JPH0912716A - Optical material made of synthetic resin containing polyamide resin originated from dimer acid - Google Patents

Abstract

PURPOSE: To obtain the subject material containing a polyamide resin derived from a dimer acid and/or a trimer acid, having a specific gravity of <=1.05, excellent transparency and high heat-resistance and useful as lens for glasses. CONSTITUTION: This material preferably having a specific gravity of 0.90-1.05 and a refractive index of 1.45-1.60 contains a polyamide resin produced by the condensation reaction of (A) a dimer acid consisting of a dimer of an 11-22C higher unsaturated fatty acid or its (11-12C) alkyl ester and/or (B) a trimer of an 11-22C higher unsaturated fatty acid or its (11-12C) alkyl ester with (C) a diamine. Preferably, the component A is a compound having the structure of the formula, etc., and the component C is an ethylenediamine expressed by the formula H2 N-R1 -NH2 (R1 is a 1-9C alkylene or phenylene), etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin optical material containing a polyamide resin derived from dimer acid and / or trimer acid.

[0002]

2. Description of the Related Art Conventionally, inorganic glass has been widely used as an optical material for various precision machines, lenses for photographers, spectacle lenses, sunglasses and the like. However, in recent years, from the viewpoint of lightness, workability, stability, dyeability, mass productivity, etc., optical materials made of plastic have begun to be used instead of inorganic glass. In particular, about 80% of eyeglass lenses are made of plastic. As an optical material made of plastic, polyalkyl methacrylate, polystyrene, polycarbonate or polydiethylene glycol bisallyl carbonate (hereinafter, represented by spectacle lenses and sunglasses,
(Also referred to as "PCR-39") and the like are used. Among various physical property values required for optical materials, low specific gravity is extremely important. By using an optical material made of a material having a small specific gravity, it is possible to reduce the weight of a lens that occupies an important position in an optical device such as a microscope, a camera, a telescope, or a spectacle lens. However, when an optical material is produced using a material such as polyalkylmethacrylate, polystyrene, polycarbonate, or PCR-39 as a raw material, even if polystyrene having the minimum specific gravity is used, the specific gravity becomes 1.06 or more. In order to solve such a problem, although an acrylic resin having a specific gravity of 0.971 is provided, the weight is further reduced and the superiority to the inorganic glass material and the existing plastic material is emphasized. For this reason, a material having a further reduced specific gravity is desired for other polymer compositions.

[0003]

DISCLOSURE OF THE INVENTION The present invention has a specific gravity of 1.0.
It is an object of the present invention to provide a synthetic resin optical material containing a polyamide resin having 5 or less and having good optical characteristics.

[0004]

The present invention has 11 carbon atoms.
Dimer acid which is a dimer of higher unsaturated fatty acid of 22
A trimeric acid which is a trimer, a mixture thereof or an esterified product thereof, and a synthetic resin optical material containing a polyamide resin obtained by condensation reaction polymerization with a specific diamine have low specific gravity and excellent optical characteristics. It was made based on the finding that the above-mentioned problems can be solved by the synthetic resin optical material containing the polyamide resin. That is, in the present invention, a dimer acid which is a dimer of a higher unsaturated fatty acid having 11 to 22 carbon atoms or its alkyl (C 1 to 12) ester, and / or a carbon number of 11 to 2
A synthetic resin optical comprising a polyamide resin obtained by condensation reaction polymerization of trimeric acid, which is a trimer of higher unsaturated fatty acid of 2, or its alkyl (C1-12) ester, and diamine. Provide materials for use.

The dimer acid, trimer acid and esterified products thereof used in the present invention are generally produced by a polymerization reaction using a higher unsaturated fatty acid or its ester. As the higher unsaturated fatty acid or its ester, one having 1 to 4 unsaturated bonds, preferably 1 to 2 unsaturated bonds can be used. The higher unsaturated fatty acid used in the present invention has a total carbon number of 11 to 22, preferably 14 to 20, and more preferably 16 to 18. Specific examples of such higher unsaturated fatty acids include, for example, oleic acid, elaidic acid, octadecenoic acid, linoleic acid, palmitoleic acid, myristoleic acid, linolenic acid, isooleic acid,
Examples thereof include eicosenoic acid, docosenoic acid, branched octadecenoic acid, branched hexadecenoic acid, and undecylenic acid. In addition, those higher unsaturated fatty acids, etc. and methanol, ethanol,
Propanol, isopropanol, butanol, isobutanol, tersialibutanol, pentanol, hexanol, octanol, 2-ethylhexanol,
Esters with decanol, lauryl alcohol and the like can also be used. In producing the dimer acid and its esterified product, the higher unsaturated fatty acid or its ester is
Although they can be used alone, they may be used in the form of a mixture. At this time, a corresponding higher saturated compound may be used in combination, and the mixing ratio thereof is 40% by weight or less, preferably 20% by weight or less.

