JPH0622959B2 - Laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate. More specifically, the present invention relates to a laminate of a porous film having breathability and moisture permeability, which is suitable for use as clothes, packaging materials, over-materials, synthetic leather and the like.

[Prior Art] The present inventors have already filed an application for a porous film having air permeability and high flexibility (Japanese Patent Application No. 59-855).
02, Japanese Patent Application No. 59-88205, Japanese Patent Application No. 59-1143.
30) The films described in each of the above applications are mainly related to single-phase films, and when used for clothing, packaging, etc., the tear strength and the tensile strength may be insufficient depending on the application, Not very satisfactory.

[Structure of Invention]

As a result of intensive studies to eliminate the above-mentioned problems, the present inventors have developed a film (sheet) excellent in strength, breathability and moisture permeability by using a special laminated structure. .

That is, the gist of the present invention is the polyolefin resin 100.
A film obtained by melt-molding a composition comprising 25 to 400 parts by weight of a filler, 1 to 100 parts by weight of a liquid or wax-like hydrocarbon polymer and / or 1 to 100 parts by weight of an epoxy group-containing organic compound is stretched in at least one axial direction. The porous film obtained by laminating a reinforcing material on at least one side has a moisture permeability of 500 g / m ² · 24 hr or more and an air permeability of 5000.
It exists in the porous film laminate of sec / 100 cc or less.

As the polyolefin resin used in the present invention, high-density polyethylene and medium-density polyethylene linear low-density polyethylene are used alone or as a mixture of two or more kinds thereof, and the melt index of the polyethylene is 0.
01-10g / 10min (ASTM D-1238-70
190 ° C. The range of (measured at 2.16 kg) is preferable. Further, a branched low density polyethylene obtained by a high pressure method may be partially mixed with the polyethylene.

Crystalline polypropylene is also used. As the crystalline polypropylene, a homopolymer of propylene or a copolymer of propylene and another α-olefin is used alone or as a mixture of two or more kinds.

Inorganic and organic fillers are used as the filler, and as the inorganic filler, calcium carbonate, talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, and hydroxide are used. Aluminum, magnesium hydroxide, zinc oxide, calcium oxide, magnesium oxide, titanium oxide,
Alumina, mica, asbestos powder, glass powder, shirasu balloon, zeolite, silicate clay and the like are used, and as the organic filler, cellulosic powder such as wood powder and pulp powder is used.

These may be used alone or as a mixture.

The surface treatment of the filler is preferably carried out from the viewpoint of dispersibility in the resin and further stretchability, and treatment with a fatty acid or a metal salt thereof gives preferable results.

As the liquid or wax hydrocarbon polymer, liquid polybutadiene, liquid polybutene, liquid polyisoprene and their derivatives are used.

Among them, a carboxyl group- or hydroxyl group-terminated liquid polybutadiene is used, and a derivative of a hydroxyl group-terminated liquid polybutadiene, for example, a liquid matter whose terminal is modified with isocyanate, modified with maleic anhydride, modified with epoxy group or the like is also used.

Furthermore, a liquid polybutadiene hydrogenated product obtained by hydrogenating liquid polybutadiene, and a polyhydroxy saturated hydrocarbon obtained by hydrogenating a hydroxyl group-terminated liquid polybutadiene are used. The polyhydroxy saturated hydrocarbon is a hydrocarbon polymer in which the main chain having at least 1.5 hydroxyl groups per molecule is saturated or mostly saturated. The number average molecular weight of these is 400 to 20,000, and further 500 to 10.0.
00 is preferable.

Alternatively, a hydrogenated product of carboxyl group-terminated liquid polybutadiene may be used.

Examples of the epoxy group-containing organic compound include epoxidized vegetable oil such as epoxidized linseed oil and epoxidized soybean oil, an epoxy resin, and preferably an epoxy plasticizer such as a liquid epoxy resin containing no curing agent.

It should be noted that a heat stabilizer, an ultraviolet stabilizer, an antistatic agent, a pigment, a fluorescent agent, etc. may be added to the polyolefin resin according to a conventional method.

The mixing ratio of the polyolefin resin and the filler is 25 to 400 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the polyolefin resin. Further, the liquid or wax hydrocarbon polymer or the epoxy group-containing organic compound is 1 to 100 parts by weight, preferably 1 to 70 parts by weight. The epoxy group-containing organic compound is preferably used in combination with a hydrocarbon polymer rather than used alone.

