JP2009046519A - Transparent heat-resistant molded body made of polycarbonate copolymer, production method thereof and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent heat-resistant molded body made of a polycarbonate copolymer, which is excellent in heat resistance, while having practically sufficient mechanical properties and melting properties. <P>SOLUTION: The polycarbonate copolymer comprises an alicyclic polycarbonate unit (a) and an aliphatic polycarbonate unit (b), and the molded body is made of the polycarbonate copolymer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a transparent heat-resistant molded article made of a polycarbonate copolymer, which is excellent in transparency and heat resistance, a method for producing the same, and an optical disk substrate, sheet and container made of the molded article.

In recent years, interest in environmental protection has increased, and in Japan, the promotion of the purchase of environmentally friendly materials by the Green Purchasing Law and the promotion of recycling of plastic materials and electrical appliances by the Containers and Packaging Recycling Law and the Home Appliance Recycling Law have emerged. is there. In such a series of flows, polymers such as aliphatic polyesters and aliphatic polycarbonates that have a low environmental load are attracting attention.
In particular, polymers using plant-derived monomers as raw materials are being developed with great expectations.

  Polylactic acid, one of such aliphatic polyesters, is a polymer that is highly transparent and tough, and is a self-condensed polymer of lactic acid produced in large quantities from corn. Since it decomposes without polluting the environment after disposal, it is environmentally friendly, and when it is placed in the living body as a medical material, it can be decomposed in vivo without causing toxicity to the living body after achieving its purpose as a medical material. Because it is absorbed, it is gentle on the living body.

However, from the viewpoint of heat resistance, it is difficult to say that polylactic acid is sufficient for use as a general-purpose resin. Therefore, the appearance of homopolymers and copolymers of aliphatic polyesters and aliphatic polycarbonates having sufficiently high heat resistance and molecular weight has been eagerly desired.
For this reason, Patent Document 1 proposes a copolymer of polylactic acid and a polycarbonate resin which is a typical general-purpose transparent heat-resistant polymer.
However, although this contributes to improving the heat resistance of polylactic acid, it cannot be said that the original heat resistance of the polycarbonate resin is greatly reduced and sufficient heat resistance is given.

  Furthermore, when using polylactic acid with low environmental impact, it is said that 50% to 90% (weight) of the polycarbonate resin is preferable in order to increase heat resistance. Is hard to say.

As one of aliphatic polycarbonates, Non-Patent Document 1 discloses a polycarbonate made from isosorbide and phosgene.
According to this, although this polycarbonate is described as Mw = 32,000, specific polymer characteristics are not described, and as shown in Comparative Example 1 to be described later, the present inventors made a retrial. However, it has been found that isosorbide polycarbonate resin having a sufficient molecular weight, although having a high Tg, is not a practical resin that is hard and brittle, has poor fluidity and cannot be molded.

  However, isosorbide is a very environmentally friendly non-petroleum raw material that has recently been manufactured using starch obtained from corn and the like as a raw material, and sorbitol from glucose. Expected to be a low material.

Patent Document 2 describes a copolymer of 1,2-O-isopropylidene-D-xyfuranose-3,5-cyclic carbonate (IPXTC), which is an aliphatic cyclic carbonate, and polylactic acid. According to this, a copolymer with polylactic acid containing 60 mol% of IPXTC as an aliphatic polycarbonate component is described as Tg = 90 ° C. However, if the copolymer of PLA and IPXTC containing 60 mol% of IPXTC is converted to a weight ratio, PLA / IPXTC = 18/82 (wt%), and a large amount of expensive IPXTC must be used. In addition, when the amount of IPXTC added is increased, the yield is lowered, and the molecular weight of the resulting copolymer is also lowered.
From the above, aliphatic polymers with low environmental impact that have sufficiently high heat resistance and molecular weight, are industrially moldable, have sufficient physical properties as general-purpose polymers, and can be economically produced. unknown.

  On the other hand, Patent Document 3 discloses a copolymer of isosorbide polycarbonate and alkanediols shown in non-patent documents.

