JPH0912712A - Polyamide resin originated from dimer diamine and optical material made of synthetic resin containing the polyamide - Google Patents

Abstract

PURPOSE: To obtain a polyamide resin having a specific gravity of <=1.05 and excellent optical characteristics and obtain an optical material made of a synthetic resin containing the polyamide. CONSTITUTION: The objective polyamide resin is produced by the condensation reaction of a dimer and/or trimer of a higher aliphatic monoamine containing 1-4 unsaturated bonds in the molecule and having a carbon number of 11-22 with a polybasic carboxylic acid expressed by the formula R2 OOC-R1 -COOR3 (R1 is a 1-16C alkyl, alkenyl or aryl; R2 and R3 are each independently H or a 1-6C lower alkyl).

Description

Detailed Description of the Invention

[0001]

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

2. Description of the Related Art Conventionally, inorganic glass has been widely used as an optical material for various precision machines, lenses for photographic machines, 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, polydiethylene glycol bisallyl carbonate (hereinafter, referred to as "PC
R-39 ") and the like are used.

Of the various physical properties required for optical materials, low specific gravity is extremely important. If an optical material made of a material having a small specific gravity is used, for example, a microscope,
It is possible to reduce the weight of a lens that occupies an important position in an optical device such as a camera or a telescope or an eyeglass 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.
Therefore, in order to further reduce the weight and emphasize the superiority to the inorganic glass material and the existing plastic material, a material having a further lower specific gravity is desired.

[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 polyamide resin having 5 or less and good optical characteristics and a synthetic resin optical material containing the polyamide resin.

The present invention has 11 carbon atoms.
A polyamide resin obtained by polymerizing a dimer and / or trimer of an unsaturated higher aliphatic monoamine which is ~ 22 by amide bond with a specific polyvalent carboxylic acid,
It was made based on the finding that this polyamide has a low specific gravity and excellent optical properties and that the above problems can be solved by using this polyamide. That is, the present invention has a dimer and / or trimer of a higher aliphatic monoamine having 1 to 4 unsaturated bonds in the molecule and having 11 to 22 carbon atoms, and a polymer represented by the general formula (I). Provided is a polyamide resin obtained by a condensation reaction with a carboxylic acid.

[0004]

Embedded image R ₂ OOC—R ₁ —COOR ₃ ─── (I) (In the formula, R ₁ is an alkyl group having _{1 to} 16 carbon atoms, an alkenyl group or an aryl group, and R ₂ and R ₃ are respectively And independently represent hydrogen or a lower alkyl group having 1 to 6 carbon atoms.) The present invention also provides a synthetic resin optical material containing the above polyamide.

The above-mentioned dimer and / or trimer used in the present invention, that is, dimer diamine and / or trimer triamine can be prepared by the following method. For example, an unsaturated fatty acid having 1 to 4, preferably 1 or 2 unsaturated bonds in the molecule and having 11 to 22, preferably 14 to 20 and more preferably 16 to 18 carbon atoms, or an unsaturated fatty acid thereof. A monoamine is prepared by a reductive amination reaction of an ester, a higher unsaturated nitrile or a higher unsaturated alcohol, and the monoamine is dimerized and / or 3
Although it may be quantified, the above-mentioned unsaturated fatty acid or ester thereof, higher unsaturated nitrile or higher unsaturated alcohol is first dimerized and / or trimerized to give the corresponding polyvalent fatty acid, polyvalent nitrile or polyhydric alcohol. Then, dimer diamine and / or trimer triamine may be obtained by reductive amination reaction. In producing the above-mentioned dimer diamine and / or trimer triamine, the unsaturated fatty acid or its ester, the higher unsaturated nitrile or the higher unsaturated alcohol can be used alone or in the form of a mixture. At this time, the corresponding higher saturated compound may be used in combination, and the mixing ratio is 4
The amount is preferably 0% by weight or less, and more preferably 20% by weight or less.