Examples of the polymerization catalyst for carrying out the above-mentioned polymerization reaction include liquid or solid Lewis acids and Bronsted acids, but it is preferable to use a solid acid catalyst which is one of Bronsted acids. As such a substance, activated clay (preferably montmorillonite activated clay, bentonite activated clay), synthetic zeolite, silica / alumina, silica / magnesia and the like are used. The amount of catalyst is 1 to 20% by weight, preferably 2 to 8% by weight, based on the polymerization raw material. The reaction temperature is 200 to 270 ° C, preferably 230 to 250 ° C. The reaction pressure may be reduced pressure, normal pressure or increased pressure, but is usually 1 to 10 atm, preferably 2 to 10 atm. The reaction time varies depending on the amount of catalyst and the reaction temperature, but 5 to 10 hours is usually sufficient. The reaction atmosphere may be air, but in order to obtain a product with a good color tone, it is preferable to use an inert gas atmosphere such as nitrogen or argon. An inert organic solvent may be used in the reaction, but it is preferable to simply add a catalyst to the higher unsaturated fatty acid and / or its ester without using a solvent.

The polymerization reaction product thus obtained is composed of a mixture of a dimer dimer acid (or its alkyl ester) and a trimer trimer acid (or its alkyl ester). , Their mixing ratio is in the range of dimer / trimer = 9/1 to 6/4. It also contains unreacted higher unsaturated fatty acids and isomerized fatty acids (or their alkyl esters). In the present invention, the unreacted higher unsaturated fatty acid or isomerized fatty acid (or its alkyl ester) is preferably separated from the polymerization reaction product before use. Alternatively, only dimers or only trimers may be separated. As the separation method, a vacuum distillation method, a thin film distillation method, a molecular distillation method, an extraction method, a chromatographic separation method, an adsorption separation method, or the like can be adopted. Further, the polymerization reaction product may contain by-products such as aromatic compounds and polycyclic compounds. The content of these compounds varies depending on the raw materials used and production conditions, but usually 1 to 20% of aromatic compounds and 1 of polycyclic compounds are used.
-40% is contained.

The dimer acid or the esterified product thereof (hereinafter sometimes referred to as "dimer acid" including the esterified product) prepared by the above method is, for example, one kind or a mixture of two or more kinds having the structures shown below. is there.

[0009]

Embedded image

(In the formula, R ₃ and R ₄ are each hydrogen or an alkyl group having 1 to 12 carbon atoms, which may be the same or different from each other, and m, n, p, q,
m ′, n ′, p ′ and q ′ are each an integer of 0 or 1 or more, m + n = 6 to 17, p + q = 8 to 19, m ′
+ N '= 5-16, p' + q '= 7-18. ) The dimer acid represented by the compounds (I) to (V) of the present invention or an esterified product thereof can be produced by the above production method. Dimer acid (III) is dimer acid (I) or (I
I) can be produced by hydrogenation, and dimer acid (V) can be produced by hydrogenation of dimer acid (IV). The ratio of the dimer acid (I), (II) or (III) to the dimer acid (IV) or (V) varies depending on the production conditions of the dimer acid, but the dimer acid (I), (II) and / or ( III): dimer acid (IV) and / or (V) =
It is 9: 1 to 1: 9 (weight ratio). In the present invention, it is preferable to use dimer acid and trimer acid in a mixing ratio of 100/0 to 20/80 (weight ratio). Dimer acid is 2
This is because if it is less than 0% by weight, the heat resistance of the obtained polyamide resin will be reduced. On the other hand, trimer acid effectively acts to improve the flexibility and transparency of the resin, so that the mixing ratio of the two is more preferably in the range of 97/3 to 30/70 (weight ratio).

The polyamide resin of the present invention can be obtained by subjecting the above-mentioned dimer acid or its ester, and / or trimer acid or its ester to a condensation reaction with a diamine. As the diamine, ethylenediamine, diaminopropane, diaminobutane, diaminopentane, hexamethylenediamine, octanediamine, nonanediamine,
Examples include decanediamine, lauryldiamine, xylenediamine, phenylenediamine, toluylenediamine, diaminodiphenylmethane, diaminodiphenylether, diaminobenzophenone, 1,3-bis (4-aminophenoxy) benzene and isophoronediamine. These diamines can be used alone or as a mixture of two or more. Among these, those represented by the general formula (a) are preferable. H ₂ N—R ₁ —NH ₂ (a) (In the formula, R ₁ is a divalent aliphatic group having 1 to 18 carbon atoms or a divalent aromatic group. In particular, C _{1 to} C ₉ Alkylene or phenylene is preferred.)

