JPH0726076A - Filled resin composition and stretched film thereof - Google Patents

Abstract

PURPOSE:To provide a filled resin compsn. improved in elastic recovery, strength, hand, gas permeability and weatherability by using a specific ethylene-3 C or higher alpha-olefin copolymer and a granular inorg. filler. CONSTITUTION:The compsn. comprises (A) 20-80wt.% ethylene-3C or higher alpha-olefin copolymer having an MFR of 0.01 to 20g/10min, a density of at most 0.935g/cm<3>, and an H/W value of at least 1 [wherein H is the peak height and W is the half width, provided that the number of peaks in the elution curve obtd. by temp. rising elution fractionation(TREF) is 1 and the peak temp. is 30 to 100 deg.C], and satisfying such conditions that Y<=-4,500D+4,105 (Y<=100) [wherein Y is the amt. of elution by TREF at 50 deg.C and D is the density of the component (A)] when D is at most 0.91g/cm<3>, and Y<=10 when D is at least 0.91g/cm<3>; and (B) 80-20wt.% granular inorg. filler of at most 10mum in average particle size and 0.1 to 0.7g/cm<3>. If necessary, 100 pts.wt. in total of the component (A) and (B) may be blended with (C) 0.1 to 15 pts.wt. dispersant for the component (B).

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is suitable for thin air-permeable molded products having excellent elastic recovery, strength, and texture for sanitary materials and having significantly excellent air permeability, and further for outdoor applications. When used in, with excellent air permeability and strength, it is also suitable for thin air-permeable molded articles having excellent weather resistance and no smoke or roll stains during processing, and a stretchable good filler-containing resin composition and The present invention relates to a stretched film using the composition.

[0002]

2. Description of the Related Art It is already known that a film made of a composition of an olefin resin and an inorganic filler is uniaxially or biaxially stretched to produce a breathable film having continuous (through) voids. The film using this composition is a sanitary material such as disposable paper diapers; a rain-preventing sheet that covers under roof tiles and outer walls to protect the water resistance of timber construction; keeps trees warm at the roots of fruit trees, etc. It is used as a ventilation sheet for outdoor use such as a protective sheet laid for protection. However, it has been difficult to reduce the thickness of the conventionally proposed resin composition because the stretchability during molding is poor and the strength is insufficient. However, in order to save resources and rationalize products, there has been a demand for thinner walls, but conventional resin compositions have not been able to sufficiently meet such required performance. Further, as the performance required for such disposable diapers and the like, in addition to the above thinning, there is breathability, texture, etc., but in recent years, the demand for fitability has increased, and elastic recovery of the film is required. Has become. . That is, since a disposable diaper absorbs moisture, a product having poor air permeability is apt to cause stuffiness, and is not preferred by consumers. In addition, consumers are now demanding higher-grade products than conventional products, and paper diapers such as pants-type products that are in close contact with the body are also desired. Materials that shrink (elastic recovery) have been required. Furthermore, naturally, the texture has been desired to be better than the conventional one. Further, conventional breathable sheets and films for outdoor use have poor breathability and insufficient strength, making it difficult to reduce the wall thickness.
Further, since the weather resistance is insufficient, it deteriorates in 1 to 2 months when used in the summer, and becomes worn out. For this reason, a method of adding a weather resistance-imparting agent (ultraviolet ray inhibitor, light stabilizer) is used, but this causes smoke during molding,
There are many problems such as the chill roll is dirty with bleeding substances, the printability is poor even after it is made into a product, the ink is easily peeled off, and dirt such as dust is easily attached. It was insufficient for practical use.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a resin containing a filler having excellent stretchability, which has excellent elastic recovery, strength, and texture, and is capable of producing a remarkably excellent breathable thin-wall ventilation molded article. It is intended to provide a composition.

[0004]

[Means for Solving the Problems]

[Summary of the Invention] As a result of intensive studies to solve the above problems, the present inventors have blended an ethylene / α-olefin copolymer having specific properties with a specific inorganic filler, The present invention has been completed based on the finding that the above objects of the present invention can be achieved. That is, the filler-containing resin composition of the present invention is composed of the following components A and B, and the mixing ratio thereof is based on the total amount of both components A and B.
Is 20 to 80% by weight, and the component B is 80 to 20% by weight. Component A: Copolymer of ethylene and α-olefin having 3 or more carbon atoms having the following properties (a) to (c) (a) MFR of 0.01 to 20 g / 10 minutes (b) Density 0.935 g / cm ³ or less (c) One peak of the elution curve obtained by temperature rising elution fractionation (TREF), and the peak temperature is 30 to 10
0 ° C., H / W value is 1 or more when the height of the peak is H and the width of 1/2 of the height of the peak is W. (d) Temperature rising elution fractionation (TREF) ), The amount eluted at 50 ° C. (Y:% by weight relative to the total amount of component A) satisfies the following condition: When the density (D) of component A is less than 0.91 g / cm ³ , Y ≦ −4500D + 4105 ( However, Y ≦ 100) When the density (D) of component A is 0.91 g / cm ³ or more, Y ≦ 10 component B: the average particle size is 10 μm or less and the bulk density is 0.1 to 10 μm.
0.7 g / cm ³ granular inorganic filler

[Detailed Description of the Invention] [I] Constituents (1) Component A (ethylene / α-olefin copolymer having 3 or more carbon atoms) (a) Properties The filler-containing resin composition of the present invention is constituted. It is important to use the ethylene-C3 or more α-olefin copolymer as the component A having the following physical properties, preferably the following physical properties.