Examples of the polymerization catalyst for carrying out the above dimerization and / or trimerization include liquid or solid Lewis acids and Bronsted acids. A solid acid catalyst which is one of Bronsted acids is used. preferable. As such a material, activated clay (preferably montmorillonite activated clay, bentonite activated clay), synthetic zeolite,
Silica / alumina, silica / magnesia, etc. 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 200-27.
The temperature is 0 ° C, preferably 230 to 250 ° C. The reaction pressure may be any of reduced pressure, normal pressure and increased pressure, but usually,
The pressure is 1 to 10 atm, preferably 2 to 10 atm. The reaction time varies depending on the amount of catalyst and the reaction temperature, but usually 5 to 1
0 hours is 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 a raw material such as unsaturated fatty acid or its ester, higher unsaturated nitrile or higher unsaturated alcohol without using a solvent. preferable.

The polymerization reaction product thus obtained is composed of a mixture of a dimer and a trimer, and the mixing ratio thereof is usually dimer / trimer = 9/1 to 6 /. The range is 4.
It also includes unreacted substances and isomerized monovalent functional group substances. In the present invention, it is preferable to separate and use an unreacted substance or an isomerized monovalent functional group substance from the polymerization reaction product. 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 dimers, trimers and mixtures thereof may then be reductively aminated to dimer diamines, trimer triamines and mixtures thereof. Such a reductive amination reaction can be carried out by a known method such as a reduction method using ammonia and a catalyst. For example, for the above dimer, trimer and mixtures thereof, metal oxides, Ni catalysts,
A copper catalyst or the like is added in an amount of 0.1 to 5% by weight, and a reductive amination reaction is carried out at 150 to 330 ° C., preferably 250 to 310 ° C. under a pressure of ammonia or a pressure of hydrogen with ammonia. The dimer amine prepared by the above method is, for example,
It is one kind or a mixture of two or more kinds having the structures shown below.

[0008]

Embedded image

[0009]

Embedded image

(Where m, n, p, q, m ', n',
p ′ and q ′ are each an integer of 0 or 1 or more, and m
+ N = 6 to 17, p + q = 8 to 19, m '+ n' = 5
16, p ′ + q ′ = 7 to 18) The dimer diamine (IV) is the dimer diamine (I
It can be produced by hydrogenating I) or (III), and dimer diamine (VI) is dimer diamine (V).
Can be hydrogenated to produce. The ratio of the dimer diamine (II), (III) or (IV) and the dimer diamine (V) or (VI) varies depending on the production conditions of the dimer acid, but the dimer diamine (II), (III) and / or (IV): dimer diamine (V) and / or (V
I) = 9: 1 to 1: 9 (weight ratio). In the present invention,
Dimer diamine and trimer triamine 100/0
It is preferably used in a mixing ratio of ˜20 / 80 (weight ratio). This is because when the dimer diamine content is less than 20% by weight, the heat resistance of the obtained polyamide is lowered. On the other hand, trimertriamine effectively acts to improve the flexibility and transparency of the resin, so that the mixing ratio of the two is more preferably 97/3 to 30/70 (weight ratio).

The polyamide of the present invention can be obtained by subjecting the above-mentioned dimer diamine, trimer triamine and a mixture thereof to a polycondensation reaction with a polyvalent carboxylic acid represented by the general formula (I). Examples of the polycarboxylic acid represented by the general formula (I) include oxalic acid, malonic acid, succinic acid,
Glutanoic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid,
Decamethylenedicarboxylic acid, undecamethylenedicarboxylic acid, dodecamethylenedicarboxylic acid, tridecamethylenedicarboxylic acid, tetradecamethylenedicarboxylic acid, pentadecamethylenedicarboxylic acid, hexadecamethylenedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, terephthalate In addition to dicarboxylic acids such as acids, their alkyl esters having 1 to 6 carbon atoms, for example, methyl, ethyl, propyl,
Examples thereof include butyl, pentyl and hexyl ester.
These polyvalent carboxylic acids can be used alone or in a mixture of two or more.

