JPH06340782A - Resin composition containing hollow inorganic microspheres - Google Patents

Abstract

(57) [Abstract] [Purpose] Without deteriorating dimensional stability, molding processability, etc.
We will develop a resin composition that not only reduces the weight of molded products but also has high rigidity, heat resistance, wear resistance, etc., and is excellent in impact resistance, especially impact resistance at low temperatures. [Structure] (A) Polypropylene polymer and / or polyethylene 50 to 98 having a density of 0.94 g / cm ³ or more
% By weight, (B) 2 to 50% by weight of at least one ethylene (co) polymer or rubber selected from the following (B1) to (B4), (B1) density is 0.86 to 0.94 g / low-density polyethylene or ethylene / α-olefin copolymer by high-pressure radical polymerization method of less than cm ³ , (B2) ethylene-vinyl ester copolymer, (B3) ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, The object can be achieved by the inorganic fine hollow body-containing resin composition containing (B4) rubber, 100 parts by weight of the above (A) + (B), and 5 to 100 parts by weight of the inorganic fine hollow body (C).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing an inorganic micro-hollow body, and more specifically, the composition comprises a polypropylene polymer and / or polyethylene having a density of 0.94 g / cm ³ or more, ethylene ( Co) polymer or rubber,
And a composition consisting of an inorganic micro hollow body, or a composition containing a specific functional group in the composition, without reducing the dimensional stability, molding processability, etc., while reducing the weight of the molded product, It is a composition with high rigidity, heat resistance, wear resistance, etc. that has excellent impact resistance, especially impact resistance at low temperatures, and is effectively used for electrical and electronic parts, construction materials, automobile parts, etc. The present invention relates to an inorganic microhollow body-containing resin composition that can be used.

[0002]

2. Description of the Related Art Conventionally, composite materials have been developed in which various plastics are used as matrices and inorganic fine hollow bodies such as glass balloons and shirasu balloons have been developed, and new applications have been developed. As such a composite material, a method for producing a resin composition for a uniaxially stretched tape by blending a polypropylene resin with a high-pressure polyethylene resin or a dulled medium- and low-pressure polyethylene resin and silica-based hollow microspheres (JP-A-54). No. -60369), engineering plastics such as polyacetal and polyamide, polyolefins such as polyethylene and polypropylene, and copolymers mainly composed of polyolefin, and the like, and a hollow filler having a specific wall thickness ratio are blended to form an automobile body, A method of using as an exterior material for electric equipment, office automation equipment, etc. (Japanese Patent Laid-Open No. 61-236859), crystalline propylene-based polymer with fibrous inorganic filler, silica.
Method for producing automobile parts, housings for electric and electronic devices by a composition comprising hollow alumina and modified propylene polymer (JP-A-3-200853), crystalline polyolefin such as polyethylene and polypropylene, and special acrylic acid A speaker box, a record player from a composition comprising an aliphatic polyolefin resin copolymerized with an alkyl ester, at least one inorganic filler selected from wollastonite and hollow spherical inorganic substances, and an inorganic filler such as mica. A resin composition for producing an acoustic diaphragm for a cabinet or the like (Patent Document 3)
No. 223355) is disclosed.

The main purpose of all of these is to reduce weight, and to improve and improve high rigidity, heat resistance, sound insulation, sound absorption, high internal loss characteristics, moldability, dimensional stability, etc. It is openly known. However, the addition of micro hollow bodies inevitably causes a decrease in mechanical strength such as tensile strength, and further increase in rigidity causes a marked decrease in impact resistance, and particularly the impact resistance at low temperatures is extremely deteriorated. Each of the above compositions is still insufficient in performance, and there is a demand for the development of a resin composition that can provide a molded product with well-balanced properties.

[0004]

The present invention solves these problems and reduces the weight of molded products without deteriorating dimensional stability, molding processability, etc., and also provides high rigidity, heat resistance, and resistance to heat. It is a composition with excellent wear resistance, especially impact resistance at low temperature, which has abrasion resistance, and is an inorganic micro hollow material that can be effectively used for electric and electronic parts, construction materials, automobile parts, etc. The object of the present invention is to provide a body-containing resin composition.