The polycarbonate disclosed here shows that the Tg of isosorbide homopolycarbonate is 86 ° C., which is greatly different from the previous non-patent document, while the copolymer polycarbonate with alkanediol is 67 ° C. to 77 ° C. .
However, since there is no description of other physical properties and no disclosure is made regarding transparency, the practical use possibility as a molded article is not shown.
Patent-3460777 US-6093792 5-10 pages JP2003-292603 Journal Fur Praktische Chemie Chemiker-Zeitung (1992), 334 (4), pp. 298-310

  An object of the present invention is to provide a high-molecular-weight polycarbonate copolymer excellent in heat resistance, melt flowability, and mechanical properties using a material having a low environmental load.

The present invention relates to a general formula (1)

(In the general formula (1), X ₁ and X ₂ are O, N—R 7 and S, and may be the same or different. R 1 and R 2 are alkylene chains having 1 to 10 carbon atoms. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group may be linear or branched, An alicyclic polycarbonate unit (a) represented by a cycloalkyl group and a phenyl group may have a substituent; and
General formula (2)

(In General Formula (2), R8 is an alkylene group or aralkyl group having 2 to 10 carbon atoms, which may be linear, branched or may contain a cyclic structure) (b) And a transparent heat-resistant molded article comprising a polycarbonate copolymer having a weight average molecular weight of 5,000 to 200,000.
A transparent molded body comprising the polycarbonate copolymer in which the composition ratio of the alicyclic polycarbonate unit (a) and the aliphatic polycarbonate unit (b) is (a) / (b) = 90 / 10-30 / 70 wt% This is a preferred embodiment of the present invention.
General formula (3)

(In General Formula (3), X ₁ and X ₂ are O, N—R 7 and S, which may be the same or different. R 1 and R 2 are alkylene chains having 1 to 10 carbon atoms. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group may be linear or branched, An alicyclic dihydric alcohol (A) represented by a cycloalkyl group or a phenyl group may have a substituent;
General formula (4)

(In the general formula (4), R8 is an aliphatic dihydric alcohol represented by a C2-C10 alkylene group or aralkyl group which may be linear, branched or may contain a cyclic structure) A transparent heat-resistant molded article comprising the polycarbonate copolymer produced from B) and a carbonate precursor is also a preferred embodiment of the present invention.

  A substrate for an optical disk comprising the transparent heat-resistant molded article is also a preferred embodiment of the present invention.

  A sheet made of the transparent heat-resistant molded article is also a preferred embodiment of the present invention.

  A container made of the transparent heat-resistant molded article is also a preferred embodiment of the present invention.

  The transparent heat-resistant molded article made of the polycarbonate copolymer shown in the present invention has excellent heat resistance, practically sufficient mechanical properties and melt properties, and is used for optical disk substrates, containers and packaging materials, and other general-purpose resins. Can be preferably used.

The present invention relates to a transparent heat-resistant molded article comprising a polycarbonate copolymer having excellent transparency, heat resistance, melt flowability, mechanical properties, workability and the like. For more information,
General formula (1)

(In the general formula (1), X ₁ and X ₂ are O, N—R 7 and S, and may be the same or different. R 1 and R 2 are alkylene chains having 1 to 10 carbon atoms. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group may be linear or branched, (Cycloalkyl group and phenyl group may have a substituent)
An alicyclic polycarbonate unit (a) represented by:
General formula (2)

(In the general formula (2), R8 is an alkylene group or aralkyl group having 2 to 10 carbon atoms, which may be linear, branched or cyclic.)
It relates to a transparent heat-resistant molded product comprising a polycarbonate copolymer having a weight average molecular weight of 5000 to 200,000 comprising an aliphatic polycarbonate unit (b) represented by
In addition, the general formula (3)

(In General Formula (3), X ₁ and X ₂ are O, N—R 7 and S, which may be the same or different. R 1 and R 2 are alkylene chains having 1 to 10 carbon atoms. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group may be linear or branched, (Cycloalkyl group and phenyl group may have a substituent)
An alicyclic dihydric alcohol (A)
And general formula (4)

(In the general formula (4), R8 is an aliphatic dihydric alcohol represented by a C2-C10 alkylene group or aralkyl group which may be linear, branched or may contain a cyclic structure) It relates to a transparent heat-resistant molded article comprising a polycarbonate copolymer having a weight average molecular weight of 5,000 to 200,000 produced from B) and a carbonate precursor.

