JPH0584879A - Polyolefin laminated product - Google Patents

Abstract

PURPOSE:To provide a polyolefin laminated product with outstanding properties such as heat retention, transparency, pliability, slippage, and anti-cloudiness. CONSTITUTION:A 20 to 120mum thick laminated product consisting of 100 pts.wt. of polyolefin containing polyethelene of lower than 0.910 of density and 20 to 20 pts.wt. of silica with a grain diameter of 5 to 200nm, is subjected to corona electric discharging process. Then an applicable anti-cloudiness agent is applied to the treated laminated product, to obtain a polyolefin laminated product. In addition, a polyolefin laminated product consisting of an ethylene/ vinyl acetate copolymer and polyethyelene of a density of lower than 0.910 and a polyolefin laminated product containing a silicone modified acryl copolymer are available.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin laminate excellent in heat retention, transparency, flexibility, slip resistance and antifogging property.

[0002]

2. Description of the Related Art Conventionally, a polyvinyl chloride film, a polyethylene film, or a polyolefin resin film such as an ethylene-vinyl acetate copolymer is mainly used as a covering material in an agricultural house. Of these, polyvinyl chloride film has been widely used in this field in recent years because it has excellent heat retention, weather resistance, transparency, and flexibility (expansion workability). However, the plasticizer contained in this film is used at high temperatures in summer. In addition to bleeding and attaching dust, there was a problem that harmful gas was generated during incineration. In addition, the polyolefin resin film does not contain plasticizer, does not adhere dust due to plasticizer bleeding, and does not generate harmful gas during incineration and is excellent in processability, but it is an additive compared to polyvinyl chloride film. Has a drawback that the transparency and the long-term antifogging property are impaired by the fact that the additive appears on the surface in a short time. Further, in recent years, a coating method in which a coating agent is applied after forming a film has been used for imparting antifogging property, but blocking problems due to the coating agent have occurred and it has not been put to practical use. In addition, since it has a defect that the heat retaining property is insufficient and the temperature of the house tends to be lower than that of a polyvinyl chloride film, an inorganic filler having absorption in the far infrared region is added to impart heat retaining property, but the transparency of the film is There is a drawback that is damaged. In addition, compared with polyvinyl chloride film, there is a drawback that it lacks flexibility and impairs the spreading workability of the house and the fitting property after spreading work. It is a resin component that improves the flexibility of the polyolefin resin film, for example ethylene-vinyl acetate. A polymer having a large amount of vinyl acetate component and a low-density polyethylene having an ethylene-α-olefin random copolymer have a low blocking property and a blocking problem occurs. Therefore, spraying an anti-blocking agent such as starch powder at the time of film formation is used, but it leaves a problem of cost increase and workability.

[0003]

Means for Solving the Problems The present inventors have found that the above-mentioned problems, such as the polyvinyl chloride film, are problems in that the plasticizer bleeds and adheres dust at high temperature in summer and generates harmful gas during incineration. was there. The polyolefin film is
Additive bleeds and transparency and long-term anti-fog property are impaired, blocking trouble occurs with anti-fog imparting coating agent, addition of inorganic filler for improving heat retention impairs transparency, lacks flexibility However, there was a drawback in that the spreading workability of the house and the fit after the spreading work were impaired. An object of the present invention is to provide a polyolefin-based laminate that solves these problems. That is, the present invention has a density of 0.9.
Polyolefin containing 10 or less polyethylene 10
A polyolefin-based laminate obtained by applying an antifogging agent to a laminated film having a layer having a thickness of 20 to 120 μm and comprising 1 to 20 parts by weight of silica having a particle diameter of 5 to 200 nm relative to 0 parts by weight, and the polyolefin is ethylene- The vinyl acetate copolymer, a polyolefin-based laminate which is polyethylene having a density of 0.910 or less, and the above-mentioned anti-fog agent are silicone-based.
It is a polyolefin-based laminate containing a vinyl-modified acrylic copolymer.