MFR The ethylene / α-olefin copolymer having 3 or more carbon atoms used in the present invention is MFR according to JIS-K7210.
(Melt Flow rate: Melt Flow rate) is 0.01 to 20 g / 10 minutes, preferably 0.1 to 10 g
/ 10 minutes, particularly preferably 0.5 to 5 g / 10 minutes. If the MFR is larger than the above range, molding becomes unstable. On the other hand, if the MFR is smaller than the above range, the resin pressure becomes too large and the production amount of the product decreases, which is not practical.

Density The ethylene / α-olefin copolymer having 3 or more carbon atoms used in the present invention has a density according to JIS-K7112 of 0.935 g / cm ³ or less, preferably 0.86 to 0.
930 g / cm ³ , particularly preferably 0.88 to 0.92
5 g / cm ³ , especially 0.88 or more 0.910 g / c
It is less than m ³ . When the density is higher than the above range, the stretched film has insufficient tensile strength and texture. Further, if the density is lower than the above range,
Blocking occurs due to stickiness on the film surface, making it unusable for practical use.

Peak Temperature of Elution Curve Obtained by Elevated Temperature Elution Fractionation The ethylene / α-olefin copolymer having 3 or more carbon atoms used in the present invention has an increased temperature elution fractionation (TREF: Te).
There is one or more peaks in the elution curve obtained by mperature Rising Elution Fractionation, and the peak temperature is 30 to 100 ° C, preferably 35 to 85 ° C, and particularly preferably 40 to 75 ° C. When the peak temperature of the elution curve exceeds the above temperature, the elastic recovery property becomes poor, so that it is not practical. Further, if the peak temperature of the elution curve is lower than the above temperature, the air permeability becomes insufficient, which is not preferable. Further, the height of this peak is set to H, and the height of the peak is 1 /
When the width of 2 is W, the value of H / W is 1 or more, preferably 1 to 20, particularly preferably 1 to 15, more preferably 1 to 10, most preferably 1 to 5 is there. If the above H / W is less than the above value, the amount of sticky components increases and the sealing property becomes poor over time, which is not practical.

Elution amount at 50 ° C. by temperature rising elution fractionation (TREF) Elution amount at 50 ° C. by temperature rising elution fractionation (TREF) of an ethylene / α-olefin copolymer having 3 or more carbon atoms used in the present invention ( (Y:% by weight based on the total amount of component A) preferably satisfies the following conditions. 1) When the density (D) of the component A is less than 0.91 g / cm ³ , Y ≦ −4500D + 4105 (where Y ≦ 1
00), preferably Y ≦ −4650D + 4238 (provided that Y ≦ 100). 2) When the density (D) of the component A is 0.91 g / cm ³ or more, Y ≦ 10, preferably Y ≦ 7. Measurement of elution curve by temperature rising elution fractionation Temperature rising elution fractionation
Ionation: TREF) is measured by "Jouranl of App
Based on the principle described in “lied Polymer Science, Vol 26, 4217-4231, (1981)” and “Procedural Meeting of the Polymer Symposium 2P1C09 (1985)”, it is performed as follows. T
The principle of REF measurement is that the polymer to be measured is first completely dissolved in a solvent. Then, it is cooled to form a thin polymer layer on the surface of the inert carrier. In such a polymer layer, the one that is easily crystallized is formed on the inside (the side close to the surface of the inert carrier), and the one that is difficult to crystallize is formed on the outside. Next, when the temperature is increased continuously or stepwise,
In the low temperature stage, the amorphous portion in the target polymer composition, that is, the one with a large degree of branching of the short-chain branch possessed by the polymer elutes, and as the temperature rises, the one with a lesser degree of branching elutes and finally branches. The measurement ends when the straight-chain portion with no elutes. It is possible to detect the concentration of the elution component at each temperature and to see the compositional distribution of the polymer from the graph drawn by the elution amount and the elution temperature.

Q value This ethylene-α-olefin copolymer having 3 or more carbon atoms has a size exclusion chromatography (Size Exclusion C
Q value (weight average molecular weight / number average molecular weight) determined by hromatography: SEC is 4 or less, preferably 3
The following, particularly preferably those showing physical properties of 2.5 or less,
The tensile strength is also large and preferable.

Boiling n-Hexane Extraction Amount When the composition of the present invention is used as a material such as a sheet for outdoor use, this ethylene / α-olefin copolymer having 4 or more carbon atoms has a boiling n-hexane extraction amount. Is 20% by weight
Or less, preferably 15% by weight or less, particularly preferably 10% by weight or less.
It is less than or equal to wt. When the amount of boiling n-hexane extracted exceeds the above range, the air permeability of the stretched film decreases, which is not preferable.

(B) Production of ethylene / α-olefin copolymer having 3 or more carbon atoms A method for producing an ethylene-α-olefin copolymer having 3 or more carbon atoms is described in JP-A-58-19309. , 59-95292, 60-35005, 60-.
No. 35006, No. 60-35007, No. 60-350
08, 60-35009, 61-130314
No. 3, JP-A-3-163088, European Patent Application Publication No. 420436, and US Pat. No. 505.
No. 5438 and International Publication WO 91/0425
No. 7, etc., that is, a metallocene catalyst, particularly a metallocene alumoxane catalyst, or a metallocene compound and a metallocene compound described below, for example, as disclosed in International Publication WO92 / 01723. It is a method of copolymerizing ethylene as a main component with α-olefin as a subordinate component by using a catalyst composed of a compound that reacts with and becomes a stable anion.