The alicyclic polycarbonate unit (a) represented by the general formula (1) shown in the present invention is represented by the general formula (1).

(In the general formula (1), X ₁ and X ₂ are O, N—R 7 and S, and may be the same or different. R 1 and R 2 are alkylene chains having 1 to 10 carbon atoms. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group may be linear or branched, A cycloalkyl group and a phenyl group may have a substituent)),
Preferably formula (5)

It is a carbonate unit which has the structural unit derived from isosorbide shown by.
The polycarbonate unit (b) shown in the present invention has the general formula (2)

(In the general formula (2), R8 is a unit having a carbon number of 2 to 10, which may be linear, branched or may contain a cyclic structure), preferably carbon. A polycarbonate unit having a structural unit derived from a dihydric alcohol having 2 to 8 examples. Specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene Glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1, 9-nonanediol, neopentyl glycol, 1,4-cyclohexanediol, 1, - cyclohexanedimethanol, p- xylylene glycol, polycarbonates unit having a unit derived from such m- xylylene glycol. A polycarbonate unit having a structural unit derived from a dihydric alcohol including a structural unit derived from lactic acid or glycolic acid can also be used. A specific example is a polycarbonate having a unit derived from an ester condensate of a dihydric alcohol and lactic acid, glycolic acid, or a cyclic two-body thereof, such as lactide or glycolide. For example, condensation of isosorbide with lactic acid or lactide Or a condensate with glycolic acid or glycolide. These may be used alone or in combination of two or more. Moreover, when it has an asymmetric carbon in a molecule | numerator, although D body, L body, and those equivalent mixtures (racemic body) exist, any of them can be used.

  Among these diols, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, p-xylylene glycol are more preferable. M-xylylene glycol, which is a condensate with lactide having a molecular weight in the range of 200 to 5000 using the diol or isosorbide as an initiator for the ring-opening reaction.

  The polycarbonate copolymer shown in the present invention includes an alicyclic polycarbonate unit (a) and an aliphatic polycarbonate unit (b), and the weight average molecular weight thereof is not particularly limited, but is generally obtained. Considering the thermophysical properties and mechanical properties of the resin, the weight average molecular weight (Mw) is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and most preferably 25,000 to 100,000. .

The composition ratio of the polycarbonate unit (a) and the polycarbonate unit (b) is in the range of (a) / (b) = 90 / 10-30 / 70, preferably 85 / 15-40 / 60, in terms of weight ratio. More preferably, it is the range of 80 / 20-50 / 50.
The block property or randomness of each unit of the polycarbonate copolymer used in the present invention is not questioned.

  It is not specifically limited with the manufacturing method of the polycarbonate copolymer used by this invention, A well-known and publicly-known method can be used, for example, it shows by General formula (3)

(In General Formula (3), X ₁ and X ₂ are O, N—R 7 and S, which may be the same or different. R 1 and R 2 are alkylene chains having 1 to 10 carbon atoms. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group may be linear or branched, A cycloalkyl group and a phenyl group may have a substituent) an alicyclic dihydric alcohol (A),
Shown by general formula (4)

(In the general formula (4), R8 is an alkylene group or an aralkyl group having 2 to 10 carbon atoms, which may be linear, branched or include a cyclic structure) and an aliphatic dihydric alcohol (B). It can be produced by reacting with a carbonate precursor.
An aliphatic polycarbonate having a structural unit derived from an alicyclic dihydric alcohol (A) obtained by reacting the alicyclic dihydric alcohol (A) represented by the general formula (3) with a carbonate precursor; An aliphatic polycarbonate having a structural unit derived from an aliphatic dihydric alcohol (B) obtained by reacting an aliphatic dihydric alcohol (B) of the general formula (4) with a carbonate precursor is converted into a polycarbonate by transesterification. A copolymer may be used.