The laminated film of the present invention is a laminated film having two or more layers having a layer of a composition composed of a specific olefin resin and a specific silica, and other resin layers. The polyolefin used for the laminated film of the present invention has a density of 0.9.
It is characterized by containing polyethylene of 10 or less. In addition to the above polyethylene having a density of 0.910 or less, an ethylene-vinyl acetate copolymer may be mixed and used in this polyolefin. The polyethylene used in the present invention is an ultra-low density polyethylene having a density of 0.910 or less, in particular an ultra-low density polyethylene having a density of 0.900 or less, and an ethylene-butene copolymer which is an ultra-low density polyethylene having a density of 0.89 or less. Polymers are preferred. Polyethylene having a density of more than 0.910 has a drawback that transparency and flexibility are impaired, which impairs the object of the present invention. This ultra-low density polyethylene having a density of 0.910 or less can be obtained by copolymerizing ethylene and butene-1 by a gas phase low pressure method using a Ziegler catalyst, but is not limited thereto. In addition, as commercially available ultra low density polyethylene, Sumitomo Chemical's Excellen VL (V
L100, VL200, VL700, VL800), GERS-1085 manufactured by Nippon Unicar, and the like can be used. The density of the present invention is based on the method according to JIS K7112 D method. Secondly, in addition to polyethylene having a density of 0.910 or less, ethylene-
You may mix and use a vinyl acetate copolymer. This ethylene-vinyl acetate copolymer preferably has a vinyl acetate content of 5 to 30% by weight in terms of transparency and blocking properties. Further, the content of the ethylene-vinyl acetate copolymer is preferably 70% by weight or less in the above polyolefin, and when it exceeds 70% by weight, the flexibility of the laminated film is impaired. More preferably, it is used in an amount of 5 to 50% by weight.

The silica used in the present invention is a silicon oxide fine powder having an average primary particle diameter of 5 to 200 nm,
Solids with a large particle size, granules, fibrous and sol-like substances are excluded. The silica used in the present invention may be wet-process silica obtained by neutralizing sodium silicate with an acid, or may be dry silica (fumed silica) obtained by a combustion hydrolysis method of silicon halide, but fumed silica having a low adsorbed water content. Is preferred. If the particle size of the silica exceeds 200 nm, the transparency of the film may be impaired, and the film size of 5 n
If it is less than m, the workability is poor and it cannot be put to practical use. It is preferably 7 to 50 nm. The silica is used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the olefin resin. If it exceeds 20 parts by weight, the workability and cost of manufacturing the film are increased, and if it is less than 1 part by weight, the film is not practical. There is a drawback that the heat retention property cannot be given. The silica used in the present invention is preferably silane-treated. The thickness of the polyolefin layer of this laminated film is 20
˜120 μm is used, and if it exceeds 120 μm, the cost becomes high and it is not practical, and if it is less than 20 μm, flexibility and heat retention are impaired.

The laminated film of the present invention is one in which other resin layers are laminated in addition to the above specified polyolefin layer, and polyolefin can be used also in the other resin layers, and further ethylene-vinyl acetate copolymer It is preferable that the thickness of the united layer is 5 to 50 μm. It is preferable to provide another resin layer on the laminate, from the viewpoint of easy application of the antifogging agent, increased weather resistance, and transparency. If the thickness of the other resin layer is less than 5 μm, molding is difficult and the function as the surface layer is impaired. If it exceeds 50 μm, it is not practical due to the thickness of the film, and preferably 10 to 30 μm. A layer of ethylene-vinyl acetate copolymer may be provided on the opposite side of the specified polyolefin layer and the other resin layer. It is also possible to add a small amount of an inorganic filler to the other resin layers within a range that does not impair the purpose. In the above-mentioned specified polyolefin layer and other resin layer of the present invention, various additives to be added, for example, phenol type, thioether type,
Antioxidants such as phosphorus, HALS, light stabilizers such as UV absorbers, heavy metal deactivators, nucleating agents, lubricants, antistatic agents, antifogging agents, surfactants, antiblocking agents, halogen scavengers The neutralizing agent can be used in combination within the range not impairing the object of the present invention. Especially on the surface layer, antioxidant, H
It is preferable to use a light stabilizer such as ALS or an ultraviolet absorber and an anti-blocking agent together.

The polyolefin-based laminate of the present invention may be a laminated film obtained by laminating the above-specified polyolefin layer film and a film of another resin layer, laminated by a multi-stage T-die, or multilayer inflation. Well, it does not specify the processing method. In the present invention, an antifogging agent is applied after the laminated film is formed. In order to improve the adhesion of the antifogging agent, it is preferable to make the surface hydrophilic by subjecting it to a surface treatment such as corona discharge treatment, sputtering or ion plating.

As the antifogging agent of the present invention, it is preferable to use a silicone-modified acrylic copolymer, and more preferable to use a mixture of a silicone-modified acrylic copolymer and an organopolysiloxane. This silicone modified acrylic copolymer is a modified copolymer obtained by copolymerizing a silane compound and an acrylic acid compound. As the silane compound, vinyl group-containing silane, hydrogen group-containing silane,
Reactive silane compounds such as amino group-containing silanes, carboxy group-containing silanes, chloro group-containing silanes, and mixtures thereof. Of these, vinyl group-containing silanes are preferable. The acrylic acid-based compound is acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, and a mixture thereof.