The compound that reacts with the metallocene compound to form a stable anion is an ionic compound or an electrophilic compound formed from an ion pair of a cation and an anion, and reacts with a metallocene compound to provide a stable ion. To form polymerization active species.

Of these, ionic compounds are represented by the following general formula (I
It is represented by I). General formula (II): [Q] ^{m +} [Y] ^m- (m is an integer of 1 or more) Q is a cation component of an ionic compound, and is a carbonium cation, tropylium cation, ammonium cation, oxonium cation, sulfonium. Cation,
Examples thereof include phosphonium cations and the like, and further examples include metal cations and organometallic cations, which are themselves easily reduced. These cations are listed in Table 1-5
Not only a cation capable of giving a proton as disclosed in Japanese Patent No. 01950 but also a cation not giving a proton may be used. Specific examples of these cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, Triphenylphosphonium, trimethylphosphonium, tri (dimethylphenyl) phosphonium,
Tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion,
Examples thereof include platinum ion, palladium ion, mercury ion, and ferrocenium ion.

Y is an anion component of the ionic compound, which is a component that reacts with the metallocene compound to form a stable anion, and is an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic phosphorus compound. Examples thereof include anions, organic arsenic compound anions, organic antimony compound anions, and specific examples include tetraphenylboron and tetrakis (3,4,4).
5-trifluorophenyl) boron, tetrakis (3,3
5-di (trifluoromethyl) phenyl) boron, tetrakis (3,5- (t-butyl) phenyl) boron, tetrakis (pentafluorophenyl) boron, tetraphenylaluminum, tetrakis (3,4,5-trifluorophenyl) ) Aluminum, tetrakis (3,5-
Di (trifluoromethyl) phenyl) aluminum, tetrakis (3,5-di (t-butyl) phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, tetraphenylgallium, tetrakis (3,3)
4,5-trifluorophenyl) gallium, tetrakis (3,5-di (trifluoromethyl) phenyl) gallium, tetrakis (3,5-di (t-butyl) phenyl)
Gallium, tetrakis (pentafluorophenyl) gallium, tetraphenyl phosphorus, tetrakis (pentafluorophenyl) phosphorus, tetraphenyl arsenic, tetrakis (pentafluorophenyl) arsenic, tetraphenyl antimony, tetrakis (pentafluorophenyl) antimony, decaborate, undeca Examples thereof include borate, carbadodegaborate, and decachlorodecaborate.

As the electrophilic compound, among the compounds known as Lewis acid compounds, those which react with a metallocene compound to form a stable anion to form a polymerization active species, and various metal halide compounds and Examples thereof include metal oxides known as solid acids. Specific examples include magnesium halides and Lewis acidic inorganic oxides.

Α-Olefin Here, the α-olefin has 3 or more carbon atoms, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4
-Methylpentene-1,4-methylhexene-1,4,
4-dimethylpentene-1, octadecene and the like can be mentioned. Among these α-olefins, the number of carbon atoms is preferably 4 to
12, particularly preferably 6 to 10 of 1 or 2 or more α
-Olefin 2-60 wt%, preferably 5-50 wt% and ethylene 40-98 wt%, preferably 50-9
It is preferable to copolymerize with 5% by weight.

[0018] The polymerization method for copolymerizing the ethylene · alpha-olefin copolymer, a gas phase method, slurry method, a solution method and a high pressure ion polymerization method. Among these, the solution method and the high-pressure ionic polymerization method are preferable, and the high-pressure ionic polymerization method is particularly preferable. The high-pressure ionic polymerization method refers to JP-A-56-18607 and JP-A-58-2251.
No. 06, the pressure is 200 kg /
cm ² or more, preferably 300 to 2,000 kg / c
m ² , the temperature is 125 ° C. or higher, preferably 130 to 250
It is a continuous process for producing an ethylene-based polymer, which is carried out under reaction conditions of 150 ° C., particularly 150 to 200 ° C.

(2) Component B (Granular Inorganic Filler) As the granular inorganic filler of the component B constituting the filler-containing resin composition of the present invention, one having the following physical properties (a) to (b) is used. is important. (A) Average particle size The average particle size of the granular inorganic filler of the component B used in the present invention is 10 μm or less, preferably 0.1 to 5 μm or less,
It is particularly preferably 0.5 to 2 μm or less. In order to obtain the average particle diameter, the specific surface area is measured by the air permeation method and calculated by the following formula. dm = 60,000 / (ρ · Sw) [In the formula, dm represents the average particle size (μm), ρ represents the true specific gravity of the filler (g / cm ³ ), and Sw represents the specific surface area of the filler (cm ^2). / G)] As a specific surface area measuring device, for example, Shimadzu powder specific surface area measuring device SS-100 type can be used, and Kozeny-Carman
The specific surface area can be determined by applying the formula When the average particle size of the granular inorganic filler is too large, the appearance of the stretched film is impaired, and in the case of producing a thin stretched film having a thickness of 100 μm or less, perforation, stretching unevenness, etc. occur, so stable stretching The sex is lost.

(B) Bulk Density The bulk density (measured according to JIS K5101) of the granular inorganic filler of the component B used in the present invention is 0.1.
0.7 g / cm ³ , preferably 0.2 to 0.6 g / c
It has a physical property of m ³ , particularly preferably 0.3 to 0.5 g / cm ³ . If the bulk density of the above-mentioned granular inorganic filler is too small, the breathability of the stretched film will be reduced, and if it is too large, the strength of the film will be reduced and there is a problem in practicality.

