JPH03200830A - Polyester or polyester carbonate resin - Google Patents

Abstract

PURPOSE:To obtain the title resin excellent in transparency, heat resistance, surface hardness, etc., by selecting a polyester or polyester carbonate resin comprising a plurality of specified structural units in specified molar fractions. CONSTITUTION:A polyester or polyester carbonate resin haivng number-average molecular weight of 10000-100000, structural units of formulas I-V (wherein (m) is 0-2; A is a bivalent saturated aliphatic, saturated alicyclic or aromatic hydrocarbon group; (n) is (m); and B is A), and such a composition that the sum of the molar fractions of structural units I-III is substantially equal to the sum of the molar fractions of structural units IV-V, the molar fractions of structural units I and IV are 5mol% or more, respectively, and the sum of these two molar fractions is 50-95mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel polyester or polyester carbonate resin.

The polyester TFC provided by the present invention has excellent f'Lfc performance such as low birefringence and high heat resistance, and is suitable for use in optical recording media such as optical discs and optical cards; lenses, prisms, Suitable as a material for optical molded products such as optical elements such as diffraction gratings.

[Conventional technology]

In recent years, transparent resins with excellent various properties have been required as materials for molded products in various fields including optical parts and automobile parts. Among optical recording media such as optical disks and optical cards, write-once types and erasable types that allow users to record information have appeared, and with the development of such recording methods, requirements for the characteristics of the base material have increased. The level is also getting higher. Three properties are particularly required: low water absorption (low water absorption warpage), low birefringence, and high heat resistance. Currently, glass and plastic materials are used as substrate materials, but glass has disadvantages such as low mass production, high cost9, heavy weight, and breakability; plastic materials, which do not have these disadvantages, are suitable for substrate materials. At present, it is the mainstream material. We met. For optical elements such as lenses such as concave/convex lenses and Fresnel lenses and diffraction gratings, plastic materials are becoming more mainstream than glass for the same reasons as in optical recording media as their applications expand.

Polymethyl methacrylate (hereinafter abbreviated as PMMA) and bisphenol A polycarbonate (hereinafter abbreviated as PC) are currently used as transparent optical materials. Although PMMA has extremely low birefringence, it has a high water absorption (thermal absorption) property, and has the disadvantage that water absorption causes warping and deformation, which tends to cause deterioration of optical properties. In particular, when PMMA is used as a material for an optical recording medium consisting of a single substrate such as a digital audio disc, faithful reproduction of information may become impossible. Furthermore, optical recording media using PMMA as a base material have some problems in heat resistance.

On the other hand, PC has low water absorption and almost no warping due to water absorption.
Although there is no problem with heat resistance, it has the disadvantage of high birefringence. For digital audio discs and small diameter lenses, it is possible to suppress birefringence to below the required level by controlling the molding conditions with high precision, but for 30 cm diameter laser vision and large diameter lenses, the molding conditions It is extremely difficult to control with high precision.

Conventionally, the glass transition temperature of polyesters having a norbornane skeleton, a perhydrodimethanonaphthalene skeleton, or a perhydrodrimetanoanthracene skeleton increases in the order of these skeletons, and these polyesters have a higher temperature than polyesters without these skeletons. [Journal of Polymer Science: Polymer Chemistry Editor E 7]
5science: Polymer ChemtryE
Polyester having the above-mentioned skeleton has excellent dimensional stability and is known to be used as a substrate for photographic film (U.S. Defense Patent Application). No. 896.033).

[Problem to be solved by the invention]

As mentioned above, PMMA, which has been conventionally used as a transparent optical material, tends to warp and deform due to water absorption.
It also has the disadvantage of insufficient heat resistance, making it difficult for PCs to
has the disadvantage of high birefringence.

Therefore, the object of the present invention is to develop a new polyester resin or polyester carbonate resin that has a high glass transition temperature, excellent heat resistance, low birefringence, and excellent transparency, and is less likely to warp or deform due to water absorption. It is about providing.