The alicyclic dihydric alcohol (A) shown in the present invention is
Shown by general formula (3)

(In General Formula (3), X ₁ and X ₂ are O, N—R 7 and S, which may be the same or different. R 1 and R 2 are alkylene chains having 1 to 10 carbon atoms. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group may be linear or branched, A cycloalkyl group and a phenyl group (which may have a substituent) are dihydric alcohols, preferably represented by formula (6)

It contains an isosorbide represented by the formula (1), and more preferably consists only of isosorbide.

The aliphatic dihydric alcohol (B) shown in the present invention is represented by the general formula (4)

(In the general formula (4), R8 is an alkylene group or aralkyl group having 2 to 10 carbon atoms, which may be linear, branched or cyclic.)
Is derived from a diol represented by

  Specific examples of the diol of the general formula (4) used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene glycol, 1,3. -Butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, Neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, p-xylylene glycol, m-xylylene glycol and the like can be mentioned. A polycarbonate unit having a structural unit derived from a dihydric alcohol including a structural unit derived from lactic acid or glycolic acid can also be used. A specific example is a polycarbonate having a unit derived from an ester condensate of a dihydric alcohol and lactic acid, glycolic acid, or lactide or glycolide which is a cyclic bibodies thereof, such as isosorbide and lactic acid or glycolic acid. It is a condensate. These may be used alone or in combination of two or more. Moreover, when it has an asymmetric carbon in a molecule | numerator, although D body, L body, and those equivalent mixtures (racemic body) exist, any of them can be used.

  Among these diols, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, p-xylylene glycol are more preferable. M-xylylene glycol, which is a condensate with lactide having a molecular weight in the range of 200 to 5000 using the diol or isosorbide as an initiator for the ring-opening reaction.

The carbonate precursor shown in the present invention is a carbonyl equivalent that reacts with a dihydric alcohol or dihydric phenol having two hydroxyl groups to give a polycarbonate. Specific examples include carbonyl halides, carbonyl esters, And haloformate. Specific examples include phosgene and diphenyl carbonate, and dimers and trimers of phosgene can also be used.
The carbonate precursors may be used alone or in combination of two or more.

  The polycarbonate copolymer shown in the present invention can be produced by a publicly known method such as a solution method or a melting method. At that time, an appropriate molecular weight regulator, a branching agent, other modifiers and the like may be added.

  The solution method is generally employed when phosgene and its dimer, trimer, or haloformate is used. Chloroform, dichloromethane, carbon tetrachloride, dichloroethane, acetonitrile, toluene, o A solvent that does not participate in the reaction, such as -xylene, m-xylene, p-xylene, mesitylene, chlorobenzene, o-dichlorobenzene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or the like is used.

  The amount of the solvent is not particularly limited. However, if the amount is too small, difficulty in stirring occurs. If the amount is too large, the volume efficiency is deteriorated. Therefore, the amount is generally 1 to 20 times, preferably about 2 to 5 times that of the raw material. Done.

  In the solvent method, the reaction can proceed smoothly by using a necessary amount of base. The base used at this time may be an organic base or an inorganic base. Specific examples include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and tertiary amines such as triethylamine, pyridine, N, N-dimethylaniline and N, N-dibutylaniline.

In the case of an inorganic base, it is often used as an aqueous solution. In the case of an organic base, it may be used in an equivalent amount, but it may be used in excess as a solvent.
The melting method is a method generally used in the production of a polycarbonate resin by a transesterification reaction using carbonate esters.

The transesterification reaction of the carbonic acid diester with isosorbide and the dihydric alcohol of the general formula (2) is usually carried out without a solvent.
As the carbonic acid diester used at this time, dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ditoluyl carbonate and the like are used, and diphenyl carbonate is preferable from the viewpoint of reactivity and cost.
In both the solvent method and the melting method, the amount of the carbonate precursor used in the reaction is 0. As the amount that reacts substantially with respect to the total amount of the isosorbide derivative of the general formula (3) and the dihydric alcohol of the general formula (4). It is 5-1.5 equivalent, Preferably it is 0.75-1.25 equivalent, More preferably, it is the range of 0.9-1.1 equivalent.

  More specifically, it is preferable to react in advance by obtaining a molar ratio at which a polycarbonate copolymer having a desired molecular weight can be obtained.

