JPH07117202A - Transparent laminate and method for producing the same - Google Patents

Abstract

PURPOSE:To enhance antifogging properties and scratch resistance by forming polyurethane from a reactive polyurethane raw material mixture containing polyfunctional sulfonate group-containing polyether polyol with a specific average mol.wt. represented by a specific formula and polyoxyalkylene chain- containing polydimethylpolysiloxane with a specific average mol.wt. CONSTITUTION:A surfactant used in a polyurethane resin used as a transparent surface layer composed of a light pervious resin is composed of an isocyanate group terminal prepolymer obtained by reacting polyfunctional sulfonate- containing polyether polyol with an average mol.wt. represented by formula (X is hydrogen, sodium or ammonium, n is 0-100, m is 0-30, n+m is 1 or more and R is an org. residue having two or more hydroxyl groups) with aliphatic or alicyclic isocyanate or a hydroxyl group terminal prepolymer being a reaction product of the prepolymer with polyol and polyoxyalkylene chain-containing polydimethylpolysiloxane with an average mol.wt. of 500-2000.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a translucent resin film protected by a transparent urethane surface layer which is excellent in fog resistance, fog resistance and scratch resistance.

[0002]

2. Description of the Related Art Considering, for example, a soft polyvinyl chloride film as a translucent resin film, it is mainly used as an agricultural coating material because of its excellent weather resistance, transparency, heat retention, strength, economy and the like. It has been. Here, since the surface of the polyvinyl chloride film is inherently hydrophobic, when used as a covering material for agricultural houses and tunnels, water vapor evaporated from the crops inside or the ground surface easily condenses on the film surface and easily fogs. . If it is left as it is, the transmittance of sunlight is reduced and the rate of temperature rise in the agricultural house is reduced, which hinders the growth of crops. Also,
Drops of water can also cause crop diseases.

Therefore, hitherto, an antifogging effect has been developed on the film surface by kneading an appropriate antifogging agent into a vinyl chloride resin. However, since it was only kneaded with the resin, this antifogging agent gradually bleeded out on the film surface, and the effect persistence was limited. Further, since such a hydrophilic substance appears on the surface of the film, there is a problem that it is easily soiled.

In addition, conventionally known transparent fluororesin films have been used in a wide range of fields because of their excellent heat resistance, weather resistance, non-adhesiveness, electrical insulation and chemical resistance. However, due to the low surface energy, which is a property peculiar to fluororesins, water or the like is likely to be condensed on the surface. Moreover, although this film has very excellent mechanical properties, its rigidity makes it easy to scratch the surface.

As described above, a translucent resin film having excellent properties in various fields, but not fully exhibiting its properties due to such problems as "cloudiness" and "easiness of scratching" on the resin surface is obtained. There are many.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to improve the antifogging property, antifog property and scratch resistance of a translucent resin film.

[0007]

Means for Solving the Problems The present invention is a laminate comprising a translucent resin and a transparent surface layer of polyurethane, wherein the polyurethane has an average molecular weight of 250 to 250 represented by the following formula (1). An isocyanate group-terminated prepolymer obtained by reacting a polyfunctional sulfonate group-containing polyether polyol of 6500 with an aliphatic or alicyclic diisocyanate, or a hydroxyl group-terminated prepolymer which is a reaction product of the prepolymer and the polyol, And a polyurethane produced from a reactive polyurethane raw material mixture containing a polyoxyalkylene chain-containing polydimethylpolysiloxane having an average molecular weight of 500 to 2000, which is a transparent laminate.

R-CH ₂ O- (C ₂ H ₄ O-) _n- (C ₃ H ₆ O-) _m -CH ₂ CH ₂ CH ₂ -SO ₃ X (1) In formula (1) X is hydrogen, sodium or ammonium ion, n = 0 to 100, m = 0 to 30 (provided that n +
m ≧ 1), R is an organic residue having two or more hydroxyl groups.

The translucent resin in the present invention is preferably in the form of a film or sheet. Resins that can be used include polycarbonate resins, polyester resins, polyepoxy resins, acrylic resins, methacrylic resins, polyamide resins, polyolefin resins, polyhalogenated olefin resins, and fluororesins. In particular, a soft polyvinyl chloride film and a fluororesin film are preferable because of their high utility value.

