JPS6271902A - Molding for optical article - Google Patents

Abstract

PURPOSE:To suppress the generation of a chlorine-base acidic material to the extent of having substantially no problems by compounding a specific ratio of an org. phosphine oxide as phosphorus atom by the weight of a polycarbonate with the polycarbonate to form a polycarbonate resin compsn. having a chlorine content of a specific ratio or below and melting and molding such resin compsn. CONSTITUTION:The org. phosphine oxide as the phosphorous atom is compounded with the polycarbonate more preferably at 0.000005-0.005wt% by the weight of the polycarbonate to form the polycarbonate resin compsn. having preferably <0.0020wt% chlorine content and having 13,000-18,000 average mol.wt. and such resin compsn. is melted and molded to form a titled molding. The strength of the resulted molding does not lend itself to practicability if the average mol.wt. is <13,000. Problems are liable to arise particularly in optical distortion, hue and transparency when the average mol.wt. exceeds 18,000.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to optical molded articles, and more particularly to optical molded articles having excellent performance. Regarding molded products.

<Prior art> Recently, polycarbonate has come into the spotlight for optical applications, especially as a material for information processing equipment parts. Among these applications, when it is used as a substrate for information recording, it is often Attaching a thin film of metal compound
A layer containing pigment may be added. Furthermore, when used in lenses for eyeglasses, a thin film is often used for the purpose of improving surface hardness, anti-rotation, anti-glare, etc. In such cases, the chemical properties of the surface of the molded article become an important factor.

Conventionally, general polycarbonate has contained all chlorine compounds, although only in small amounts, such as n-th methylene chloride used as a solvent and compounds with chloroformate groups that are unreacted residues. When molded at high temperatures such as 300°C or higher, it decomposes to produce acidic substances Xt, which causes corrosion of the mold, and thin films containing pigments such as metals and metal compounds on the surface of molded products, or When other thin films are applied, K causes deterioration of the pigments in those thin films. However, if all such chlorine compounds are removed as much as possible, polycarbonate will not produce acidic substances during high-temperature molding, but it will not be possible to avoid burning and discoloration when molding at temperatures of 350°C or higher, for example. In such cases, adding organic phosphitera, which is the most widely used heat stabilizer for conventional general-purpose polycarbonate, may eliminate the burning and discoloration, but the resulting molded product may not remain in a hot and humid atmosphere for a long time. Exposure over time can result in a decrease in the average molecular weight of the polycarbonate, and at the same time can have an adverse effect on the surface of said thin film.

<Objective of the Invention> The object of the present invention is to produce a thin film of metal or metal compound that generates chlorine-based acidic substances only to the extent that there is virtually no problem and that does not form on the surface of the substance even in a high temperature and high humidity atmosphere. Our objective is to provide all optical molded products that will not adversely affect other thin layers.

(Structure of the Invention) The present invention is characterized in that 0.00001% by weight or more and 0.01% by weight or less of organic phosphine oxyto are blended as phosphorus atoms based on the weight of polycarbonate, and the chlorine content is 0. .0040 It is less than 8%.It is an optical molded article made by completely melt-molding a polycarbonate resin assembly having an average molecular weight of 13,000 to 18,000.

The polycarbonate used in the present invention is a transparent resin obtained by reacting dihydric phenol with a carbonate precursor, and the dihydric phenol includes hydroquinone,
4.4'-dioquinodiphenyl, bis(hydroxyphenyl)alkane.

Bis(hydroxyphenyl)cycloalkane.

Bis(hydroxyphenyl)ether, bis(hydroquinphenyl)ketone, bis(hydroxyphenyl)sulfide, bis(hydroxyphenyl)sulfone and their lower alkyls.

Substituents such as halogen can be mentioned, but 2.2-
Bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A), 1,1-bis(4-hydroxyphenyl)ethane, etc. can be preferably used. These two
The hydric phenol can be used alone or heated.

Furthermore, the polycarbonate used in the present invention may have some of the carbonic acid residues substituted with aromatic dibasic acid residues, or may have a branched structure (.

These polycarbonates are made of methylene chloride at 20°C.
00- and 0.7 g of resin + = C) Measure the specific viscosity ηsp of the completely dissolved bath liquid using an Ostwald viscometer and calculate ηsp/
C= l:η) +0.4 s (η:]2C obtained n
It is necessary that the average molecular weight, which is obtained by substituting the value of the limiting viscosity into K in the following equation (1), is in the range of 13.000 to 18.000.

-0,83 [η)=1.23XlO-'M...
・・・・・・・・・・・・fl + average molecular weight is 13
If it is less than 18.000, the strength of the resulting molded product will not be suitable for practical use, and 18. If it exceeds OOO', it is not appropriate because it tends to cause problems with the optical properties of the molded product, such as 1% optical distortion, 9 hue, and transparency.

