JPH03140345A - Oxygen-permeable film - Google Patents

Abstract

PURPOSE:To obtain the subject film having durability and improved mechanical strength by molding a mixture derived from kneading ethylenic polymer and specific organopolysiloxane with heating. CONSTITUTION:100 pts.wt. ethylenic polymer is mixed with 10-900 pts.wt., preferably 50-600 pts.wt. organopolysiloxane expressed by the formula [R<1> is aliphatic unsaturated group; R<2> is (substituted) monofunctional hydrocarbon not containing aliphatic unsaturated group, 0<=a<=1, 0.5<b<3 and 1<a+b<3] and kneaded with heating, then resultant kneaded material containing >=10% gel content is molded to afford the aimed film.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an oxygen permeable film with improved mechanical strength, which is made of an ethylene polymer and a polysiloxane polymer.

[Prior Art] Polysiloxane polymers are known for their excellent properties such as slipperiness, mold releasability, easy oxygen permeability, water repellency, and electrical insulation properties.
It has been widely used, and there is an oxygen permeable film that utilizes it. The film has conventionally been produced by crosslinking polysiloxane polymers.

[Problems to be solved by the invention] Polysiloxane-based polymers have the disadvantages of low mechanical strength, difficulty in film formation, and poor moldability. Even when films were produced, only those with low mechanical strength could be obtained.

The present invention was made to solve this problem, and the object to be solved is to improve the mechanical strength of an oxygen permeable film manufactured from a polysiloxane polymer.

[Means for Solving the Problems] The present inventors have taken advantage of the excellent properties of polysiloxane polymers while addressing their drawbacks such as low mechanical strength and poor film forming properties. discovered that it could be improved by bonding with an ethylene polymer, and completed the present invention.

That is, the oxygen permeable film with improved mechanical strength of the present invention has an ethylene polymer 100-layer plate part and the following formula (A): R', R"l, SiO4-, -, (A) (In the formula, R
' represents an aliphatic unsaturated group, R2 represents an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated group, and a and b meet the following conditions: 0≦a<1, 0.5<b< 3.1 <
It is characterized by forming a film from a kneaded product having a gel content of 10% or more obtained by heating and mixing 10 to 900 parts by weight of an organopolysiloxane represented by the formula (representing a numerical value satisfying a+b<3).

The ethylene polymer used in the present invention is a polymer whose main component is ethylene, and includes high-pressure polyethylene, linear low-density polyethylene (LLDPE), ethylene-α olefin copolymer, and ethylene-vinyl acetate copolymer. , ethylene-acrylic acid copolymer, ethylene-meccrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-
Examples include ethyl acrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-vinyl alcohol copolymer, and others.

In the organopolysiloxane represented by formula (A) used in the present invention, examples of the R1 group include a vinyl group, allyl group, acrylic group, methacrylic acid, etc., and examples of the R2 group include a methyl group, an ethyl group, Alkyl groups such as propyl groups, aryl groups such as phenyl groups and tolyl groups, cycloalkyl groups such as cyclohexyl groups and cyclobutyl groups, and hydrogen groups bonded to carbon atoms of these hydrocarbon groups are partially halogen atoms and cyano groups. Examples include groups substituted with , mercapto groups, etc., but these may be a combination of the same or different types.

Further, a is 0 or greater than O and less than 1; if it is 0, the reaction with the ethylene polymer will not occur so much, which is undesirable; if it is 1 or more, the film made from the composition of the present invention will become hard. Too undesirable.

a is preferably 0.0004 to 0.06. b is 0.
If it is greater than 5 and less than 3, and if it is less than 0.5, it will be difficult for the composition of the present invention to cross-wire and the processability will be poor, and if it is greater than 3, the film made from the composition of the present invention will be hard. Too undesirable.

b is preferably 1-2.

The molecular structure of the organopolysiloxane of the present invention has the formula (A
) may be in the form of a chain, a branched chain, a ring, a network, a three-dimensional network, or the like.

The organopolysiloxane used in the present invention includes, for example, so-called silicone gum stock, which is commercially available as a bow tear strength improving material for silicone rubber. Further, as the linear organopolysiloxane used in the present invention.

Ikki formula (wherein R represents an unsubstituted or substituted monovalent hydrocarbon group,
n represents a number of 10 or more). There is something commonly called silicone oil.

