JPH05170981A - Sheet or film molded from resin composite - Google Patents

Abstract

PURPOSE:To obtain an inexpensive and lightweight sheet or film molded from a resin composite, excellent in moldability, antistatic properties and printability, producible in a short production process and having sufficient mechanical properties. CONSTITUTION:A sheet or a film is molded from a resin composite prepared by compounding polyethylene and/or polypropylene (A) with a polyurethane resin (B) in the presence of a dispersing agent (C). In the resin composite, the weight ratio (A/B) of the components (A) to (B) therein is (99/1) to (40/60) and the component (C) is contained in an amount of 1-40wt.% based on the total weight of the components (A) and (B).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a sheet or film molded from a resin composite of polyethylene and / or polypropylene and a polyurethane resin.

[0002]

2. Description of the Related Art Polyethylene and / or polypropylene are used in a wide range of fields because they are inexpensive, lightweight and have excellent moldability. However, since the antistatic property and printability are inferior, a method of using various antistatic agents to improve antistatic property and a method of corona discharge treatment to improve printability are known.

[0003]

However, there has been a problem that various antistatic agents for improving antistatic properties and corona discharge treatment for improving printability are not effective.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have taken advantage of the antistatic property, while maintaining the features of polyethylene and / or polypropylene which are inexpensive and lightweight and have excellent moldability.
The present invention has been achieved as a result of intensive studies to obtain a sheet or film made of a resin composite having excellent printability, a short manufacturing process, and sufficient mechanical properties such as tensile strength. That is, the present invention is formed from a resin composite in which polyethylene and / or polypropylene (A) and a polyurethane resin (B) are combined in the presence of a dispersant (C),
The weight ratio A / B of (A) and (B) in the resin composite is 99.
/ 1 to 40/60, and (C) is a sheet or film molded from a resin composite having 1 to 40% by weight based on the total weight of (A) and (B).

In the present invention, polyethylene and / or polypropylene (A) are preferably those having a weight average molecular weight of 10,000 to 3,000,000,
More preferably, it is 10,000 to 1,000,000.

In the present invention, the polyurethane resin (B)
Is a compound (b1) having two or more active hydrogens.
And a polyisocyanate (b2) are polymerized. Examples of (b1) include low molecular weight diols having 2 to 30 carbon atoms (ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); polyethers having a number average molecular weight of 400 to 50,000. Diol [Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the low-molecular-weight diols exemplified above (addition mole number 2 to 100), ring-opening polymer of alkylene oxide (polytetramethylene glycol, etc.)]; Average molecular weight 4
Condensation of polyester diol of 0 to 50,000 [aliphatic dicarboxylic acid (adipic acid, maleic acid, dimerized linoleic acid, etc.) or aromatic dicarboxylic acid (phthalic acid, terephthalic acid, etc.) with the low molecular weight diols exemplified above. Polyester diol, polylactone diol by ring-opening polymerization of ε-caprolactone, etc.]; C2-5
0 diamines (isophoronediamine, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, polyetherdiamine, etc.); C2-C50 trivalent or higher alcohols (trimethylolpropane, pentaerythritol, Sorbitol, etc.); 3 with 2 to 50 carbon atoms
And amines having a valency or higher (diethylenetriamine, triethylenetetramine, etc.); amino alcohols having 2 to 50 carbon atoms (triethanolamine, etc.); and active hydrogen-containing urethane prepolymers obtained by the reaction of these with the following polyisocyanates. Be done.

Examples of (b ₂ ) include aromatic diisocyanates (tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, etc.), alicyclic diisocyanates (isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, diisocyanate methyl). Cyclohexane etc.), aliphatic diisocyanates (hexamethylene diisocyanate etc.), trifunctional or higher polyisocyanates [triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, cyclic trimer of hexamethylene diisocyanate etc.], and the above Isocyanate group-containing obtained by reaction with active hydrogen-containing compound Urethane prepolymers, and the like.

