JPH0467499B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyurethane laminate. More specifically, the present invention relates to a simplified method for producing a polyurethane laminate in which the steps of urethanization reaction and lamination (composite) with plastic or glass are integrated.

[Conventional technology and problems]

In general, polyurethane laminates are used in the field of safety glass by combining them with glass or engineering plastic films, taking advantage of polyurethane's high strength, abrasion resistance, and good adhesion to various materials. It is used in the clothing field and sanitary material field by combining with other materials. Such polyurethane laminates are made by dissolving polyurethane in a solvent and making it into glass, plastic film,
It is manufactured by coating an adherend such as a nonwoven fabric or by laminating thermoplastic polyurethane onto an adherend by melt extrusion molding.
This makes the manufacturing process complicated and causes high costs. Furthermore, since conventional methods are limited to non-crosslinked (thermoplastic) polyurethanes, it is currently impossible to obtain products with higher physical properties. Furthermore, the conventional method has the drawback of being somewhat inferior in adhesion to various adherends.

[Means for solving problems]

The inventors of the present invention conducted intensive studies aimed at solving the above-mentioned drawbacks, and as a result, they were able to integrate the steps of urethanization reaction and lamination (composite) with plastic or glass, etc., and obtained the results obtained by this method. The present invention was achieved by discovering that the laminate produced by the present invention has excellent physical properties.

That is, in the present invention, a polyol component and a polyisocyanate compound, which are raw materials for polyurethane, are mixed and stirred, the mixture is injected into a twin-screw extruder, polymerized, and the mixture is attached to the twin-screw extruder with or without a metering pump. Glass is formed into a film through a die,
The present invention provides a method for producing a polyurethane laminate, which is characterized in that it is composited onto an adherend such as a plastic film or nonwoven fabric.

In the method of the present invention, the polyol component has a number average molecular weight of 500 to 5000 and an average number of functional groups (f) of 22
It is necessary to use high molecular weight polyols with ≦f<4 and those containing chain extenders and/or crosslinkers. When the molecular weight is less than 500, the viscosity is too low and operability is poor. Moreover, the final physical properties of the obtained polyurethane are also not good. On the other hand, when the molecular weight exceeds 5000, the viscosity is too high and mixing becomes difficult. The average number of functional groups (f) is f
= 1, it becomes a monol and does not polymerize, while f≧5
However, it is not preferable because it is too polyfunctional and the viscosity of the polymer increases and the physical properties deteriorate.

Conventionally known components can be used for producing the polyurethane according to the present invention. Examples of high molecular weight polyols include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol, and polyether type polyols such as alkylene oxide adducts such as bisphenol A and glycerin with ethylene oxide and propylene oxide; Dibasic acids such as adipic acid, phthalic anhydride, isophthalic acid, maleic acid, fumaric acid, and succinic acid and ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, Examples include polyester type polyols obtained by polycondensation reaction with glycols such as trimethylolpropane, polycaprolactone diol, polycarbonate diol, and the like.

The number average molecular weight of these high molecular weight polyols is
The range is from 500 to 5000, particularly preferably from 1000 to 3000.

Further, as polyisocyanate compounds, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, Examples include isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate.

These polyols and polyisocyanate compounds may be reacted by any of the one-shot method, pseudo-prepolymer method, and prepolymer method employed in conventional polyurethane production methods, but it is preferable to use the pseudo-prepolymer method or the prepolymer method. This will improve the properties of the product obtained.

Furthermore, as a chain extender, ethylene glycol,
Mention may be made of low molecular weight diols such as 1,4-butanediol, diethylene glycol, 1,6-hexanediol, neopentyl glycol and N-methyldiethanolamine, and diamines such as ethylenediamine, hexamethylenediamine and isophoronediamine. Preferably, low molecular weight diols are used.

Furthermore, trimethylolpropane, triethanolamine, glycerin, and ethylene oxide and propylene oxide adducts thereof may be added as polyfunctional components if necessary. In the production of the polyurethane of the present invention, the OH group/NCO group equivalent ratio is preferably in the range of 0.95 to 1.05, preferably in the range of 0.98 to 1.02, in view of the physical properties of the polyurethane produced.