In the urethane resin used as the transparent surface layer of the present invention, the surfactant used is a polyfunctional sulfonate group-containing polyether polyol (reaction represented by the above formula (1) having an average molecular weight of 250 to 6500. Anionic surfactant) and an average molecular weight of 500 to 20
No. 00 polyoxyalkylene chain-containing polydimethylpolysiloxane (non-reactive nonionic surfactant).

The urethane resin is capable of achieving both anti-fogging and anti-fog properties and other physical properties of the film, particularly scratch resistance and stain resistance.
This is because they are used together as a surfactant. More specifically, these surfactants partially or completely dissolve in the water adhering to the surface of the film to reduce the surface energy of the water and form a good water film on the surface of the film. Both of them have ethylene oxide moieties in the molecule and interact with each other, so that the non-reactive surfactant does not bleed out more than necessary on the resin surface. The initial anti-fogging property is sufficiently exhibited even if only the non-reactive nonionic surfactant is blended.
Considering the durability of the antifogging effect, a reactive anionic surfactant is used in combination.

As the polyfunctional sulfonate group-containing polyether polyol, it is particularly preferable that R in the above formula (1) is any group represented by Chemical formula 3 or Chemical formula 4. Here, in the formula (1), 1,2-diols are represented by Chemical formula 3 in which R is represented by Chemical formula 3, and 1,3 are represented by R in Chemical formula 4.
-It is called diol.

[0013]

[Chemical 3]

[0014]

[Chemical 4]

As the polyfunctional sulfonate group-containing polyether polyol, polyether-1,3-diol having an average molecular weight of about 1300 is particularly preferably used. This class of polyether polyols and methods for making them are described in more detail in DE-PS3407563. The content of the polyfunctional sulfonate group-containing polyether polyol residue in the reactive polyurethane raw material mixture is preferably 5 to 12% by weight. Here, the polyfunctional sulfonate group-containing polyether polyol residue refers to a polyfunctional sulfonate group-containing polyether polyol before being made into a prepolymer.

As the polyoxyalkylene chain-containing polydimethylpolysiloxane, specifically those represented by Chemical formula 5 are preferable.

[0017]

[Chemical 5]

In the formula, x / y ratio = 5/1 to 1 /
1, a / b weight ratio = 80-100 / 20-0.

The content of the polyoxyalkylene chain-containing polydimethylpolysiloxane in the reactive polyurethane mixture is preferably 1 to 5% by weight.

The polyfunctional sulfonate group-containing polyether polyol is an isocyanate group-terminated prepolymer obtained by reacting an aliphatic or alicyclic diisocyanate, or a hydroxyl group-terminated prepolymer obtained by reacting the prepolymer with the following polyol. A prepolymer is used. This is because the multifunctional sulfonate group-containing polyether polyol is compared to other polyol components.
Since the reactivity to isocyanate is poor, if the isocyanate excess ratio to the hydroxyl group is low, the reactive anionic surfactant is left unreacted in the urethane matrix, causing bleedout to the resin surface. is there.

As the aliphatic or alicyclic diisocyanate used here, isophorone diisocyanate is particularly preferable because of its resistance to yellowing, low cost and high reactivity.

As the isocyanate component used in addition to the isocyanate which is preliminarily reacted with the polyfunctional sulfonate group-containing polyether polyol, a substantially trifunctional 1,6-hexamethylene diisocyanate having a buret or isocyanurate structure is preferable. .

The average molecular weight of the polyol component is 3
A trifunctional polycaprolactone triol having an average molecular weight of 0 to 1500 and / or a polyoxyethylene glycol having an average molecular weight of 300 to 1000 is preferable.

A preferred method for producing a polyurethane is a trifunctional compound having an average molecular weight of 300 to 1500 obtained from an isocyanate group-terminated prepolymer obtained by reacting a polyfunctional sulfonate group-containing polyether polyol with an aliphatic or alicyclic diisocyanate. A hydroxyl group-terminated prepolymer obtained by reacting with polycaprolactone triol and / or polyoxyethylene glycol having an average molecular weight of 300 to 1000, and a substantially trifunctional 1,6-hexamethylene having a buret or isocyanurate structure. It is a method for producing by reacting diisocyanate and polydimethylpolysiloxane containing a polyoxyalkylene chain. It is also possible to use a chain extender if necessary.

In the production of polyurethane, the ratio of total free isocyanate groups / total released hydroxyl groups is preferably 0.9 to 2.5.

As a method for laminating the urethane resin and the translucent resin film, a urethane resin sheet is first produced and the sheet-shaped polyurethane and the translucent resin film are laminated, or a translucent resin film. There may be mentioned a method of directly coating the reaction mixture of urethane or a solution thereof on the above. When the reaction mixture of urethane or its solution is directly coated on the film, the viscosity of the urethane reaction solution can be adjusted by using an appropriate organic solvent, so that coating such as spray coating becomes possible.

Therefore, as the molding method, solution coating such as spray coating method, roll coating method, flow coating method and knife coating method is possible, and from the viewpoint that it is a cross-linking resin when it is once formed into a sheet. Japanese Patent Application Sho 62-60
What is obtained by the reactive casting method as described in Japanese Patent No. 107 is most preferable.

If necessary, stabilizers such as ultraviolet absorbers, antioxidants and light stabilizers, urethanization catalysts, extenders, colorants, flame retardants and other additives may be added to the urethane resin. It is possible.

It is preferable that the outermost layer of the urethane transparent surface layer is transparent and has self-healing property and scratch resistance. Also,
An adhesive layer or an adhesive layer may be provided for adhering or sticking to the surface of the transparent substrate.

If desired, the film may have a coloring or a pattern, which may be directly added with a coloring agent or printed, or a new film having a coloring or a pattern may be adhered or printed. It is also possible to stack them.

In accordance with the present invention, the urethane resin of the present invention is applied to a transparent substrate which is desired to have the anti-fogging effect, the scattering prevention effect when the base material is broken, and the scratch resistance effect. A scattering prevention effect and a scratch resistance effect can be imparted.

[0032]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Typical properties for evaluating the mechanical and physical properties of the anti-fogging, transparent, flexible-elastic polyurethane surface layer are self-repairing property, light transmittance, Taber abrasion, stain resistance, and Antifogging property was measured.

Self-healing property: The maximum load at which scratches generated within 5 minutes at 23 ° C. can be eliminated by scratching the surface of the urethane resin with a loaded diamond tip having a diameter of 15 mm. The disappearance of the scratch was performed visually. In the case of an inorganic glass having no self-healing property, a scratch was caused by a load of about 5 g by this method. Light transmittance, Taber wear: According to JIS K 6301. Contamination resistance: Marking was made on the surface of the urethane resin with a felt-tipped pen, and after 1 hour, wiping with ethanol was performed. Anti-fogging property: In a normal atmosphere, the surface of the urethane resin was directly blown, and the degree of fogging immediately after that was visually inspected, and evaluated as ◯: good, ×: poor.