(C) Water Content The granular inorganic filler of the component B used in the present invention has a water content of 3,000 ppm or less, preferably 1,000 ppm or less. If the water content in the granular inorganic filler exceeds the above range, a foaming phenomenon easily occurs during molding, making it difficult to perform stable film molding, or causing poor appearance such as hue failure or film,
The filler is likely to be secondarily aggregated, which tends to cause poor appearance and poor stretching. Such inorganic fillers include calcium carbonate, calcium oxide, zeolite, amorphous aluminosilicate, clay,
Synthetic silica, titanium oxide, alumina, barium sulfate, aluminum sulfate, magnesium hydroxide and the like, among which calcium carbonate, zeolite, amorphous aluminosilicate, barium sulfate, synthetic silica, magnesium hydroxide and the like are preferred, especially calcium carbonate and Barium sulfate is preferred. These may be used alone or in combination of two or more.

(3) Component C (Dispersant) The filler-containing resin composition of the present invention basically comprises the above-mentioned components A and B, but additionally, a dispersant for granular inorganic filler is added. 0.1 to 15 parts by weight, preferably 0.5 to 7 parts by weight, based on 100 parts by weight of both components.
Parts by weight, particularly preferably 1 to 5 parts by weight, can be added. As the dispersant, a saturated or unsaturated fatty acid ester having 9 to 40 carbon atoms, a triglyceride using a saturated or unsaturated fatty acid having 2 to 30 carbon atoms, a liquid or a waxy hydroxyl-terminated liquid polybutadiene hydrogenated poly Hydroxy saturated hydrocarbons, liquid or waxy hydrocarbon polymers or mixtures of the copolymers with epoxy group-containing organic compounds, titanic acid esters, monohydric higher alcohols or their derivatives, higher fatty acid amides, higher amines, saturated or Use of liquid or wax-like components such as homopolymers, copolymers, ether compounds, amine compounds, amide compounds, ester compounds and other alcohol derivatives derived from unsaturated dihydric or higher alcohols. You can These may be used alone or in combination of two or more. Among the above, saturated or unsaturated fatty acid ester having 9 to 40 carbon atoms, triglyceride using saturated or unsaturated fatty acid having 2 to 30 carbon atoms, polyhydroxy saturated obtained by hydrogenating liquid or waxy hydroxyl-terminated liquid polybutadiene Preference is given to using hydrocarbons. Of these, saturated or unsaturated fatty acid esters having 9 to 40 carbon atoms are particularly preferable.

[0023] Specific examples of the unsaturated fatty acid esters above unsaturated fatty acid esters, for example, (poly) ethylene glycol oleate, (poly) propylene glycol oleate, glyceryl oleate,
Sorbitan oleate, (poly) ethylene glycol sorbitan oleate, butyl oleate, pinacol oleate, m-cresol oleate, pentaerythritol oleate, glyceryl linoleate, glyceryl ricinoleate, methylricinoleate, ethylricinoleate, butylricinate Nolate, methyl acetyl ricinoleate, ethyl acetyl ricinoleate, butyl acetyl ricinoleate, (poly) ethylene glycol ricinoleate,
Examples thereof include glyceryl acetyl ricinoleate and glyceryl erucate. Among these, glyceryl hydroxy unsaturated fatty acid ester is preferable, and glyceryl ricinoleate is particularly preferable, and glyceryl triricinoleate is particularly preferable.

[0024] Specific examples of the saturated fatty acid ester wherein the saturated fatty acid esters, (poly) ethylene glycol laurate, (poly) propylene glycol laurate, glyceryl Rirura weight, sorbitan laurate, glyceryl myristate, glyceryl palmitate, Buchirusutea Rate, ethylene glycol stearate, propylin glycol stearate, pinacol stearate, m-cresol stearate,
(Poly) ethylene glycol stearate, (poly) propylene glycol stearate, glyceryl stearate, pentaerythritol stearate, sorbitan stearate, (poly) ethylene glycol sorbitan stearate, methyl hydroxystearate, ethyl hydroxy stearate, butyl hydroxy Stearate, methyl acetyl hydroxy stearate, ethyl acetyl hydroxy stearate, butyl acetyl hydroxy stearate, ethylene glycol hydroxy stearate, propylene glycol hydroxy stearate, pinacol hydroxy stearate, m-cresol hydroxy stearate, (poly) ethylene glycol Hydroxy stearate, (poly) propylene glycol hydroxys Areto, pentaerythritol hydroxystearate, sorbitan hydroxystearate, ethylene glycol sorbitan hydroxystearate, glyceryl hydroxystearate, mention may be made of glyceryl acetyl hydroxystearate like.

Among these, ethylene glycol hydroxystearate, propylene glycol hydroxystearate, pinacol hydroxystearate, m
-Cresol hydroxy stearate, (poly) ethylene glycol hydroxy stearate, (poly) propylene glycol hydroxy stearate, pentaerythritol hydroxy stearate, sorbitan hydroxy stearate, ethylene glycol sorbitan hydroxy stearate, glycerin hydroxy stearate, glyceryl acetyl hydroxy Glyceryl hydroxy saturated fatty acid esters such as stearate are preferred. More preferred is glyceryl hydroxystearate, and particularly preferred is glyceryl tri-12-hydroxystearate.

When a saturated ester is used as the fatty acid ester, there is almost no smoke during molding, as compared with the case where an unsaturated ester is used. Moreover, the obtained stretched film is excellent in odorlessness. By adding the above components, the dispersibility of the granular inorganic filler in the polymer is remarkably improved, and thereby the stretchability of the film is improved, so that the film can be thinned and the air permeability is also improved, It also enhances the softness and makes the texture good.

