JPH04304237A - Spectacle frame made from resin composition - Google Patents

Abstract

PURPOSE:To improve the alcohol resistance while maintaining the characteristics inherent in a polyamide resin by molding a resin compsn. contg. a specifc copolyamide and an aliph. polyamide. CONSTITUTION:A copolyamide is prepd. by reacting 50-10mol% isophthalic acid, 0-40mol% terephthalic acid, 45-5mol% hexanethylenediamine, and 5-45mol% alicyclic diamine of the formula (wherein R1 to R5 are each H or 1-3C alkyl) in water to form salts, precondensing the salts at 200-350 deg.C under the reaction pressure in a hermetically closed actoclave, releating the pressure, and polycondensing the precndensate under atmospheric or reduced pressure. 97-40wt.% the copolyamide, 3-60wt.% aliph. polyamide, and necessary amts. of a flame retardant, a reinforcement, a pigment, a dye, a thermal stabilizer, etc., are compounded to give a resin compsn., which is molded into a spectacle frame.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an eyeglass frame made of a resin composition that maintains the excellent properties of polyamide resin and has improved alcohol resistance.

0002

BACKGROUND OF THE INVENTION Transparent copolyamides obtained from isophthalic acid and/or terephthalic acid, a cycloaliphatic diamine and hexamethylene diamine have been known for a long time. For example, Japanese Patent Publication No. 46-41024 discloses a method for producing a quaternary copolyamide obtained from isophthalic acid, terephthalic acid, bis(4-aminocyclohexyl)methane, and hexamethylene diamine. Such copolyamides have excellent transparency, have a high glass transition temperature, and therefore have excellent heat resistance, and have the advantage that changes in dimensions and physical properties due to water absorption are extremely small.

0003

[Problem to be Solved by the Invention] However, such copolyamides have poor resistance to certain solvents such as alcohol, and cracks often occur when they come into contact with alcohol or its vapor under a strain load, for example. was recognized. This has hindered the wide application of such copolyamides.

[0004] Alcohol resistance is a very important property, especially when used as eyeglass frames, since alcohol is often contained in hair styling products and the like. Although the copolyamide obtained from isophthalic acid and/or terephthalic acid, alicyclic diamine, and hexamethylene diamine has excellent basic properties as an eyeglass frame as mentioned above, it has poor alcohol resistance, so it is not suitable for eyeglass frames. Its application as such had not been realized.

[0005] In view of the above circumstances, the present invention provides a resin with improved alcohol resistance while retaining the excellent properties of a polyamide resin obtained from isophthalic acid and/or terephthalic acid, an alicyclic diamine, and hexamethylene diamine. The object of the present invention is to provide an eyeglass frame made of a composition.

[0006]

[Means for Solving the Problems] The present invention achieves the above object, and includes (A) 50 to 10 mol% of isophthalic acid, 0 to 40 mol% of terephthalic acid, and 45 to 5 mol% of hexamethylene diamine. Alicyclic diamine represented by formula [1]

[Chemical formula 2] (However, R1, R2, R3, R4, and R5 may be the same or different, and each has hydrogen or 1 carbon number.
~3 represents an alkyl group. ) 5 to 45 mol% of a copolymerized polyamide obtained from 97 to 40% by weight, and (B) 3 to 60% by weight of an aliphatic polyamide. It is.

The alicyclic diamine, which is one of the diamine components of the copolyamide used in the present invention, has the general formula [1
].

[Chemical formula 3] (However, R1, R2, R3, R4, and R5 may be the same or different, and each has hydrogen or 1 carbon number.
~3 represents an alkyl group. )

Preferred specific examples of these alicyclic diamines include bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexyl)propane, and bis(4-aminocyclohexyl)propane.
Amino-3-methylcyclohexyl)methane, bis(4
-amino-3-methylcyclohexyl)propane, bis(4-amino-3,5-dimethylcyclohexyl)methane, bis(4-amino-3,5-dimethylcyclohexyl)propane, bis(4-amino-3- Methyl-5-ethylcyclohexyl)methane, bis(4-amino-3-
Methyl-5-ethylcyclohexyl)propane, bis(
4-amino-3,5-diethylcyclohexyl)methane, bis(4-amino-3,5-diethylcyclohexyl)propane, bis(4-amino-3-methyl-5-isopropylcyclohexyl)methane, bis(4-amino −
3-Methyl-5-isopropylcyclohexyl)propane, bis(4-amino-3,5-diisopropylcyclohexyl)methane, bis(4-amino-3,5-diisopropylcyclohexyl)propane, bis(4-amino-3-ethyl) cyclohexyl)methane, bis(4-amino-3-ethylcyclohexyl)propane, bis(4-
Examples include amino-3-isopropylcyclohexyl)methane and bis(4-amino-3-isopropylcyclohexyl)propane.