The polycondensation reaction is carried out according to a conventional method. That is, a solution in which the above dimer diamine, trimer triamine and a mixture thereof and the polycarboxylic acid represented by the general formula (I) are mixed in an equivalent amount is heated to increase the molecular weight while removing generated water and alcohol. It is better to do by. The reaction conditions include a reaction temperature of 100 to 300 ° C., preferably 120 to 230 ° C., and more preferably 130 to 200 ° C. The reaction time is not determined because it is carried out until the polycondensation is completed. It is within 10 minutes. In order to carry out the main condensation polymerization reaction, it is preferable to dissolve and mix the reaction raw material in methanol, ethanol, isopropanol, water or the like before heating. Before heating, the solution may be depressurized 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 of the present invention thus obtained has a specific gravity of 0.90 to 1.05 and a refractive index of 1.4.
5 to 1.60 and the total light transmittance (thickness 5 mm) is 88
It has excellent optical characteristics such as% -93%. The polyamide resin of the present invention has a molecular weight of 5,000 to 500,
000 is preferred.

Next, a method for molding an optical material using the polyamide 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,
Before molding, it is possible to add to the polyamide of the present invention an amorphous polyolefin, a polycarbonate, an alicyclic acrylic resin, polystyrene, polymethylmethacrylate, etc., which is a thermoplastic resin that can be an optical resin material that does not impair the effect. it can. The amount of addition depends on the specific gravity of the final product, but is usually 50% by weight or less, preferably 30% by weight.
Or less, more preferably 20% by weight or less. further,
Stabilizer to the extent that does not impair the effect of the polyamide of the present invention,
UV absorbers, antistatic agents, etc. can also be added. The resin containing the additive thus obtained is melt-mixed with an extruder or the like after mixing with a Henschel mixer or the like, or
It can be dissolved in a hydrocarbon solvent or an aromatic solvent to give a polymer solution, which can be cooled and solidified after injection into a mold using an extruder or the like. Of these, injection molding, injection compression molding,
Press molding is preferable, and injection molding is more preferable from the viewpoint of production. After performing injection molding on the optical material of the present invention,
Surface treatment, dyeing, antifogging and water repellency can also be applied.

[0014]

INDUSTRIAL APPLICABILITY The polyamide resin and the optical material of the present invention are 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, it can be made lighter with a specific gravity of 1.05 or less and is also excellent in transparency, so it is optimal when considering commercialization that appeals to the eyes. Therefore, eyeglass lenses, contact lenses, camera lenses, automobile parts, illuminators, LCD light guides,
It is preferably used for electrical parts. Further, since the polyamide of the present invention is a thermoplastic resin, it is suitable for fields such as hot melt adhesives and flexographic printing inks. Examples of the present invention will be described below, but the present invention is not limited thereto. In addition,% is weight% unless otherwise specified.

[0015]

【Example】

Reference Example Dimer diamine, trimer triamine, dimer diamine / trimer triamine used in the examples = 7/3
Was prepared as follows. First, a higher unsaturated fatty acid methyl ester containing 72% of methyl oleate, 18% of methyl linoleate and 10% of other higher saturated fatty acid methyl was used as a raw material, and activated clay (7%) was used as a catalyst to obtain 230
The dimerization reaction was performed at 5 ° C for 5 hours. Subsequently, the unreacted fatty acid methyl ester fraction and the isomerized fatty acid methyl ester fraction were distilled under reduced pressure (230 ° C / 1 torr) from the product obtained.
The residue was subjected to molecular distillation (280 ° C./0.1 torr) to obtain dimethyl dimer acid and trimethyl trimerate as a distillation residue. Next, 0.5% of zinc oxide was added to dimethyl dimer acid, and ammonia gas was passed at a reaction temperature of 300 ° C. for 10 hours to obtain dimer dinitrile. Furthermore, 0.3% of Ni catalyst was added to this dinitrile, the reaction temperature was 150 ° C., the ammonia pressure was 20 kg / cm ² , and the hydrogen pressure was 1
The reaction mixture was kept at 5 kg / cm ² and reacted for 3 hours to obtain a crude dimer diamine. Add 2% of Ni catalyst to this diamine, and add hydrogen pressure 3
Hydrogenation reaction was carried out at a reaction temperature of 200 ° C. for 15 hours at 0 kg / cm ² to obtain a dimer diamine having a color tone (APHA) = 30 (dimer diamine A). Trimer triamine was also synthesized according to the above dimer diamine. The property is
The color tone (APHA) was 50 (trimertriamine B). Furthermore, dimerdiamine / trimertriamine = 7/3 was also synthesized according to dimerdiamine. The color tone (APHA) was 40 (mixture C).