[0005]

The first invention of the present invention is (A) a polypropylene polymer and / or 50 to 98% by weight of polyethylene having a density of 0.94 g / cm ³ or more, and (B) the following ( At least one ethylene (co) polymer or rubber selected from B1) to (B4) 2 to 50% by weight, (B1) High-pressure radical polymerization method having a density of 0.86 to less than 0.94 g / cm ^3. By low density polyethylene or ethylene
α-olefin copolymer, (B2) ethylene-vinyl ester copolymer, (B3) ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, (B4) rubber, (A) + (B) 100 parts by weight And (C) 5 to 100 parts by weight of the inorganic microhollow body, the resin composition containing the inorganic microhollow body is provided.

A second invention of the present invention is (A) a polypropylene polymer and / or polyethylene having a density of 0.94 g / cm ³ or more (B) at least one selected from the following (B1) to (B4) One ethylene (co) polymer or rubber (B1) density is 0.8
Low density polyethylene or ethylene / α-olefin copolymer by high pressure radical polymerization of ^{6 to} less than 0.94 g / cm ³ , (B2) ethylene-vinyl ester copolymer, (B
3) Ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, (B4) rubber, (A) + (B) 100 above
A composition comprising 5 parts by weight and (C) 5 to 100 parts by weight of an inorganic micro hollow body, wherein the content of the (A) component in the (A) + (B) components is 50 to 98% by weight, The content of the component B) is from 2 to 50% by weight, and the following a is contained in all the polymer components.
The present invention provides a resin composition containing an inorganic micro-hollow body, which contains at least one functional group selected from the group (1) to (f) in an amount of 10 ^-3 g equivalent or less per 1 g of the total polymer. a: carboxylic acid group or acid anhydride group b: epoxy group c: hydroxyl group d: amino group e: alkenyl cyclic iminoether group f: silane group

The present invention will be described in detail below. The component (A) used in the present invention is a polypropylene polymer and / or polyethylene having a density of 0.94 g / cm ³ or more. As the polypropylene-based polymer, specifically, a known polypropylene copolymer such as propylene homopolymer (hereinafter referred to as polypropylene), ethylene-propylene block copolymer or random copolymer, or a mixture thereof is used. Among these, propylene homopolymer is desirable as an acoustic member requiring high rigidity, and isotacticity of 95% or more, particularly isotactic pentad ratio of 0.95 or more is preferably selected. . Further, ethylene-propylene block copolymers are preferable as the housing members and automobile members required to have low-temperature impact resistance and the like. The melt flow rate (hereinafter referred to as MFR) of the polypropylene is 0.1
˜50 g / 10 min., Preferably 1-40 g / 10 min., More preferably 5-30 g / 10 min.

The polyethylene having a density of 0.94 g / cm ³ or more, which is another component of the component (A) used in the present invention, is ethylene alone or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms. Specific examples of α-olefins in the mixture and their mixtures include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-dodecene and the like. Of these α-olefins, propylene and 1-butene are particularly preferable. Its density is 0.94 g / cm ^{3 to} 0.9
In the range of 8 g / cm ³ , MFR is 0.1-50 g / 10 min.,
Preferably 1 to 40 g / 10 min., More preferably 5 to
It is better to select from the range of 30 g / 10 min.

The amount of the polypropylene polymer (A) and / or polyethylene having a density of 0.94 g / cm ³ or more is 50 to 98% by weight, preferably 60 to 90% by weight.
Is. If it is less than 50% by weight, the rigidity, moldability and molding processability are deteriorated, and if it is more than 98% by weight, the impact resistance, especially the impact resistance at low temperature is insufficient, so it is preferable to select from this range.

The component (B) in the present invention includes (B
1) Low-density polyethylene or ethylene / α produced by high-pressure radical polymerization with a density of 0.86 to less than 0.94 g / cm ^3.
-Olefin copolymer, (B2) ethylene-vinyl ester copolymer, (B3) ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, (B4) at least one ethylene (copolymer ) Polymers or rubbers.