When the polycarbonate copolymer of the present invention is produced by a melting method, a catalyst may be used. As the catalyst, a generally known transesterification catalyst, in particular, a catalyst used for the production of a polycarbonate resin by a transesterification method of bisphenol A and a carbonic acid diester can be used. Specific examples of such a catalyst include, for example, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium salts, quaternary ammonium hydroxides of alkali metals and alkaline earth metals. , Phosphonium salts, amines periodic table II, III, IV, group V metals, oxides thereof or salts thereof.
More specifically, metals such as zinc powder, tin powder, aluminum, magnesium, germanium, tin oxide (II), antimony oxide (III), zinc oxide, aluminum oxide, magnesium oxide, titanium oxide (IV), germanium oxide (II), metal oxides such as germanium oxide (IV), tin chloride (II), tin chloride (IV), tin bromide (II), tin bromide (IV), antimony fluoride (III), fluoride Metal halides such as antimony (V), zinc chloride, magnesium chloride, aluminum chloride, sulfates such as tin (II) sulfate, zinc sulfate, aluminum sulfate, carbonates such as magnesium carbonate, zinc carbonate, zinc borate, etc. Organic carboxylates such as borate, tin (II) acetate, tin (II) octoate, tin (II) lactate, zinc acetate, aluminum acetate, tin (II) trifluoromethanesulfonate, trifluorometa Zinc sulfonate, magnesium trifluoromethane sulfonate, methanesulfonate, tin (II), organic sulfonic acid salts such as such as p- toluenesulfonic tin (II).

  Other examples include organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid, organometallic oxides of the above metals such as dibutyltin oxide, or metal alkoxides of the above metals such as titanium isopropoxide, or Examples thereof include alkyl metals of the above metals such as diethyl zinc.

  Among these, tin-based catalysts represented by tin powder (metal tin), tin oxide (II), tin (II) octoate, tin lactate (II), tin (II) chloride and the like are preferable. These can be used alone or in combination of two or more.

The amount of the catalyst used in the present invention is not particularly limited as long as it is an amount that allows the reaction to proceed substantially. Although the specific amount of the catalyst used varies depending on the type of catalyst used, it is generally preferably in the range of 0.00005 to 5% by weight of the obtained polycarbonate copolymer. A range of 0001 to 1% by weight is more preferable.
In general, a reagent contains a basic compound that can be an extremely small amount of a catalyst as an impurity. Therefore, when purification is not particularly performed, the reaction often proceeds without the addition of a catalyst.

  The glass transition temperature of the polycarbonate of the present invention is preferably 60 ° C. to 200 ° C., more preferably 75 ° C. to 180 ° C., mainly depending on the ratio of the isosorbide derivative to the dihydric alcohol and the type of the dihydric alcohol. It is possible to adjust.

If the content of isosorbide is more than this, although heat resistance such as glass transition point (Tg) is improved, mechanical properties such as melt fluidity, tensile strength, elastic modulus and elongation are inferior, and it is hard and brittle. It becomes a virtually impossible resin.
Further, if the content of isosorbide is further reduced, the heat resistance characteristic of the present invention is not exhibited.

  For the polycarbonate copolymer shown in the present invention, other resins, stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, etc.), difficult, depending on the use within the range not impairing the object of the present invention. Flame retardants (bromine flame retardants, phosphorus flame retardants, melamine compounds, etc.), lubricants, mold release agents, antistatic agents, surface wetting improvers, colorants including dyes and pigments, nucleating agents (organic carboxylic acid metal salts, etc.) And a plasticizer and a terminal blocker (epoxy compound, oxazoline compound) can be added to form a transparent heat-resistant molded article according to the present invention. These additives can be used alone or in combination of two or more.

The transparent heat-resistant molded article made of the polycarbonate copolymer according to the present invention is a molded article molded from the polycarbonate copolymer shown in the present invention, and its molding method is not particularly limited, and the publicly known methods are scattered. Specifically, injection molding, extrusion molding, inflation molding, extrusion hollow molding, foam molding, calender molding, blow molding, balloon molding, vacuum molding, spinning and the like are applied.
In the present invention, the sheet refers to a sheet including both a sheet or a film having a thickness of about 10 μm to 10 mm.

  The transparent heat-resistant molded article comprising the polycarbonate copolymer in the present invention is excellent in heat resistance, transparency, mechanical properties, etc., and has a glass transition temperature (Tg) in the range of 60 ° C. or more and less than 200 ° C., preferably The range is 65 ° C. or higher and lower than 180 ° C., more preferably 70 ° C. or higher and lower than 150 ° C. The tensile elongation at break is in the range of 0.5% to less than 200%, more preferably in the range of 1% to less than 200%, and still more preferably in the range of 1.5% to less than 200%.

  The polycarbonate copolymer in the present invention is not necessarily used as a transparent material, but in applications where transparency is required, the value of Haze is preferably 0.1% to less than 30% as an index, more Preferably it is used in the range of 0.1% to less than 20%, more preferably in the range of less than 0.1 to 10%.

  The measured values shown in the present invention are those measured by the following measuring methods unless otherwise specified. The weight average molecular weight (Mw) of the polycarbonate copolymer was measured by gel permeation chromatography (column temperature 40 ° C., chloroform solvent), and the weight average molecular weight was determined by comparison with a sample using polystyrene as a standard. The glass transition temperature (Tg) is obtained by differential thermal analysis (DSC analysis) with a scanning calorimeter (DSC-60 manufactured by Shimadzu Corporation) at a temperature rising rate of 10 ° C./min and a temperature range of 30 ° C. to 250 ° C. The tensile elongation at break test is a method according to JIS K-7113, measured using a 1 (1/5) type test piece, under the conditions of a temperature of 23 ° C., a humidity of 50%, and a tensile speed of 10 mm / min. A test was conducted. For transparency, Haze (cloudiness) is used as an index of transparency, and a sheet having a thickness of 0.5 mm, a width and a length of 4 mm is measured with a Haze meter TC-HIII (Tokyo Denshoku Co., Ltd.) according to JIS K-6714. This is a measurement of a specimen.

  The use of the molded article made of the polycarbonate copolymer in the present invention is not particularly limited, but it can be used as a substrate, a sheet, and a container for an optical disk by taking advantage of its heat resistance and transparency. It can be suitably used as an alternative to materials and commonly used resins.

  Specifically, writing instrument parts such as ballpoint pens, mechanical pens, pencils, stationery parts, golf tees, starting ball fuming golf ball parts, capsules for oral medicine, carriers for suppositories for anus / vagina, skin / Carrier for mucous membrane sticking agent, agrochemical capsule, fertilizer capsule, seedling capsule, compost, fishing line spool, fishing float, fishing fake bait, lure, fishing buoy, hunting decoy, hunting shot capsule, tableware, etc. Camping equipment, nails, piles, binding materials, anti-slip materials for muddy and snowy roads, blocks, lunch boxes, tableware, lunch boxes and prepared food containers such as those sold at convenience stores, chopsticks, chopsticks, forks, spoons, skewers, Toothpicks, cup ramen cups, cups used in beverage vending machines, containers for groceries such as fresh fish, meat, fruits and vegetables, tofu, sugar beet Lei, trobaco used in the fresh fish market, bottles for dairy products such as milk, yogurt and lactic acid bacteria beverages, bottles for soft drinks such as carbonated drinks and soft drinks, bottles for alcoholic drinks such as beer and whiskey, With or without pump for shampoo or liquid soap, tube for toothpaste, cosmetic container, detergent container, bleach container, cold box, flower pot, water purifier cartridge casing, casing for artificial kidney or liver, etc. Syringe materials, cushioning materials used when transporting home appliances such as televisions and stereos, cushioning materials used when transporting precision machines such as computers, printers and watches, ceramic products such as glass and ceramics Although it can be used as a cushioning material for use during transportation, it has excellent heat resistance and transparency. Food container, egg pack, blister pack, compact disc (CD), CD-R, CD-ROM, LD, DVD, transparent conductive film, mini-disc (MD), cassette tape, video tape, personal computer and mobile phone It can be suitably used for applications such as phone cases, baby bottles, and sucking and drinking.