A more desirable copolymer of the silicone-modified acrylic copolymer can be produced by copolymerizing the following monomers. Vinyl group-containing alkoxysilane Vinyl group-containing polysiloxane Methacrylic acid ester and / or acrylic acid ester having a hydroxyl group Methacrylic acid ester and / or acrylic acid ester Among these, in order to obtain the best coating physical properties, The use ratio in the production of the combined product is 0.5 to 20% by weight of a vinyl group-containing alkoxysilane, 0.1 to 20% by weight of a vinyl group-containing polysiloxane, and 10 to 30% by weight of a hydroxyl group-containing acrylate ester or methacrylic acid ester. Preferably. The characteristics of the thermoplastic film coated with the silicone-modified resin obtained when any one or more of the amounts of the compounds of are out of the above range are lower than those of the present invention, and the amounts of the compounds of The same applies when the ratio is above the above range, and when the ratio is below the above range, the coating film tends to be insufficient.

Specific examples of the vinyl group-containing alkoxysilane include methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane. Specific examples of the vinyl group-containing polysiloxane include vinyl dimethyl polysiloxane having both ends or one end and methacryloxypropyl dimethyl polysiloxane having both ends or one end. The viscosity range of these polysiloxanes is preferably about 5 to 1000 cP. The molecular weight is preferably 200 to 100,000.

Specific examples of the acrylic acid ester and / or methacrylic acid ester containing a hydroxyl group of 2 are methyl 2-hydroxyacrylate, ethyl 2-hydroxyacrylate, pentyl 2-hydroxymethacrylate and butyl 2-hydroxymethacrylate. , 2-hydroxymethacrylic acid acrylic, 2-hydroxybenzylmethacrylic acid, and 2-hydroxyvinylmethacrylic acid. The number of carbon atoms of the ester group of the methacrylic acid ester and / or the acrylic acid ester is preferably 1 to 12, and specific examples from this point include methyl acrylate, ethyl allylate, butyl acrylate, allyl acrylate, phenyl acrylate, methacrylic acid. Methyl acid, butyl methacrylate, pentyl methacrylate, lauryl methacrylate, vinyl methacrylate, allyl methacrylate, etc. may be mentioned. Two or more compounds may be used in combination.

When copolymerizing the compounds (monomers) of to, preferably, an organic acid having 3 or more carbon atoms is used in an amount of 0.1 to 5% by weight of the polymerization mixture (the total amount of the compounds of note to). As the polymerization catalyst, 0.1 to 3% by weight, preferably 0.2 to 2% by weight, of a radical initiator such as benzoyl peroxide or azobisisobutyronitrile is used with respect to the total amount of all the monomers. The polymerization can be carried out by either bulk polymerization or solution polymerization, but solution polymerization is most preferable in the compounding step for coating. As such a solvent, alcohol
Examples thereof include methanol, ethanol, isopropyl alcohol, n-butanol, isoamyl alcohol and the like. Other,
Aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, and ketones such as acetone and methyl ethyl ketone are used alone or in combination. Polymerization conditions (temperature, time) of the silicone-modified acrylic copolymer are not particularly limited, but are usually 60 to 150.
Completed in 2 to 10 hours at ℃. The organopolysiloxane of the present invention has a molecular weight of 100 including a siloxane bond.
It is a polymer of 0 or more. Of these, organopolysiloxanes having a siloxane bond and having at least one hydrolyzable group and at least one polyethylene oxide group in one molecule are preferable. Further, the mixing ratio of the silicone modified acrylic copolymer and the organopolysiloxane is not particularly limited, but in order to obtain basic physical properties and antifogging property as a coating film and other properties, 20: 1 to 1: 1, It is preferably 10: 1 to 2: 1. In some cases, a condensation reaction between the hydrolyzable groups may occur by coating and drying a coating agent in which a silicone-modified acrylic copolymer and an organopolysiloxane are mixed. It seems to suppress more strongly.

The formation of the coating film of the film of the present invention is achieved by applying the coating agent of the present invention to the film. The method is not particularly limited, and it is applied by using a coating means such as a roll coater, a blade coater, a curtain coater, a bar coater, and a gravure coater. To do. Then, it is dried by heating to scatter the solvent in the coating material. The drying temperature depends on the solvent used, but is usually 80 to 120 ° C., and the time is 0.1.
5 to 10 minutes. The thickness of the coating film in the film of the present invention is 0.2 to 4 μm, preferably 0.5 to 2 μm. Alternatively, various additives can be used in combination with the coating type antifogging agent as needed. In particular, by using a fluorine-containing surfactant together, it is possible to suppress the generation of fog in the house.