Furthermore, the present invention is not limited to polyurethane, and various thermoplastic resins can be added to polyurethane.

The twin screw extruder used in the present invention is L/D
(length/diameter ratio) must be in the range of 30 to 70. Moreover, it is preferable that the rotation speed is 30 to 400 rpm. Examples of commercially available twin screw extruders include
PCM-45 (Ikegai Iron Works Co., Ltd.), ZSK-57 (West German Werner
), TEM-50A (Toshiba Machine Co., Ltd.), BT-40-S (Plastic Engineering Research Institute), TEX44-30AW-2V
(Japan Steel Works), etc.

In the present invention, a metering pump is installed between the twin-screw extruder and the die in order to improve metering feedability when laminating polyurethane. By using this metering pump, the process from reaction to laminated sheet formation can be integrated, and there is no need to re-melt the polyurethane, so there is less risk of side reactions occurring, and the quality of the polyurethane is highly stable. It has remarkable effects such as improving productivity.
Further, a single screw extruder may be provided between the die and the twin screw extruder. As the die, a T-die is preferable from the viewpoint of simplicity of the device.

In view of the reaction time during polyurethane synthesis, the barrel temperature of the twin-screw extruder is preferably set at 150° to 250°C.

Plastic sheets (films) to be composited with the polyurethane film in the present invention include polyethylene, polypropylene, polymethyl methacrylate, polycarbonate, polyethylene phthalate, nylon, polyurethane, polyether ether ketone, polyacetal, polyimide, polyamideimide, and polybutylene terephthalate. Examples include films and sheets such as. Engineering plastics and super engineering plastics with a softening point of 100° or higher are desirable. As the nonwoven fabric, those made of the resins mentioned above can be preferably used.

As described above, the method of the present invention makes it possible to polymerize and combine polyurethane raw materials with adherends in one step, thereby simplifying the manufacturing process and making thermosetting type It became possible to produce polyurethane composites. Moreover, it was found that the adhesion of the obtained polyurethane composite was significantly improved compared to conventional composites.

The polyurethane composite according to the present invention can be preferably used in the fields of safety glass, intermediate materials for safety glass, clothing, and sanitary materials.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Production examples of the polyol component and polyisocyanate compound used in Examples 1 to 4 are shown below.

Production example 1 (A) 15 kg of polybutylene adipate with a number average molecular weight of 1000, 30 kg of polybutylene adipate with a number average molecular weight of 2000, and 4.24 kg of 1,4-butanediol
Kg was put into a 50 ml reaction vessel and stirred and mixed at 80°C in a nitrogen stream. The resulting polyol mixture had a hydroxyl value of 175.7 KOHmg/g.

(B) 24.8 kg of diphenylmethane diisocyanate, 9 kg of polybutylene adipate with a number average molecular weight of 1000, and 18 kg of polybutylene adipate with a number average molecular weight of 2000 were placed in a 50-liter reaction vessel and stirred at 70°C in a nitrogen stream for 3 hours. A prepolymer was obtained by the reaction. The free isocyanate groups of the obtained prepolymer was 13.2%.

Production example 2 (A) 42 kg of polyoxytetramethylene glycol with a number average molecular weight of 2000, 1,4-butanediol
5.05Kg and 0.83Kg of trimethylolpropane 50
The mixture was added to a reaction vessel and stirred and mixed at 80°C in a nitrogen stream. The resulting polyol mixture had a hydroxyl value of 202.5 KOHmg/g.

(B) 25Kg of diphenylmethane diisocyanate and 23.8Kg of polyoxytetramethylene glycol with a number average molecular weight of 2000 were placed in a 50mm reactor and reacted with stirring at 70℃ for 3 hours in a nitrogen stream to obtain a prepolymer. . The free isocyanate groups of the obtained prepolymer was 15.2%.

Production Example 3 (A) 31 kg of polyoxytetramethylene glycol with a number average molecular weight of 1000 and 18.1 kg of N-methyldiethanolamine were placed in a 50-liter reaction vessel and heated in a nitrogen stream.
The mixture was stirred and mixed at 80°C. The resulting polyol mixture had a hydroxyl value of 418.4 KOHmg/g.