(4) Component D (Copolymer of Ethylene and Cyclic Amino Vinyl Compound) The filler-containing resin composition of the present invention is basically composed of the above-mentioned components A and B. It may contain a copolymer with a cyclic aminovinyl compound represented by the following general formula (I). When this component D is used for applications requiring weathering resistance such as outdoor use, the weatherability and printability of the resin composition are improved, and smoke and roll stains during processing do not occur. A product with high properties can be obtained.

[0028]

[Chemical 2]

In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, and R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Typical examples of the cyclic aminovinyl compound represented by the above general formula (I) are as follows. 1) 4-acryloyloxy-2,2,6,6-tetramethylpiperidine 2) 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine 3) 4-acryloyloxy-1-ethyl-2 , 2,
6,6-Tetramethylpiperidine 4) 4-Acryloyloxy-1-propyl-2,2
6,6-Tetramethylpiperidine 5) 4-acryloyloxy-1-butyl-2,2
6,6-Tetramethylpiperidine 6) 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 7) 4-methacryloyloxy-1,2,2,6,6-
Pentamethylpiperidine 8) 4-methacryloyloxy-1-ethyl-2,2,2
6,6-Tetramethylpiperidine 9) 4-methacryloyloxy-1-butyl-2,2,2
6,6-Tetramethylpiperidine 10) 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine 11) 4-crotonoyloxy-1-propyl-2,
2,6,6-tetramethylpiperidine

The content of cyclic aminovinyl compound in the copolymer of ethylene and cyclic aminovinyl compound is less than 1 mol%,
It is preferably 0.1 to 0.7 mol%. The MFR of the copolymer is 0.1 to 200 g / 10 minutes, preferably 0.5 to 100 g / 10 minutes, and particularly preferably 0.7 to
It is 50 g / 10 minutes. The copolymer is disclosed, for example, in JP-A-4
It can be produced by the high pressure radical polymerization method described in JP-A-80215, and specifically, ethylene and a cyclic aminovinyl compound are contained in an amount of 1,000 to 5,000 kg /.
Radical polymerization is carried out at a pressure of cm ² and a temperature of 100 to 400 ° C.

[II] Amount ratio The mixing ratio of the above components A and B is based on the total amount of the components A and B, component A: component B = 20-80% by weight: 80-20% by weight, preferably Is component A: component B = 3
0 to 70% by weight: 70 to 30% by weight, particularly preferably component A: component B = 35 to 60% by weight: 65 to 40% by weight. If the blending ratio of the component B is less than the above range, the texture of the obtained stretched film is deteriorated, and if it is too much, the stretchability at the time of film molding is deteriorated, resulting in lack of practicality. When the component C (dispersant) is blended, the total amount of the component A and the component B is 100 parts by weight.
0.1 to 15 parts by weight, preferably 0.5 to 7 parts by weight, particularly preferably 1 to 5 parts by weight can be added. If the blending amount of this component is too small than the above range, when a stretched film is manufactured with a thin wall and at a low magnification, local necking occurs and the thickness becomes uneven, unevenness occurs, and the commercial value is significantly impaired. It will be. On the other hand, if the amount is too large, the molding processability is deteriorated, and the air permeability of the obtained stretched film is deteriorated, which is not preferable because it is impractical. Component D (copolymer of ethylene and cyclic amino vinyl compound)
In the copolymer, the cyclic aminovinyl compound unit in the copolymer is 0.05 to 5% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.1% by weight based on the total amount of the resin composition.
An amount of component D of 1 to 1% by weight is used. If the compounding ratio of the cyclic aminovinyl compound unit in the resin composition is less than the above range, the weather resistance will be insufficient and the effect of improving the printability will be reduced. On the other hand, if the amount exceeds the above range, the film strength will be insufficient and the film will be impractical.

[III] Production of Filler-Containing Resin Composition (1) Blending The filler-containing resin composition of the present invention is the same as the ordinary production method of resin compositions, and the ethylene of the component A and the number of carbon atoms are 3 or more. And the average particle size of the component B is 10 μm or less, and the bulk density is 0.1 to 0.7 g / cm ^3.
It can be produced by blending the granular inorganic filler (1), and optionally a dispersant of component C, and further a copolymer of ethylene and a cyclic aminovinyl compound of component D. Specifically, each component is well mixed with a Brabender such as a Henschel mixer, and if necessary, other additives are further added and mixed, and a twin-screw kneading extruder,
After being melted and kneaded by using a Banbury mixer, a kneader blender or the like, it is usually made into pellets by a commonly used method. The order of blending each component is basically arbitrary, but when blending component D, component A is blended.
It is preferable to mix component B after mixing and component D. However, in the master batch of component B and component D, or component A and component B, component A or component D
Can also be blended.

(2) Other additives In the filler-containing resin composition of the present invention, in addition to the above-mentioned dispersant, auxiliary additives generally used for resin compositions, such as antioxidants and heat stabilizers. A light stabilizer, an ultraviolet absorber, a neutralizing agent, a lubricant, an antifogging agent, an antiblocking agent, an antistatic agent, a slip agent, a colorant and the like may be added. Ethylene / α-olefin copolymers other than the above component A, high-pressure low-density polyethylene, high-density polyethylene,
Resins and rubber components such as polypropylene, polybutene, and ethylene / vinyl acetate copolymer can be used in the present invention as long as the effects of the present invention are not significantly impaired.