Example 1 Isophorone diisocyanate; 18.44 parts, long-chain oxyalkylene sulfonate having a hydroxyl value of 83.75 (Tegomer DS 311 manufactured by Gold Schmidt).
7); 5.99 parts, dibutyltin dilaurate; 0.03 parts, were heated and stirred at 80 ° C. for 3 hours to obtain a uniform isocyanate-terminated prepolymer. Then, polycaprolactone triol having a hydroxyl value of 196.4;
37.43 parts, silicone-based surfactant (Gegschmitt Teg
opren 5878); 3.00 parts, silicone extender (BYK-300); 0.58 parts, light stabilizer (MARK LA-7H); 0.38 parts, benzotriazole ultraviolet absorber (TINUVIN3)
28); 0.58 parts Antioxidant (IRGANOX 1010); 0.38 parts was added, and the mixture was stirred and mixed under heating and melting at 80 ° C. for 3.0 hours with stirring and degassing under vacuum to obtain a uniform isocyanate-terminated prepolymer. The prepolymer thus obtained was slowly added to a reaction vessel containing 1,4-butanediol; 7.49 parts with stirring. Then, the mixture was heated and stirred at 60 ° C. to complete the reaction. Thus, a hydroxyl-terminated prepolymer was obtained. With this prepolymer,
34.57 parts of a nurate-modified hexamethylene isocyanate having an NCO content of 21.3%; 34.57 parts were continuously discharged and mixed by stirring using a die, and a continuous release-treated smooth polyethylene terephthalate film (thickness 0 0.1 mm) and a uniform film thickness of 0.15 mm. This liquid film was heated in a continuous polymerization oven at 120 ° C. for 20 minutes to essentially complete the polymerization, and then wound with a base film. The base film and the product film were separated while paying out the obtained roll-shaped two-layer film to obtain a transparent protective film having excellent anti-fogging property, self-healing property, and scratch resistance. Then, an acrylic pressure-sensitive adhesive was applied on one surface of this film in a solution form and dried, and then a low density polyethylene film (thickness: 0.01 mm) was laminated as a release film. The obtained film could be easily pressure-bonded to the soft polyvinyl chloride resin film using a nip roll after peeling the release film. The performance of the obtained film is shown in Table 1.

[Examples 2 to 6] Films having the following compositions were produced in the same manner as in Example 1 and pressure-bonded to a soft polyvinyl chloride resin film. The film thickness and film performance are shown in Tables 1 and 2. In addition, 0.3% by weight of extender, 0.2%
Wt% light stabilizer, 0.2 wt% antioxidant, 0.3
% Of benzotriazole-based UV absorber (these compounds are the same as in Example 1). Then, it contains 30 ppm of dibutyltin dilaurate based on the total weight of the resin.

Example 2 Isophorone diisocyanate; 18.78 parts, Tegomer DS 3117; 6.14 parts, polycaprolactone triol having a hydroxyl value of 308.5;
38.21 parts, silicone surfactant (Silwet FZ-2165 manufactured by Nippon Unicar Co., Ltd.); 3.00 parts, 1,4-butanediol; 5.73 parts, nurate-modified hexa with an NCO content of 21.3%. Methylene isocyanate; 28.17 parts.

Example 3 Isophorone diisocyanate; 18.63 parts, Tegomer DS 3117; 6.54 parts, polycaprolactone triol having a hydroxyl value of 136.0;
40.88 parts, Silwet FZ-2165; 3.00 parts, 1,4-butanediol; 8.18 parts, Nurate-modified hexamethylene isocyanate with an NCO content of 21.3%; 22.77 parts.

Example 4 Isophorone diisocyanate; 18.78 parts, Tegomer DS 3117; 6.14 parts, polycaprolactone triol having a hydroxyl value of 308.5;
38.21 parts, polyethylene glycol having a hydroxyl value of 280.6; 10.
00 parts, Tegopren 5878; 3.00 parts, nurate-modified hexamethylene isocyanate with an NCO content of 21.3%; 28.17 parts.

Example 5 Isophorone diisocyanate; 18.78 parts, Tegomer DS 3117; 6.14 parts, polycaprolactone triol having a hydroxyl value of 308.5;
38.21 parts, polyethylene glycol having a hydroxyl value of 280.6; 10.
00 parts, silicone-based surfactant (Silwet L-77 manufactured by Nippon Unicar Co., Ltd.); 3.00 parts, nurate-modified hexamethylene isocyanate having an NCO content of 21.3%; 28.17 parts.

Example 6 Isophorone diisocyanate; 18.78 parts, Tegomer DS 3117; 6.14 parts, polycaprolactone triol having a hydroxyl value of 308.5;
38.21 parts, polyethylene glycol having a hydroxyl value of 280.6; 10.
00 parts Silwet FZ-2165; 3.00 parts, nurate-modified hexamethylene isocyanate with an NCO content of 21.3%; 28.17 parts.

[Embodiment 7] The system liquids of the respective compositions of Embodiments 1 to 6 are continuously discharged and mixed with stirring by using a die to continuously supply a fluororesin film which has been previously subjected to corona discharge treatment. And coated directly.
First, dry it by touch in a continuous oven at 80 ° C,
Polymerization was essentially complete in a continuous oven at 120 ° C. The translucent resin used at this time is 120
Heat resistance of about ℃ is required. The properties of the transparent laminate thus obtained were exactly the same as those of the pressure-bonding type of Examples 1 to 6.

