by Dow Corning Toray Co., Ltd.)
30 g of the surface-active polymer (I-
1) 0.3 g and 70 g of polybutylene terephthalate (Novatur 5010 manufactured by Mitsubishi Kasei Co., Ltd.) were melt-kneaded at a temperature of 200 to 240 ° C. by a single screw extruder and molded to obtain a polymer alloy. When the cross section of the molded article was observed with an electron microscope, the silicone resin and polybutylene terephthalate were compatible.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Taku Oda 1334 Minato, Wakayama-shi, Wakayama Prefecture F-term in Kao Corporation Laboratory (reference) 4J002 AA00W BA01W BB03W BB12W BC03W BD03W BD13W BD15W BE02W BG05W BG10W BJ00W BL01W BN07W CC CD00W CF00W CF21W CG00W CH07W CH09W CK02W CL01W CL03W CM01W CM04W CN03W CP03W CP03Y CP17X DA026 DA076 DA086 DA116 DD056 DE046 DE076 DE086 DE106 DE116 DE136 DE146 DE156 DE186 DE206 DE226 DE236 DF006 DJ016 GA016 FB 016 016 016 016 016 016 006 LA03 LB06 LB20

Claims (4)

[Claims] 1. A compound of the general formula (1): wherein at least one silicon atom of the organopolysiloxane segment is linked via an alkylene group containing a hetero atom. (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and n represents a number of 2 or 3). A poly (N-acylalkyleneimine) segment comprising a repeating unit represented by Wherein the weight ratio ((A) / (B)) of the organopolysiloxane segment (A) to the poly (N-acylalkyleneimine) segment (B) is 5/95 or more and 99 / A synthetic resin composition containing an inorganic solid whose surface is at least partially coated with a polymer having a weight average molecular weight of 10,000 to 5,000,000, which is less than 1. 2. The method according to claim 1, wherein the alkylene group containing a hetero atom in the polymer has (a) a secondary amine or a tertiary amine, and (b) a secondary amine at the carbon-carbon and / or terminal of the alkylene chain.
Ammonium salts obtained by adding H ⁺ to tertiary amines or tertiary amines, (c) quaternary ammonium salts, (d) having 2 to 20 carbon atoms containing an oxygen atom and / or (e) a sulfur atom.
The synthetic resin composition according to claim 1, which is an alkylene group represented by the formula: 3. A synthetic resin composition other than a silicone resin, comprising a solid silicone whose surface is at least partially coated with the polymer according to claim 1 or 2. (B) an inorganic solid and / or silicone;
And (c) a synthetic resin composition containing the polymer according to claim 1 or 2.