Dimer diamine and polyvalent carboxylic acids
The polycondensation reaction with and a flask having an internal volume of 4 liters were equipped with a stirrer, a thermometer, a nitrogen introducing pipe having an introducing pipe extending into the liquid and a cooling condenser. A solution in which 1.0 amino group equivalents of amine such as dimer diamine are dissolved in methanol so as to have a concentration of 50%, and polyvalent carboxylic acids shown in Table 1 methanol so that 1.0 carboxyl group equivalents have a concentration of 50% The solution dissolved in was mixed at room temperature with stirring. The flask was cooled as the temperature of the solution increased upon mixing. Next, after reducing the pressure (10 mmHg), nitrogen gas was introduced and the pressure was returned to normal pressure to keep the reaction system in a nitrogen atmosphere, and then the reaction temperature was gradually raised to distill off methanol. 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 is raised to 200 for 30 minutes.
The temperature was raised to 0 ° C., and the reaction was carried out for 30 minutes under reduced pressure (10 mmHg).
The reaction was kept uncooled in a nitrogen atmosphere and removed from the flask and pelletized by an extruder.

Preparation of spectacle lens The pellets of polyamide obtained by the above-mentioned method are heated at 250 ° C.
It was melted in and was injected into a mold 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 70
mm, thickness 7 mm, center thickness 1.65 mm, diopter was -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 ─────────────────────────────────── present Invention No. 1 2 3 4 5 Dimer diamine A 50 15 Trimer triamine B 35 Mixture C 50 50 50 Adipic acid 50 50 50 Azelaic acid 50 Phthalic acid 50 Specific gravity 0.958 0.953 0.958 0.951 1.021 Total light transmittance (%) 90.6 91.1 90.8 91.3 90.1 Refractive index 1.499 1.496 1.497 1.491 1.587

As is clear from the results shown in Table-1,
It can be seen that the synthetic resin optical materials Nos. 1 to 5 of the present invention are spectacle lenses having a specific gravity of 1.05 or less and good total light transmittance. Example 2 The polyamide prepared in Example 1 (Product 3 of the invention) was used as 200
It was found to have an effect as an adhesive when it was melted at ℃ and was thinly coated between wood and wood and iron and iron and cooled.

Claims (3)

[Claims] 1. A dimer and / or trimer of a higher aliphatic monoamine having 1 to 4 unsaturated bonds in the molecule and having 11 to 22 carbon atoms, and a polyvalent compound represented by the general formula (I). Polyamide resin obtained by condensation reaction with carboxylic acids. Embedded image R ₂ OOC-R ₁ —COOR ₃ ─── (I) (In the formula, R ₁ is an alkyl group having _{1 to} 16 carbon atoms, an alkenyl group or an aryl group, and R ₂ and R ₃ are respectively And independently represent hydrogen or a lower alkyl group having 1 to 6 carbon atoms.) 2. A synthetic resin optical material comprising the polyamide resin according to claim 1. 3. A specific gravity of 0.90 to 1.05 and a refractive index of 1.45.
The synthetic resin optical material according to claim 2, wherein the optical material is about 1.60.