[IV] Stretched Film A filler-containing stretched film can be produced by melt-extruding the filler-containing resin composition of the present invention by a conventional method and then uniaxially stretching. As a method for producing the stretched film, a general method in stretched film molding, such as inflation molding or T-die molding, can be adopted. The resin composition of the present invention is melt extruded at a temperature equal to or lower than the melting point and uniaxially or biaxially stretched to obtain a stretched film. As the uniaxial stretching method, flat roll stretching, oven stretching, tube stretching or the like, and in biaxial stretching, a flat tenter stretching method, a tubular inflation stretching method, a mandrel stretching method or the like may be adopted. it can. A draw ratio of 1.2 to 6 times, preferably 1.2 to 4 times is suitable.

The stretched film formed from the resin composition of the present invention has many voids finely and uniformly compared to those formed from the conventional filler-containing resin composition, when the cross section in the longitudinal direction is observed. It is dispersed and the area occupied by only the resin surface is narrow (see FIGS. 1 and 2). When the range occupied by only this resin is wide or voids do not exist continuously from the front surface to the back surface of the film, the air permeability of the film becomes extremely poor, but this does not occur in the stretched film of the present invention. Therefore, the stretched film according to the present invention, for example, a film for sanitary materials such as paper diapers, sanitary products, medical clothes, and a rain protection sheet for wood construction,
It can be suitably used as a protective sheet for trees and the like.

A large void area ratio of the stretched film can be mentioned as an index showing that the stretched film formed by using the resin composition of the present invention has good air permeability. The void area ratio is a film cross section 100 in the machine direction (MD) of the stretched film.
The average void area per μm ² . The average void area is measured as follows. The filler-containing composition is melt-extruded, the stretch-formed film is cut into an appropriate size (for example, 10 mm × 2 mm), and this is embedded with an epoxy resin. The obtained sample is approximately −
It is cooled to 2.3 ° C. and the cross section of the film in the machine direction (MD direction) is cut vertically. Cut surface 15 with platinum / palladium
Coat to ~ 20 nm thickness. The coating surface was scanned with a scanning electron microscope and the acceleration voltage was 10 Kv, 2000
Observe at 2x and take a photo. From the photograph obtained, 10μ
The void area in m × 10 μm (100 μm ² ) is counted, and this is repeated about 6 to 10 times by changing the place,
The average value is calculated, and the value is defined as the void area ratio.

[0037]

EXAMPLES The present invention will be described in more detail below by describing experimental examples consisting of examples and comparative examples. [I] Physical Property Measuring Method and Evaluation Method Physical property measurement and evaluation in Examples and Comparative Examples were carried out by the following methods. (1) Measurement of physical properties (a) MFR: according to JIS-K7210 (b) Density: according to JIS-K7112

(C) Measurement of elution curve: Temperature rising elution fraction in the present invention
ation: TREF), the peak of the elution curve is that once the polymer is completely dissolved at a high temperature and then cooled, a thin polymer layer is formed on the surface of the inert carrier, and then the temperature is raised continuously or stepwise. And collect the eluted components,
The concentration is continuously detected, and the compositional distribution of the polymer is measured at the peak of a graph (elution curve) drawn by the amount of elution and the elution temperature.

The elution curve was measured as follows. Cross sorter as a measuring device (Mitsubishi Yuka Co., Ltd.)
Manufactured by CFC T150A) according to the measurement method in the attached operation manual. This cross sorting device
Temperature rising elution fractionation (TREF) mechanism that separates samples using the difference in melting temperature and size exclusion chromatograph (Size Exclusi) that separates the separated fractions by molecular size
on Chromatography (SEC) is an online device.

First, a sample (copolymer) to be measured is used in a solvent (o-dichlorobenzene) at a concentration of 4 mg /
It is melted at 140 ° C. so that it becomes ml, and this is injected into the sample loop in the measuring device. The following measurements are automatically performed according to the set conditions. The sample solution held in the sample loop is separated by utilizing the difference in melting temperature.
0.4 ml is injected into a REF column (a stainless steel column with an inner diameter of 4 mm and a length of 150 mm, which is attached to the apparatus and is filled with glass beads as an inert carrier). The sample is then cooled at a rate of 1 ° C./min from 140 ° C. to 0 ° C. and coated on the inert carrier. At this time,
A polymer layer is formed on the surface of the inert carrier in the order of the highly crystalline component (those that are easily crystallized) to the low crystalline component (that is difficult to crystallize). After the TREF column was kept at 0 ° C for an additional 30 minutes, 2 ml of the dissolved component at the temperature of 0 ° C
Is injected from the TREF column to the SEC column (3 AD80M / S manufactured by Showa Denko KK) at a flow rate of 1 ml / min. While the SEC classifies by molecular size,
In the TREF column, the temperature is raised to the next elution temperature (5 ° C),
Hold at that temperature for about 30 minutes. The measurement of each elution section by SEC was performed at 39 minute intervals. The elution temperature is raised stepwise at the following temperatures. 0, 5, 10, 15, 20, 25, 30, 35, 40,
45, 49, 52, 55, 58, 61, 64, 67, 7
0,73,76,79,82,85,88,91,9
4,97,100,102,120,140 ℃

The solution classified by the SEC column according to the molecular size was measured for the absorbance proportional to the concentration of the polymer with an infrared spectrophotometer attached to the apparatus (wavelength 3.42 μ, detected by stretching vibration of methylene). A chromatogram of the elution temperature range is obtained. Using the built-in data processing software, the baseline of the chromatogram of each elution temperature section obtained in the above measurement is drawn and the calculation processing is performed. The area of each chromatogram is integrated and an integrated elution curve is calculated. Also,
This integrated elution curve is differentiated with temperature to calculate the differential elution curve. The plot of the calculation result is output to the printer.
The plot of the output differential elution curve shows the elution temperature as 1 on the horizontal axis.
89.3 mm per 00 ° C, differential amount on vertical axis (total integrated elution amount was standardized to 1.0, and change amount at 1 ° C was used as differential amount)
It was performed at 76.5 mm per 0.1. Next, the peak height (mm) of this differential elution curve is ½ height width (mm)
The value divided by was taken as H / W.