The present invention is described in detail below with reference to examples. It should be noted that the description of the examples in the specification of the present application is an explanation for supporting the understanding of the contents of the present invention, and the description is not of a nature that serves as a basis to narrowly interpret the technical scope of the present invention. Absent. The evaluation method used in this example is as follows.
1) Weight average molecular weight (Mw)
The weight average molecular weight (Mw) was measured by gel permeation chromatography (column temperature 40 ° C., chloroform solvent), and the weight average molecular weight was determined by comparison with a sample using polystyrene as a standard.
2) Glass transition temperature (Tg)
Differential thermal analysis (DSC analysis) was performed with a scanning calorimeter (DSC-60 manufactured by Shimadzu Corporation) at a temperature rising rate of 10 ° C./min and a temperature range of 30 ° C. to 250 ° C.
3) Transparency Haze value (haze) and parallel light transmittance used as an index of transparency are based on JIS K-7136 (ISO14782) and JIS K-7361-1 (ISO13468-1). Haze value (cloudiness) (HZ:%) and parallel light transmittance (PT:%) were measured by NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The measured value is an average value of 5 times. For the measurement, a sheet-like test piece having a thickness of 0.5 mm, a width and a length of 4 mm was used.
4) Tensile elongation at break Measured according to JIS K-7113 using a 1 (1/5) type test piece. The test was conducted under the conditions of a temperature of 23 ° C., a humidity of 50%, and a tensile speed of 10 mm / min.
5) A press sheet having a Young's modulus thickness of 0.5 mm was left for 3 days in a condition of 23 ° C. and a relative humidity of 50%. A tensile test was performed at a strain rate of 100% / min under the conditions of 23 ° C. and 50% relative humidity to determine the Young's modulus.

[Example 1]
In a 300 ml round bottom flask equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a nitrogen introducing tube, 14.7 g (0.1006 mol) of isosorbide, 6.3 g (0.0699 mol) of 1,4-butanediol, 138. 4 g (1.75 mol) was charged and dissolved at room temperature under a nitrogen stream. The temperature was raised to about 50 ° C. with stirring, and a solution of 25.3 g of triphosgene and 60 g of 1,2-dichloroethane was slowly added dropwise over 3.5 hours. Since the internal temperature increased due to reaction heat as the reaction started, the reaction was carried out with care to keep the internal temperature at 50 to 55 ° C.

  After completion of the dropwise addition, the mixture was further stirred for 1 hour while maintaining the same temperature to sufficiently advance the reaction. After completion of the reaction, 100 ml of water was slowly added dropwise into the reaction mass while paying attention to bumping by the generated carbon dioxide gas to decompose unreacted triphosgene. The reaction mass was gently poured into 146 g (1.4 mol) of concentrated hydrochloric acid and 265 g of hydrochloric acid in water and decanted to obtain a brown solid. This was pulverized and washed twice with a homomixer using 300 ml of methanol, further washed with 300 ml of slurry, rinsed with wet cake after filtration, dried in a nitrogen atmosphere, and isosorbide 70 21.2 g of a polycarbonate copolymer of 30 parts by weight of 1,4-butanediol was obtained.

  The obtained polycarbonate copolymer (1) had Mw = 35,000 and a glass transition temperature = 85 ° C. The obtained polycarbonate copolymer (1) was melted at a pressure of 100 kg / cm 2 with a press set at a glass transition temperature + 100 ° C., and then rapidly cooled with a press set at 20 ° C. A press-molded test piece was obtained and the mechanical properties were measured. The results are shown in Table 1. The melt fluidity was good and could be processed without any particular problems.

[Example 2]
70 parts by weight of isosorbide in the same manner as in Example 1 except that 1,4-butanediol was changed to 6.3 g (0.0828 mol) of 1,3-propanediol and triphosgene was changed to 27.2 g (0.0917 mol). Thus, 21.0 g of a polycarbonate copolymer (2) containing 30 parts by weight of 1,4-butanediol was obtained.