The low density polyethylene or ethylene / α-olefin copolymer (B1) having a density of 0.86 to less than 0.94 g / cm ³ by a high pressure radical polymerization method means a density of 0.91 to 0 by a high pressure radical polymerization method. A low-density polyethylene of less than 94 g / cm ³ and a copolymer of ethylene and an α-olefin having a carbon number of 3 to 12 by a high, medium and low pressure method using a Ziegler catalyst and the like, and a density of 0.86 to Ethylene / α-olefin copolymer less than 0.91 g / cm ³ (ultra low density polyethylene, hereinafter VLDPE
And an ethylene / α-olefin copolymer having a density of 0.91 to less than 0.94 g / cm ³ (linear low density polyethylene, hereinafter referred to as LLDPE). Specific α-olefins include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1
-Dodecene and the like can be mentioned. Of these, preferred are 1-butene, 4-methyl-1-pentene, and 1.
-Hexene and 1-octene, and particularly preferred is 1-butene. The α-olefin content in the ethylene copolymer is preferably 5 to 40 mol%.

The VLDPE has a density of 0.86 g / cm ³
Is less than 0.91 g / cm ³ , and the differential scanning calorimetry (D
SC) maximum peak temperature (Tm) 50 ° C. or higher, preferably 100 ° C. or higher, and boiling n-hexane insoluble matter 10
It is a polyethylene having a property of not less than wt% and showing a property intermediate between the linear low-density polyethylene and the ethylene / α-olefin copolymer rubber. More specifically, it is a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, and this VLDPE has both a highly crystalline portion represented by LLDPE and an amorphous portion represented by an ethylene / α-olefin copolymer rubber. Resin, the mechanical characteristics, heat resistance, etc., which are the characteristics of the former, and the self-adhesion, rubber-like elasticity, low-temperature impact resistance, etc., which are the characteristics of the latter, coexist in a well-balanced manner, and when used in the present invention. Is extremely useful. The VLD
PE can be produced using a catalyst system in which a solid catalyst component containing at least magnesium and titanium and / or vanadium is combined with an organoaluminum compound.

The ethylene-vinyl ester copolymer (B2) is a vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, stearin produced by a high pressure radical polymerization method and containing ethylene as a main component. It is a copolymer with vinyl ester monomers such as vinyl acid acid and vinyl trifluoroacetate and other unsaturated monomers. Among these, ethylene-vinyl acetate copolymers are particularly preferable. That is, ethylene 50 to 99.5% by weight, vinyl acetate 0.5
Copolymers consisting of .about.50% by weight and 0 to 25% by weight of other unsaturated monomers are preferred.

The copolymer (B3) with the ethylene-α, β-unsaturated carboxylic acid alkyl ester derivative is a copolymer of ethylene with an α, β-unsaturated carboxylic acid alkyl ester and other unsaturated monomers. Examples thereof include polymers and their metal salts, amides, imides, and the like, with preference given to ethylene-ethyl acrylate copolymers and the like produced by a high-pressure radical polymerization method. That is, a copolymer composed of 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of acrylic acid ethyl ester and 0 to 25% by weight of another unsaturated monomer is preferable.

The other unsaturated monomer is propylene,
Butene-1, hexene-1, 4-methylpentene-1,
C3-10 olefins such as octene-1, decene-1, vinyl esters of C2-C3 alkanecarboxylic acids, acrylic acid or methyl methacrylate, acrylic acid or ethyl methacrylate, acrylic acid or propyl methacrylate, glycidyl acrylate Or acrylic acid or methacrylic acid esters such as glycidyl methacrylate, acrylic acid, methacrylic acid, maleic acid,
It is at least one selected from the group consisting of ethylenically unsaturated carboxylic acids such as fumaric acid and maleic anhydride, or their anhydrides.

Examples of the (B4) rubber include ethylene propylene rubber, butadiene rubber, isoprene rubber, natural rubber, nitrile rubber and isobutylene rubber, and these may be used alone or as a mixture.

The ethylene propylene rubber is a random copolymer (EPM) containing ethylene and propylene as main components, and a diene monomer (dicyclopentadiene, ethylidene norbornene, etc.) as a third component added as a main component. Random copolymer (EPDM)
Refers to.

The butadiene-based rubber means a copolymer having butadiene as a constituent element, and is a styrene-butadiene block copolymer (SBS) and its hydrogenated or partially hydrogenated derivative, styrene-butadiene-ethylene copolymer. Examples thereof include polymer (SBES), 1,2-polybutadiene (1,2-PB), maleic anhydride-butadiene-styrene copolymer, and modified butadiene rubber having a core-shell structure.

The above isoprene rubber means a copolymer having isoprene as a constituent element, and is a styrene-isoprene block copolymer (SIS) and a styrene-isoprene-ethylene copolymer which is a hydrogenated or partially hydrogenated derivative thereof. (SIES), modified isoprene rubber having a core-shell structure and the like are exemplified.