The compound (b ₁ ) and polyisocyanate (b ₂ ) having two or more active hydrogens can be used in combination of two or more kinds.

The polyurethane resin (B) can be obtained by reacting (b1) and (b2) in the presence of a catalyst, if necessary. In this case, the use ratio of (b ₁₎ and (b _2), it equivalent ratio b ₁ / b ₂ of isocyanate groups of the active hydrogen group (b ₂₎ of (b _1), usually 1 / (0 .8-1.3),
The ratio is preferably 1 / (0.9 to 1.1).

The catalyst used if necessary may be one known as a catalyst for urethanization reaction, and examples thereof include organometallic compounds such as dibutyltin dilaurate and dioctyltin dilaurate, amines such as triethylamine and diazabicycloundecene, Is mentioned.

The dispersant (C) assists the dispersion of the polyurethane resin (B) in the polyethylene and / or polypropylene (A) or the dispersion of the (A) in (B), and is a uniform and fine sea island. It is used for the purpose of forming a structure. For this reason, (C) needs to be a dispersant that is compatible or reactive with (A) and is compatible or reactive with (B).

That is, the dispersant (C) is preferably a modified polyolefin dispersant and / or a polyolefin-polyurethane resin dispersant.

A compound (b ₁ ) having two or more active hydrogens, which is a raw material for the polyethylene and / or polypropylene (A) and the polyurethane resin (B), a polyisocyanate (b ₂ ) and a dispersant (C). More specifically exemplifying the relationship of, for example, (A) is polypropylene,
When (b ₁ ) is polycaprolactone diol (number average molecular weight 2,000) and (b ₂ ) is diphenylmethane diisocyanate, preferable examples of (C) include maleic anhydride modified polypropylene, maleic anhydride modified polypropylene and active hydrogen-containing compound. A block copolymer in which a urethane prepolymer [polycaprolactone diol (number average molecular weight 2,000) and a polyaddition product of diphenylmethane diisocyanate] are linked by diphenylmethane diisocyanate, and maleic anhydride-modified polypropylene and polycaprolactone diol are isophorone. A block copolymer linked with diisocyanate may be mentioned.

The weight average molecular weight of (C) is usually 800-
3,000,000, preferably 1,000 to 100
It is 10,000.

Regarding the ratio of each component of the resin composite, the weight ratio A / B of polyethylene and / or polypropylene (A) to polyurethane resin (B) is 99/1 to 40/6.
0, preferably 95/5 to 45/55, and the dispersant (C) is 1 to 40% by weight, preferably 3 to 20% by weight based on the total weight of (A) and (B).

The resin composite can be obtained by melt-mixing (A), (B) and (C), and the temperature range of this melt-mixing is not lower than the lower limit temperature at which (A) melts. It is below the temperature at which A) causes thermal decomposition. This temperature range is usually within the range of 50 to 350 ° C. and varies depending on the type of (A).

The pressure is not particularly limited, but in view of industrial production, it is usually reduced pressure (0.1 mmHg) to 20 atm, preferably reduced pressure (0.1 mmHg) to 10 atm.

The time is preferably as short as possible so as not to cause thermal deterioration of each component during polymerization, and is usually 0.5.
-60 minutes, preferably 1-30 minutes.

The order of introducing (A), (B) and (C) is not particularly limited, and a method of melt-mixing (A), (B) and (C) at the same time, while (A) is melted ( Any method such as a method of charging B) and (C) or a method of charging (B) while melt-mixing (A) and (C) can be used.

Examples of the mixer include various known mixers such as an extruder, a kneader, and a Banbury mixer.

In the present invention, the resin composite is obtained by melting the compound (b1) having two or more active hydrogens and the polyisocyanate (b) in the presence of (A) and (C).
It may be a resin composite obtained by polymerizing 2) and.

At this time, various conditions except the order of charging may be the same as the conditions when the above-mentioned (A), (B) and (C) are melt-mixed.