When the blending ratio of the filler is less than 25 parts by weight, the uniaxially or biaxially stretched film does not sufficiently form pores and the porosity becomes low. On the other hand, if the blending ratio of the filler exceeds 400 parts by weight, the kneadability, dispersibility, and film formability are deteriorated.

When blending a liquid or wax-like hydrocarbon polymer or an epoxy group-containing organic compound, a polyolefin resin 1
If the amount exceeds 100 parts by weight with respect to 00 parts by weight, the properties of the polyolefin resin are weakened, and satisfactory kneading properties, film moldability and stretchability cannot be secured.

In mixing the polyolefin resin, the filler, the liquid or wax-like hydrocarbon polymer or the epoxy group-containing organic compound, an ordinary blender or mixer is used.

As the mixer, a drum, a tumbler type mixer, a ribbon blender, a Hensiel mixer, a super mixer or the like is used, but a high speed stirring type mixer such as a Henschel mixer is preferable.

Next, the kneading of the mixture is appropriately carried out by a conventionally known device, for example, a normal screw extruder, a twin screw extruder, a mixing roll, a Banbury mixer, a twin screw kneader and the like.

The film may be formed according to a usual film forming apparatus and forming method, and inflation molding with a circular die, T die extrusion with a T die, or the like may be appropriately adopted.

A porous film can be obtained by uniaxially or biaxially stretching the above film. The uniaxial stretching may be a tubular stretching in which the uniaxial direction (the take-up direction) is emphasized, but roll stretching is usually preferable. The stretching may be carried out in one stage or in multiple stages of two or more stages. Stretch ratio is 1.2
-6 times is preferable.

In the biaxial stretching, longitudinal stretching and transverse stretching may be performed sequentially or simultaneously, and the stretching ratio is 1.2 for both longitudinal stretching and transverse stretching.
It is preferably at least twice, more preferably at least 1.4 times.

In the sequential stretching, the stretching order may be the longitudinal stretching, that is, the transverse stretching or the reverse. As a stretching method,
Roll stretching, tenter method stretching or tube method stretching may be appropriately adopted. For example, a film obtained by inflation molding or T-die extrusion molding may be longitudinally stretched by rolls and then transversely stretched by a tenter, or inflation may be performed. The film obtained by molding may be longitudinally stretched by rolls and then transversely stretched by the tubula method, or vice versa. Further, simultaneous biaxial stretching may be carried out by a tenter method or a cubula method.

In the stretching, the longitudinal stretching may be performed in one stage or in multiple stages of two or more stages, and the same applies in the transverse stretching.

Further, heat treatment can be carried out to stabilize the dimensional accuracy of the film obtained by stretching.

The porous film used in the present invention has a moisture permeability of 500 g.
/ M ² · 24 hr or more, preferably 1000g / m ² · 24
hr or more, air permeability 5000 sec / 100 cc or less, preferably 3000 sec / 100 cc or less, and further 2000 sec / 1
It is desirable to use less than 00cc, but these will vary depending on the end use. The thickness of the film varies depending on the application, but is preferably 10 to 300 μm.

A feature of the film used in the present invention is that it has a low bending resistance in the machine and transverse directions.

The bending resistance of the film of the present invention is expressed by the following equation (1).

Bending degree ≦ 0.193 × film thickness + 35 (1) Here, the unit of the degree of bending is mm, and the unit of the film thickness is μ.

Therefore, by selecting the type of the reinforcing material, a flexible, air-permeable and moisture-permeable product can be obtained.

In the present invention, a reinforcing material is laminated on at least one surface of a highly flexible porous film obtained by the above method, and the reinforcing material may be a breathable material that does not impair the physical properties of the present film. For example, a split cloth made from a split yarn obtained by stretching a resin film, or a non-woven fabric or paper made by a wet or dry spunbond method or the like is used.

The laminating method in the present invention is not particularly limited. Generally, a hot melt type adhesive is applied in a spray or linear form, or a dry laminating adhesive is applied with a gravure roll, and a porous film and a reinforcing material are laminated and adhered. And a method of thermocompression-bonding the reinforcing material, and a method of thermocompression-bonding using a heat-fusion adhesive between the porous film and the reinforcing material.

The laminate of the present invention has an air permeability of 5000 sec / 100 cc or less and a moisture permeability of 500 g / m ² · 24 hr or more, and can be suitably used for packaging, clothing, and the like.