Example 8 Hydroxyl group-terminated prepolymer solution synthesized in Example 1 and NCO content 21.3%
Of the nurate-modified hexamethylene isocyanate of 1 to 0.478 was added to the solid content concentration of 65%.
% Thinner (xylene / n-butyl acetate /
Cellosolve acetate = 1/1/1 (weight ratio)) is added and mixed with stirring. 5 kg of this solution was stirred at room temperature for 15 minutes, and then allowed to stand for 10 minutes for defoaming. This was introduced into an overflow type flow coater, and a dry film thickness of 30 was formed on a continuously supplied fluororesin film which had been previously subjected to corona discharge treatment.
The coating was performed so that the thickness would be 0 micrometer. This was first finger-dried in a continuous oven at 80 ° C., then essentially complete the polymerization in a continuous oven at 120 ° C., and then wound with a substrate film. The performance of the obtained film is shown in Table 2.
Shown in.

Table 2 shows the performance of a soft polyvinyl chloride resin film (Comparative Example 1), a fluororesin film (Comparative Example 2) and a glass plate (Comparative Example 3) as Comparative Examples.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

EFFECTS OF THE INVENTION According to the present invention, including the antifogging effect,
It is possible to obtain a transparent layered product which has an effect of preventing scattering when the base material is broken and an effect of scratch resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Shimoda 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory

Claims (9)

[Claims] 1. A laminate obtained by applying a transparent surface layer of polyurethane to a translucent resin, wherein the polyurethane is a polyfunctional sulfonate group represented by the following formula (1) and having an average molecular weight of 250 to 6500. An isocyanate group-terminated prepolymer obtained by reacting a contained polyether polyol and an aliphatic or alicyclic diisocyanate, or a hydroxyl group-terminated prepolymer which is a reaction product of the prepolymer and a polyol, and an average molecular weight of 500 to 20.
A transparent laminated body, which is a polyurethane produced from a reactive polyurethane raw material mixture containing 00 polyoxyalkylene chain-containing polydimethylpolysiloxane. _{R-CH 2 O- (C 2} H 4 O-) n - (C 3 H 6 O-) m -CH 2 CH 2 CH 2 -SO 3 X ··· (1) Equation (1) Medium X is Hydrogen, sodium or ammonium ion, n = 0 to 100, m = 0 to 30 (however, n +
m ≧ 1), R is an organic residue having two or more hydroxyl groups. 2. A reactive polyurethane raw material mixture comprising a prepolymer having an isocyanate group or a hydroxyl group and a polyoxyalkylene chain-containing polydisiloxane, as well as a substantially trifunctional 1,6-hexa having a buret or isocyanurate structure. Methylene diisocyanate, trifunctional polycaprolactone triol having an average molecular weight of 300 to 1500 and / or an average molecular weight of 300 to 100
The transparent laminated body according to claim 1, which comprises 0, which is polyoxyethylene glycol. 3. The transparent laminate according to claim 1, wherein the content of the polyoxyalkylene chain-containing polydimethylpolysiloxane in the reactive polyurethane raw material mixture is 1 to 5% by weight. 4. The transparent laminate according to claim 1, wherein the content of the polyfunctional sulfonate group-containing polyether polyol residue in the reactive polyurethane raw material mixture is 5 to 12% by weight. 5. The transparent laminate according to claim 1, wherein the aliphatic or alicyclic diisocyanate is isophorone diisocyanate. 6. The transparent laminate according to claim 1, wherein R in the formula (1) is a group represented by Chemical formula 1 or Chemical formula 2. [Chemical 1] [Chemical 2] 7. The transparent laminate according to claim 1, wherein the translucent resin has a film or sheet shape. 8. The method for producing a transparent laminate according to claim 1, wherein the sheet-like polyurethane is laminated on a translucent resin. 9. A light-transmissive resin film coated with polyurethane, which is selected from 1 to 7 above.
Item 6. A method for producing a transparent laminate according to item.