The order of introducing (A), (C), (b ₁ ) and (b ₂ ) is not particularly limited, and (A), (C), (b ₁ )
And (b ₂ ) are melt-mixed at the same time, (C), (b ₁ ) and (b ₂ ) are added to the melted (A), and (A) and (C) are melt-mixed. how to put the (b ₁₎ and (b ₂₎ in the mixture and (b of (C) and (b ₁₎ after premixing, into the molten (a) and (C) (b _{1) 2} ), a method in which (C) and (b ₂ ) are mixed in advance, and then (b ₁ ) and a mixture of (C) and (b ₂ ) are added to the molten (A), ( how to put a) and a (b ₁₎ in the melted mixture (C) and the (b _2), (a) and (b ₂₎ and the inside of the molten mixture (C) and (b ₁₎ Method (A), (C)
And (b ₁ ) are melt-mixed, (b ₂ ) is charged, and (A), (C) and (b ₂ ) are melt-mixed, (b ₁ ) is charged. Can also be taken.

The temperature range in which the resin composite according to the present invention is formed into a sheet or film is not lower than the lower limit temperature at which the resin composite melts and not higher than the temperature at which the resin composite undergoes thermal decomposition. This temperature range is usually within the range of 100 to 350 ° C. and varies depending on the type of resin composite.

The melting time at the time of molding is preferably as short as possible so that thermal deterioration of each component does not occur, and is usually 0.1 to 20 minutes, preferably 0.5 to 10 minutes.

As the molding machine, a commonly used conventional sheet or film molding machine such as an inflation molding machine or a T-die molding machine can be used.

Sheets or films molded from the resin composites of the present invention are useful in current polyethylene and / or polypropylene sheet or film applications because they require little fabrication.

[0028]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. In the following description, part means part by weight. 100% tensile stress, tensile strength, elongation, tear strength described in Examples and Comparative Examples,
The methods for measuring printability, antistatic property, moldability, and dispersed particle size are as follows. (1) 100% tensile stress It was measured according to JIS-K7127. Unit: kgf / cm ² (2) Tensile strength Measured according to JIS-K7127. Unit: kgf / cm ² (3) Elongation Measured according to JIS-K7127. Unit:% (4) Tear strength It was measured according to JIS-K7127. Unit: kgf / cm (5) Printability Applicability of PET ink (urethane type) to a test piece with a bar coater, and 24 hours after application, a peeling test is performed with cellophane tape (manufactured by Nichiban Co., Ltd., 15 mm width). The ink adhesion was investigated. The ink components are Sampren I
B-1700 {manufactured by Sanyo Kasei Co., Ltd.} 50 parts, titanium oxide 25 parts, toluene 8.3 parts, methyl ethyl ketone
8.3 parts and isopropyl alcohol 8.3 parts. ○… Ink does not peel off × ・ ・ ・ Ink easily peels off ×× ・ ・ ・ Ink does not deposit (6) Antistatic property After leaving the test piece in a temperature control room at 20 ° C and 65% RH for 4 days,
In the same atmosphere, the surface resistivity was measured using a super insulation meter {manufactured by Advantest Corporation}. Unit: Ω (7) Moldability The condition of the test piece during molding was observed. An air-cooled inflation film molding apparatus {manufactured by Toyo Seiki Seisakusho Co., Ltd., 40 mm biaxial extrusion kneader + inflation film take-up apparatus} was used for molding the test pieces. ○… (Can be molded with air-cooled inflation film molding machine) ×… It is difficult to mold (with air-cooled inflation film molding machine) (8) Dispersed particle size Measure the dispersed particle size by observing the surface of the test piece with a scanning electron microscope. did. Unit: μm