Among the ethylene (co) polymers or rubbers which are the component (B) in the present invention, VLDPE is most preferable. The MFR of the VLDPE is 0.1-50g / 10mi
n., preferably 0.5 to 20 g / 10 min. If the MFR is less than 0.1 g / 10 min., The fluidity of the resin composition will be poor, and if it exceeds 50 g / 10 min. The amount of the ethylene (co) polymer or rubber compounded is 2 to 50% by weight. If it is more than 50% by weight, the rigidity and heat resistance are inferior, and if it is less than 2% by weight, the impact resistance, especially the impact resistance at low temperature is inferior, so it is preferable to select from this range.

Examples of the inorganic fine hollow body which is the component (C) in the present invention include glass balloons, silica balloons, alumina balloons, carbon balloons, shirasu balloons, aluminosilicate balloons, and the like. , Glass balloons are most preferred.
Glass balloons have an average particle size of 5 to 200 μm, preferably 10 to 100 μm, and an apparent specific gravity of 0.4 to 1.0 g / c.
m ³ , preferably 0.5 to 1.0 g / cm ³ , pressure strength 400
It is desirable to be kg / cm ² or more. Average particle size is 200μ
If it exceeds m, the surface smoothness of the molded product will be deteriorated and the appearance will be deteriorated. If the apparent specific gravity is 0.4 g / cm ³ or less, the compression strength will be decreased, and when extruded when the resin component is mixed and melted. When the hollow body is destroyed by the pressure and shearing force of the molding machine or injection molding machine, and the contraction pressure when the crystalline resin is solidified, the specific gravity of the molded product is 1.0 g / cm ³ or more. Becomes higher and the purpose of weight reduction cannot be achieved. The compounding amount of the inorganic micro hollow body is 5 to 10 parts by weight based on 100 parts by weight of (A) + (B).
0 parts by weight. If the amount is less than 5 parts by weight, the rigidity is insufficient and the object of weight reduction cannot be achieved. If the amount is more than 100 parts by weight, kneading is difficult.

When the inorganic micro hollow body is used in the present invention, the surface thereof is coated with a fatty acid such as stearic acid and oleic acid or paraffin, wax, organic silane, organic titanate, epoxy resin and the like. It is preferably applied.

The functional groups contained in the resin composition containing an inorganic microhollow body in the present invention include a: carboxylic acid group or acid anhydride group, b: epoxy group, c: hydroxyl group, d:
Amino group, e: alkenyl cyclic iminoether group, f:
It is at least one functional group selected from silane groups.

The functional group a: a compound for introducing a carboxylic acid group or an acid anhydride group, maleic acid, fumaric acid,
Α, β-Unsaturated dicarboxylic acids such as citraconic acid and itaconic acid, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, furanic acid, crotonic acid, vinylacetic acid and pentenoic acid, or these α, β-unsaturated dicarboxylic acids Examples thereof include esters of acid or unsaturated monocarboxylic acids or anhydrides.

B: As a compound for introducing an epoxy group, glycidyls such as glycidyl acrylate and glycidyl methacrylate, monoglycidyl itaconic acid ester,
Butene tricarboxylic acid monoglycidyl ester, butene tricarboxylic acid diglycidyl ester, butene tricarboxylic acid triglycidyl ester, α-chloroacrylic acid glycidyl ester, maleic acid glycidyl ester,
Glycidyl esters such as glycidyl crotonic acid and glycidyl fumaric acid, or glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyl oxyethyl vinyl ether, and styrene-p-glycidyl ether Examples thereof include p-glycidyl styrene and the like, and particularly preferable examples include glycidyl methacrylate and allyl glycidyl ether.

C: 1-hydroxypropyl (meth) acrylate as a compound for introducing a hydroxyl group,
2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate and the like can be mentioned.

D: As a compound for introducing an amino group,
Aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, phenylaminoethyl (meth ) Acrylate, cyclohexylaminoethyl (meth) acrylate and the like.