The copolyamide of component (A) used in the present invention can be produced by various known methods. (
Copolyamide obtained from four components with 4-amino-3,5-diethylcyclohexyl)methane]. In the copolyamide used in the present invention, for example, a diamine component and a dicarboxylic acid component are first reacted in water to form a salt, and then the salt is condensed and polycondensed. The salt solution is preferably first precondensed in a closed autoclave at a temperature of 200 DEG C. to 350 DEG C. under reaction pressure, then the pressure is released and the reaction is carried out under atmospheric or reduced pressure until the polycondensation reaches equilibrium.

In order to obtain good physical properties, the relative viscosity of the copolyamide (measured at 20°C using a 1% by weight m-cresol solution of the copolyamide) is in the range of 1.2 to 3.0. This is desirable. It is also possible to add known monofunctional amines or carboxylic acids during polymerization to adjust the relative viscosity of the copolyamide. The copolyamide thus obtained is amorphous, exhibits no melting point, and is completely transparent and colorless.

The aliphatic polyamide of component (B) of the present invention includes ring-opening polymers of lactams such as ε-caprolactam and ω-laurolactam, 6-aminocaproic acid, 1
Polycondensates of aminocarboxylic acids such as 1-aminoundecanoic acid and 12-aminododecanoic acid, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4/2,4,4
- Polycondensates of diamines such as trimethylhexamethylene diamine and 5-methylnonamethylene diamine and dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid. Specific examples include nylon 46, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, and nylon 61.
2. Nylon 1212, etc. These can be used alone or in combination of two or more.

The blending ratio of the copolyamide (A) component and the aliphatic polyamide component (B) in the resin composition of the present invention is 97-40% by weight: 3-60% by weight. If the blending ratio of the aliphatic polyamide of component (B) is less than 3% by weight, the effect of improving alcohol resistance will not be significant;
If the amount exceeds % by weight, transparency will be impaired, which is not preferable.

[0013] It is also possible to add other polymers to the resin composition of the present invention, if necessary. Such polymers include polybutadiene, butylene-
Rubbery polymers such as styrene copolymer, acrylic rubber, ethylene-propylene copolymer, polyisoprene, chlorinated butyl rubber, chlorinated polyethylene, styrene-butadiene copolymer, and polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate , polyoxymethylene, polyphenylene oxide, polysulfone,
polyether sulfone, polyphenylene sulfide,
Examples include polyethylene terephthalate, polybutylene terephthalate, and polyarylate.

Furthermore, the resin composition of the present invention may contain flame retardants, reinforcing agents, pigments, dyes, heat resistant agents, antioxidants, weather resistant agents, etc., depending on the use and purpose, within a range that does not adversely affect the inherent physical properties of the resin. One or more types of various additives such as additives, plasticizers, lubricants, antistatic agents, and crystal nucleating agents can be added.

[0015] As a compounding method for obtaining an eyeglass frame made of the resin composition of the present invention, a predetermined amount of a mixture of a copolymerized polyamide as a component (A) and an aliphatic polyamide as a component (B) is charged through a hopper mouth. It can also be made directly into a molded product of the intended eyeglass frame using a molding method such as injection molding.
Alternatively, the copolyamide of component (A) and the aliphatic polyamide of component (B) are mixed in a measuring device such as a screw feeder, table feeder, or belt feeder.
Various methods are known in the art, such as melt-kneading in a single-screw or multi-screw extruder while weighing each product, extruding the strands, pelletizing them with a cutter, and molding them into eyeglass frames using methods such as injection molding. It can be done.

Eyeglass frames made of the resin composition of the present invention are transparent and have excellent alcohol resistance, and also have excellent stainability, so they can be applied to a very wide range of uses.