Example 1 Polypropylene [UBE-Polypro F manufactured by Ube Industries, Ltd.]
109K, hereinafter abbreviated as PP; corresponding to polyethylene and / or polypropylene (A)] 60 parts, terminal hydroxypolyethylene butylene adipate [number average molecular weight 2,500, hereinafter abbreviated as PEBA; compound having two or more active hydrogens (b ₁ )] 25.8 copies, 1,4
-Butanediol [hereinafter abbreviated as BG; corresponding to a compound (b ₁ ) having two or more active hydrogens] 3.1 parts; diphenylmethane diisocyanate [hereinafter abbreviated as MDI; corresponding to a polyisocyanate (b ₂ )] 11.1 parts; And 10 parts of maleic anhydride-modified polypropylene [bound maleic acid amount 5%, number average molecular weight 5,000, abbreviated as PP-MA; hereinafter referred to as dispersant (C)] are twin-screw extruder [manufactured by Toyo Seiki Seisakusho Co., Ltd.]. , 20 mmφ] at a cylinder temperature of 190 ° C. for 8 minutes at the same time.
The resin composite thus obtained is fed to an air-cooled blown film forming apparatus at a supply unit of 160 ° C. and a compression unit of 200.
° C, metering section 190 ° C, die 190 ° C, discharge speed 25 rpm, take-up speed 30 rpm, take-up speed 40 rp
m, and a die diameter of 0.7 mm, a test piece of the film of the present invention was prepared. 100% tensile stress of this test piece,
The tensile strength, elongation, tear strength, printability, antistatic property, moldability, and dispersed particle size were evaluated. The results of the characteristic evaluation are shown in Table 1 below.

Example 2 25.8 parts PEBA, 3.1 parts BG, and MDI
11.1 parts and the same twin-screw extruder as in Example 1 were simultaneously melt-kneaded at a cylinder temperature of 190 ° C. for 4 minutes to obtain a polyurethane resin (hereinafter abbreviated as PU-1). PP
Using the same twin-screw extruder as in Example 1, 60 parts, PU-140 parts and PP-MA 10 parts were simultaneously melt-kneaded under the same conditions. A test piece of the film of the present invention was prepared from the obtained resin composite by using the same film forming apparatus as in Example 1 under the same conditions. The characteristics of this test piece were evaluated in the same manner as in Example 1. The characteristic evaluation results are shown in Table 1 below.

Comparative Example 1 Using PP, the same film forming apparatus as in Example 1 was used to prepare a film test piece under the same conditions. The characteristics of this test piece were evaluated in the same manner as in Example 1. The characteristic evaluation results are shown in Table 1 below.

Comparative Example 2 PP 60 parts, PEBA 25.8 parts, BG 3.1
And 11.1 parts of MDI were simultaneously melt-kneaded using the same twin-screw extruder as in Example 1 under the same conditions. A film test piece was prepared from the obtained composition using the same film forming apparatus as in Example 1 under the same conditions. The characteristics of this test piece were evaluated in the same manner as in Example 1. The characteristic evaluation results are shown in Table 1 below.

[0033]

[Table 1]

Example 3 Polyethylene [UBE-Polyethylene HF manufactured by Ube Industries, Ltd.]
019, hereinafter abbreviated as PE; corresponds to polyethylene and / or polypropylene (A)] 60 parts, PEBA 2
5.8 parts, BG 3.1 parts, MDI 11.1 parts, and maleic anhydride-modified polyethylene [bound maleic acid amount 5%, number average molecular weight 5,000, hereinafter abbreviated as PE-MA; dispersant (C). 10 parts were melt-kneaded using the same twin-screw extruder as in Example 1 under the same conditions. A test piece of the film of the present invention was prepared from the obtained resin composite by using the same film forming apparatus as in Example 1 under the same conditions. The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 2 below.

Example 4 60 parts PE, 40 parts PU-1 and PE-MA 1
0 part was melt-kneaded at the same time using the same twin-screw extruder as in Example 1 under the same conditions. A test piece of the film of the present invention was prepared from the obtained resin composite by using the same film forming apparatus as in Example 1 under the same conditions. The characteristics of this test piece are shown in Example 1.
It evaluated similarly to. The results of the characteristic evaluation are shown in Table 2 below.