(B) 43 kg of isoporone diisocyanate and 7.09 kg of polyoxytetramethylene glycol with a number average molecular weight of 1000 were put into a 50-kg reaction vessel, and the
A prepolymer was obtained by reacting at °C for 5 hours with stirring. The free isocyanate groups of the obtained prepolymer was 31.3%.

Production Example 4 (A) 33.0Kg of polyoxytetramethylene glycol with a number average molecular weight of 1000, 11.8Kg of N-methyldiethanolamine, and 4.3Kg of triethanolamine.
50° C. and stirred and mixed at 80° C. in a nitrogen stream. The resulting polyol mixture had a hydroxyl value of 399.7 KOHmg/g.

(B) 47.0 kg of methylene bis(cyclohexyl isocyanate) and 2.58 kg of polyoxytetramethylene glycol with a number average molecular weight of 1000 were placed in a 50 reaction vessel and reacted with stirring at 80°C for 5 hours in a nitrogen stream to obtain a prepolymer. . The free isocyanate groups of the obtained prepolymer was 30.0%.

Examples 1 to 4 were prepared using the above polyol component and polyisocyanate compound, and by the manufacturing process shown in Figure 1.
A polyurethane film laminate was manufactured as follows.
In FIG. 1, 1 is a polyol tank, 2 is a prepolymer tank, and 3 is a quantitative mixer. 4 undergoes polymerization through a twin-screw extruder, then passes through a metering feed pump 5 and a T-die 6 to form a film while laminating with a nonwoven fabric etc. from a base material feed roll 7. 8 is a pressure roll, 9 is a cooling roll, and 10 is a laminate winding roll.

Example 1 The polyol mixture obtained in Production Example 1A and the prepolymer obtained in Production Example 1B were sent to a mixing device at a rate of 150 g per minute through a gear wheel type pump, and in a uniformly mixed state, It is injected into the inlet tube of a twin-screw extruder (L/D=45) with two shafts rotating at 200 revolutions per minute and at equal intervals.

The barrel temperature of the extruder was 160°C at the inlet and 200°C at the outlet.

T connected to the extruder outlet via a metering pump
- The sheet produced through the die was laminated with a nonwoven fabric (polyester fiber) to form a sheet with a thickness of 2 mm.

Example 2 A laminate film (thickness: 100 μm) with a polypropylene film (thickness: 20 μm) was manufactured in the same manner as in Example 1 using the products obtained from Production Examples 2A and 2B.

Example 3 A laminate sheet (1 mm thick) with a polyethylene terephthalate film (100 μm thick) was produced in the same manner as in Example 1 using the products obtained from Production Examples 3A and 3B.

Example 4 A laminate sheet (thickness 100 μm) with a polyurethane sheet (thickness 0.8 mm) was prepared in the same manner as in Example 1 using the products obtained from Production Example 4A and Production Example 4B.
m) was produced.

〔Effect of the invention〕

As is clear from the examples and manufacturing schematics, manufacturing has been streamlined and it has become possible to manufacture not only conventional thermoplastic polyurethane but also composites of thermosetting polyurethane, and its industrial value is extremely large. be.

According to the method of the present invention, the polyurethane film and the base material can be easily adhered to each other, and the resulting laminate has extremely strong adhesive strength.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of the manufacturing process of the present invention. DESCRIPTION OF SYMBOLS 1... Polyol tank, 2... Prepolymer tank, 4... Twin screw extruder, 5... Metering feed pump, 6... T-die, 7... Base material delivery roll.

Claims (1)

[Claims] 1. It consists of polymerizing a polyol component and a polyisocyanate compound, which are the raw material components of polyurethane, through a twin-screw extruder, and then compounding it with glass, plastic or non-woven fabric while forming a film through a die connected via a metering pump,
The polyol component contains a high molecular weight polyol with a number average molecular weight of 500 to 5000 and an average number of functional groups (f) of 2≦f<4, a chain extender and/or a crosslinking agent, and D (length/diameter ratio) is 30 to 70
A method for producing a polyurethane laminate, characterized by: