JP2007523972A - Polyformal and copolyformal as hydrolysis protection layers on polycarbonate - Google Patents

Abstract

  In addition to compositions containing polyformal or copolyformal and possible additives, the present invention further includes the use of polyformal or copolyformal in the production of a layer that protects against hydrolysis, and is protected from hydrolysis and thermoplastic. It relates to a multilayer product comprising at least one layer containing a resin and at least one layer containing at least one polyformal or copolyformal.

Description

Detailed Description of the Invention

  The present invention relates to a hydrolysis-protective multilayer product, in particular a sheet, film, container (e.g. water bottle, feeding bottle) containing at least one layer containing a thermoplastic resin and at least one layer containing at least one polyformal or copolyformal. Bottles or medical products), and compositions containing polyformal or copolyformal and possible additives, and the use of polyformal and / or copolyformal to produce a hydrolytic protective layer.

  The invention further relates to a process for the production of such multilayer products (for example sheets, medical products or various containers such as bottle products, baby bottles, water bottles and other products comprising the described sheet).

  For example, solid or multilayer sheets are generally protected from UV damage (eg yellowing) by coating one or two outer surfaces with a UV coextruded layer. However, other multi-layer products are similarly protected from damage from ultraviolet radiation. In contrast, the application of thermoplastics as a layer that provides protection against hydrolysis damage is not described in the prior art.

The prior art on multilayer protection products is summarized below:
(EP-A 0 110 221 discloses a sheet comprising two layers of polycarbonate, one layer containing at least 3 wt.% Of UV absorber. These sheets are simultaneously formed according to EP-A 0 110 221. It can be produced by extrusion.
EP-A 0 320 632 discloses a molded article comprising two layers of a thermoplastic polymer, preferably polycarbonate, one layer containing a special substituted benzotriazole as UV absorber. EP-A 0 320 632 further discloses the production of these shaped articles by coextrusion.
EP-A 0 247 480 is a sheet made from a branched polycarbonate in addition to one sheet made from a thermoplastic polymer (the sheet made from the polycarbonate contains a special substituted benzotriazole as a UV absorber) ) Is disclosed.
EP-A 0 500 496 discloses a polymer composition stabilized against UV light with a special triazine and its use as an outer layer in a multilayer system. Polycarbonate, polyester, polyamide, polyacetal, polyphenylene oxide and polyphenylene sulfide are listed as polymers. )

  According to the prior art, water bottles (eg 5 gallon bottles) do not have a multilayer structure (DE 19943642, DE 19943643, EP-A 0411433). The same applies to reusable milk bottles or baby bottles.

  Polycarbonate containers are produced, for example, by extrusion blow molding or injection blow molding.

  In extrusion blow molding, the granules are generally melted in a single screw extruder and molded through a die to form a free-standing parison. This parison is then placed in a blow mold that holds the parison together at the lower end. The parison is inflated in this mold and the parison is shaped as desired. After cooling, the mold can be opened and the blow molded product can be removed. , Munich, Vienna 1992, pages 257 to 264).

  For extrusion blow molding, it is advantageous to use a highly pseudoplastic polycarbonate to obtain high melt stability. Branched polycarbonates are particularly pseudoplastic.

  Injection blow molding is a combination of injection molding and blow molding.

This method is done in three steps:
1) Parison injection molding in the plastic temperature range of polycarbonate
2) Inflation of the parison in the thermoplastic range of polycarbonate (injection mold core is also a blow mandrel)
3) Peeling of blow molded parts and cooling of blow mandrels with air if necessary
(For more details, see Anders, S., Kaminski, A., Kappenstein, R., "Polycarbonate" in Becker / Braun, Kunststoff-Handbuch, Volume 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag, Munich, Vienna 1992, pages 223 to 225).

  However, none of the products known from the prior art achieves satisfactory results in all respects, especially as far as long-term stability with respect to hydrolysis. Water damages polycarbonate at temperatures above 60 ° C. Long-term contact with hot water causes a decrease in molecular weight. This is further accelerated in the presence of heat stabilizers (eg organic phosphites). In addition, the polycarbonate can preferably be alkali hydrolyzed. Microwave irradiation further accelerates this degradation.

  Prior art patents have never made reference to a hydrolytic protective layer that overcomes this disadvantage.

  Thus, starting from the prior art, the aim is to improve the properties of the long-term stability with respect to hydrolysis in water (e.g. at elevated temperatures and even in acidic and even basic environments). Providing a multilayer sheet or coated container (eg water bottle or medical product, which must be able to be sterilized in superheated steam).

  This object is the basis of the present invention.

  This object is surprisingly achieved by a coating containing polyformal or copolyformal as the main polymer component.

  The coatings of products based on polyformal or copolyformal show surprising excellence over the prior art in terms of hydrolytic stability which is markedly superior compared to polycarbonate.

  This is particularly surprising since polyformal can be considered a complete acetal. Acetals show outstanding sensitivity to hydrolysis, at least in an acidic environment, according to recent theories considered by those skilled in the art. However, in contrast, coatings made from polyformal are stable to hydrolysis even in acidic solutions and even at high temperatures.

(式中、O-D-OおよびO-E-O基はジフェノラート基を意味する。ここで-D-および-E-が6〜40のC原子、好ましくは6〜21のC原子を有する芳香族基であり、一以上の芳香環または芳香縮合環(任意にヘテロ原子を含有してもよい)を含有してもよく、任意にC₁〜C₁₂アルキル基またはハロゲンで置換されてもよく、脂肪族基、脂環式基、芳香環またはヘテロ原子を結合体(binding link)として含有してもよい。kは1〜1500、好ましくは2〜1000、特に好ましくは2〜700、および最も特に好ましくは5〜500および特別好ましくは5〜300の自然数を意味し、oは1〜1500、好ましくは1〜1000、特に好ましくは1〜700および最も特に好ましくは1〜500および特別好ましくは1〜300の数を意味し、mは分数z/oを、nは分数(o-z)/oを意味する。ここでzは0とoとの間の数を意味する。)
を有するポリホルマールまたはコポリホルマールを含有する被膜を提供する。 Therefore, the present application has the general formula (1a) or (1b),

(Wherein the ODO and OEO groups mean diphenolate groups, wherein -D- and -E- are aromatic groups having 6 to 40 C atoms, preferably 6 to 21 C atoms, one or more of may contain an aromatic ring or aromatic fused ring (which may optionally contain hetero atom), and may optionally be substituted by C ₁ -C ₁₂ alkyl group or a halogen, an aliphatic group, alicyclic Formula groups, aromatic rings or heteroatoms may be included as binding links, k is 1-1500, preferably 2-1000, particularly preferably 2-700, and most particularly preferably 5-500 and Specially preferably means a natural number of 5 to 300, o means a number of 1 to 1500, preferably 1 to 1000, particularly preferably 1 to 700 and most particularly preferably 1 to 500 and particularly preferably 1 to 300. , M means fraction z / o, n means fraction (oz) / o, where z means a number between 0 and o.)
A coating containing polyformal or copolyformal having

(式中、角型括弧は基礎となるジフェノラート基を描き、ここでR¹およびR²は互いに独立してH、直鎖または分枝したC₁〜C₁₈アルキルまたはアルコキシ基、ハロゲン(例えばClまたはBr)または任意に置換アリールまたはアラルキル基でもよく、好ましくはHまたは直鎖または分枝したC₁〜C₁₂アルキル、特に好ましくはHまたはC₁〜C₈アルキル基および最も特に好ましくはHまたはメチルを意味し、
Xは単結合、C₁〜C₆アルキレン、C₂〜C₅アルキリデン、C₅〜C₆シクロアルキリデン基(C₁〜C₆アルキル、好ましくはメチル基またはエチル基で置換されてもよい)、またはC₆〜C₁₂アリーレン基(任意に他のヘテロ原子含有芳香環と縮合してもよい)を意味し、ここでpは1〜1500、好ましくは2〜1000、特に好ましくは2〜700、および最も特に好ましくは5〜500、および特別に5〜300の自然数を意味し、pは1〜1500、好ましくは1〜1000、特に好ましくは1〜700、および最も特に好ましくは1〜500、および特別好ましくは1〜300の数を意味し、およびqは分数z/pおよびrは分数(p-z)/pを意味し、ここでzは0とpとの間の数を意味し、および-O-D-O-および-O-E-O-基の一部は互いに独立して更に一以上の三官能価化合物から誘導される基を意味し、その結果として第三の結合部位、ポリマー鎖の分枝がこの地点で起こる)
を有する一般構造から誘導される。 Preferred structural units of the polyformal and copolyformal according to the invention are represented by the formulas (2a), (2b), (2c) and (2d),