E: The compound having an alkenyl cyclic iminoether group introduced is represented by the following structural formula (Formula 1). Here, n is an integer of 1 to 3, preferably 2 and 3, and more preferably 2. Also R ¹ , R
² , R ³ and R each represent a C1 to C12 inactive alkyl group and / or hydrogen, and the alkyl group may have an inactive substituent. The term "inert" as used herein means that the graft reaction and the function of the product are not adversely affected. Also, all R need not be the same. Preferably R ¹ = R ² = hydrogen, R ³ = hydrogen or methyl group, R = hydrogen ie 2-vinyl and / or 2-isopropenyl-2-oxazoline, 2-vinyl and / or 2-isopropenyl-5 , 6-dihydro-4H-1,3-oxazine. These may be used alone or as a mixture. Among these, especially 2-vinyl and /
Alternatively, 2-isopropenyl-2-oxazoline is preferable.

[0029]

[Chemical 1]

F: As a compound for introducing a silane group,
Examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, vinyltrichlorosilane and the like. Of these functional groups, those containing a maleic anhydride group are most preferred.

As a specific method for introducing at least one kind of the functional group into the resin composition containing an inorganic micro-hollow body in the present invention, a method of introducing the functional group as a modified polyolefin resin obtained by grafting the functional group on a polyolefin resin. , A method of introducing as a random copolymer of ethylene and the functional group-containing compound, a method of introducing a polyolefin resin and the functional group by addition reaction with an extruder or the like in the presence of an organic peroxide and the like. Can be mentioned.

The polyolefin resin is a polypropylene polymer or a highly crystalline polyolefin resin such as polyethylene having a density of 0.94 g / cm ³ or more,
Low-density polyethylene or ethylene / α by high-pressure radical polymerization having a density of 0.86 to less than 0.94 g / cm ^3.
Examples thereof include ethylene (co) polymers such as -olefin copolymers, ethylene-vinyl ester copolymers, ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymers, and rubbers. Among these, the density is 0.86-0.
Ethylene / α-olefin copolymers of less than 94 g / cm ³ are preferred.

At least one of the compounds having the above functional group
Examples of the method for graft-modifying the seed to the polyolefin-based resin or rubber include a solution method in which the polyolefin-based resin or rubber is dissolved and reacted in an appropriate organic solvent, and a melting method in which the components are melt-kneaded and reacted. However, among these, the melting method is preferable.

Further, the content of the functional group in the polyolefin resin is 10 ^-8 to 10 ^-5 g equivalent, preferably 10 ^-7 , per 1 g of the resin in the case of the graft modified copolymer.
It is difficult to produce a graft-modified copolymer having an addition amount in the range of 10 ^-6 g equivalent and a concentration exceeding 10 ^-5 g equivalent. Further, in the case of a random copolymer, it is 10 ^-6 to 10 ^-3 g equivalent per 1 g of resin, preferably 10 ^-5.
It is selected in the range of 10 ^-4 g equivalent. It is difficult to produce a random copolymer having an added amount of a concentration exceeding 10 ⁻³ g equivalent.

The resin composition containing an inorganic micro-hollow body in the present invention is prepared so that the functional group is in the range of 10 ^-3 g equivalent or less per 1 g of the whole polymer, preferably in the range of 10 ^-8 to 10 ^-3. To be done. When prepared in the range of 10 ⁻⁸ to 10 ^−3, the effect of improving mechanical strength such as tensile strength and impact resistance is remarkable. In the present invention, 1 g equivalent of the functional group contained per 1 g of the whole polymer means 1 mol of the compound introducing the functional group. Among the modified polyolefin resins containing these functional groups or random copolymers of ethylene and functional group-containing compounds, maleic anhydride modified ethylene.
α-Olefin copolymers are preferably used.

In the present invention, with respect to the composition containing the components (A) to (C) and the specific functional group, an inorganic filler and a flame retardant are used as long as the characteristics of the present invention are not impaired. At least one kind can be blended to impart and improve properties such as heat resistance and flame retardancy. Examples of the inorganic filler include powders, flat plates, needles, spheres, fibers, and the like. Specific examples include calcium carbonate, magnesium carbonate, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, and alumina. Powder filler such as silica sand, iron oxide, metal powder, antimony trioxide, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, foil of mica, sericite, pyrophyllite, aluminum flake, etc. Fillers, flat or scaly fillers such as carbon graphite, glass fibers, carbon fibers, graphite fibers, whiskers, metal fibers, silicone carbide fibers, asbestos, mineral fibers such as wollastonite, etc. You can

As the flame retardant, a generally effective flame retardant can be used, and at least one selected from the group consisting of halogen flame retardants, phosphorus flame retardants, inorganic flame retardants and the like depending on the purpose and application. Is selected. For example, an organic flame retardant such as a halogen-based flame retardant can impart excellent flame retardancy with a small amount of addition, and an inorganic flame-retardant such as magnesium hydroxide can be used when providing a halogen-free composition. It is preferably used for.

When the inorganic filler is used in the present invention, its surface is subjected to surface treatment such as coating with a fatty acid such as stearic acid or oleic acid or paraffin, wax, organic silane, organic titanate, epoxy resin or the like. Is preferred.

Further, in the present invention, (A) to (C)
When a component containing a component and a specific functional group is mixed and melted and molded, an antistatic agent, an antifogging agent, an organic filler, an antioxidant, a lubricant, an organic or Inorganic pigments, UV inhibitors, dispersants, plasticizers,
Known additives such as a nucleating agent, a foaming agent, and a crosslinking agent can be added within a range that does not substantially impair the characteristics of the present invention.

The composition of the present invention can be easily prepared by a known method which is generally used as a conventional resin composition preparation method. For example, a composition comprising the above components (A) to (C), or a composition containing the components (A) to (C) and a specific functional group, optionally a flame retardant, an additive in a tumbler, a ribbon blender or a Henschel. After dry blending using a mixer such as a type mixer, the resin composition is obtained by melt-mixing with a continuous melt-kneader such as a single-screw extruder or a twin-screw extruder and extruding to prepare pellets. be able to. In addition, a part of the components are dry blended and supplied to a single-screw extruder, a twin-screw extruder, etc.
Among the rest of the constituent components, pellets may be prepared by a method such as supplying a component such as a glass balloon that is easily broken during melt mixing by side-feeding from the intermediate portion of the extruder to obtain the resin composition. it can. In the present invention, of these methods, the method of supplying a glass balloon by side feed is preferable. The pellets thus obtained can be molded into electric and electronic parts, building materials, automobile parts and the like, which are the fields of application of the present invention, by a commonly used injection molding method, extrusion molding method or the like.

[0041]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention. (A) Used in Examples and Comparative Examples
The component (D) is shown below. (A) component: A1: polypropylene [Density = 0.905 g / cm ³ , MFR = 8 g / 10 min., Product name: Nisseki Polypro J650G, Nippon Petrochemical Co., Ltd.
Made] A2: Polyethylene [Density = 0.948g / cm ³ , MFR = 7g / 10min., Product name: Nisseki Stafren E870, Nippon Petrochemical Co., Ltd.
Made]

Component (B) (ethylene copolymer or rubber): B1: VLDPE [Density = 0.905 g / cm ³ , MFR = 5 g / 10 min., Tm
= 120 ° C. n-hexane insoluble matter = 94 Wt%, trade name:
Nisseki Softlex D9550, Nippon Petrochemical Co., Ltd.
Made] B2: ethylene-propylene copolymer rubber [propylene = 27 Wt%, MFR = 0.7 g / 10 min.,
Trade name: EP07P manufactured by Nisseki Synthetic Rubber Co., Ltd.] B3: Ethylene-ethyl acrylate copolymer [EA content = 10 Wt%, MFR = 3 g / 10 min., Trade name: Nisseki Lexlon A3100, Nippon Petrochemical ( stock)
Made]

Component (C) (inorganic micro hollow material): C1: glass balloon [average particle size = 50 μm, average particle density = 0.60 g / c
m ³ , pressure strength = 700 kg / cm ² , product name: Glass Bubbles S60 / 1000, manufactured by Sumitomo 3M Ltd.]

Component (D) (polyolefin resin containing a functional group): D1: Maleic anhydride-modified ethylene / α-olefin copolymer [density = 0.92 g / cm ³ , MFR = 1.2 g / 10 min.
, Product name: Nisseki N Polymer L6200, manufactured by Nippon Petrochemical Co., Ltd.] D2: ethylene-glycidyl methacrylate copolymer [density = 0.928 g / cm ³ , MFR = 3 g / 10 min.,
Product name: Nisseki Lexpearl RA3050 manufactured by Nippon Petrochemical Co., Ltd.]