[0014]

EXAMPLES The present invention will be shown below with reference to Examples and Comparative Examples.
These examples are merely illustrative and not limiting. For the films shown in the following examples and comparative examples, a resin laminate having a thickness of 100 μm was produced by a two-kind three-layer inflation film molding method. A synthetic example of a coating type antifogging agent will be shown. [Preparation of Silicone-Modified Acrylic Resin (A)] Synthesis Example-1 42.5 parts by weight of methyl methacrylate (hereinafter referred to as "parts"), 2-hydroxyethyl methacrylate 18.0 parts,
27.5 parts of n-butyl methacrylate, 5.0 parts of n-butyl acrylate, 5.0 parts of 3-methacryloxypropyltrimethoxysilane, 1.0 part of methacryloxypropyldimethylpolysiloxane with one terminal (Mw = 5000). , 1.0 part of methacrylic acid and azobisisobutyronitrile 1.
0 parts were mixed to prepare a monomer mixture for polymerization. A mixed solution of isopropyl alcohol and ethyl acetate (3/1 by weight) kept at 80 ° C. was added to this mixed solution to obtain a solid concentration of 2
It was adjusted to be 0%. This is designated as (a-a). Synthesis Example-2 Lauryl Methacrylate 27.5 in place of n-butyl methacrylate as a copolymer monomer, one-end methacryloxypropyldimethylpolysiloxane with Mw = 5000, one-end methacryloxy with Mw = 1000 A silicone-modified acrylic resin solution (a-b) was obtained in the same manner as in Synthesis Example-1 except that 1.0 part of propyldimethylpolysiloxane was used. [Preparation of Organopolysiloxane (b)] Synthesis Example-3 50 parts of hydrogen-silicon polysiloxane having a viscosity of 340 cP and a content of hydrogen atoms bonded to silicon atoms of 0.2% by weight, C
H2 = CHCH2 (OCH2 CH2) 17 OCH341
Parts, vinyltrimethoxysilane 7.4 parts Toluene 200
Was added as a catalyst and 0.003 part of chloroplatinic acid was added, and the mixture was reacted at 100 ° C. for 4 hours. After the toluene was removed from the reaction solution by heating under reduced pressure, isopropyl alcohol
And a mixed solvent of ethyl acetate and ethyl acetate (3/1 in weight ratio) were added to adjust the solid concentration to 20%. This is designated as (ro-a). Synthetic Example-4 A polysiloxane (polysiloxane) was prepared in the same manner as in Synthetic Example-3 except that 26.3 parts of hydrogen-silicon polysiloxane having a viscosity of 20 cP and a content of hydrogen atoms bonded to silicon atoms was 0.38% by weight. b) was obtained.

Example 1 The components of the surface layer and the inner layer were melt flow rate (3), and ethylene vinyl acetate copolymer containing 10% by weight of vinyl acetate component was blended with 5% by weight of CHIMASSORB 944FL (manufactured by Ciba Geigy). It was used. The core layer component is melt flow
Rate (0.9), ethylene vinyl acetate copolymer containing 18% by weight of vinyl acetate component, 52% by weight and density of 0.88
4 ultra-low density polyethylene (ethylene-butene-1 copolymer made by gas-phase low-pressure method: GERS-1085 manufactured by Nippon Unicar) was added to 48 parts by weight of 100 parts by weight of Aerosil R-972 (average particle size: 16 nm). A laminated body made of a film made of 5 parts by weight of fumed silica (made by Nippon Aerosil) has a surface layer of 15 μm and a core layer of 70 μm.
m and the inner layer was 15 μm. The inner layer surface of the laminate was subjected to corona discharge treatment [using Kasuga Denki Co., Ltd. HFS-203 at a speed of 5 m / min], and then the treated surface was treated with a synthetic example (a-a) and (ro). -A) was mixed in a weight ratio of 5: 1, coated with a bar coater and dried in an oven at 105 ° C for 1 minute to prepare a laminated film having a coating thickness of 1.5 µm, and the performance of the film was evaluated. .. The following items were evaluated for the film.