[Means to solve the problem]

According to the present invention, the above object is achieved by the following formulas (1), (n)
, (III), (■), (IV) structural units (
In the formula, m represents 0.1 or 2. ) (In the formula, A represents a divalent saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group.) and the molar fraction of the structural unit (1) and a number average molecular weight of 10,000 to 100.000 having a composition in which the sum of the mole fractions of structural unit (IV) is 50 to 95 moles.
polyester or polyester carbonate resin.

The above structural units will be explained in detail.

Structural units (specifically, the following are:

(In the formula, n represents O, 1 dimension or 2.) (■): Mo0-B-0S (In the formula, B is a divalent saturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group) group or aromatic hydrocarbon group), and the mole fraction of the structural unit (1) and the structural unit (It
) and the mole fraction of the structural unit (I[[) is substantially equal to the sum of the mole fraction of the structural unit (IV) and the mole fraction of the structural unit (V), and Since the heat resistance of a resin having a polystructural unit (1) with a mole fraction of 1) and a mole fraction of structural unit (IV) of 5 moles each is better as m in general formula (1) is larger, Preferably, the resin has m of 1 or 2, that is, the resin has the following structural units.

Structural unit (II) is - A in the hole (II) is a divalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and 3 to 2 carbon atoms.
0 divalent saturated alicyclic hydrocarbon group or carbon number 6 to 20
Divalent aromatic hydrocarbon groups are preferred, particularly divalent saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, and divalent saturated alicyclic hydrocarbon groups having 4 to 15 carbon atoms. The group is preferably a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms.

Preferred examples of structural unit (II) are shown below.

(i) When A represents a divalent saturated aliphatic hydrocarbon group: G11) When A represents a divalent aromatic hydrocarbon group: Among the above structural units (II), the following structural units are particularly Provides excellent heat resistance to the resin of the present invention.

H3 (ii) When A represents a divalent saturated alicyclic hydrocarbon group: Furthermore, the following structural unit provides the resin of the present invention with the most excellent heat resistance.

Specifically, the structural unit (IV) is as follows.

In addition, regarding the resin of the present invention having the structural unit (n) belonging to the above (iii), when it is used in applications that particularly require low birefringence, such as a substrate for magneto-optical recording media, It is necessary that the molar fraction of its structural units be kept low.

Structural unit (1) and structural unit (II) are both corresponding dicarboxylic acid derivatives, such as phenyl esters, alkyl esters, cycloalkyl esters,
Derived from acid chlorides, etc. It is preferable to use phenyl ester or alkyl ester because of ease of polymerization when producing the resin of the present invention.

Structural unit (III) is derived from carbonic acid derivatives, such as diphenyl carbonate, dialkyl carbonate, dicyclocarbonate or phosgene.

It is preferable to use diphenyl carbonate or dialkyl carbonate because the resin of the present invention can be easily produced.

Since the heat resistance of a resin having a structural unit (EV) is better when n is larger in ml, it is preferable for the resin to have n of 1 or 2, that is, to have the following structure. Yes.

The structural unit (V) is - B in the hole (V) has 1 or more carbon atoms.
20 divalent saturated aliphatic hydrocarbon group, a divalent saturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, or 2 having 6 to 20 carbon atoms
In particular, divalent saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, divalent saturated alicyclic hydrocarbon groups having 4 to 15 carbon atoms, etc. or carbon number 6
~12 divalent aromatic hydrocarbon groups are more tE
It's so good.

Note that the saturated alicyclic hydrocarbon group also includes one having a spiro ring which may contain an oxygen atom.

Preferred examples of the structural unit (V) are shown below.

(a) When B represents a divalent saturated aliphatic hydrocarbon group: NiocHz ( ) BCHzO- (c) When B represents a divalent aromatic hydrocarbon group: (b) When B represents a divalent saturated When representing an alicyclic hydrocarbon group: Among the above structural units (V), the following structural units particularly impart excellent heat resistance and mechanical strength to the resin of the present invention.

H3Ha to C:kls Furthermore, the following structural units provide the resin of the present invention with the most excellent heat resistance and mechanical strength.