〔Example〕

Examples will be shown below for specifically explaining the present invention.
The present invention is not particularly limited to the following examples as long as the gist thereof is not exceeded.

Reference Example 1 (Production of Polyhydroxy Saturated Hydrocarbon) Liquid polybutadiene commercially available in an autoclave with a capacity of 10 [manufactured by Nippon Soda Co., Ltd .: G-2000 average molecular weight 200]
0] 3 kg, cyclohexanone 3 kg and carbon-supported ruthenium (5%) catalyst (manufactured by Nippon Engelhard Co., Ltd.) 300
After purifying the inside of the system with purified argon gas, high-purity hydrogen gas was supplied to the autoclave and heating was started at the same time, and it took about 30 minutes to achieve steady-state conditions (internal temperature approximately 100 ° C, internal pressure approximately 50 kg / cm2). ² ) was reached.

This condition was maintained for about 15 hours and then the hydrogenation reaction was stopped. The polymer obtained has an iodine value of 4.4 g / 100.
g, a liquid polyhydroxy saturated hydrocarbon having a hydroxyl value of 52 KOH mg / g.

Example 1 Melt index 1.2 g / 10 minutes, density 0.9
It is 24 g / cm ³ . Linear low density polyethylene 3.06k
g, melt index 2.0 g / 10 min, density 0.9
0.34 kg of 18 g / cm ³ high-pressure low-density polyethylene and calcium carbonate (average particle size 1.2 μ, fatty acid treatment, treatment amount is 2.5 parts by weight per 100 parts by weight of calcium carbonate)
5.8 kg were mixed by stirring in a Henschel mixer, and then 0.45 kg of the polyhydroxy saturated hydrocarbon obtained in Reference Example 1
Epoxidized soybean oil [Adeka Argus Chemical Co., Ltd .; AD
K Cizer 0-130 L] 0.15 kg was added, and the mixture was further stirred and mixed to obtain a mixture of 9.8 kg. The compounding operation was carried out 5 times to finally obtain 45 kg of a mixture.

The melt index is ASTM D1238-7.
0 indicates the extrusion amount of the resin at 190 ° C. and a load of 2.16 kg, and the density is determined by the density gradient tube method at 20 ° C. according to ASTM D1505. The mixture thus obtained was kneaded by a twin-screw kneader DSM-65 (manufactured by Japan Steel Works, Ltd.) and granulated. 50mm% this
An inflation molding machine equipped with an extruder was used for inflation molding, and a film having a thickness of 100 μm was formed.

Here, the extrusion conditions are as follows.

Cylinder temperature: 170-190-190 ° C Head die temperature: 195-195 ° C Blow ratio: 2.7 The film thus obtained was uniaxially stretched by a roll stretching machine and then heat-treated to obtain a porous film having a thickness of 80μ. I got a film.

The stretching conditions are as follows.

Stretching temperature: 70 ° C. Stretching ratio: 3.0 Further, heat treatment was performed at a temperature of 100 ° C. and a longitudinal relaxation rate of 10%.

The obtained porous film has a thickness of 80μ and a moisture permeability of 4,600.
g / m ² · 24hr, air permeability 630sec / 100cc in the longitudinal direction of the tear strength of the film is 75 g, the tensile strength is the vertical direction of the film 1.3 kg, lateral Atsuta at 0.4 kg.

Then, a non-woven fabric [spunbond N5 is added to the porous film.
031: Asahi Kasei Kogyo Co., Ltd.] is a net-shaped heat-fusion adhesive [TEXIRON GLA-23-HM7-SS: SCHAEFFER PR
ODUCTIONS] was used to perform thermocompression bonding between a metal roll and a rubber roll at 80 ° C. at a speed of 5 m / min.

The obtained laminate had a moisture permeability of 3500 g / m ² · 24 hr, an air permeability of 840 sec / 100 cc, a longitudinal tear strength of 230 g, and a tensile strength of 2.9 kg in the longitudinal direction and 1.1 kg in the lateral direction.

The measuring methods for these evaluation items are as follows.

1) Water vapor transmission rate (g / m ² · 24 hr): Measured at a temperature of 30 ° C and a relative humidity of 90% according to JIS Z0208.

2) Air permeability (sec / 100cc): Measured with a Gurley tensometer manufactured by Toyo Seiki Seisakusho.

3) Tear strength (g): in accordance with JIS P8116
It was measured at a temperature of 20 ° C. and a relative humidity of 65% using “ELMEN DOLF PAPER TESTER” manufactured by Toyo Seiki Seisakusho.