In addition, polycarbonate is a chloroformate of methylene chloride and dihydric phenol used in the polymerization reaction,
*Has a chloroformate fund at the U end (contains novomers and polymers, and the content of these is usually expressed as the chlorine content. Used for molding at 30Q'C or higher) If the chlorine content of the polycarbonate or its composition exceeds 0.004%, these chlorine compounds will decompose in the molding machine, producing acidic substances that may cause corrosion of the mold or cause further damage to the molding process. It is not suitable when thin films containing pigments such as metals, metal compounds, etc., or other thin films are attached to the surface of the product, as it may cause deterioration of the pigments in those thin films.Thin films with 0 chlorine content .0
When the amount of 040 is less than 9% by weight, these adverse effects are negligible from the practical point of view of the product.Also, polycarbonate is free from phosphorus stabilizers added during the manufacturing process, such as organic phosphites. , organic phosphonite etc. may contain gold, but the content is 0 as phosphorus atoms.
．． It is desirable that the electric charge is 0003% or less.

The polycarbonate resin composition used in the present invention has an organic phosphine oxide content of 0.00001% or more as a phosphorus atom based on the weight of the polycarbonate,
o Contains 1 ftt% or less. A more preferable formulation 1 is o, o o o o s 0.0% by weight or more.
0 F1 weight or less.

If the amount of II atoms is less than 0.00001% by weight, there is almost no stabilizing effect, and if the amount exceeds 0.01% by weight)1
Since the effect is saturated, there is no need to do so (・.

It is known, for example, from Japanese Patent Publication No. 47-22088 that hard phosphine is effective as a stabilizer for polycarbonate. These organic phosphines are reducing 3
In contrast, the organic phosphine oxyto used in the present invention contains pentavalent phosphorus and does not have reducing properties. Nevertheless, it is quite surprising that organophosphine oxyto exhibits a stabilizing effect comparable to that of monophosphine and organophosphite. Also, 5
Trimethyl phosphate, which contains valent phosphorus, has a slightly inferior stabilizing effect on polycarbonate alone, and on the contrary, it exhibits its full cleaning effect when it contains all inorganic substances, whereas organic phosphine oxide has a stabilizing effect on polycarbonate alone. It is also unexpected that it also exhibits an excellent stabilizing effect on.

Thus, the polycarbomate compositions used in the present invention have a salt I content of 0.0040% by weight, preferably 0.002% by weight, based on the total weight of the carbonate.
0 weight% or less, and the phosphorus atom is -CO,0O00] weight% or more and 0.0 weight% or less, preferably 0.00005 weight% or more and 0.0 weight% or less.
0.05% by weight or less.

Organophosphine oquinide Id fl used in the present invention
l Eba, triethylphosphine oxide/do, triisobrobylphosphine oxide, trilobylphosphine oxide, trinochlorohexylphosphine oxide,
Aryrunphenylhonuphine oxide, triphenylphosphine oxide, 1-lis(2,4-trimethylphenyl)phosphine oxide, tris(2,4,6-trimethylphenyl)phosphine oxide, tris(0 -tolyl)phosphine oxide, tris(0-ani/lylphosphine oxide, diphenylbutylphosphine oxide 7-do,
diphenyl octadecylphosphine oxinodo, tris-
(p-7nylphenyl)-phosphine oxide, trinaphthylphosphine oxide, diphenyl-(hydroquinomethyl)-phosphine oxide, diphenylacetooxide/
Methylphosphine oxide, diphenyl-(β-ethyl sulfoquinethyl)phosphine oxide, diphenylbenzylphosphine oxide, diphenyl-(p-hydroxyphenyl)-phosphine oxide, diphenyl-2
, 5-dihydroxy7phenylhonuphine oxide, and phenylnaphthylbennulfonuphine oxide.

Furthermore, the compositions used in the present invention include esters or partial esters of higher fatty acids and monovalent or polyvalent alphal, such as stearyl heptearate, montan acid wax, glycerin monostearate, and pentaerythritol stearate. molding agent < o, o i ~ 0.5% by weight),
UV absorbers such as benzotriazole type, acetophenone type, and salicylic acid ester type (0.1 to 0.7% by weight)
), epoxy compounds, oxetane compounds, and other stabilizing aids (0.01 to 0.5% by weight) may be added.

The polycarbonate resin composition used in the present invention can be obtained by completely mixing polycarbonate and organic phosphine oxide. It can be easily mixed. It can also be easily prepared by known means such as mixing an organic phosphine oxide into a solution of polycarbonate and then removing the solvent.
Furthermore, it is also possible to continuously feed polycarbonate powder or pellets and organic phosphide into an extruder! 4! I can do it.