* Heat retention The average transmittance of the black body radiant energy at 20 ° C. is the transmittance spectrum of the film measured by using a far infrared spectrophotometer with the black body radiant energy spectrum of temperature as the incident energy. The transmitted energy obtained by multiplying by is integrated to obtain the transmitted energy, and the incident energy
The average transmittance was obtained by dividing by. The smaller the average transmittance, the better the heat retention. * Transparency According to ASTM-D-1003. * Sticky peeling load Two test films cut into 50 x 120 mm are stacked so that the coated and non-coated surfaces of the coating agent are in contact with each other.
50 × 50 mm on one side is sandwiched from above and below by smooth glass plates. Furthermore, a load of 1 kg is placed on the glass plate, and the glass plate is placed in a thermo-hygrostat at a temperature of 70 ° C. and a humidity of 80% for 2 hours.
After 2 hours, remove the load and put it in a room at 23 ° C and 50% humidity.
Leave for 4 hours. The peeling load of the two-layered film was measured. The peeling load of three sets of films was measured, and the average value of the measured values was used as the measured value. The smaller the measured value, the less sticky the film becomes and the better the slip property of the film. * Adhesion of coating film to film In accordance with JISK5400 general coating test method 6.15 cross-cut test, a cut is made with a cutter knife, and a cellophane adhesive tape (Sekisero tape 18 mm wide J
(Equivalent to ISZ1522) and apply a constant load by hand.
Peel off at a constant speed, and if there is no change in the coating film, set to O,
When the coating film adhered to the cellophane adhesive tape, it was evaluated as ×, and the middle thereof was evaluated as Δ. * Long-term antifogging property The surface coated with the coating agent on the film was housed inside (tunnel type, length 7 m, diameter 2 m), and the change with time in the antifogging flow property of the coated portion was visually observed. Observations were carried out in Kumamoto for 1 year and 10 months from May 1989 to March 1991. The film observation was evaluated as O when the coated portion had good anti-fogging flowability, and when the coating film was peeled off or the anti-fogging flow property was impaired, X, and the middle thereof was Δ. The performance evaluation results of the film are shown in Table 1. * Flexibility According to ASTM-D-882. The smaller the Young's modulus value, the better the flexibility.

Example-2 Same as Example-1 except that a mixture of the coating agents of Example-1 (ro-a) and (ro-b) in a weight ratio of 5: 1 was applied. The film was evaluated. Example-3 As the core layer component of Example-1, 100 ultra-low density polyethylene having a density of 0.884 (ethylene-butene-1 copolymer produced by the gas-phase low pressure method: GERS-1085 manufactured by Nippon Unicar) was used.
The film was evaluated in the same manner as in Example 1 except that the weight% was used. Example-4 5% by weight of fumed silica of Aerosil R-972 (made by Nippon Aerosil Co., Ltd., average particle size: 16 nm) was added to the core layer component of Example-1; The film was evaluated in the same manner as in Example 1 except that the weight% was used. Example-5 Instead of the coating agent of Example-1, a general methyl methacrylate-based coating agent (manufactured by Osaka Organic Chemical Industry Co., Ltd. [OCV R-04
The film was evaluated in the same manner as in Example 1 except that 1) was dissolved in an ethyl acetate solvent at 17% by weight). Comparative Example-1 A film was evaluated in the same manner as in Example-1 except that the core layer component of Example-1 was replaced by fumed silica of Aerosil R-972 (produced by Nippon Aerosil Co., Ltd., average particle size: 16 nm). Comparative Example-2 A film was evaluated in the same manner as in Example-1 except that the inner layer surface of the laminate of Example-1 was not subjected to corona discharge treatment. Comparative Example-3 A film was evaluated in the same manner as in Example-1 except that the inner layer surface of the laminate of Example-1 was not treated with corona discharge and no coating agent was applied.

[0018]

EFFECT OF THE INVENTION It is an object of the present invention to provide a polyolefin-based laminate which is desired to have the above-mentioned polyolefin laminated film having heat-retaining property, transparency, flexible slip property and anti-fog property. In particular, it can be used as an agricultural film.

[0019]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 23/04 LDG 7107-4J 33/04 LHZ 7921-4J // A01G 13/00 D 8502-2B

Claims (3)

[Claims] 1. A particle size of 5 to 2 with respect to 100 parts by weight of a polyolefin containing polyethylene having a density of 0.910 or less.
Thickness of 20 to 1 consisting of 1 to 20 parts by weight of 00 nm silica
A polyolefin-based laminate obtained by applying an antifogging agent to a laminated film having a layer of 20 μm. 2. The polyolefin laminate according to claim 1, wherein the polyolefin of claim 1 is polyethylene having a density of 0.910 or less and an ethylene-vinyl acetate copolymer. 3. The polyolefin-based laminate according to claim 1, wherein the antifogging agent according to claim 1 contains a silicone-modified acrylic copolymer.