4) Tensile strength (kg): 20mm according to ASTM D882
× width 50 mm length, tensile speed 50 mm / min Example 2 3.15 kg of linear low density polyethylene used in Example 1
And 0.35 kg of high-pressure low-density polyethylene and 5.9 kg of calcium carbonate were mixed by stirring in a Henschel mixer, and then the polyhydroxy saturated hydrocarbon used in Example 1 was added.
7 kg was added and further mixed by stirring to obtain 10 kg of a mixture. The mixture thus obtained was kneaded and granulated in the same manner as in Example 1, and then inflation molding was carried out to obtain a film having a thickness of 120 μm. The film was uniaxially stretched and then heat treated in the same manner as in Example 1 to obtain a porous film.

The obtained porous film has a thickness of 95μ and a moisture permeability of 4,500.
G / m ² · 24 hr, air permeability 700 sec / 100 cc, film tear strength in the machine direction was 87 g, and tensile strength was 1.5 kg in the machine direction and 0.5 kg in the machine direction.

Then, a non-woven fabric [Syntex PX is added to the porous film.
102: Mitsui Petrochemical Industry Co., Ltd.] was laminated in the same manner as in Example 1 using a net-shaped heat-fusion adhesive to obtain a laminate.

The obtained laminate had a moisture permeability of 3350 g / m ² · 24 hr, an air permeability of 960 sec / 100 cc, a tear strength of 220 g in the longitudinal direction, and a tensile strength of 1.9 kg in the longitudinal direction and 0.7 kg in the lateral direction.

Example 3 4.2 kg of the linear low-density polyethylene used in Example 1, 0.2 kg of the high-pressure low-density polyethylene and 5.0 kg of calcium carbonate were mixed by stirring in a Henschel mixer, and then used in Example 1. Hydroxy saturated hydrocarbon 0.6kg
Was added, and the mixture was further mixed by stirring to obtain 10 kg of a mixture. The mixture thus obtained was kneaded and granulated in the same manner as in Example 1 and then inflation-molded to obtain a film having a thickness of 60 μm. The film was stretched in the machine direction by a roll stretching machine, and then stretched in the transverse direction by a tenter stretching machine.

The stretching conditions are as follows.

Longitudinal stretching temperature 70 ° C. 〃 magnification 2.4 Lateral stretching temperature 100 〃 magnification 2.7 Heat treatment conditions after lateral stretching were performed at a temperature of 105 ° C. and a transverse relaxation rate of 8%.

The obtained porous film has a thickness of 31μ and a moisture permeability of 5300.
The tear strength in the longitudinal direction of the film was 90 g at g / m ² · 24 hr, air permeability of 200 sec / 100 cc.

Then, a two-component curing type dry laminating adhesive [Polybond NS-30 / CA-30: Sanyo Kasei Co., Ltd.] was applied to the porous film with a gravure roll, and a speed of 1 was applied.
A nonwoven fabric [Sontara 8010: Toray Deyupon] was laminated at 5 m / min.

The obtained laminate had a moisture permeability of 4300 g / m ² · 24 hr and an air permeability of 260 sec / 100 cc.

〔The invention's effect〕

Since the laminate of the present invention is excellent in moisture permeability and air permeability, and also has excellent strength of the laminate, it can be used in various applications such as clothing, packaging materials, excess materials, and synthetic leather, and is very suitable for practical use. It is something.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location B29K 105: 04 B29L 9:00 4F (72) Inventor Minoru Kashino 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Address Sanryoh Kasei Kogyo Co., Ltd., Research Center (72) Inventor Hiroshi Kamata 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Kogyo Co., Ltd. (72) Inventor Yu Suzuki Kamoshida, Midori-ku, Yokohama-shi, Kanagawa 1000-cho, Sanritsu Kasei Co., Ltd.

Claims (1)

[Claims] 1. 100 parts by weight of a polyolefin resin to 25 to 400 parts by weight of a filler, a liquid or wax hydrocarbon polymer and / or an organic compound containing an epoxy group 1 to 100.
Moisture vapor transmission rate 500, which is obtained by laminating a reinforcing material on at least one surface of a porous film obtained by stretching a film obtained by melt-molding a composition consisting of parts by weight in at least one axial direction.
A porous film laminate having a g / m ² · 24 hr or more and an air permeability of 5000 sec / 100 cc or less.