-0CR2G(20--0CH2CH2CH2CH20
+, -0CH2-C)CH20-1 Note that the resin of the present invention having the structural unit (V) belonging to the above ← is used for materials that require particularly low birefringence, such as substrates for magneto-optical recording media. When used in applications where the structural unit is used, it is necessary that the molar fraction of the structural unit is kept low.

Structural unit (IV) and structural unit (V) are both derived from the corresponding dihydroxyl compound.

In the resin of the present invention, the structural unit (I) and the structural unit (
II) is bonded to the structural unit (It/)t or the structural unit (V) through an ester bond. size, structural unit (III
) is the structural unit (IV)-! or bond with structural unit (V) through a carbonate bond.

In the resin of the present invention, the mole fraction V of the structural unit (1) and the mole fraction y of the structural unit (IV) are each 5 moles or more, and their sum (v+y) is 50 to 95 moles. . The sum of mole fractions (v+y) is preferably in the range of 60 to 95 moles, more preferably in the range of 70 to 90 moles. If the mole fraction is less than 50 moles, the resin may not have sufficient heat resistance; if it exceeds 1 or 95 moles, the resin may have sufficient heat resistance, but its mechanical strength may be poor. are both impractical. The mole fractions w, x and 2 of the structural units (n), (III) and (■ are of the formula v-1-w-1
-x=50, y+z=so.

The resin of the present invention has a number average molecular weight (polystyrene equivalent) determined by gel permeation chromatography (hereinafter referred to as GPC) of 10,000 to 10.
It is in the range of 0,000.

The number average molecular weight of the resin of the present invention is from 15.000 to go, o
It is preferable to be in the range of oo, 20,000 to s
It is preferable that it be in the range of o, o o o. Resins with a number average molecular weight as small as 10,000 are brittle and do not have sufficient strength for practical use.
Resins larger than ,000 are difficult to manufacture.

The resin of the present invention can be produced according to known methods. Known methods include, for example, dephenolization and/or dealcoholization reactions from mixtures of diphenyl esters and/or dialkyl esters of dicarboxylic acids, diphenyl carbonates and/or dialkyl carbonates, and dihydroxyl compounds, and phosgene and dicarboxylic acids. Reactions such as dehydrochlorination reaction from a mixture of chloride and dihydroxyl compound, dealkali metal chloride reaction from mixture of phosgene, dicarboxylic acid chloride, and alkali metal salt of dihydroxyl compound, etc., can be carried out using a suitable catalyst as necessary. It is carried out by carrying out in the presence of. As for the form of the reaction, techniques such as a melt method and a solution method can be adopted depending on the type of reaction, but the melt method is preferred because of the ease of reaction.

The case where the resin of the present invention is manufactured by a melting method will be explained below. Examples of catalysts include tetraalkyl orne titanates, zinc acetate, antimony oxide, germanium oxide; various metal alkoxides such as sodium methoxide and potassium t-butoxide; alkali metals such as lithium and sodium; lithium hydride, sodium hydride, etc. Alkali metal hydrides such as lithium hydroxide and sodium hydroxide; metal halides and the like are used. When an aromatic dihydroxyl compound is used as a raw material compound, it is preferable to use an alkali metal, an alkali metal hydride, or an alkali metal hydroxide as a catalyst because of its high reactivity. The amount of catalyst used is not particularly limited, but it is usually 0% based on the entire raw material compound.
．． It is in the range of 0,001 to 1 mol. If the amount of the catalyst used is too small, the reaction rate will be extremely low, and if the amount of the catalyst used is too large, the resulting resin may have increased water absorption and coloration. The polycondensation reaction uses nitrogen,
This is carried out by stirring the raw material compound while heating it in the presence of a catalyst in an inert gas atmosphere such as argon or carbon dioxide, and distilling off the generated alcohol or phenol. The reaction temperature varies depending on the boiling point of the raw material compound and the alcohol phenol generated and the required reaction rate, but is usually in the range of 150 to 300°C.