R in the formula is a group selected from an alkyl group, an aryl group, and hydrogen, and includes a methyl group, an ethyl group, an n-propyl group, a l-propyl group, an n-butyl group, an i-butyl group, and a t-butyl group.
Typical examples are -butyl group, phenyl group, and hydrogen, but even if all the groups are the same group or some of the R's are different groups, some of the R's may be vinyl. may be a group or a hydroxyl group.

n is 10 to 10,000, preferably 100 to 1,000.

If n is 10 or less, crosstalk with polyethylene will be difficult, and if n is 10,000 or more, it will be difficult to form a film, which is not desirable.

The viscosity at 23°C of the organopolysiloxane polymer of formula (A) used in the present invention is 10C3 or more, preferably 1000 to 1.000.000C8.If the viscosity is lower than 1ocs, heating Crosstalk is difficult, and the organopolysiloxane polymer may ooze out from the surface of the molded product.

The organopolysiloxane represented by the formula (A) used in the present invention is required in an amount of 10 to 900 parts by weight, preferably 5 parts by weight, based on 100 parts by weight of the ethylene polymer.
0 to 600 parts by weight are required. If it is less than 10 parts by weight, releasability will be difficult to exhibit. Further, if the amount is more than 600 parts by weight, film formation etc. may become difficult.

In the present invention, the composition may contain oxidation stabilizers, ultraviolet stabilizers, inorganic fillers, pigments, flame retardants, rubbers, etc., if necessary.

In the present invention, crosstalk is preferably performed at 160° C. or higher. It is necessary to perform the crosstalk until the gel content reaches 10% or more. If the amount is less than 10%, unreacted polysiloxane polymer may ooze out, and a slip phenomenon may occur in the extrusion mold, making molding impossible.

In the present invention, crosstalk time can be shortened by adding an organic peroxide to the composition consisting of an ethylene resin and an organopolysiloxane polymer.

The organic peroxide used in the present invention has a decomposition temperature with a half-life of 10
Preferably, the temperature is 100 to 220°C per minute, that is, the half-life (Tp) is 100 to 220°C in 10 minutes.
Examples of such things include the following: However, the value in parentheses is the decomposition temperature ('C).

Succinic acid peroxide (1101, benzoyl peroxide (1101), t-butylperoxy-2-ethylhexanoate (113), p-chlorobenzoyl peroxide (115), t-butylperoxyisopropyl carbonate (1351, t-butylperoxylhexanoate) rate (1401,2,5-dimethyl-2,5-di(benzoylperoxy)hexane (140), t-butylperoxyacetate) (1401, di-t-butylperoxyphthale)-(1401, t -Butylperoxymaleic acid (140), cyclohexanone peroxide f1451.

t-Butyl peroxybenzoate (1451, dicumyl peroxide (1501,2,5-dimethyl-2,5
-di(t-butylperoxy)hexane (1551, t
-butylcumyl peroxide (1551, t-butyl hydroperoxide (158), di-butyl peroxide (16), 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 (170), Di-isopropylbenzene hydroperoxide (1701), p-menthane hydroperoxide (180), 2,5-dimethylhexane-25-dihydroperoxide (213).

The mixing can be carried out using a Banbury mixer, a 12-screw extruder, or other conventional mixing machines. Such a kneaded material can be molded into a film using a conventional molding machine such as an inflation molding machine or a T-Guy molding machine.

The thickness of the film is usually about several microns to several tens of microns.

The gel content was calculated from the ratio of the existing gel amount to the weight of the original sample after immersing the sample in torunin at 95° C. for 24 hours and vacuum drying the sample for 24 hours.

[Example] Example 1 8 kg of high-pressure polyethylene NLIC-8008 (manufactured by Nippon Unicar) and silicone gum stock 1 with a methylvinylsiloxane content of 0.8 mol% and a plasticity of 80 (70°C)
2 kg were kneaded at 180° C. for 50 minutes using a Moriyama Seisakusho DS20-40MWA-H type Neigu. The rotation speed of the blade was 45 rpm.The gel content of the obtained kneaded product was 70%.

Braco'440mm inflation molding machine 2
A kneaded product film was obtained at 00°C. The fold diameter of the film is 20
cm and the thickness was 20 microns each.

The tensile strength and elongation of this film are 45
kg/c and 500%.

The oxygen permeability coefficient of this kneaded material is 5X10cm'cm/cr
n”, s cmHg.

