JP2002187931A - Polyurethane resin material composition for casting and impact resistant optical lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane resin material composition for casting having sufficient color change resistance and durability, and having a long enough pot life, capable of taking sufficient time for casting operation, when using a polyurethane elastomer as a molding material for an optical lens. SOLUTION: In a polyurethane resin material composition for casting comprising a polyisocyanate, a polyhydroxy compound, and an aromatic polyamine, this polyurethane resin material composition for casting contains 4,4'-methylene- bis(cyclohexylisocyanate) or isophoronediisocyanate as the polyisocyanate, a polyetherdiol or a polyesterdiol having an average molecular weight of 700-1,200 or their mixture as the polyhydroxy compound, and 4,4'-methylene-bis(2- chloroaniline) as the aromatic polyamine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyurethane resin material composition for casting, which is a molding material for optical lenses and the like.
The present invention relates to an impact-resistant optical lens molded from this material and a method for casting a polyurethane resin.

[0002]

2. Description of the Related Art In general, plastic lenses have been rapidly spread to spectacle lenses and camera lenses in recent years because they are lighter and harder to break than inorganic glass lenses and are easier to dye.

A resin widely used for plastic lenses is diethylene glycol bis (allylcarbonate).
G) Resin (CR-39) and the like, and other thermoplastic resins such as polymethyl methacrylate resin, polystyrene resin and polycarbonate resin are known.

[0004] However, inorganic glass lenses and plastic lenses other than polycarbonate resins have a disadvantage that they do not have sufficient impact resistance and are easily broken.

[0005] On the other hand, polycarbonate resins are hard to crack but have insufficient optical characteristics, and in particular, have distortion and insufficient solvent resistance and chemical resistance.

In order to compensate for the fragile physical properties of inorganic glass lenses and plastic lenses, laminated safety glass is known, which is formed of an elastic synthetic resin such as a polyurethane elastomer between one or more glass plates or on the surface thereof. The sheet or film is laminated and integrated.

As a method for producing the polyurethane elastomer used in this manner, a method of curing a polyurethane prepolymer composed of tolylene diisocyanate represented by adiprene and polyether polyol with an aromatic polyamine manufactured by Uniroyal Chemical Co., or Bayer: There is a method of curing naphthylene diisocyanate represented by vulcolan and polyester polyol.

[0008] Cured polyurethane elastomers are widely used for papermaking rolls, solid tires, timing belts and the like because of their excellent mechanical properties, abrasion resistance and rebound resilience.

[0009]

However, since these polyurethane elastomers use an aromatic polyisocyanate, they cannot be said to have sufficient discoloration resistance and durability.

Further, when a prepolymer produced from an aromatic isocyanate is cured with an aromatic polyamine, the pot life is short, so that there is a problem that sufficient time cannot be taken for casting.

[0011] Therefore, an object of the present invention is to solve the above-mentioned problems, and when a polyurethane elastomer is used as a molding material for an optical lens, discoloration resistance and durability are sufficient, the pot life is long, and An object of the present invention is to provide a method for casting a polyurethane resin material composition for impact or an impact-resistant optical lens or a polyurethane resin, which can take a sufficient time for a mold operation.

[0012]

Means for Solving the Problems In order to solve the above-mentioned problems, the inventors of the present application have conducted intensive studies and have found that an isocyanate-terminated prepolymer obtained by reacting a predetermined alicyclic diisocyanate with a polyhydroxy compound. It has been found that the object can be achieved by curing with an aromatic polyamine.

That is, a means for solving the above-mentioned problems employed in the inventions claimed in the present application is to provide a polyurethane resin composition for casting comprising a polyisocyanate, a polyhydroxy compound and an aromatic polyamine, wherein the polyisocyanate is not used. , 4,4'-methylene-bis (cyclohexyl isocyanate) or isophorone diisocyanate.

The polyurethane resin composition for casting of the present invention constituted as described above uses an NCO-terminated prepolymer obtained by reacting a predetermined alicyclic polyisocyanate with a specific polyhydroxy compound. By curing this with a specific aromatic polyamine, a molding material such as an optical lens having excellent transparency and excellent impact resistance can be obtained.

In order to constitute such a polyurethane resin composition for casting, a more preferred polyhydroxy compound is a polyether diol or polyester diol having an average molecular weight of 700 to 1200 or a mixture thereof.

It is preferable that the aromatic polyamine is 4,4'-methylene-bis (2-chloroaniline).

The reaction molar ratio (NCO / OH) of the polyisocyanate and the polyhydroxy compound is 2.
A polyurethane resin material composition for casting, in which a polyisocyanate and a polyhydroxy compound are blended so that the NCO content of the resulting polyurethane prepolymer is from 7.0 to 14.0%. Is more preferable.

Further, in order to obtain an impact-resistant optical lens which solves the above-mentioned problems, an impact-resistant optical lens obtained by casting the above-mentioned polyurethane resin material composition for casting is provided. Such an impact resistant optical lens can be used for a transparent lens, a sunglass lens or a polarized lens. That is, the above-mentioned polyurethane resin material composition for casting can be applied to the polyurethane resin material composition for optical lenses.

Further, in order to obtain a polyurethane resin material composition for casting which solves the above-mentioned problems, a polyisocyanate and a polyhydroxy compound are reacted with each other at a molar ratio (NCO / OH) of 2.5 to 4.0. The resulting polyurethane prepolymer having an NCO content of 7.0 to 14.0% and an aromatic polyamine were reacted at a reaction molar ratio (N
CO / NH ₂ ) was adjusted so as to be 1.10 to 0.90, and the mixture was cast and cured at 60 to 120 ° C. to adopt a polyurethane resin casting method.

[0020]

DETAILED DESCRIPTION OF THE INVENTION The polyisocyanate used in the present invention is a cycloaliphatic diisocyanate such as 4,4'-methylenebis (cyclohexyl isocyanate) or isophorone diisocyanate.

If a polyisocyanate other than the above is used, the object of the present invention cannot be solved. For example, examples of diisocyanates that cannot be used include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, hydrogenated XDl, norbornane diisocyanate, and the like, but if these are used, the pot life of the resulting urethane resin will not be sufficiently long.

The polyhydroxy compound used in the present invention is a polyether diol or polyester diol having an average molecular weight of 700 to 1200 and a mixture thereof.

As the polyether diol, polyoxytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran and other polyether diols can be used. As the polyester diol, various known polyesters can be used, and 1,4-butanediol adipate and 1,6-hexanediol adipate are preferable.

The viscosity of the prepolymer obtained by reacting with the diisocyanate is lower for the prepolymer from polyether diol, which is advantageous for the casting operation. Therefore, polyether diol is particularly preferable as the polyhydroxy compound used in the present invention.

In order to improve hardness and chemical resistance, an aliphatic polyol having a molecular weight of 300 or less may be used in combination. As the aliphatic polyol, ethylene glycol,
Diethylene glycol, propylene glycol, 1,4
-Diols such as butanediol, and triols such as trimethylolethane and trimethylolpropane.

The aromatic polyamine used in the present invention is:
4,4'-methylene-bis (2-chloroaniline). Polyurethanes obtained using other aromatic polyamines have a short pot life and cannot be used in the present invention.

In the present invention, when producing a prepolymer obtained by reacting a polyisocyanate with a polyhydroxy compound, the reaction molar ratio (NCO / OH) is set to 2.
5 to 4.0 and the NCO content of the resulting prepolymer is 7.0 to 14.0%. When the reaction molar ratio and the NCO content are smaller than the above ranges, the prepolymer viscosity becomes too high, so that the casting operation becomes difficult and the hardness becomes low. Also,
If it is larger than the above range, the cured physical properties deteriorate, which is not preferable.

The mixing molar ratio (NCO / NH ₂ ) between the prepolymer of the present invention and the aromatic polyamine is 1.10 to 10.
0.90, and known curing conditions can be adopted.

In order to produce the above-mentioned polyurethane resin material composition for casting to produce an impact-resistant optical lens used for a transparent lens such as an eyeglass lens, a sunglass lens or a polarized lens, a well-known casting method is used. Can be adopted.

That is, in the casting method, a mold member is used which is formed by fitting a concave mold and a convex mold in a liquid-tight manner via a gasket to mold a lens, and a monomer is injected into a cavity of the mold member. Polymerize and cure. Especially when manufacturing polarized lenses,
When the concave and convex mold members are fitted via a ring-shaped gasket, a polarizing element (polarizing film) is set in the gasket in advance. Then, a monomer of a resin raw material is injected from an injection hole formed in a mold member or a gasket so as to be covered with the resin along both surfaces of the polarizing element, and is polymerized and cured.

[0031]

EXAMPLES AND COMPARATIVE EXAMPLES In the following Examples and Comparative Examples, all “parts” and “%” are unless otherwise specified.
"Parts by weight" and "% by weight". [Production of Prepolymer] Production Example 1: 50 equipped with a thermometer, a stirrer, and a nitrogen sealed tube
In a 0 ml separable flask, a polyoxytetramethylene glycol having an average molecular weight of 1014 (Hodogaya Chemical Industry:
PTG-1000N) Take 200 parts, heat with stirring in a nitrogen stream, and heat at 100 ~ 110 ° C / 3 ~ 5mmHg under reduced pressure.
Dehydrated for 1 hour. After dehydration, 170 parts of 4,4'-methylene-bis (cyclohexyl isocyanate) (manufactured by Sumitomo Bayer Urethane: Desmodur W) was added, and 120 to 1
The reaction was carried out at 30 ° C. for 2 hours to produce a prepolymer. The obtained prepolymer was a colorless and transparent liquid having an NCO content of 9.9%, a viscosity of 8600 mPa · s / 30 ° C. and 750 mPa · s / 6.
It was 0 ° C. This prepolymer is designated as A.

Production Example 2: Using the apparatus of Production Example 1, polytetraoxymethylene glycol 2 having an average molecular weight of 1014
00 parts and 4 parts of trimethylolpropane were placed in a separable flask and dehydrated under the same conditions as in Production Example 1. After dehydration, 190 parts of 4,4'-methylene-bis (cyclohexyl isocyanate) was added and reacted at 120 to 130 ° C for 2 hours to obtain a prepolymer. The obtained prepolymer was a substantially colorless and transparent liquid having an NCO content of 10.1%, a viscosity of 8,000 mPa · s / 30 ° C, and a viscosity of 920 mPa · s / 60 ° C. This prepolymer is designated as B.

Production Example 3 Using the apparatus of Production Example 1, polytetraoxymethylene glycol 2 having an average molecular weight of 1014
00 parts were placed in a separable flask and dehydrated under the same conditions as in Production Example 1. After dehydration, 131 parts of isophorone diisocyanate (Desmodur 1 manufactured by Bayer AG) was added, and 1
The reaction was carried out at 20 to 130 ° C. for 2 hours to obtain a prepolymer.
The resulting prepolymer is a nearly colorless and transparent liquid,
NCO content: 9.7%, viscosity: 6900 mPa · s / 30 ° C, 90
It was 0 mPa · s / 60 ° C. This prepolymer is designated as C.

Production Example 4: Using the apparatus of Production Example 1, polytetraoxymethylene glycol 2 having an average molecular weight of 1014
00 parts and 4 parts of trimethylolpropane were placed in a separable flask and dehydrated under the same conditions as in Production Example 1. After dehydration, 155 parts of isophorone diisocyanate were added, and 120
The mixture was reacted at ~ 130 ° C for 2 hours to obtain a prepolymer. The obtained prepolymer is a nearly colorless and transparent liquid,
O content 10.4%, viscosity 9400mPa · s / 30 ° C, 120
It was 0 mPa · s / 60 ° C. This prepolymer is designated as D.

Production Example 5: Using the apparatus of Production Example 1, 200 parts of 1,6-hexanediol adipate having an average molecular weight of 1007 (Nipporan 164, manufactured by Nippon Polyurethane) was placed in a separable flask, and the same conditions as in Production Example 1 were used. Dehydrated under. After dehydration, 170 parts of 4,4'-methylene-bis (cyclohexyl isocyanate) was added and 120-130.
The reaction was carried out at 2 ° C. for 2 hours to obtain a prepolymer. The obtained prepolymer is an almost colorless and transparent liquid having an NCO content of 9.0%, a viscosity of 19000 mPa · s / 30 ° C., and a 2000 mPa
・ It was s / 60 ° C. This prepolymer is designated as E.

Production Example 6: Using the apparatus of Production Example 1, 1,6-hexanediol adipate 2 having an average molecular weight of 1007
00 parts and 4 parts of trimethylolpropane were placed in a separable flask and dehydrated under the same conditions as in Production Example 1. After dehydration, 199 parts of 4,4'-methylene-bis (cyclohexyl isocyanate) was added and reacted at 120 to 130 ° C for 2 hours to obtain a prepolymer. The resulting prepolymer is a nearly colorless and transparent liquid having an NCO content of 10.1%,
The viscosity was 22000 mPa · s / 30 ° C and 2100 mPa · s / 60 ° C. This prepolymer is designated as F.

Production Example 7: Using the apparatus of Production Example 1, polytetraoxymethylene glycol 2 having an average molecular weight of 1014
00 parts were placed in a separable flask and dehydrated under the same conditions as in Production Example 1. After dehydration, 104 parts of 4,4'-methylene-bis (cyclohexyl isocyanate) was added and 120 parts were added.
The mixture was reacted at ~ 130 ° C for 2 hours to obtain a prepolymer. The resulting prepolymer is a nearly colorless and transparent liquid, NC
O content 5.5%, viscosity 30000 mPa · s / 30 ° C, 270
It was 0 mPa · s / 60 ° C. This prepolymer is designated G.

Production Example 8: Using the apparatus of Production Example 1, polytetraoxymethylene glycol 2 having an average molecular weight of 1014
00 parts were placed in a separable flask and dehydrated under the same conditions as in Production Example 1. After dehydration, the mixture is cooled to 80 ° C.
3 parts were added and reacted at 80 to 85 ° C. for 5 hours to obtain a prepolymer. The obtained prepolymer is a pale yellow transparent liquid, having an NCO content of 10.8% and a viscosity of 2000 mPa · s / 30.
° C, 150 mPa · s / 60 ° C. This prepolymer is designated as H.

Production Example 9: A prepolymer was obtained in the same manner as in Production Example 8 except that tolylene diisocyanate was used in an amount of 70 parts. The obtained prepolymer is a pale yellow transparent liquid having an NCO content of 6.3%, a viscosity of 7000 mPa · s / 30 ° C. and 600 mPa · s /
60 ° C. This prepolymer is designated as I.

[Example 1] 100 g of the prepolymer A obtained in Production Example 1 was heated to 70 ° C and defoamed under reduced pressure.
The mixture was degassed and mixed with 31.4 g of 4,4'-methylene-bis (2-chloroaniline) melted at 120 ° C. This mixture is poured into a mold preheated at 100 ° C.
For 24 hours. The molar ratio at this time (NCO
/ NH ₂ ) was 1.0, and the physical properties of the obtained cast product are shown in Table 1.

[0041]

[Table 1]

Examples 2 to 6 Castings were prepared in the same manner as in Example 1 for each of the prepolymers BF obtained in Production Examples 2 to 6, and the physical properties are shown in Table 1.

Comparative Example 1 Casting was performed in the same manner as in Example 1 using prepolymer G of Production Example 7, and the viscosity of the prepolymer was so high that casting was difficult.

[Comparative Example 2] Casting was performed in the same manner as in Example 1 using the prepolymer H of Production Example 8, and the viscosity of the prepolymer was low and the workability was good, but the pot life was short. Was.

[Comparative Example 3] Casting was carried out in the same manner as in Example 1 using Prepolymer I of Production Example 9, and the viscosity of the prepolymer was low and the workability was good, but the pot life was short. .