The optical molded article of the present invention can be molded by injection molding, funfretsu molding, or injection-funfretsu molding, but the molding conditions for injection molding preferred for 1% are resin temperatures of 320 to 380.
℃, the mold wall Fij is 70-120℃.

The optical molded product of the present invention is extremely transparent with a light transmittance of around 90%, and the optical distortion represented by wandering refraction is extremely small, so there is almost no light refraction phenomenon in the molded product. It has excellent performance such that even if various thin films such as those mentioned above are attached without causing any change in quality, it is suitable for use with optical discs, Plasma II, Fresnel lenses, and various information recording disks. It is a scale that can be put to practical use as a basis for optical components.

<Effects of the Invention> The molded product of the present invention has extremely poor transparency, optical distortion, etc., and has a history of thin films containing recording materials such as metals, gold, -compounds, or pigments, or has poor surface hardness and antifogging. It has sufficient properties necessary for an optical molded product, such as excellent durability even when a thin film is applied for anti-glare purposes.

<Examples> The present invention will be described below with reference to Examples and Comparative Examples. The birefringence and transmittance of the molding plate were measured and the deposited product was evaluated (determined appearance) using the following method.

Birefringence measurement Beret 1r 3oz injection molding machine (Neomat 150/
Type 75 (manufactured by Sumitomo Heavy Industries)'lr, resin temperature 35
0℃, mold temperature 110℃, thickness 1.2mm, diameter 120
Formed into a disc of arm, and measured from the center toward the 30-meter periphery using a polarization analyzer made by Mizojiri Optical Co., Ltd.
Displayed in m.

Measurement of transmittance The molded disk was measured using a Hitachi self-recording spectrophotometer U-3400 in the wavelength range of 500 to 11000 nm, and the transmittance was expressed in %.Evaluation of the deposited product. Fully insert molded plate 3
After vapor-depositing only one side of aluminum ramura using 0-')-ru and applying urethane resin, the humidity was 95% RH and the temperature was 85%.
The sample was left in a constant temperature and humidity chamber at ℃ for 72 hours, and the number of pinholes generated before and after the treatment was counted and evaluated. If pinholes occur, information cannot be distributed accurately, which is undesirable.

Examples 1 to 3 Organic phosphine oxide was blended with polycarbonate resin powder having an average molecular weight of 14,900 in the proportions listed in Table 1,
The threads were extruded at 260° C. using a 30 mm 1i5 extruder with pent and cut with a cutter to obtain pellets.

The average molecular weight and chlorine content of the pellets were as shown in Table 1.

The resulting pellets were molded using a 3-ounce injection molding machine at a resin temperature of 350°C and a mold temperature of 110°C to a thickness of 1.
．． Since no coloration was observed in the 2m+m, 120m diameter disk, birefringence and transmittance were measured.

Further, this molded plate was completely vapor-deposited with aluminum, further coated with urethane resin, and subjected to moist heat treatment. Table 1 shows the results of evaluating changes in appearance based on the number of pinholes generated.

Examples 4-5 Average minute +*17. The procedure was carried out in the same manner as in Examples 2 and 3 except for using the loo polycarbonate resin powder, and the results were? :* Shown in table 1.

Comparative Example 1 The same procedure as in Example 1 was carried out except that organic phosphine oxyto was not blended. The results are shown in Table 1.

Comparative Example 2 The operation was carried out in the same manner as in Example 2, except that the vent of the extruder was not fully suctioned. The results are shown in Table 1.

Comparative Example 4 The same procedure as in Example 2 was carried out except that triphenylphosphite was used instead of organic phosphine oquinide. The result is the first
Shown in the table.

Example 6 The same procedure as in Example 1 was carried out except that 0.04% by weight of stearic acid monoglyceride was blended with all-organic phosphine oxide.

The average molecular weight of the pellet is 14.800. Chlorine content is 0
．． 0035% by weight, the transmittance of the emissive disk was 91%, and the birefringence was 8 nm. There were no pinholes in the secondary disk, and no pinholes were observed even after moist heat treatment.

A: Triphenylphosphine oxide B Nidiphenyl-4-hydroquine phenylphosphine oxide

Claims (1)

[Claims] Based on the weight of the polycarbonate, 0.00001% to 0.01% by weight of organic phosphine oxide is blended as a phosphorus atom, and the chlorine content is less than 0.0040% by weight, with an average molecular weight of 13, 00
An optical molded article formed by melt-molding a polycarbonate resin composition of 0 to 18,000.