(D) Q value: Measured using size exclusion chromatography (SEC) under the following measurement conditions, and weight average molecular weight /
The Q value was determined from the number average molecular weight. A universal calibration curve was prepared using monodisperse polystyrene and calculated as the molecular weight of linear polyethylene. Machine type: Waters Model 150C GPC Solvent: o-dichlorobenzene Flow rate: 1 ml / min Temperature: 140 ° C Measurement concentration: 2 mg / ml Injection volume: 200 μl Column: Showa Denko KK AD80M / S 3 bottles

(E) Average particle size: Determined by the Coulter counter method (dispersion method: 28KC ultrasonic wave for 5 minutes, 0.01% sodium hexametaphosphate). (F) Bulk density: According to JIS-K5101 (g) Boiling n-hexane Extraction amount: 5 ml of a film extruded by air-cooled inflation molding at 200 ° C. to a film thickness of 30 μm was put into a cylindrical filter paper, and then 200 ml
With a Soxhlet extractor infused with normal hexane,
Extract for 8 hours at boiling point. After drying this cylindrical filter paper for 60 minutes with a vacuum dryer, the weight loss is measured.

(2) Evaluation method (a) Tensile strength / elongation: in accordance with ASTM-D882-67 (b) Elastic recovery measurement: The film was measured at a gauge length of 10
mm, width 5 mm, punched into a dumbbell shape for a tensile test, and 100% at a tensile test speed of 500 mm / min. Elastic recovery property = [{100% distance between gauge marks after 2 cycles of stretching (mm) -10 mm} / 10 mm] x 100 (%) (c) Water vapor transmission rate: in accordance with JIS-Z0208 (d) Weather resistance: The film test piece was irradiated with ultraviolet rays under the conditions, and the tensile strength of the irradiated piece was measured. Time required for the elongation at the start of the weather resistance test to halve (h
r) was determined. Machine type: Sunshine weather meter manufactured by Suga Test Instruments Temperature: Adjusted to 63 ± 3 ° C using a black panel Light source: UV irradiation through a glass filter Cycle: Total 60 minutes, water 12 minutes, none 48 minutes (e) Printability: Wetting tension was measured. The measuring method is JIS
According to K6768 (f) Void area ratio: Performed by the method described above.

[II] Experimental Example Example 1 Preparation of Component A (Ethylene / C-C3 or more α-olefin
The copolymer) was prepared by the method described in JP-A-61-130314. That is, to a complex ethylene-bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride (2.0 mmol), methyl alumoxane (produced by Toyo Stoffer Co., Ltd.) was added in a molar amount of 1,000 times, and 10 liters of toluene were added. A catalyst solution was prepared by diluting the mixture with the above and polymerized by the following method. A mixture of ethylene and 1-hexene was added to a stirred autoclave-type continuous reactor having an internal volume of 1.5 liters so that the composition of 1-hexene was 8%.
It is supplied so as to be 0% by weight, and the pressure in the reactor is adjusted to 1,0
The reaction was carried out at a temperature of 160 ° C. while maintaining the pressure at 00 kg / cm ² . After the reaction was completed, the MFR was 3.3 g / 10 minutes, the density was 0.905 g / cm ³ , and the boiling n-hexane extraction amount was 1.
0.7 wt%, Q value is 2.0, TREF elution curve has one peak, its peak temperature is 62 ° C., H / W of the peak temperature is 4, and elution amount at 50 ° C. is 12 wt. %
To obtain an ethylene / α-olefin copolymer (1-hexene content 16% by weight).

Production of Filler-Containing Resin Composition The ethylene / α-olefin copolymer of the above component A and calcium carbonate having an average particle size of 1.0 μm and a bulk density of 0.4 were used as the component B. First, component A and component B were mixed with a Henschel mixer so that component A: component B = 40: 60% by weight, and then 3 parts by weight of glyceryl triricinolate (castor oil) was added and mixed, and biaxial kneading was performed. Using an extruder (screw diameter: 65 mm), the composition was extruded at a temperature of 200 ° C. to obtain pellets of each composition.

The pellets made from formed form this filler-containing resin composition, by the following method was subjected to a molding process. The pellets are extruded into a film at a temperature of 230 ° C. using a extruder (screw: diameter 40 mmφ, L / D: 24) and a T-die (die width: 300 mm, lip width: 1.2 mm), and this is short-term hot stretched. The film was uniaxially stretched with a roll at a stretching temperature of 85 ° C. and a stretching ratio of 2 to produce a breathable film having a thickness of about 20 μm or ˜30 μm. The film was evaluated. The results are shown in Table 1.

Examples 2 to 3 Resin compositions were obtained in the same manner as in Example 1 except that the components A, B and other components having the physical properties shown in Table 1 were used. . This was molded and evaluated. Table 1 shows the obtained evaluation results.

Comparative Examples 1 to 3 Molded and evaluated in the same manner as in Example 1 except that an ethylene / α-olefin copolymer having the physical properties shown in Table 1 prepared by using a Ziegler catalyst as the component A was used. did. The results obtained are shown in Table 1.

[0050]

[Table 1]

Example 4 Component D (ethylene / cyclic aminovinyl compound copolymer)
In a stirred autoclave-type continuous reactor, 4-acryloyloxy-2 dissolved in ethylene and ethyl acetate,
2,6,6-Tetramethylpiperidine was continuously supplied together with tertiary butyl peroxypivalate dissolved in normal hexane as a catalyst to obtain a polymerization pressure of 2,0.
Copolymerization was carried out under the conditions of 00 kg / cm ² and a polymerization temperature of 200 ° C. The MFR of the obtained copolymer was 2.7 g / 10.
Min, the content of 4-acryloyloxy-2,2,6,6-tetramethylpiperidine unit is 7.0% by weight (0.99
Mol%).

Production of Filler-Containing Resin Composition The same components A and B as those used in Example 1, glyceryl trilysylate (castor oil) as the component C and the above component D were used. 40 parts by weight of the component A, 60 parts by weight of the component B and 3.3 parts by weight of the component C were mixed in a Henschel mixer, and 3 parts by weight of the above dispersant was added to and mixed therewith to prepare a uniaxial kneading extruder ( Screw diameter 65mm)
Was extruded at a temperature of 200 ° C. to obtain pellets containing 0.22% by weight of 4-acryloyloxy-2,2,6,6-tetramethylpiperidine unit in the composition.

Molding The pellets made of this filler-containing resin composition were molded by the following method. The pellets are extruded into a film at a temperature of 230 ° C. using a extruder (screw: diameter 40 mmφ, L / D: 24) and a T-die (die width: 300 mm, lip width: 1.2 mm), and this is short-term hot stretched. Using a roll, the film was uniaxially stretched at a stretching temperature of 85 ° C. and a stretching ratio of 3 to produce a breathable film having a thickness of about 35 μm. The film was evaluated. At the time of molding, the presence or absence of smoke and stains on the chill roll was visually observed. The results are shown in Table 2.

Example 5 A resin composition was prepared in the same manner as in Example 4, except that the components A, B and other components having the physical properties shown in Table 1 were used. This was molded and evaluated. Table 2 shows the obtained evaluation results.

Comparative Examples 4 to 6 An ethylene / α-olefin copolymer having the physical properties shown in Table 2 which was produced by using a Ziegler catalyst as the component A was used, and according to the formulation shown in Table 2, the same as Example 4 The obtained stretched film was evaluated by molding. Comparative Example 5
Is a compound in which benzotriazole is blended as a weathering agent instead of the C component, and Comparative Example 6 is not blended. The obtained results are shown in Table 2.

[0056]

[Table 2]

[0057]

EFFECT OF THE INVENTION The filler-containing resin composition of the present invention as described above has excellent elastic recovery, strength, texture, weather resistance, good stretchability, and thin-wall ventilation molding having remarkably excellent air permeability. Since it is suitable for the body, it is particularly useful as a film material for sanitary materials such as disposable diapers, sanitary products, and clothing. Further, in particular, the resin composition containing the component D is
It has further improved weather resistance and printability, and is useful as a material for a rain shelter sheet for wood construction and a sheet for outdoor use which is laid for heat retention and protection of trees.

[Brief description of drawings]

FIG. 1 is an electron micrograph (× 2000) showing a cross-sectional structure of a stretched film (stretch ratio = 3) produced from the filler-containing resin composition described in Example 1.

FIG. 2 is an electron micrograph (× 2000) showing a cross-sectional structure of a stretched film (stretch ratio = 3) produced from the filler-containing resin composition described in Comparative Example 3.

[Explanation of symbols] 1 filler 2 voids

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area // B29K 23:00 105: 16

Claims (4)

[Claims] 1. The following component A and component B are contained, and the mixing ratio thereof is based on the total amount of both components A and B.
Component A is 20-80% by weight, component B is 80-20% by weight
A filler-containing resin composition comprising: Component A: Copolymer of ethylene and α-olefin having 3 or more carbon atoms having the properties (a) to (d) shown below (a) MFR of 0.01 to 20 g / 10 minutes (b) Density 0.935 g / cm ³ or less (c) One peak of the elution curve obtained by temperature rising elution fractionation (TREF), and the peak temperature is 30 to 10
0 ° C., H / W value is 1 or more when the height of the peak is H and the width of 1/2 of the height of the peak is W. (d) Temperature rising elution fractionation (TREF) ), The amount eluted at 50 ° C. (Y:% by weight relative to the total amount of component A) satisfies the following condition: When the density (D) of component A is less than 0.91 g / cm ³ , Y ≦ −4500D + 4105 ( However, Y ≦ 100) When the density (D) of component A is 0.91 g / cm ³ or more, Y ≦ 10 component B: the average particle size is 10 μm or less and the bulk density is 0.1 to 10 μm.
0.7 g / cm ³ granular inorganic filler 2. The component C further contains 0.1 to 15 parts by weight of a dispersant for the granular inorganic filler.
The resin composition described. 3. As component D, ethylene and the following general formula (I): embedded image (In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, and
³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) and a copolymer with a cyclic aminovinyl compound represented by the following formula: the cyclic aminovinyl compound unit in the copolymer is based on the total amount of the resin composition. The resin composition according to claim 1 or 2, which is contained in an amount of 0.05 to 5% by weight. 4. A breathable stretched film formed by melt-extruding the filler-containing composition according to any one of claims 1, 2 and 3 and uniaxially or biaxially stretching it.