The polycondensation reaction is carried out according to a conventional method.
That is, it is preferable that the dimer acid or the ester thereof and / or the trimer acid or the ester thereof and the diamine be mixed in an equivalent amount to be heated to increase the molecular weight while removing water or alcohol. The reaction conditions include a reaction temperature of 100 to 300 ° C., preferably 1
It is carried out at 20 to 230 ° C, more preferably 130 to 200 ° C, and the reaction time cannot be determined because it is carried out until the polycondensation is completed, but it is usually within 10 hours. Before heating to carry out the polycondensation reaction, the dimer acid or ester thereof, and / or trimer acid or ester thereof and the diamine are mixed in an equivalent amount. At this time, the reaction raw material is added to methanol, ethanol, isopropanol or water. It is better to dissolve and mix. Before heating, the solution may be decompressed and an inert gas may be introduced to keep the solution in an inert gas atmosphere. The dehydration and dealcoholation reaction by heating are usually carried out under normal pressure while slightly introducing an inert gas, but they may be carried out in a reduced pressure system or a pressurized system.
Since the viscosity of the polycondensation reaction increases gradually as described above, it is preferable to keep the temperature above the melting temperature of the polycondensation product. The polyamide resin of the present invention has a molecular weight of 5,000.
Those of up to 500,000 are preferred.

Next, a method of molding an optical material using the polyamide resin of the present invention will be described. The polyamide resin of the present invention is thermoplastic and can be molded by being melted by heating and then being cooled and solidified in a mold. In the present invention, the polyamide resin itself can be used, but before molding, it is a thermoplastic resin that can be an optical resin material that does not impair the effect on the polyamide resin, such as amorphous polyolefin, polycarbonate, alicyclic ring. Formula acrylic resin, polystyrene, polymethylmethacrylate, etc. can be added. The addition amount is usually 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less, though it depends on the specific gravity of the final product. Further, stabilizers, UV absorbers, antistatic agents, etc. may be added to the above polyamide resin to the extent that the effects are not impaired. The resin containing the additive thus obtained is melted and mixed in an extruder or the like after being mixed in a Henschel mixer or the like, or is dissolved in a hydrocarbon solvent or an aromatic solvent to obtain a polymer solution, which is then used in a mold using an extruder or the like. It can be cooled and solidified after injection. Of these, preferably injection molding,
Injection compression molding and press molding are preferable, and injection molding is more preferable from the viewpoint of production. The optical material of the present invention may be subjected to surface treatment, dyeing, antifogging and water repellency after injection molding. The synthetic resin optical material of the present invention thus obtained has a specific gravity of 0.90 to 1.05, preferably
It has excellent optical characteristics such as 0.90 to 0.97, a refractive index of 1.45 to 1.60, and a total light transmittance (thickness 5 mm) of 88 to 93%.

[0014]

Industrial Applicability The synthetic resin optical material of the present invention is excellent in transparency and heat resistance. Furthermore, since it has a feature that it has a low specific gravity that conventional resins do not have, it is most suitable for applications in which inorganic glass or conventional acrylic resins are used and weight reduction is required.
In particular, since it has a specific gravity of 1.05 or less and is lightweight and excellent in transparency, it is ideal for commercializing visually appealing lenses such as eyeglass lenses, contact lenses, camera lenses, automobile parts, illuminators, and LCDs. It is suitable for use in light guides, electrical parts, etc. Examples of the present invention will be described below, but the present invention is not limited thereto. In addition,% is% by weight unless otherwise specified.

[0015]

【Example】

Reference Example Methyl dimerate, trimethyl trimerate, methyl dimerate / trimethyl trimerate used in the examples = 7 /
3, dimer acid / trimer acid = 7/3 was prepared as follows. First, using a higher unsaturated fatty acid methyl ester containing 72% methyl oleate, 18% methyl linoleate and 10% other higher saturated fatty acid methyl as a raw material,
A dimerization reaction was carried out at 230 ° C. for 5 hours using 17% of activated clay as a catalyst. Subsequently, the unreacted fatty acid methyl ester fraction and the isomerized fatty acid methyl ester fraction were removed from the obtained product by vacuum distillation (230 ° C / 1 torr), and the residue was subjected to molecular distillation (230 ° C / 0.1 torr). Thus, dimethyl dimer acid was obtained, and trimethyl trimerate was obtained as a distillation residue. Next, 2% of Ni catalyst was added to this dimethyl dimer acid, and hydrogenation reaction was performed at a hydrogen pressure of 30 kg / cm ² at a reaction temperature of 200 ° C. for 15 hours to obtain a color tone (APHA) = 40.
To give methyl dimerate (methyl dimer A). Trimethyl trimerate was also synthesized according to the above methyl dimerate A. The color tone (APHA) was 60 (trimethyl trimerate B). Further, methyl dimerate / trimethyl trimerate = 7/3 was also synthesized according to the above methyl dimerate A. The color tone (APH
A) = 40 (mixture C). The dimer acid / trimer acid = 7/3 was obtained by saponifying the mixture C at 80 ° C. with 1.5 times the amount of methyl ester equivalent of sodium hydroxide and subsequently using sulfuric acid in excess with respect to sodium hydroxide. It was synthesized by neutralizing and obtaining the corresponding fatty acid. The color tone (APHA) was 70 (mixture D).