Comparative Example 3 A PE film test piece was prepared using the same film forming apparatus as in Example 1 under the same conditions. The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 2 below.

Comparative Example 4 PE 60 parts, PEBA 25.8 parts, BG 3.1
And 11.1 parts of MDI were simultaneously melt-kneaded using the same twin-screw extruder as in Example 1 under the same conditions. A film test piece was prepared from the obtained composition using the same film forming apparatus as in Example 1 under the same conditions. The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 2 below.

[0038]

[Table 2]

Example 5 PP 60 parts, polyethylene glycol [number average molecular weight 2,000, hereinafter abbreviated as PEG; corresponds to compound (b ₁ ) having two or more active hydrogens] 22.6 parts, trimethylolpropane and ethylene Compound with 24 mol of oxide added (hereinafter abbreviated as TMP-EO; corresponds to compound (b ₁ ) having two or more active hydrogens) 3.3 parts, BG
2.7 parts, MDI 11.4 parts, and PP-MA 1
Using 0 parts of the same twin-screw extruder as in Example 1, under the same conditions,
At the same time, they were melt-kneaded. The obtained resin composite was used in Example 1
A film test piece of the present invention was prepared under the same conditions using the same film forming apparatus as described above. The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 3 below.

Example 6 PEG 22.6 parts, TMP-EO 3.3 parts, BG
2.7 parts, and MDI 11.4 parts using the same twin-screw extruder as in Example 1 at a cylinder temperature of 190 ° C. for 4 minutes,
At the same time, melt kneading was performed to obtain a polyurethane resin (hereinafter abbreviated as PU-2). Using the same twin-screw extruder as in Example 1, 60 parts of PP, 40 parts of PU-2 and 10 parts of PP-MA were melt-kneaded simultaneously under the same conditions. A test piece of the film of the present invention was prepared from the obtained resin composite by using the same film forming apparatus as in Example 1 under the same conditions. The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 3 below.

Comparative Example 5 PP 60 parts, PEG 22.6 parts, TMP-EO
3.3 parts of BG, 2.7 parts of BG, and 11.4 parts of MDI were simultaneously melt-kneaded using the same twin-screw extruder as in Example 1 under the same conditions. A film test piece was prepared from the obtained composition using the same film forming apparatus as in Example 1 under the same conditions. The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 3 below.

[0042]

[Table 3]

[0043]

Advantages of the Invention A sheet molded from the resin composite of the present invention
The film or film has the following effects. 1. The sheet or film of the present invention is a machine such as polyethylene and / or polypropylene, which is excellent in antistatic property and printability, has a short manufacturing process, and has a high tensile strength while maintaining the features of inexpensive and lightweight and excellent moldability. The physical properties are also sufficient. 2. The sheet or film of the present invention has excellent secondary processability, and thus is useful for the current polyethylene and / or polypropylene sheet or film applications.

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Claims (3)

[Claims] 1. A resin composite obtained by combining polyethylene and / or polypropylene (A) and a polyurethane resin (B) in the presence of a dispersant (C),
The weight ratio A / B of (A) and (B) in the resin composite is 99.
/ 1 to 40/60, and (C) is 1 to 40% by weight based on the total weight of (A) and (B). 2. The weight average molecular weight of polyethylene and / or polypropylene (A) is 10,000 to 3,0.
2. The sheet or film according to claim 1, wherein the dispersant (C) is a modified polyolefin-based dispersant and / or a polyolefin-polyurethane resin-based dispersant. 3. The compound (b ₁ ) having two or more active hydrogens and polyisocyanate (wherein the resin complex is in the presence of molten polyethylene and / or polypropylene (A) and a dispersant (C)). The sheet or film according to claim 1, which is a resin composite obtained by polymerizing with b ₂ ).