(Wherein square brackets depict the underlying diphenolate group, where R ¹ and R ² are independently of each other H, linear or branched C ₁ -C ₁₈ alkyl or alkoxy groups, halogens (e.g. Cl Or Br) or optionally substituted aryl or aralkyl groups, preferably H or linear or branched C _{1 to} C ₁₂ alkyl, particularly preferably H or C _{1 to} C ₈ alkyl groups and most particularly preferably H or Means methyl,
X is a single bond, C ₁ -C ₆ alkylene, C ₂ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene group (C ₁ -C ₆ alkyl, preferably may be substituted with a methyl group or an ethyl group), or C ₆ -C ₁₂ means an arylene group (optionally may be condensed with other hetero atom-containing aromatic ring), where p is 1-1500, preferably 2 to 1000, particularly preferably from 2 to 700, And most particularly preferably means a natural number of 5 to 500, and especially 5 to 300, p is 1 to 1500, preferably 1 to 1000, particularly preferably 1 to 700, and most particularly preferably 1 to 500, and Specially preferably means a number between 1 and 300, and q means a fraction z / p and r means a fraction (pz) / p, where z means a number between 0 and p, and- Some of the ODO- and -OEO- groups mean groups derived from one or more trifunctional compounds independently of each other, resulting in a third binding site, Branched-mer chain occurs at this point)
Derived from a general structure having

  Thus, the polyformal or copolyformal may be linear or branched.

  The bisphenolate groups of the formulas (1) and (2) are particularly preferably derived from suitable bisphenols listed below.

  Hydroquinone, resorcinol, dihydroxybiphenyl, bis (hydroxyphenyl) alkane, bis (hydroxyphenyl) cycloalkane, bis (hydroxyphenyl) sulfide, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) ketone, bis (hydroxyphenyl) sulfone, Bis (hydroxyphenyl) sulfoxide, α, α′-bis (hydroxyphenyl) diisopropylbenzene, and their ring-alkylated and ring-halogenated compounds, and also α, ω-bis ( Hydroxyphenyl) polysiloxanes are listed as examples of bisphenols on which the general formula (1) is based.

  Preferred bisphenols are, for example, 4,4′-dihydroxybiphenyl (DOD), 4,4′-dihydroxybiphenyl ether (DOD ether), 2,2-bis- (4-hydroxyphenyl) propane (bisphenol A), 1,1- Bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC), 1,1-bis- (4-hydroxyphenyl) cyclohexane, 2,4-bis- (4-hydroxyphenyl) -2 -Methylbutane, 1,1-bis- (4-hydroxyphenyl) -1-phenylethane, 1,4-bis- [2- (4-hydroxyphenyl) -2-propyl] benzene, 1,3-bis- [ 2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis- (3-methyl-4-hydroxyphenyl) propane, 2,2-bis- (3-chloro-4- Hydroxyphenyl) propane, bis- (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propyl Lopan, bis- (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 2,2-bis- (3, 5-dichloro-4-hydroxyphenyl) propane and 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane.

  Particularly preferred bisphenols are, for example, 2,2-bis- (4-hydroxyphenyl) propane (bisphenol A), 4,4′-dihydroxybiphenyl (DOD), 4,4′-dihydroxybiphenyl ether (DOD ether), 1,3 -Bis- [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis- ( 4-hydroxyphenyl) -1-phenylethane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane 1,1-bis- (4-hydroxyphenyl) cyclohexane and 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC).

  The most particularly preferred bisphenols are 2,2-bis- (4-hydroxyphenyl) propane (bisphenol A), 4,4′-dihydroxybiphenyl (DOD), 4,4′-dihydroxybiphenyl ether (DOD ether), 1,3 -Bis- [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M) and 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC) .

  The most particularly preferred bisphenols are 2,2-bis- (4-hydroxyphenyl) propane (bisphenol A) and 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC). is there.

Bisphenols can be used both alone and in a mixture with each other; both homopolyformals and copolyformals are included. This bisphenol is known from the literature or can be prepared by methods known from the literature (e.g. HJ Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5 ^th Edition, Vol. 19, (See p. 348).

  The polyformals according to the invention can be consciously branched in a controlled manner by the use of small amounts of trifunctional compounds known as branching agents. Some suitable branching agents are: phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptene-2; 4,6-dimethyl-2,4,6- Tri- (4-hydroxyphenyl) heptane; 1,3,5-tri- (4-hydroxyphenyl) benzene; 1,1,1-tri- (4-hydroxyphenyl) ethane; tri- (4-hydroxyphenyl) 2,2-bis- [4,4-bis- (4-hydroxyphenyl) cyclohexyl] propane; 2,4-bis- (4-hydroxyphenylisopropyl) phenol; 2,6-bis- (2- Hydroxy-5'-methylbenzyl) -4-methylphenol; 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane; hexa- (4- (4-hydroxyphenylisopropyl) phenyl) ortho Terephthalic acid ester; tetra- (4-hydroxyphenyl) methane; tetra- (4- (4-hydroxyphenylisopropyl) phenoxy) methane; α, α, α ''-tri -(4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 2,4-dihydroxybenzoic acid; trimesic acid; cyanuric chloride; 3,3-bis- (3-methyl-4-hydroxyphenyl) -2 -Oxo-2,3-dihydroindole; 1,4-bis- (4 ', 4' '-dihydroxytriphenyl) methyl) benzene and especially 1,1,1-tri- (4-hydroxyphenyl) ethane and Bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

  The use of such branching agents leads to a corresponding deviation from the idealized structure of equations (1) and (2). This corresponds to the amount of branching agent used and is a structural unit with three binding units derived from the branching agent used (this depends on the branching agent used, such as ester groups etc. Is produced).

  A branching agent of 0.05 to 2 mol% with respect to the diphenol used or a mixture of branching agents that may optionally be mixed may be added with the diphenol, but may also be added at the last stage of the synthesis. .

  Phenol (for example phenol), alkylphenol (for example cresol and 4-tert-butylphenol), chlorophenol, bromophenol, cumylphenol or mixtures thereof are preferably used as polyformal chain terminators used as materials in coextrusion coatings. It is used in an amount of 1 to 20 mol%, preferably 2 to 10 mol%, relative to the moles of bisphenol. Phenol, 4-tert-butylphenol or cumylphenol is preferred.

  Polyformals and copolyformals having the formulas (1a) and (1b) or (2 ad) are produced, for example, by a solution process, in which bisphenol and a chain terminator are combined with methylene chloride or alpha, alpha-dichlorotoluene and chlorinated. Methylene or α, α-dichlorotoluene and suitable high boiling solvents (e.g. N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylcaprolactam (NMC), chlorobenzene, dichlorobenzene, It is characterized by reacting at a temperature of 30 ° C. to 160 ° C. in the presence of a base, preferably sodium hydroxide or potassium hydroxide, in a homogeneous solution with trichlorobenzene or tetrahydrofuran (THF). Preferred high boiling solvents are NMP, DMF, DMSO and NMC, particularly preferably NMP, NMC, DMSO and most particularly preferably NMP and NMC. This reaction may be carried out in several stages. Separation of the necessary cyclic impurities is carried out after neutral washing of the organic phase by precipitation or by fractional compounding with a solvent (eg acetone) that dissolves the crude product cyclic compound. Cyclic impurities can be dissolved almost completely in the solvent and can be almost completely separated by mixing the portions and changing the solvent. After blending, a content of less than 1% of the cyclic compound can be achieved, for example, by using about 10 liters of acetone, for example, in about 5 parts of polyformal in an amount of about 6 kg.

  Cyclic polyformals and copolyformals can also be separated by precipitation methods in suitable solvents which act as precipitants for the desired polymer and serve as solvents for undesired cyclic compounds. These solvents are preferably alcohols or ketones.

  The reaction temperature for the polycondensation is 30 ° C to 160 ° C, preferably 40 ° C to 100 ° C, particularly preferably 50 ° C to 80 ° C and most particularly preferably 60 ° C to 80 ° C.