In the latter half of the reaction, the pressure of the system is reduced as necessary to drive the reaction. The pressure at this time is in the range of 0.001 to 100 wHy. After the reaction is completed, the obtained resin is extruded from the reactor in the form of a strand and then pelletized using a pelletizer, or taken out in the form of a casing or block and pulverized.

The resin of the present invention produced as described above has a high glass transition temperature, excellent heat resistance, low birefringence, and excellent transparency. The resin of the present invention contained in the casing does not undergo deformation or deformation due to water absorption.

The resin of the present invention can be molded by any known method, for example, melt molding methods such as press molding, extrusion molding, injection molding, and injection compression molding. Alternatively, the resin of the present invention can be dissolved in a suitable solvent to form a film by a casting method.

In the case of melt molding, the resin temperature is usually set in the range of 200 to 400°C, and the mold temperature is set in the range of 40 to 150°C.

During molding, a heat stabilizer,
Light stabilizers, antistatic agents, lubricants, inorganic or organic fillers, dyes, pigments, etc. may be added.

The resin of the present invention can be formed into a flat plate or a simple shape and then laminated with inorganic or organic materials, or can be made into a complex shape by adhesion or fusion, or can be formed into a high-quality material such as embossing on the surface. It is also possible to perform processing.

When the resin of the present invention is used, for example, as a material for a substrate for a read-only optical recording medium, the resin of the present invention is used in a mold in which groups, signals, etc. are recorded, and is used for injection molding, etc.)
The substrate is obtained by molding. On this substrate, a metal such as aluminum is deposited on the information surface using a method such as vacuum evaporation, and then a protective polymer layer is formed, or the information surface on which the surface is made of metal is placed face-to-face. Paste the two sheets together.

The information recording layer may be provided by a 2P method using a photocurable resin on a flat substrate made of the resin of the present invention. For example, the information recording layer can also be formed by providing a thin film of an inorganic material such as tellurium oxide or terbium-iron-conolite alloy, or an organic material such as cyanine dye on the surface of a molded substrate. can.

The resin of the present invention can be used for the following applications by taking advantage of the above-mentioned excellent properties.

■ Lighting equipment parts ■ Various signboards ■ Glass substitutes for windows, windshields, etc. ■ Substrates for various display elements such as liquid crystals ■ Various lenses such as concave/convex lenses and Fresnel lenses used in glasses, cameras, loupes, video projectors, etc. ■ Diffraction gratings for optical disk player pickups, spectroscopic elements, optical low-pass filters, etc. ■ Various optical elements such as prisms, optical waveguides, beam splitters, etc. ■ Optical fibers ■ Substrates for optical recording media such as optical disks and optical cards [Example] Below The present invention will be specifically explained using Examples.

In addition, the physical property values were measured according to the following method.

■ Number average molecular weight: Determined by GPC (polystyrene equivalent).

(2) Glass transition temperature: Measured by differential thermal analysis (in nitrogen, heating rate 10°C/min).

(2) Light transmittance: The transmittance of light at wavelengths of 400 nm%, 600 nm, and 800 nm of a sample molded to a thickness of 2 wm by hot pressing was measured using a spectrophotometer.

■ Birefringence (retardation): diameter 40jIII1
Heat press a sample molded into 1 thickness and 6 layers! 1llsa
The sample was rolled to a thickness of 30 cm and measured using a polarizing microscope (wavelength: 5 g 9 run ) at a point 30 cm from the center.

■ Surface hardness: Pencil hardness test (JIS K5400)
asked.

(2) Saturated water absorption rate = Measured by determining the weight increase rate when no weight increase due to water absorption was observed in distilled water at 23°C.

■ Water absorption anti-F): 2crnX 10mX 2511
Aluminum was vapor-deposited to a thickness of 1000 on one side of a 1-thick plate sample, and the sample was immersed in distilled water at 23° C., and the maximum value of rumination generated was taken as the water absorption rumination.