[0046]

As described above, the invention relating to the casting polyurethane resin composition of the present invention provides a casting polyurethane resin composition comprising a predetermined polyisocyanate, polyhydroxy compound and aromatic polyamine. Accordingly, there is an advantage that the polyurethane resin material composition for casting has sufficient discoloration resistance and durability, and has a long pot life and a sufficient time for casting.

When the polyhydroxy compound is a polyether diol or polyester diol having a predetermined average molecular weight or a mixture thereof, or when the aromatic polyamine is 4,4′-methylene-bis (2-chloroaniline) In some cases, the above effects can be obtained more reliably.

The reaction molar ratio (NCO / OH) of the polyisocyanate and the polyhydroxy compound is within a predetermined range, and the resulting polyurethane prepolymer has an NC
The above-mentioned effects can be obtained more reliably even in a polyurethane resin material composition for casting in which a polyisocyanate and a polyhydroxy compound are blended so that the O content is within a predetermined range.

In the case of a transparent lens, a lens for sunglasses or an impact-resistant optical lens made of a polarized lens, which is obtained by casting the polyurethane resin composition for casting of the present invention, the discoloration resistance and durability are sufficient. In addition, since the pot life is long and sufficient time can be taken for the casting operation, optical distortion is reduced.

A polyisocyanate and a polyhydroxy compound are blended so that their reaction molar ratio (NCO / OH) falls within a predetermined range, and the obtained polyurethane prepolymer having a predetermined NCO content and an aromatic polyamine are mixed with each other. According to a method of casting a polyurethane resin which is blended in a reaction molar ratio (NCO / NH ₂ ), and is cast at a predetermined temperature, the discoloration resistance and durability are sufficient, and the pot life is long. This is a manufacturing method that can take a sufficient time for the casting operation, and has an advantage that a precise non-defective product with little optical distortion can be efficiently and reliably manufactured.

Continued on front page F-term (reference) 4F204 AA42 AB03 AB19 AH74 AR06 EA03 EB01 EF01 EF02 EK17 EK26 4J034 BA08 CA15 CB01 CC12 CC52 CC61 CD13 DA01 DB04 DF01 DF16 DF20 DG01 DG08 HA01 HA07 HC17 HC22 HC46 HC73 HC61 HC71

Claims (7)

[Claims] 1. A polyurethane resin composition for casting comprising a polyisocyanate, a polyhydroxy compound and an aromatic polyamine, wherein the polyisocyanate is 4,4′-methylene-bis (cyclohexyl isocyanate) or isophorone diisocyanate. A polyurethane resin material composition for casting, characterized by comprising: 2. The polyhydroxy compound has an average molecular weight of 7
The polyurethane resin material composition for casting according to claim 1, which is a polyether diol or polyester diol of 00 to 1200 or a mixture thereof. 3. The polyurethane resin composition for casting according to claim 1, wherein the aromatic polyamine is 4,4′-methylene-bis (2-chloroaniline). 4. The reaction molar ratio (NCO / OH) of the polyisocyanate and the polyhydroxy compound is 2.5 to 2.5.
The polyurethane resin material composition for casting according to claim 1, wherein the polyisocyanate and the polyhydroxy compound are blended such that the NCO content of the resulting polyurethane prepolymer is 4.0 to 14.0%. . 5. An impact-resistant optical lens obtained by casting the polyurethane resin material composition for casting according to any one of claims 1 to 4. 6. The impact-resistant optical lens according to claim 5, wherein the impact-resistant optical lens is a transparent lens, a sunglass lens, or a polarized lens. 7. A polyisocyanate and a polyhydroxy compound having a reaction molar ratio (NCO / OH) of 2.
The resulting polyurethane prepolymer having an NCO content of 7.0 to 14.0% and an aromatic polyamine were mixed so that the reaction molar ratio (NCO / NH ₂ ) was 1.1 to 5.0 to 4.0.
A method of casting a polyurethane resin, which is blended so as to be 0 to 0.90, is cast, and is cured at 60 to 120 ° C.