Comparative Example 1 Methylvinylsiloxane content 0□8 mol%, plasticity 8
o, i g of dicumyl peroxide (manufactured by NOF) to 60 kg of silicone gum stock at 0 (70°C)
100 kg/c rn” using a compression molding machine.
The mixture was pressurized at 180° C. for 10 minutes and formed into a sheet with a thickness of 1 mm.

The tensile strength of this sheet is 3 kg/crn'
Met.

The oxygen permeability coefficient of this sheet is 35X10cm m'c
m/cm', scm Hg.

Comparative Example 2 High-pressure polyethylene NUC-8008 (manufactured by Nippon Unicar) lokg and dimethylpolysiloxane FZ-3112 (
Nippon Unicar) 10kg and Moriyama Seisakusho DS20-4
The mixture was kneaded at 180°C for 50 minutes using a 0MW △-H type Ni-Goo. The rotation speed of the blade was 45 rpm.

The gel content of the obtained kneaded product was less than 10%. ・ 200 ° C. using a 40 mm inflation molding machine made by Braco.
I tried to obtain a film of the kneaded product, but it slipped inside the extruder and the kneaded product could not be extruded.

Example 2 Low pressure polyethylene NUCG-5511 (manufactured by Nippon Unicar) 10 kg, dimethylpolysiloxane FZ-3112
(manufactured by Nippon Unicar) and 30 g of dicumyl peroxide (manufactured by Nihon Yushi) were added to Moriyama Seisakusho DS20-40M.
The mixture was kneaded at 180° C. for 20 minutes using a WA-H type Neegoo. The rotation speed of the blade was 45 rpm.

The gel content of the obtained kneaded product was less than 60%.

200″ with 40mm inflation molding machine made by Braco
A kneaded product film was obtained in step C. The fold diameter of the film is 20cm
The thickness of each layer was 20 microns.

The tensile strength and elongation of this film are each 50
kg/crr? and 6'00%.

The oxygen permeability coefficient of this kneaded material is 3X10 crr? am
/crn”, s cmHg.

Example 3 Ethylene-ethyl acrylate copolymer DPDJ-916
9 (manufactured by Nippon Unicar) and 14 kg of dimethylpolysiloxane FZ-3112 (manufactured by Nippon Unicar) were heated at 180°C using a Moriyama Seisakusho DS20-4ONWA-1 (type Niegoo).
The mixture was kneaded for 50 minutes. The rotation speed of the blade was 45 rpm.

The gel content of the resulting kneaded product was less than 75%.

Braco 40mm inflation molding machine 00℃
A kneaded product film was obtained. The folded diameter of the films was 20 cm and the thickness was 20 microns each.

The tensile strength and elongation of this film are respectively 35
kg/c rn' and 500%.

The oxygen permeability coefficient of this kneaded product is 11XIOcrr? am
/cm', s cmHg.

Example 4 High-pressure polyethylene NUC-8008 (manufactured by Nippon Unicar) 8 kg, methylvinylsiloxane content 0.8 mol%
, silicone gum stock 1 with a plasticity of 80 (70°C)
2kg and dicumyl peroxide (NOF) 30
g was kneaded at 180° C. for 20 minutes using a Moriyama Seisakusho DS20-40MWA-H type Nigu. The number of revolutions of the blade is 45
It was rpm.

The gel content of the obtained kneaded product was 65%.

200° with a 40mm inflation molding machine made by Plako
A kneaded product film was obtained in step C. The fold diameter of the film is 20cm
The thickness of each layer was 20 microns.

The tensile strength and elongation of this film are 45
kg/cm' and 500%.

The oxygen permeability coefficient of this kneaded product is 5X10 crn'cm
/cm”, s cmHg.

[Effect of the Invention 1 The film of the present invention has superior mechanical strength compared to films made from conventional organopolysiloxane polymers, and therefore can be used for durable oxygen-electrified membranes.

Japan Unicar Co., Ltd.

Claims (1)

[Claims] 100 parts by weight of an ethylene polymer and the following formula (A): R^1_aR^2_bSiO_4_-_a_-_b_/
_2(A) (wherein R^1 represents an aliphatic unsaturated group, R^2 represents an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated group, and a and b meet the following conditions: 0≦a<1, 0.5<b<3, 1<a+b<3) with a gel content of 10% or more obtained by heating and kneading 10 to 900 parts by weight of an organopolysiloxane represented by Oxygen permeable film formed by forming a kneaded material.