  The obtained polycarbonate copolymer (2) had Mw = 34,000 and a glass transition temperature = 100 ° C. The obtained polycarbonate copolymer (2) was molded in the same manner as in Example 1, and the mechanical properties were measured. The results are shown in Table 1. Melt fluidity was good and could be processed without any problems

[Example 3]
A reactor equipped with a stirrer, thermometer, toroidal tube and air-cooled tube, receiver, nitrogen inlet pipe, and dropping funnel was charged with 70 g (0.479 mol) of isosorbide and 173.92 g (0.8119 mol) of diphenyl carbonate. The temperature was raised to 215 ° C. under a nitrogen stream. The mixture was stirred for 3.5 hours while maintaining the same temperature, and the reaction was allowed to proceed by transesterification. The resulting phenol was removed out of the system. Subsequently, at the same temperature, 32.2 g (0.357 mol) of 1,4-butanediol was slowly added dropwise over 3.5 hours. After completion of dropping, the mixture was further aged for 5 hours. Similarly, the phenol produced at this time was also removed from the system.

Thereafter, phenol produced while gradually reducing the pressure of the reaction system was removed from the system, and the reaction was terminated at a maximum of 215 ° C. and 4 mmHg, and 70 parts by weight of isosorbide and 30 parts by weight of 1,4-butanediol were added. 83.2 g of a polycarbonate copolymer (3) was obtained.
The obtained polycarbonate copolymer (3) had Mw = 31,000 and a glass transition temperature = 95 ° C. The obtained polycarbonate copolymer (3) was molded in the same manner as in Example 1 and measured. The results are shown in Table 1. Melt fluidity was good and could be processed without any problems

[Comparative Example 1]
In the same reaction apparatus as in Example 1, 14.6 g (0.1 mol) of isosorbide, 0.133 g (0.00133 mol) of cyclohexanol, 79.1 g of pyridine, and 50 g of 1,2-dichloroethane were charged. The reaction was carried out in the same manner while adding dropwise a solution of 83 g (0.05 mol) and 1,2-dichloroethane 50 g. After completion of the reaction, the same treatment was carried out to obtain 15.3 g of isosorbide homopolycarbonate resin (4).
The resulting isosorbide homopolycarbonate resin (4) had a Mw of 116,000 and a glass transition temperature of 166 ° C.
An attempt was made to mold the resulting isosorbide homopolycarbonate resin (4), but the melt flowability was poor and it was cracked during molding, so it could not be molded and measurement was impossible.

The polycarbonate copolymer of the present invention has excellent heat resistance, is suitable for optical disk substrates, containers and packaging materials, and can be used as an alternative to general-purpose resins.

Claims (6)

General formula (1)

(In the general formula (1), X ₁ and X ₂ are O, N—R 7 and S, and may be the same or different. R 1 and R 2 are alkylene chains having 1 to 10 carbon atoms. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group may be linear or branched, An alicyclic polycarbonate unit (a) represented by a cycloalkyl group and a phenyl group may have a substituent; and
General formula (2)

(In General Formula (2), R8 is an alkylene group or aralkyl group having 2 to 10 carbon atoms, which may be linear, branched or may contain a cyclic structure) (b) A transparent heat-resistant molded article comprising a polycarbonate copolymer having a weight average molecular weight of 5,000 to 200,000. 2. The polycarbonate according to claim 1, wherein the composition ratio of the alicyclic polycarbonate unit (a) and the aliphatic polycarbonate unit (b) is (a) / (b) = 90 / 10-30 / 70% by weight. A transparent molded body made of a copolymer. General formula (3)

(In General Formula (3), X ₁ and X ₂ are O, N—R 7 and S, which may be the same or different. R 1 and R 2 are alkylene chains having 1 to 10 carbon atoms. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group may be linear or branched, An alicyclic dihydric alcohol (A) represented by a cycloalkyl group or a phenyl group may have a substituent;
General formula (4)

(In the general formula (4), R8 is an aliphatic dihydric alcohol represented by a C2-C10 alkylene group or aralkyl group which may be linear, branched or may contain a cyclic structure) 2. A transparent heat-resistant molded article comprising a polycarbonate copolymer according to claim 1, which is produced from B) and a carbonate precursor. An optical disk substrate comprising the transparent heat-resistant molded article according to claim 1. A sheet comprising the transparent heat-resistant molded article according to claim 1. A container comprising the transparent heat-resistant molded article according to claim 1.