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

(Reference Example 1): Polymerization example of copolyamide (PA-1) 45 mol% of isophthalic acid, 5 mol% of terephthalic acid, 45 mol% of hexamethylenediamine, bis-(4-amino-
10 kg of a raw material containing 5 mol % of 3-methylcyclohexyl)methane was charged into a reaction tank together with 8 kg of pure water, and the air in the reaction tank was purged several times with nitrogen. After raising the temperature to 90°C and reacting for about 5 hours, the reaction temperature was gradually lowered to 1
The temperature was raised to 280° C. over 0 hours under pressure (18 bar) while stirring the tank.

[0018] Then, after releasing the pressure and lowering the pressure to atmospheric pressure, polymerization was further carried out at the same temperature for 6 hours. After the reaction was completed, it was discharged from the reaction vessel and cut to obtain pellets. The relative viscosity of the obtained pellets (measured at 20° C. using a 1% by weight m-cresol solution of the pellets) was 1.50. Further, the glass transition temperature was 150°C. This copolyamide is designated as PA-1.

(Reference Example 2): Copolymer polyamide (PA-2) 40 mol% of isophthalic acid, 10 mol% of terephthalic acid, 40 mol% of hexamethylenediamine, 10% of bis-(4-amino-3-methylcyclohexyl)propane A copolymerized polyamide was obtained in the same manner as in Reference Example 1 by adding acetic acid as a relative viscosity modifier such that the amount was 1% by mole and 1% by weight based on the total amount. The relative viscosity of this copolyamide (according to the same measuring method as described above) was 1.42. This copolyamide is designated as PA-2.

Examples 1 to 8, Comparative Examples 1 and 2 Copolymerized polyamides PA-1 and PA-2 of component (A), and various aliphatic polyamides of component (B) [Nylon 46 (Unitika
Co., Ltd. F5000), Nylon 6 (Unitika Co., Ltd.)
A1030BRT) and nylon 610 (CM2001, manufactured by Toray Industries, Inc.) at various weight percentages shown in Table 1 and blended using a tumbler. The blended raw materials were vacuum dried at a temperature of 95° C. for 6 hours. The dried raw materials were processed using a 45 mmφ twin-screw extruder (manufactured by Ikegai Tekko Co., Ltd.) for 30 minutes.
The mixture was melt-kneaded at 0°C and cut to obtain pellets. The obtained pellets were dried at a temperature of 95° C. for 16 hours and injection molded to obtain various test pieces and eyeglass frames. The molding temperature was 260°C and the mold temperature was 40°C. Using the obtained test piece and eyeglass frame, various performances were measured and evaluated using the following methods.

Bending elastic modulus: ASTM D790 Heat distortion temperature: ASTM D648 Load 18.6 kg/cm2 Light transmittance: ASTM D1003, sample thickness 3.2 mm Alcohol resistance: 3.2 mm sample span length 10 cm
A bending strain was applied using a three-point support method, ethanol was applied to this part at room temperature, and the bending strain at which cracks occurred was determined. Bending strain is 0.3, 0.6, 0.9, 1.2, 1.5%
Five types were used. Damage to eyeglass frames: Eyeglass frames were molded by injection molding, bent, and immersed in ethanol to examine whether damage occurred. These results are shown in Table 1.

As is clear from Table 1, the eyeglass frame made of the resin composition of the present invention has significantly improved alcohol resistance compared to the comparative example while maintaining high light transmittance, and also has excellent bending elasticity. It also has extremely excellent properties with no major differences from the comparative examples in terms of heat deformation temperature, heat distortion temperature, etc.

[0023]

[Effects of the Invention] According to the present invention, isophthalic acid and/or
Alternatively, it maintains the excellent properties of a copolyamide made of terephthalic acid, alicyclic diamine, and hexamethylene diamine, and has excellent stability against alcohol, which is often included in hair styling products. It is possible to provide an eyeglass frame that is also excellent in other necessary performances.

[Table 1]

Claims (1)

[Claims] Claim 1: (A) 50 to 10 mol% of isophthalic acid, 0 to 40 mol% of terephthalic acid, and hexamethylene diamine 4
5 to 5 mol% and an alicyclic diamine represented by the general formula [1] [Formula 1] Number 1
~3 represents an alkyl group. ) 5 to 45 mol% of a copolymerized polyamide obtained from 97 to 40% by weight, and (B) 3 to 60% by weight of an aliphatic polyamide. .