Example 1 Polycondensation reaction of dimer acid and diamine A flask having an internal volume of 4 liters was equipped with a stirrer, a thermometer, a nitrogen introducing tube having an introducing tube extending into the liquid, and a cooling condenser. The equivalent of 1.0 carboxyl group of dimer acid is 5
A solution dissolved in methanol to a 0% concentration,
The diamine 1.0 amino group equivalent shown in Table 1 was dissolved in methanol to a concentration of 50% and the solution was mixed at room temperature with stirring. The flask was cooled as the temperature of the solution increased upon mixing. Next, after decompressing (10 mmHg),
After introducing nitrogen gas and returning the pressure to normal pressure and maintaining the reaction system in a nitrogen atmosphere, the reaction temperature was gradually raised and methanol was distilled off. When the distillation of methanol stopped, the reaction temperature was raised to 150 ° C. over 1 hour to dehydrate or dealcoholize. After distilling most of the water or alcohol,
The reaction temperature was raised to 200 ° C over 30 minutes and reduced pressure (10 mm
The reaction was carried out under Hg) for 30 minutes. The reaction was kept uncooled in a nitrogen atmosphere and removed from the flask and pelletized by an extruder.

Preparation of spectacle lens 25 pellets of polyamide resin obtained by the above method were used.
It was injected into a mold which was melted at 0 ° C and cooled to 100 ° C. Here, the mold is composed of a main mold and a slave mold, and a nozzle was pushed into the injection port and the resin melted at high pressure was injected from this nozzle. After cooling for a while after the injection was completed, the mold was opened and the molded lens was taken out. The lens obtained has a diameter of 7
It was a concave lens with a thickness of 0 mm, a thickness of 7 mm, a center thickness of 1.65 mm, and a power of -4.00. The following items were evaluated for the obtained spectacle lens. Specific gravity: Measured according to ASTM D792. Total light transmittance: Performed according to JIS K7105. Refractive index: Measured according to ASTM D542. The results are summarized in Table 1. The compositions in the table are equivalent ratios.

[0018]

[Table 1] Table 1 Composition and properties of various spectacle lenses ─────────────────────────────────── The present invention Product No. 1 2 3 4 5 Methyl dimer A 50 Trimethyl trimer B 50 Mixture C 50 50 Mixture D 50 Ethylenediamine 50 50 50 Hexamethylenediamine 50 Nandiamine xylendiamine Isophoronediamine Specific gravity 0.957 0.959 0.958 0.957 0.951 Total light transmittance (%) 91.2 91.3 90.8 91.5 90.5 Refractive index 1.496 1.499 1.497 1.497 1.495

[0019]

[Table 2] ─────────────────────────────────── This invention product No. 6 7 8 9 10 dimer Methyl acid A 40 Trimethyl trimethyl B 10 Mixture C 50 50 50 50 Mixture D Ethylenediamine 50 25 Hexamethylenediamine Nonanediamine 50 Xylylenediamine 50 25 Isophoronediamine 50 Specific gravity 0.949 1.030 0.971 0.956 0.944 Total light transmittance (%) 90.7 90.1 90.5 91.4 90.8 Refractive index 1.493 1.598 1.511 1.497 1.548

As is apparent from the results shown in Table 1, the synthetic resin optical materials Nos. 1 to 10 of the present invention all have a specific gravity of 1.05 or less and good total light transmittance. It turns out to be a lens.

Claims (2)

[Claims] 1. A dimer acid which is a dimer of a higher unsaturated fatty acid having 11 to 22 carbon atoms or its alkyl (having 1 carbon atom).
To 12) ester, and / or polyamide obtained by condensation reaction polymerization of trimeric acid, which is a trimer of higher unsaturated fatty acid having 11 to 22 carbon atoms, or its alkyl (1 to 12 carbon atoms) ester, and diamine An optical material made of synthetic resin, which contains a resin. 2. A specific gravity of 0.90 to 1.05 and a refractive index of 1.45.
The synthetic resin optical material according to claim 1, wherein the optical material is about 1.60.