■Izotsu impact strength: JIS K7110 (
(with a notch), and based on the izod impact strength of bisphenol A polycarbonate, those with the same izod impact strength as that are considered average, those with higher izod impact strength are considered good, and Those with low Izod impact strength were judged as defective.

Example 1 Dimethyl perhydro-1,4:5.8-dimethanonaphthalene-2,3-dicarboxylate 139 was placed in a 1-volume three-neck flask equipped with a stirrer, a nitrogen gas inlet, and a cooling tube.
F (0.50 mol), trans-1゜4-cyclohexanedicarboxylic acid dimethyl 100F (0.50 mol),
Berhydro-1,4:5,8-dimethanonaphthalene-2
,3,-dimethatol 222f (1,0 mol) and tetrabutylorone titanate 0.342 (l rimole)
was charged, heated to 200°C in an oil bath in a nitrogen stream, and stirred for 30 minutes. Then, at 230°C for 50 minutes,
After stirring at 250°C for 80 minutes, 1. Ojl
The pressure was reduced to 1W Hf, and the mixture was further stirred for 60 minutes under this reduced pressure to obtain a pale yellow transparent resin 380f. I of this resin
The HNMR spectrum (in 90 MHz monochloroform, based on tetramethylsilane) is shown in FIG.

Table 2 shows the measurement results for various physical properties of the obtained resin.

Examples 2 to 8, Comparative Example 1 and Comparative Example 2 Various resins were obtained by carrying out the reaction in the same manner as in Example 1 except that the raw material compound and/or the amount charged thereof were changed. However, when diphenyl carbonate is used as a part of the raw material compound, tetrabuterolonetetanate 0.34
In place of f (1 mmol), 8.0% of lithium hydride (
1 mmol) was used. The raw material compounds used and the amounts charged are shown in Table 1.

Table 2 shows the measurement results for various physical properties of the resins obtained in Examples 2 to 3, Comparative Example 1, and Comparative Example 2. The same table shows the physical properties of bisphenol A polycarbonate as Comparative Example 3.

The resins obtained in Examples 4 to 8 also had a glass transition temperature of 130.
It had a high retardation of about 5 nm or less, and had good physical properties.

In addition, all of the resins obtained in Examples 1 to 8 had a low saturated water absorption of 0.4 or less, a small water absorption coefficient of 0.1 or less, and a high casing surface hardness of H or more. there were.

Margins below [Effects of the Invention] The present invention provides a polyester or polyester carbonate resin that has the following features and is suitably used for various uses including optical molded products.

■Have excellent transparency.

■ High glass transition point and good heat resistance.

■ High surface hardness of H or higher.

■ The saturated water absorption rate is as low as 0.4% or less, and there is almost no cracking or deformation due to water absorption.

■ The birefringence of the molded product is extremely small, about 1/4 or less of that of bisphenol A polycarbonate.

[Brief explanation of drawings]

Figure 1 shows the 1HN polyester resin obtained in Example 1.
This is an MR spectrum.

Claims (1)

[Claims] The following formulas (I), (II), (III), (IV) and (V)
Structural unit represented by (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, m represents 0, 1, or 2.) (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Formula (A represents a divalent saturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, or an aromatic hydrocarbon group.) (III): ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (IV) ▲ Mathematical formulas , chemical formulas, tables, etc. ▼ (In the formula, n represents 0, 1, or 2.) (V): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, B is divalent saturated aliphatic carbonization represents a hydrogen group, a saturated alicyclic hydrocarbon group, or an aromatic hydrocarbon group), and the molar fraction of the structural unit (I) and the structural unit (II)
) and the sum of the mole fractions of the structural unit (III) are substantially equal to the sum of the mole fractions of the structural unit (IV) and the mole fraction of the structural unit (V), and the structural unit (I) The mole fraction of the structural unit (I) and the mole fraction of the structural unit (IV) are each 5 mol% or more, and the mole fraction of the structural unit (I) and the structural unit (IV
) A polyester or polyester carbonate resin having a number average molecular weight of 10,000 to 100,000 and having a composition in which the sum of the mole fractions of 50 to 95 mol %.