  Thus, the present invention relates to the use of the disclosed polyformals and copolyformals to produce multilayer products (e.g., coextruded articles (e.g., multilayer sheets)), these multilayer sheets themselves, and further of these multilayer sheets by coextrusion. Processes and methods for coating suitable compositions containing these polyformals or copolyformals are provided.

  The present invention further provides products or other coated products comprising the listed multilayer sheets based on polyformal. This product comprising, for example, the multilayer sheet listed, or itself coated, is preferably selected from the group consisting of baby bottles, water bottles or medical products that can be sterilized with superheated steam.

  The multilayer product according to the invention has numerous advantages. In particular, it has the advantage that a clear improvement in long-term stability, in particular hydrolysis stability with respect to water-containing media, is achieved by a hydroform protective layer based on polyformal. In addition, the sheet is easy to manufacture and inexpensive, and all starting materials are available and inexpensive. In addition, the positive properties (eg good optical and mechanical properties) of the polycarbonate in the multilayer product according to the invention are not impaired or only slightly impaired.

  The multilayer product according to the invention has further advantages compared to the prior art. Multi-layer products (eg bottles) according to the present invention may be produced, for example, by coextrusion blow molding. This leads to advantages over products made with paint. For example, as in the case of a coating system, the solvent does not evaporate at all by coextrusion.

  In addition, paints have a limited storage capacity. Coextrusion does not have this drawback.

  Furthermore, coating requires complex techniques. For example, if an organic solvent is used, it requires an explosion-proof unit, solvent recycling, and therefore an expensive investment in equipment. Coextrusion does not have this drawback.

  Preferred embodiments of the present invention are the listed multilayer sheets or various types of bottles (polycarbonate and / or copolycarbonate and / or polyester and / or copolyester and / or polyester carbonate and / or polymethyl methacrylate and / or poly A base layer consisting of a blend of acrylate and / or polycarbonate and polyester and / or a polymethylmethacrylate and a coextruded layer consisting of a polyformal or copolyformal or a blend thereof with (co) polycarbonate and / or (co) polyester).

  A multilayer product with a hydrolysis protection layer of 1 to 5000 μm thick, preferably 5 to 2500 μm, most particularly preferably 10 to 500 μm is a preferred multilayer product according to the invention.

  This sheet may be a solid sheet, a multilayer sheet, a two-layer sheet, a three-layer sheet, a four-layer sheet, or the like. The multilayer sheet may further include various profiles (eg, X or XX profiles). This multilayer sheet may additionally be a corrugated multilayer sheet.

  A preferred embodiment of the present invention is a two-layer sheet comprising one polycarbonate layer and a hydrolysis protective layer of polyformal or copolyformal or polycarbonate-polyformal blend.

  A further preferred embodiment of the present invention is a three-layer sheet consisting of one polycarbonate layer as the base sheet and two overlying identical, or different, hydrolytic protective layers consisting of the same or different polyformal or copolyformal or polycarbonate-polyformal blends.

  Similarly preferred embodiments of the present invention are various types of containers (eg, bottles (eg, water bottles (5 gallon bottles), baby bottles or reusable milk bottles)).

  Within the purpose of the present invention, containers can be used for the packaging, storage or transport of liquids, solids or gases. Liquid packaging, storage or transport containers (liquid containers) are preferred, and water packaging, storage or transport containers (water bottles) are particularly preferred.

  Among the objects of the present invention, the container is preferably a blow molded container having a volume of 0.1 l to 50 l, preferably 0.5 l to 50 l, with volumes of 1 l, 5 l, 12 l and 20 l most particularly preferred. preferable.

  Most preferred is a water bottle having a volume of 3-5 gallons.

  This container preferably has an empty weight of 0.1 g to 3000 g, preferably 50 g to 2000 g and particularly preferably 650 g to 900 g.

  The wall thickness of this container is preferably 0.5 mm to 5 mm, preferably 0.8 mm to 4 mm.

  For the purposes of the present invention, the container preferably has a length of 5 mm to 2000 mm, particularly preferably 100 mm to 1000 mm.

  This container preferably has a maximum perimeter of 10 mm to 250 mm, preferably 50 mm to 150 mm and most particularly preferably 70 to 90 mm.

  For the purposes of the present invention, the container preferably has a bottleneck length of preferably 1 mm to 500 mm, preferably 10 mm to 250 mm, particularly preferably 50 mm to 100 mm and most particularly preferably 70 to 80 mm. .

  The wall thickness of the bottleneck of this container preferably varies from 0.5 mm to 10 mm, particularly preferably from 1 mm to 10 mm, and most particularly preferably from 5 mm to 7 mm.

  The diameter of this bottleneck preferably varies from 5 mm to 200 mm. 10 mm to 100 mm is particularly preferred, and 45 mm to 75 mm is most particularly preferred.

  The bottle base of the container according to the invention preferably has a diameter of 10 mm to 250 mm, preferably 50 mm to 150 mm, and most particularly preferably 70 to 90 mm.

  For the purposes of the present invention, the container can take any geometrical shape, for example circular, elliptical or polygonal, i.e. it forms an angle with eg 3 to 12 faces. Circular, elliptical and hexagonal shapes are preferred.

  The container design may be based on any surface texture. This surface composition is preferably smooth or ribbed. The container according to the invention may further exhibit several different surface compositions. Ribs or beads may wrap around the container. They can be any spaced apart, i.e. several different spaced apart. The surface composition of the container according to the present invention may show rough or integrated textures, symbols, decorations, emblems, company logos, trademarks, monograms, manufacturer's instructions, material details and / or volume information. Good.

  A container according to the present invention may have any number of handles, which may be located on the side, top or bottom. This handle may be external or may be integrated into the contour of the container. The handle may be folded or installed. The handle may be any shape (eg, oval, circular or polygonal). The length of this handle is preferably 0.1 mm to 180 mm, preferably 20 mm to 120 mm.

  In addition to the polycarbonate according to the invention, the container according to the invention may also contain small amounts of other substances (for example seals made of rubber or handles made of other materials).

  The container according to the invention is preferably produced by extrusion blow molding or injection blow molding.

  In a preferred embodiment of the process for producing the container according to the invention, the polycarbonate according to the invention is processed in a smooth or grooved, preferably smooth, extruder having a feed.

  The driving force of the extruder is selected based on the screw diameter. As an example, the driving force of the extruder is about 30-40 kW with a screw diameter of 60 mm, and about 60-70 kW with a screw diameter of 90 mm.

  A common three-section screw conventionally used in engineering thermoplastic processing is preferred.

  For the production of containers having a volume of 1 l, screw diameters of 50-60 mm are preferred. For the production of containers having a volume of 20 l, a screw diameter of 70 to 100 mm is preferred. The length of the screw is preferably 20 to 25 times the diameter of the screw.

  In the case of blow molding, the blow mold is preferably heated to 50 to 90 ° C. to obtain a glossy high-grade container surface.

  In order to allow homogeneous and effective heating of the blow mold, the base area and the jacket area may be heated separately.

  The blow mold is preferably closed with a compressive force of 1000-1500 N per centimeter length of the pinch-off weld.

  The polycarbonate according to the invention is preferably dried prior to processing so that the optical properties of the container are not degraded by vertical streaks or bubbles and so that the polycarbonate is not hydrolytically degraded during processing. The residual moisture content after drying is preferably lower than 0.01 wt /%. A drying temperature of 120 ° C. is preferred. Lower temperatures do not guarantee adequate drying, while higher temperatures risk that the polycarbonate granules stick to each other and can no longer be processed. A dry-air dryer is preferred.

  During processing of the polycarbonate according to the invention, the preferred melting temperature is 230 ° to 300 ° C.

  Containers according to the present invention may be used for liquid, solid or gas packaging, storage or transport. For example, an embodiment as a container used for packing, storing or transporting liquid is preferable. For example, an embodiment as a water bottle that can be used for packing, storage or transportation of water is particularly preferable.

  A preferred embodiment of the present invention is characterized in that a container made from a branched polycarbonate is characterized in that the branched polycarbonate contains THPE and / or IBC as branching agent, and is linked to the production of a branched polycarbonate of phenol or alkylphenol. Used as a stopper, this container is a water bottle.

A particularly preferred embodiment of the present invention is characterized in that a container made from polycarbonate contains THPE containing branched polycarbonate and / or IBC as branching agent, and is used in the production of phenol branched polycarbonate. There have shear rate melt viscosity and 1000 s ^-1 at 260 ° C. 5500-7000 Pas at a shear rate and 260 ° C. melt viscosity and ^{10 s -1 900~1100 Pas, 3.5 g} / 10 min is less than MFR (Melt Flow Index, measured according to ISO 1133) and this container is a water bottle.

  In a special embodiment, this multilayer product is transparent.

  Both the substrate and the hydrolysis protection layer in the multilayer molded article according to the present invention may contain additives.

  Depending on the place of application, this hydrolysis protection layer may contain in particular UV stabilizers or mold release agents.

  This layer further comprises other conventional processing aids, in particular release agents and flow control agents, and stabilizers conventionally used in polycarbonate, in particular UV stabilizers, heat stabilizers, and colorants and optical brighteners. And may contain inorganic pigments.

  In addition to the polyformal and copolyformal layers, layers made from all known polycarbonates are suitable as additive layers, in particular as substrates for multilayer products according to the invention.

  Suitable polycarbonates are, for example, homopolycarbonates, copolycarbonates and thermoplastic polyester carbonates.

They are preferably measured by measuring the relative solution viscosity in dichloromethane or in a mixture of equal amounts of phenol / o-dichlorobenzene by weight, calibrated by light scattering, 18,000-40,000, preferably 26,000-36,000 and especially having an average molecular weight M _w of the 28,000～35,000.

  For polycarbonate production, see "Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York, London, Sydney 1964" and "DC PREVORSEK, BT DEBONA and Y. KESTEN, Corporate Research Center. , Allied Chemical Corporation, Moristown, New Jersey 07960, 'Synthesis of Poly (ester) carbonate Copolymers' in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 19, 75-90 (1980) ", and" D. Freitag, U Grigo, PR Mueller, N. Nouvertne, BAYER AG, 'Polycarbonates' in Encyclopedia of Polymer Science and Engineering, Vol. 11, Second Edition, 1988, pages 648-718 "and finally" Drs U. Grigo, K. Kircher and PR Mueller 'Polycarbonate' in Becker / Braun, Kunststoff-Handbuch, Volume 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pages 117-299 ".

  The production of the polycarbonate is preferably carried out by an interfacial polycondensation process or a melt transesterification process and will be described below using the interfacial polycondensation method as an example.

Compounds preferably used as starting materials have the general formula
HO-Z-OH,
(In the formula, Z is a divalent organic group having 6 to 30 carbon atoms and having one or more aromatic groups.)
A bisphenol having

  Examples of such compounds are dihydroxydiphenyl, bis (hydroxyphenyl) alkane, indanbisphenol, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) sulfone, bis (hydroxyphenyl) ketone and α, α'-bis (hydroxyphenyl). ) A bisphenol belonging to the group of diisopropylbenzene.

  Particularly preferred bisphenols belonging to the group of pre-listed compounds are bisphenol A, tetraalkylbisphenol A, 1,3-bis- [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 1,1 -Bis- [2- (4-hydroxyphenyl) -2-propyl] benzene, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BP-TMC) and optionally those It may be a mixture.

  The bisphenol compounds for use according to the invention are preferably reacted with a carbonic acid compound, in particular phosgene, or with diphenyl carbonate or dimethyl carbonate in the case of the melt transesterification process.

  The polyester carbonate is preferably obtained by reacting the previously listed bisphenols, at least one aromatic dicarboxylic acid and optionally a carbonic acid equivalent. Examples of suitable aromatic dicarboxylic acids are phthalic acid, terephthalic acid, isophthalic acid, 3,3′- or 4,4′-diphenyldicarboxylic acid and benzophenone dicarboxylic acid. A part of the carbonate group in the polycarbonate (up to 80 mol%, preferably 20 to 50 mol%) may be substituted with an aromatic dicarboxylic acid ester group.

  Examples of inert organic solvents used in the interfacial polycondensation method are dichloromethane, various dichloroethane and chloropropane compounds, tetrachloromethane, trichloromethane, chlorobenzene and chlorotoluene, chlorobenzene or dichloromethane or a preferred mixture of dichloromethane and chlorobenzene It is.

  The interfacial polycondensation reaction may be accelerated by catalysts (eg tertiary amines, especially N-alkylpiperidines or onium salts). Tributylamine, triethylamine and N-ethylpiperidine are preferably used. In the melt transesterification process, the catalysts listed in DE-A 4 238 123 are preferably used.

  The polycarbonate may be intentionally branched in a controlled manner through the use of small amounts of branching agents. Some suitable branching agents are: phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptene-2; 4,6-dimethyl-2,4,6- Tri- (4-hydroxyphenyl) heptane; 1,3,5-tri- (4-hydroxyphenyl) benzene; 1,1,1-tri- (4-hydroxyphenyl) ethane; tri- (4-hydroxyphenyl) 2,2-bis- [4,4-bis- (4-hydroxyphenyl) cyclohexyl] propane; 2,4-bis- (4-hydroxyphenylisopropyl) phenol; 2,6-bis- (2- Hydroxy-5'-methylbenzyl) -4-methylphenol; 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane; hexa- (4- (4-hydroxyphenylisopropyl) phenyl) ortho Terephthalic acid ester; tetra- (4-hydroxyphenyl) methane; tetra- (4- (4-hydroxyphenylisopropyl) phenoxy) methane; α, α, α'-tris -(4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 2,4-dihydroxybenzoic acid; trimesic acid; cyanuric chloride; 3,3-bis- (3-methyl-4-hydroxyphenyl) -2 -Oxo-2,3-dihydroindole; 1,4-bis- (4 ', 4 "-dihydroxytriphenyl) methyl) benzene and especially: 1,1,1-tri- (4-hydroxyphenyl) ethane and bis -(3-Methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

  0.05-2 mol% branching agent or mixture of branching agents, optionally mixed together, with respect to the diphenol used, may be added together with the diphenol, but also added at the final stage of the synthesis May be.

  Phenol (e.g. phenol), alkylphenols (e.g. cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof are 1-20 mol%, preferably 2-10 mol%, relative to the moles of bisphenol Are preferably used as chain terminators in the amount of phenol, 4-tert-butylphenol or cumylphenol.

  Chain terminators and branching agents may be added separately or together with the bisphenol for synthesis.

  The production of polycarbonate by the melt transesterification process is disclosed by way of example in DE-A 42 38 123.

  Preferred polycarbonates are homopolycarbonates based on bisphenol A, homopolycarbonates based on 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and two monomeric bisphenol A and 1,1-bis- ( Copolycarbonates based on 4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and copolycarbonates based on the two monomers bisphenol A and 4,4′-dihydroxydiphenyl (DOD).

  A homopolycarbonate based on bisphenol A is particularly preferred.

  All thermoplastic resins used in the products according to the invention may contain stabilizers. Suitable stabilizers include, for example, phosphines, phosphites or other compounds disclosed in Si and EP-A 0 500 496. Triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, tetrakis- (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite and triaryl Phosfit may be listed as an example. Triphenylphosphine and tris- (2,4-di-tert-butylphenyl) phosphite are particularly preferred.

  These stabilizers may be present in all layers of the multilayer product according to the invention. In other words, it may be present in both the so-called base and the so-called coextruded layer. Different additives or additive concentrations may be present in each layer.

  The multilayer product according to the invention may further comprise 0.01 to 0.5 wt.% Mono- to hexahydric alcohols, in particular esters or partial esters of glycerol, pentaerythritol or guerbet alcohols.

  Monohydric alcohols are, for example, stearyl alcohol, palmityl alcohol and Gerve alcohol.

  An example of a dihydric alcohol is glycol.

  An example of a trihydric alcohol is glycerol.

  Examples of tetrahydric alcohols are pentaerythritol and mesoerythritol.

  Examples of pentahydric alcohols are arabitol, ribitol and xylitol.

  Examples of hexahydric alcohols are mannitol, glucitol (sorbitol) and dulcitol.

Esters are preferably saturated aliphatic C ₁₀ -C ₃₆ monocarboxylic acids and optionally hydroxymonocarboxylic acids, preferably monoesters of saturated aliphatic C ₁₄ -C ₃₂ monocarboxylic acids and optionally hydroxymonocarboxylic acids, diesters, tri Esters, tetraesters, pentaesters, and hexaesters or mixtures thereof, in particular random mixtures.

  Commercially available fatty acid esters, particularly those of pentaerythritol and glycerol, may contain less than 60% of various partial esters as a result of the manufacturing process.

  Saturated aliphatic monocarboxylic acids having 10 to 36 C atoms are, for example, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, stearic acid, hydroxystearic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid and octacosanoic acid.

  Preferred saturated aliphatic monocarboxylic acids having 14 to 22 C atoms are, for example, tetradecanoic acid, hexadecanoic acid, stearic acid, hydroxystearic acid, eicosanoic acid and docosanoic acid.

  Saturated aliphatic monocarboxylic acids such as hexadecanoic acid, stearic acid and hydroxystearic acid are particularly preferred.

Saturated aliphatic C ₁₀ -C ₃₆ carboxylic acids and fatty acid esters are either or may be prepared by methods known from one document is known by itself literature. Examples of pentaerythritol fatty acid esters are the particularly preferred esters of monocarboxylic acids specified above.

  Particular preference is given to esters of pentaerythritol and glycerol with stearic acid and hexadecanoic acid.

  Even more particularly preferred are esters of Gerve alcohol and glycerol with stearic acid and hexadecanoic acid and optionally hydroxystearic acid.

  These esters may be present in both the base and coextruded layers. Different additives or concentrations may be present in each layer.

  The multilayer product according to the invention may contain an antistatic agent.

  Examples of antistatic agents are cationic compounds (e.g. quaternary ammonium, phosphonium or sulfonium salts), anionic compounds (e.g. alkyl sulfonates, alkyl sulfates, alkyl phosphates, alkali metal salts or alkaline earth metal salt forms of carboxy). And non-ionogenic compounds (eg, polyethylene glycol esters, polyethylene glycol ethers, fatty acid esters, ethoxylated fatty amines).

  These antistatic agents may be present in both the base and the coextruded layer. Different additives or concentrations may be present in each layer. They are preferably used in the coextruded layer.

  The multilayer product according to the invention may contain organic dyes, inorganic colored pigments, fluorescent dyes and particularly preferably optical brighteners.

  These colorants may be present in both the base and coextruded layers. Different additives or concentrations may be present in each layer.

  All molding compositions, feedstocks and their solvents used in the production of multilayer products according to the invention can be contaminated with corresponding impurities as a result of the production of the object made with the purest possible starting materials and in storage conditions. .

  The individual components in the molding composition can be mixed in a known manner, either sequentially or simultaneously, and at room and elevated temperatures.

  Additives, especially the aforementioned additives, are preferably unitized with conventional additives (eg closed mixers, uniaxial) with the polymer granules at a temperature of about 200-330 ° C. by means of known methods to the molding compositions of the products according to the invention. By mixing in a screw extruder and double-shaft extruder (e.g. by melt compounding or melt extrusion) or by mixing the polymer solution with the additive solution Mixed by evaporation. The content of additives in the molding composition can vary within a wide range and is determined by the desired properties of the molding composition. The total content of additives in the molding composition is preferably up to about 20 wt.%, Preferably 0.2-12 wt.%, With respect to the weight of the molding composition.

  Coextrusion is known per se from the literature (see for example EP-A 0 110 221 and EP-A 0 110 238). In this case, the procedure is preferably carried out as follows. Connect the extruder with a coextrusion adapter to produce the core and outer layers. The adapter is designed in such a way that the melt forming the outer layer is adhesively applied as a thin layer to the melt of the core. The multilayer melt strand produced in this way is then transferred to the adjacent die with the desired foam (multilayer sheet or solid sheet). This melt is then cooled under certain conditions by methods known by calendering (solid sheets) or vacuum calibration (multilayer sheets) and then cut to length To do. If necessary, a conditioning oven may be attached after the calibration stage to remove the stress. Instead of an adapter mounted in front of the die, the die itself may be designed in such a way as to bring the melt there.

  The multilayer composition may be further prepared by prior art by extrusion coating, coextrusion and coextrusion blow molding.

  The invention is further illustrated by the following examples, without being limited thereby. The examples according to the invention are merely preferred embodiments of the invention.

ビスフェノールTMC 7 kg (22.55 mol)、水酸化ナトリウムペレット2.255 kg (56.38 mol)および塩化メチレン500 ml中の微粉砕p-tert-ブチルフェノール(Aldrich)51.07 g (0.34 mol)を塩化メチレン28.7 kgおよびN-メチル-2-ピロリドン(NMP)40.18 kgからなる溶媒配合物に攪拌しながら窒素保護気体下添加する。ホモジナイズ後、この混合物を還流(78℃)し、この温度で一時間攪拌する。25℃に冷却した後、反応バッチを塩化メチレン35 lおよび脱イオン水20 lで希釈する。このバッチをセパレーター中で中性になり塩がなくなるまで(導電率＜15 μS.cm^-1)水で洗う。セパレーターからの有機相を分離し、塩化メチレンのクロロベンゼンとの溶媒交換をエバポレータ中で行う。この材料を次にZSK 32蒸発押出機の方法によって270℃の温度で続く粗砕と共に押出す。この合成手順を二回行う。供給材料の廃棄後、透明グラニュールとして全部で9.85 kgのポリホルマールが得られる。これはまだ不純物として低分子量環状ホルマールを含有する。この材料を二つの部分に分け、それぞれを約5 lのアセトンで一晩膨潤させる。環状化合物がもはや検出されなくなるまで、得られる生成物を数部分のきれいなアセトンと混ぜる。精製された材料を組み合わせ、クロロベンゼンに溶かした後、蒸発押出機を通して280℃で再び押し出される。供給材料を廃棄した後、全部で7.31 kgのポリホルマールを透明グラニュールとして得る。 Example
Example 1
Synthesis of homopolyformal from bisphenol TMC:

Bisphenol TMC 7 kg (22.55 mol), sodium hydroxide pellets 2.255 kg (56.38 mol) and finely ground p-tert-butylphenol (Aldrich) 51.07 g (0.34 mol) in 500 ml methylene chloride were added 28.7 kg methylene chloride and N- To a solvent formulation consisting of 40.18 kg of methyl-2-pyrrolidone (NMP) is added with stirring under a nitrogen protective gas. After homogenization, the mixture is refluxed (78 ° C.) and stirred at this temperature for 1 hour. After cooling to 25 ° C., the reaction batch is diluted with 35 l methylene chloride and 20 l deionized water. The batch is washed with water until neutral in the separator and free of salt (conductivity <15 μS.cm ⁻¹ ). The organic phase from the separator is separated and the solvent exchange of methylene chloride with chlorobenzene is carried out in an evaporator. This material is then extruded with subsequent grinding at a temperature of 270 ° C. by means of a ZSK 32 evaporator extruder. This synthesis procedure is performed twice. After disposal of the feed material, a total of 9.85 kg of polyformal is obtained as transparent granules. This still contains low molecular weight cyclic formal as impurities. This material is divided into two parts, each swelled overnight with about 5 l of acetone. The resulting product is mixed with several portions of clean acetone until the cyclic compound is no longer detected. The purified materials are combined, dissolved in chlorobenzene, and then extruded again at 280 ° C. through an evaporation extruder. After discarding the feed, a total of 7.31 kg of polyformal is obtained as a transparent granule.

analysis:
-Molecular weight by GPC (calibration to polycarbonate) Mw = 38345, Mn = 20138, D = 1.90.
・ Glass transition point Tg = 170.8 ℃
-Relative solution viscosity in methylene chloride (0.5 g / 100 ml solution) = 1.234
Confirmation that the polymer is free of cyclic compounds by GPC (oligomers in the low molecular weight range) and MALDI-TOF (molecular weight of the cyclic compound compared to the molecular weight of the open chain analog).

ビスフェノールA (Bayer AG) 7 kg (30.66 mol)、水酸化ナトリウムペレット3.066 kg (76.65 mol)および塩化メチレン500 ml中の微粉砕p-tert-ブチルフェノール(Aldrich) 69.4 g (0.462 mol)を塩化メチレン28.7 kgおよびN-メチル-2-ピロリドン(NMP) 40.18 kgからなる溶媒配合物に攪拌しながら窒素保護気体下添加する。ホモジナイズ後、混合物を還流(78℃)し、この温度で一時間攪拌する。25℃に冷却した後、反応バッチを塩化メチレン20 lおよび脱イオン水20 lで希釈する。このバッチをセパレーター中で中性になり塩がなくなるまで(導電率＜15 μS.cm^-1)水で洗う。セパレーターからの有機相を分離し、塩化メチレンのクロロベンゼンとの溶媒交換をエバポレータ中で行う。この材料を次にZSK 32蒸発押出機の方法によって200℃の温度で続く粗砕と共に押出す。この合成手順を二回行う。供給材料の廃棄後、透明グラニュールとして全部で11.99 kgのポリホルマールが得られる。 Example 2
Homopolyformal from bisphenol A:

Bisphenol A (Bayer AG) 79.4 (30.66 mol), sodium hydroxide pellets 3.066 kg (76.65 mol) and 69.4 g (0.462 mol) finely ground p-tert-butylphenol (Aldrich) in 500 ml of methylene chloride To a solvent formulation consisting of kg and N-methyl-2-pyrrolidone (NMP) 40.18 kg is added with stirring under nitrogen protective gas. After homogenization, the mixture is refluxed (78 ° C.) and stirred at this temperature for 1 hour. After cooling to 25 ° C., the reaction batch is diluted with 20 l of methylene chloride and 20 l of deionized water. The batch is washed with water until neutral in the separator and free of salt (conductivity <15 μS.cm ⁻¹ ). The organic phase from the separator is separated and the solvent exchange of methylene chloride with chlorobenzene is carried out in an evaporator. This material is then extruded with subsequent grinding at a temperature of 200 ° C. by means of a ZSK 32 evaporator extruder. This synthesis procedure is performed twice. After disposal of the feed material, a total of 11.99 kg of polyformal is obtained as transparent granules.

analysis:
-Molecular weight by GPC (calibration to polycarbonate) Mw = 31732, Mn = 3465. In this case, the cyclic compound is not separated. This material cannot swell with acetone, indicating that separation of cyclic compounds is likewise impossible.
・ Glass transition point Tg = 89 ℃
-Relative solution viscosity in methylene chloride (0.5 g / 100 ml solution) = 1.237 / 1.239 (twice measurements)

ビスフェノールTMC (x=70 mol%) 5.432 kg (17.5 mol)、ビスフェノールA (y=30 mol%) 1.712 kg (7.5 mol)、水酸化ナトリウムペレット2.5 kg (62.5 mol)および塩化メチレン500 ml中の微粉砕p-tert-ブチルフェノール(Aldrich)56.33 g (0.375 mol)を塩化メチレン28.7 kgおよびN-メチル-2-ピロリドン(NMP)40.18 kgからなる溶媒配合物に攪拌しながら窒素保護気体下添加する。ホモジナイズ後、混合物を還流(78℃)し、この温度で一時間攪拌する。25℃に冷却した後、反応バッチを塩化メチレン35 lおよび脱イオン水20 lで希釈する。このバッチをセパレーター中で中性になり塩がなくなるまで(導電率＜15 μS.cm^-1)水で洗う。セパレーターからの有機相を分離し、塩化メチレンのクロロベンゼンとの溶媒交換をエバポレータで行う。この材料を次にZSK 32蒸発押出機の方法によって280℃の温度で続く粗砕と共に押出す。供給材料の廃棄後、透明グラニュールとして全部で5.14 kgのコポリホルマールが得られる。これはまだ不純物として低分子量環状化合物を含有する。この材料を約5 lのアセトンで一晩膨潤させる。環状化合物がもはや検出されなくなるまで、得られる生成物を数部分のきれいなアセトンと混ぜる。精製された材料をクロロベンゼン中に溶かし、蒸発押出機を通して270℃で再び押し出す。供給材料を廃棄した後、ポリホルマール3.11 kgが透明グラニュールとして得られる。 Example 3
a) Synthesis of copolyformal from bisphenol TMC and bisphenol A:

Bisphenol TMC (x = 70 mol%) 5.432 kg (17.5 mol), bisphenol A (y = 30 mol%) 1.712 kg (7.5 mol), sodium hydroxide pellets 2.5 kg (62.5 mol), and fine particles in methylene chloride 500 ml 56.33 g (0.375 mol) of ground p-tert-butylphenol (Aldrich) is added under stirring to a solvent mixture consisting of 28.7 kg of methylene chloride and 40.18 kg of N-methyl-2-pyrrolidone (NMP) under nitrogen protective gas. After homogenization, the mixture is refluxed (78 ° C.) and stirred at this temperature for 1 hour. After cooling to 25 ° C., the reaction batch is diluted with 35 l methylene chloride and 20 l deionized water. The batch is washed with water until neutral in the separator and free of salt (conductivity <15 μS.cm ⁻¹ ). The organic phase from the separator is separated and the solvent exchange of methylene chloride with chlorobenzene is carried out with an evaporator. This material is then extruded with subsequent grinding at a temperature of 280 ° C. by the method of a ZSK 32 evaporator extruder. After disposal of the feed, a total of 5.14 kg of copolyformal is obtained as transparent granules. This still contains low molecular weight cyclic compounds as impurities. This material is swollen overnight with about 5 l of acetone. The resulting product is mixed with several portions of clean acetone until the cyclic compound is no longer detected. The purified material is dissolved in chlorobenzene and extruded again at 270 ° C. through an evaporator extruder. After disposal of the feed material, 3.11 kg of polyformal is obtained as transparent granules.

analysis:
-Molecular weight by GPC (calibration to polycarbonate) Mw = 39901, Mn = 19538, D = 2.04.
・ Glass transition point Tg = 148.2 ℃
-Relative solution viscosity in methylene chloride (0.5 g / 100 ml solution) = 1.244 / 1.244 (granule)
¹ H-NMR in CDCl ₃ is the expected insertion ration of TMC / BPA monomer (integral of chemical shift of alicyclic group (TMC) to integral of chemical shift of methyl group (BPA)) x / indicates y = 0.7 / 0.3

b) to i) Synthesis of copolyformal from bisphenol TMC and bisphenol A with indefinite composition:
Further copolyformals are prepared in the same way as the synthesis of Example 3a) (see Table 1).

ビスフェノールTMC (x=90 mol%) 3.749 kg (12.07 mol)、4,4'-ジヒドロキシビフェニル(DOD) (y=10 mol%) 0.2497 kg (1.34 mol)、水酸化ナトリウムペレット1.339 kg (33.48 mol)および塩化メチレン200 ml中の微粉砕p-tert-ブチルフェノール(Aldrich) 20.12 g (0.134 mol)を塩化メチレン12.0 lおよびN-メチル-2-ピロリドン(NMP)22.25 kgからなる溶媒配合物に攪拌しながら窒素保護気体下添加する。ホモジナイズ後、混合物を還流(78℃)し、この温度で一時間攪拌する。25℃に冷却した後、反応バッチを塩化メチレン35 lおよび脱イオン水20 lで希釈する。このバッチをセパレーター中で中性になり塩がなくなるまで(導電率＜15 μS.cm^-1)水で洗う。セパレーターからの有機相を分離し、塩化メチレンのクロロベンゼンとの溶媒交換をエバポレータで行う。この材料を次にZSK 32蒸発押出機の方法によって280℃の温度で続く粗砕と共に押出す。供給材料の廃棄後、透明グラニュールとして全部で2.62 kgのコポリホルマールが得られる。これはまだ不純物として低分子量環状化合物を含有する。この材料を約5 lのアセトンで一晩膨潤させる。環状化合物がもはや検出されなくなるまで、得られる生成物を数部分のきれいなアセトンと混ぜる。精製された材料をクロロベンゼンに溶かし、蒸発押出機を通して240℃で再び押し出す。供給材料を廃棄した後、ポリホルマールを透明グラニュールとして得る。 Example 4
Synthesis of copolyformal from bisphenol TMC and 4,4'-dihydroxybiphenyl (DOD):

Bisphenol TMC (x = 90 mol%) 3.749 kg (12.07 mol), 4,4'-dihydroxybiphenyl (DOD) (y = 10 mol%) 0.2497 kg (1.34 mol), sodium hydroxide pellets 1.339 kg (33.48 mol) With stirring, 20.12 g (0.134 mol) of finely ground p-tert-butylphenol (Aldrich) in 200 ml of methylene chloride was stirred into a solvent mixture consisting of 12.0 l of methylene chloride and 22.25 kg of N-methyl-2-pyrrolidone (NMP). Add under nitrogen protective gas. After homogenization, the mixture is refluxed (78 ° C.) and stirred at this temperature for 1 hour. After cooling to 25 ° C., the reaction batch is diluted with 35 l methylene chloride and 20 l deionized water. The batch is washed with water until neutral in the separator and free of salt (conductivity <15 μS.cm ⁻¹ ). The organic phase from the separator is separated and the solvent exchange of methylene chloride with chlorobenzene is carried out with an evaporator. This material is then extruded with subsequent grinding at a temperature of 280 ° C. by the method of a ZSK 32 evaporator extruder. After disposal of the feed material, a total of 2.62 kg of copolyformal is obtained as transparent granules. This still contains low molecular weight cyclic compounds as impurities. This material is swollen overnight with about 5 l of acetone. The resulting product is mixed with several portions of clean acetone until the cyclic compound is no longer detected. The purified material is dissolved in chlorobenzene and extruded again at 240 ° C. through an evaporator extruder. After discarding the feed material, the polyformal is obtained as a transparent granule.

analysis:
-Molecular weight by GPC (calibration to polycarbonate) Mw = 44287, Mn = 17877, D = 2.48.
・ Glass transition point Tg = 167 ℃

ビスフェノールA (x=70 mol%) 22.37 g (0.0098 mol)、4,4'-ジヒドロキシビフェニル(DOD) (y=30 mol%) 7.82 g (0.0042 mol)、水酸化ナトリウムペレット14.0 g (0.35 mol)および微粉砕p-tert-ブチルフェノール(Aldrich)0.21 g (0.0014 mol)を塩化メチレン125 mlおよびN-メチル-2-ピロリドン(NMP)225 mlからなる溶媒配合物に攪拌しながら窒素保護気体下添加する。ホモジナイズ後、混合物を還流(78℃)し、この温度で一時間攪拌する。25℃に冷却した後、反応バッチを塩化メチレンおよび脱イオン水で希釈する。次に中性になり塩がなくなるまで(導電率＜15 μS.cm^-1)水で洗う。有機相を分離する。ポリマーをメタノール中での沈殿によって単離する。生成物を水およびメタノールで洗浄し80℃で乾燥した後、白色ポリマーフィラメントしてポリホルマールを得る。 Example 5
Synthesis of copolyformal from bisphenol A and 4,4'-dihydroxybiphenyl (DOD):

Bisphenol A (x = 70 mol%) 22.37 g (0.0098 mol), 4,4'-dihydroxybiphenyl (DOD) (y = 30 mol%) 7.82 g (0.0042 mol), sodium hydroxide pellets 14.0 g (0.35 mol) And 0.21 g (0.0014 mol) of finely ground p-tert-butylphenol (Aldrich) are added to a solvent mixture consisting of 125 ml of methylene chloride and 225 ml of N-methyl-2-pyrrolidone (NMP) with stirring under a nitrogen protective gas . After homogenization, the mixture is refluxed (78 ° C.) and stirred at this temperature for 1 hour. After cooling to 25 ° C., the reaction batch is diluted with methylene chloride and deionized water. Then wash with water until neutral and free of salt (conductivity <15 μS.cm ⁻¹ ). Separate the organic phase. The polymer is isolated by precipitation in methanol. The product is washed with water and methanol, dried at 80 ° C., and then white polymer filaments to obtain polyformal.

analysis:
-Molecular weight by GPC (calibration to polycarbonate) Mw = 19057, Mn = 4839, D = 3.94.

Example 6
Hydrolysis test of BPA polyformal from Example 2:
The hydrolysis test is carried out by measuring the change in molecular weight by loading the following hydrolysis medium / temperature conditions and measuring the relative solution viscosity all the time in methylene chloride (0.5 g / 100 ml solution):
Hydrolysis medium: 0.1 N HCl / 80 ° C
0.1 N NaOH / 80 ℃
Distilled water / about 100 ℃

  The following results are obtained for a total loading period of up to 21 days (each with multiple measurements):

a) Hydrolysis medium: 0.1 N HCl / 80 ° C

a) Hydrolysis medium: 0.1 N NaOH / 80 ℃

a) Hydrolysis medium: distilled water / about 100 ° C

Example 7
Hydrolysis test of TMC / BPA copolyformal (70/30) from Example 3:
The hydrolysis test is carried out by measuring the change in molecular weight by loading the following hydrolysis medium / temperature conditions and measuring the relative solution viscosity all the time in methylene chloride (0.5 g / 100 ml solution):
Hydrolysis medium: 0.1 N HCl / 80 ° C
0.1 N NaOH / 80 ℃
Distilled water / about 100 ℃

  The following results are obtained for a total loading period of up to 21 days (each with multiple measurements):

a) Hydrolysis medium: 0.1 N HCl / 80 ° C

a) Hydrolysis medium: 0.1 N NaOH / 80 ℃

a) Hydrolysis medium: distilled water / about 100 ° C

Example 8
Hydrolysis test of TMC polyformal:
(Same as Example 1 except for higher molecular weight)
-Molecular weight by GPC (calibration to polycarbonate) Mw = 50311, Mn = 21637, D = 2.32.
・ Glass transition point Tg = 172 ℃
-Relative solution viscosity in methylene chloride (0.5 g / 100 ml solution) = 1.288 / 1.290

The hydrolysis test is carried out by measuring the change in molecular weight by loading the following hydrolysis medium / temperature conditions and measuring the relative solution viscosity all the time in methylene chloride (0.5 g / 100 ml solution):
Hydrolysis medium: 0.1 N HCl / 80 ° C
0.1 N NaOH / 80 ℃
Distilled water / about 100 ℃

  The following results are obtained for a total loading period of up to 21 days (each with multiple measurements):

a) Hydrolysis medium: 0.1 N HCl / 80 ° C

a) Hydrolysis medium: 0.1 N NaOH / 80 ℃

a) Hydrolysis medium: distilled water / about 100 ° C

Example 9
Polycarbonate from Bayer AG Makrolon Hydrolysis test ^{(registered trademark)} 2808 (comparative test):

This hydrolysis test is performed by loading the following hydrolysis media / temperature conditions and the molecular weight change is measured by measuring the relative solution viscosity all the time in methylene chloride (0.5 g / 100 ml solution):
Hydrolysis medium: 0.1 N HCl / 80 ° C
0.1 N NaOH / 80 ℃
Distilled water / about 100 ℃

  The following results are obtained for a total loading period of up to 21 days (each with multiple measurements):

a) Hydrolysis medium: 0.1 N HCl / 80 ° C

a) Hydrolysis medium: 0.1 N NaOH / 80 ℃

a) Hydrolysis medium: distilled water / about 100 ° C

  It can be clearly seen that the solution viscosity of the polycarbonate after hydrolysis loading is clearly lower than in the case of polyformal. This means that polycarbonate is even more easily degradable by polyformal and is therefore more unstable. A coextruded layer made from polyformal therefore serves as a protective layer against premature damage of the sheet or container.

ビスフェノールTMC (x=90 mol%) 39.1 g (0.126 mol)、レソルシノール(y=10 mol%) 1.542 g (0.014 mol)、水酸化ナトリウムペレット14.0 g (0.35 mol)および微粉砕p-tert-ブチルフェノール(Aldrich) 0.21 g (0.0014 mol)を塩化メチレン125 mlおよびN-メチル-2-ピロリドン(NMP)225 mlからなる溶媒配合物に攪拌しながら窒素保護気体下添加する。ホモジナイズ後、混合物を還流(78℃)し、この温度で一時間攪拌する。25℃に冷却した後、反応バッチを塩化メチレンおよび脱イオン水で希釈し、次に中性になり塩がなくなるまで(導電率＜15 μS.cm^-1)水で洗う。有機相を分離する。ポリマーをメタノール中で沈殿によって単離する。製品を水およびメタノールで洗浄し、アセトンで環状化合物を分離し、80℃で乾燥した後、ポリホルマールを白色ポリマーフィラメントとして得る。 Example 10
Synthesis of copolyformal from bisphenol TMC and resorcinol:

Bisphenol TMC (x = 90 mol%) 39.1 g (0.126 mol), resorcinol (y = 10 mol%) 1.542 g (0.014 mol), sodium hydroxide pellets 14.0 g (0.35 mol) and finely ground p-tert-butylphenol ( Aldrich) 0.21 g (0.0014 mol) is added with stirring to a solvent mixture consisting of 125 ml of methylene chloride and 225 ml of N-methyl-2-pyrrolidone (NMP) under nitrogen protective gas. After homogenization, the mixture is refluxed (78 ° C.) and stirred at this temperature for 1 hour. After cooling to 25 ° C., the reaction batch is diluted with methylene chloride and deionized water and then washed with water until neutral and free of salt (conductivity <15 μS.cm ⁻¹ ). Separate the organic phase. The polymer is isolated by precipitation in methanol. After washing the product with water and methanol, separating the cyclic compound with acetone and drying at 80 ° C., the polyformal is obtained as white polymer filaments.

analysis:
-Molecular weight by GPC (calibration to polycarbonate) Mw = 32008, Mn = 12251, D = 2.6.
・ Glass transition point Tg = 163 ℃

ビスフェノールTMC (x=50 mol%) 14.84 g (0.065 mol)、m,p-ビスフェノールA (3,4-イソプロピリデンジフェノール) (y=50 mol%) 20.18 g (0.065 mol)、水酸化ナトリウムペレット14.0 g (0.35 mol)および微粉砕p-tert-ブチルフェノール(Aldrich) 0.21 g (0.0014 mol)を塩化メチレン125 mlおよびN-メチル-2-ピロリドン(NMP)225 mlからなる溶媒配合物に攪拌しながら窒素保護気体下添加する。ホモジナイズ後、混合物を還流(78℃)し、この温度で一時間攪拌する。25℃に冷却した後、反応バッチを塩化メチレンおよび脱イオン水で希釈し、次に中性になり塩がなくなるまで(導電率＜15 μS.cm^-1)水で洗う。有機相を分離する。ポリマーをメタノール中で沈殿によって単離する。生成物を水およびメタノールで洗浄し、アセトンで環状化合物を分離し、80℃で乾燥した後、ポリホルマールを白色ポリマーフィラメントとして得る。 Example 11
Synthesis of copolyformal from bisphenol TMC and m, p-bisphenol A:

Bisphenol TMC (x = 50 mol%) 14.84 g (0.065 mol), m, p-bisphenol A (3,4-isopropylidenediphenol) (y = 50 mol%) 20.18 g (0.065 mol), sodium hydroxide pellets While stirring 14.0 g (0.35 mol) and finely ground p-tert-butylphenol (Aldrich) 0.21 g (0.0014 mol) in a solvent mixture consisting of 125 ml of methylene chloride and 225 ml of N-methyl-2-pyrrolidone (NMP) Add under nitrogen protective gas. After homogenization, the mixture is refluxed (78 ° C.) and stirred at this temperature for 1 hour. After cooling to 25 ° C., the reaction batch is diluted with methylene chloride and deionized water and then washed with water until neutral and free of salt (conductivity <15 μS.cm ⁻¹ ). Separate the organic phase. The polymer is isolated by precipitation in methanol. After washing the product with water and methanol, separating the cyclic compound with acetone and drying at 80 ° C., the polyformal is obtained as white polymer filaments.

analysis:
-Molecular weight by GPC (calibration to polycarbonate) Mw = 28254, Mn = 16312, D = 1.73.
・ Glass transition point Tg = 92 ℃

4,4'-スルホンジフェノール(x=50 mol%) 36.29 g (0.145 mol)、ビスフェノールA (y=50 mol%) 33.46 g (0.145 mol)、水酸化ナトリウムペレット28.8 g (0.72 mol)および微粉砕p-tert-ブチルフェノール(Aldrich) 0.436 g (0.0029 mol)を塩化メチレン300 mlおよびN-メチル-2-ピロリドン(NMP)570 mlからなる溶媒配合物に攪拌しながら窒素保護気体下添加する。ホモジナイズ後、混合物を還流(78℃)し、この温度で一時間攪拌する。25℃に冷却した後、反応バッチを塩化メチレンおよび脱イオン水で希釈し、次に中性になり塩がなくなるまで(導電率＜15 μS.cm^-1)水で洗う。有機相を分離する。ポリマーをメタノール中で沈殿によって単離する。製品を水およびメタノールで洗浄し、アセトンで環状化合物を分離し、80℃で乾燥した後、ポリホルマールを白色ポリマーフィラメントとして得る。 Example 12
Synthesis of copolyformal from bisphenol A and 4,4'-sulfone diphenol:

4,4'-sulfone diphenol (x = 50 mol%) 36.29 g (0.145 mol), bisphenol A (y = 50 mol%) 33.46 g (0.145 mol), sodium hydroxide pellets 28.8 g (0.72 mol) and fine 0.436 g (0.0029 mol) of ground p-tert-butylphenol (Aldrich) is added with stirring to a solvent mixture consisting of 300 ml of methylene chloride and 570 ml of N-methyl-2-pyrrolidone (NMP) under nitrogen protective gas. After homogenization, the mixture is refluxed (78 ° C.) and stirred at this temperature for 1 hour. After cooling to 25 ° C., the reaction batch is diluted with methylene chloride and deionized water, then until the salt becomes neutral and free (conductivity <15 μS.cm ^-1) washed with water. Separate the organic phase. The polymer is isolated by precipitation in methanol. After washing the product with water and methanol, separating the cyclic compound with acetone and drying at 80 ° C., the polyformal is obtained as white polymer filaments.

analysis:
-Molecular weight by GPC (calibration to polycarbonate) Mw = 21546, Mn = 7786, D = 2.76.
・ Glass transition point Tg = 131 ℃

4,4'-ジヒドロキシフェニルエーテル(Bayer AG) 28.30 g (0.14 mol)、水酸化ナトリウムペレット14.0 g (0.35 mol)および微粉砕p-tert-ブチルフェノール(Aldrich) 0.21 g (0.0014 mol)を塩化メチレン125 mlおよびN-メチル-2-ピロリドン(NMP) 225 mlからなる溶媒配合物に攪拌しながら窒素保護気体下添加する。ホモジナイズ後、混合物を還流(78℃)し、この温度で一時間攪拌する。25℃に冷却した後、反応バッチを塩化メチレンおよび脱イオン水で希釈し、次に中性になり塩がなくなるまで(導電率＜15 μS.cm^-1)水で洗う。有機相を分離する。ポリマーをメタノール中で沈殿によって単離する。生成物を水およびメタノールで洗浄し、アセトンで環状化合物を分離し、80℃で乾燥した後、ポリホルマールを白色ポリマーフィラメントとして得る。 Example 13
Synthesis of polyformal from 4,4'-dihydroxyphenyl ether:

4,4'-dihydroxyphenyl ether (Bayer AG) 28.30 g (0.14 mol), sodium hydroxide pellets 14.0 g (0.35 mol) and finely ground p-tert-butylphenol (Aldrich) 0.21 g (0.0014 mol) To a solvent formulation consisting of ml and N-methyl-2-pyrrolidone (NMP) 225 ml is added with stirring under nitrogen protective gas. After homogenization, the mixture is refluxed (78 ° C.) and stirred at this temperature for 1 hour. After cooling to 25 ° C., the reaction batch is diluted with methylene chloride and deionized water and then washed with water until neutral and free of salt (conductivity <15 μS.cm ⁻¹ ). Separate the organic phase. The polymer is isolated by precipitation in methanol. After washing the product with water and methanol, separating the cyclic compound with acetone and drying at 80 ° C., the polyformal is obtained as white polymer filaments.

analysis:
-Molecular weight by GPC (calibration to polycarbonate) Mw = 24034, Mn = 9769, D = 2.46.
・ Glass transition point Tg = 57 ℃

Claims (4)

  Use of at least one polyformal or copolyformal to produce a hydrolysis protective coating for containers. General formula (1a) or (1b)

(In the formula, ODO and OEO groups mean diphenolate groups, wherein -D- and -E- are aromatic groups having 6 to 40 C atoms, and include one or more aromatic rings or aromatic condensed rings (optional in may contain also may) contain heteroatoms, and may optionally be substituted by C ₁ -C ₁₂ alkyl group or a halogen, an aliphatic group, an alicyclic group, an aromatic ring or a hetero atom It may be contained as a conjugate, k means a natural number from 1 to 1500, m means a fraction z / o, n means a fraction (oz) / o, where z is between 0 and o -ODO- and part of the -OEO- group independently of each other means a group derived from one or more trifunctional compounds, resulting in a third binding site, a polymer chain. Branch of this occurs at this point.)
Use according to claim 1, characterized by polyformal or copolyformal having   A container having the hydrolysis protective coating film according to claim 1.   A water bottle, a baby bottle and a medical product having the hydrolysis protective coating film according to claim 1.