(Pellet preparation device and conditions) Blender: Tumbler Extruder: [65 mmφ, same direction twin-screw extruder, screw L / D = 30, with side feed supply section] Extrusion temperature: 230 ° C. (cylinder temperature 230 ° C., die Temperature 210 ℃) Glass balloon: Supplied by side feeder

(Physical property test method) Density: According to JIS K6758 MFR: 〃 〃 Tensile fracture strength: 〃 〃 Tensile fracture elongation: 〃 〃 Bending elastic modulus: ASTM D790 〃 Iso impact value: JIS K7110 〃

(Examples 1 to 5) The compositions shown in Table 1 were tested using polypropylene as the component (A). The test results are shown in Table 1.

Comparative Example 1 A test was conducted in the same manner as in Example 1 except that the component (B) was not used. The test results are shown in Table 1. Izod impact strength is extremely poor.

Comparative Example 2 The same test as in Example 4 was conducted except that the component (B) was not used. The test results are shown in Table 1. Izod impact strength is insufficient.

(Comparative Example 3) The component (A) was 40% by weight and the component (B) was 60% by weight.
The same test as in Example 1 was carried out except that the scope of the present invention was exceeded. The test results are shown in Table 1. The tensile strength and flexural modulus are extremely poor.

Comparative Example 4 The same test as in Example 1 was carried out except that the component (C) was not used. The test results are shown in Table 1. The tensile strength and flexural modulus were remarkably poor, and the initial purpose of weight reduction could not be achieved.

[0052]

[Table 1]

Example 6 The composition shown in Table 2 was tested using high density polyethylene as the component (A). The test results are shown in Table 2.

Comparative Example 5 A test was conducted in the same manner as in Example 6 except that the component (B) was not used. The test results are shown in Table 2. Poor tensile strength and Izod impact strength.

[0055]

[Table 2]

[0056]

Industrial Applicability The resin composition containing an inorganic micro hollow body of the present invention comprises (A) a polypropylene polymer and / or polyethylene having a density of 0.94 g / cm ³ or more, and (B) a specific ethylene ) A composition in which a specific amount of (C) the inorganic microhollow body is mixed with a polymer component having a specific composition of a polymer or rubber, or a composition containing a specific amount of a specific functional group in the composition. Therefore, the weight of molded products is reduced without deteriorating dimensional stability and molding processability, and high rigidity, heat resistance, wear resistance, etc. are added. Impact resistance, especially impact resistance at low temperature It is an excellent composition. INDUSTRIAL APPLICABILITY The resin composition containing an inorganic microhollow body of the present invention can be widely and effectively used for electric and electronic parts, building materials, automobile parts and the like, and thus has high industrial utility value.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display area C08L 23/16 LCY

Claims (2)

[Claims] 1. (A) Polypropylene polymer and / or polyethylene having a density of 0.94 g / cm ³ or more 50 to 98% by weight, (B) at least one selected from the following (B1) to (B4) 2-50% by weight of ethylene (co) polymer or rubber, and (B1) low-density polyethylene or ethylene by high-pressure radical polymerization with a density of 0.86 to less than 0.94 g / cm ^3.
α-olefin copolymer, (B2) ethylene-vinyl ester copolymer, (B3) ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, (B4) rubber, 100 parts by weight of (A) + (B) above And (C) 5 to 100 parts by weight of the inorganic microhollow body, an inorganic microhollow body-containing resin composition. 2. A polypropylene-based polymer and / or a polyethylene having a density of 0.94 g / cm ³ or more. (B) At least one ethylene (co) selected from the following (B1) to (B4). Polymer or rubber (B1) density 0.8
Low density polyethylene or ethylene / α-olefin copolymer by high pressure radical polymerization of ^{6 to} less than 0.94 g / cm ³ , (B2) ethylene-vinyl ester copolymer, (B
3) Ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, (B4) rubber, (A) + (B) 100 parts by weight, and (C) inorganic microhollow body 5-100 parts by weight The content of the component (A) in the components (A) + (B) is 50 to 98% by weight, the content of the component (B) is 2 to 50% by weight, and the total polymer An inorganic microhollow body-containing resin composition, wherein the component contains at least one functional group selected from a to f below in an amount of 10 ^-3 g equivalent or less per 1 g of the total polymer. a: carboxylic acid group or acid anhydride group b: epoxy group c: hydroxyl group d: amino group e: alkenyl cyclic iminoether group f: silane group