WO1991008103A1 - Pellicule ou feuille transparente en polyester - Google Patents

Pellicule ou feuille transparente en polyester Download PDF

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Publication number
WO1991008103A1
WO1991008103A1 PCT/JP1990/001569 JP9001569W WO9108103A1 WO 1991008103 A1 WO1991008103 A1 WO 1991008103A1 JP 9001569 W JP9001569 W JP 9001569W WO 9108103 A1 WO9108103 A1 WO 9108103A1
Authority
WO
WIPO (PCT)
Prior art keywords
sheet
film
heat
crystallinity
transparency
Prior art date
Application number
PCT/JP1990/001569
Other languages
English (en)
Japanese (ja)
Inventor
Kuniaki Kawaguchi
Toshio Nakane
Hiroaki Konuma
Yukihiko Kageyama
Kenji Hijikata
Original Assignee
Polyplastics Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polyplastics Co., Ltd. filed Critical Polyplastics Co., Ltd.
Priority to KR1019910700813A priority Critical patent/KR920700894A/ko
Publication of WO1991008103A1 publication Critical patent/WO1991008103A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/006—PBT, i.e. polybutylene terephthalate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a highly crystalline and transparent polyester film and sheet.
  • the Yoshikazoku Polyester which is represented by the Polyethylene Terephthalate (PET) and the Polybutene Telephthalate (PUT), is excellent. Due to the well-balanced physical properties such as heat resistance, mechanical strength, and air-permeability, engineering engineering plus It is widely used as a chip in a wide area.
  • PBT Is said to exhibit the above-mentioned excellent properties because of its high crystallinity, but on the other hand, because of its high crystallinity, transparency is required It could not be used for the required application.
  • the crystallization speed of PET is low, the crystallinity of the film can be reduced by rapidly cooling the molten polymer, thereby reducing the crystallinity of the film.
  • the mechanical strength and the permeability of the gas and the like are insufficient until then. It is necessary to proceed with crystal crystallization.
  • 70 to 99 mol% of the repeating unit was composed of terephthalic acid or its ester-forming derivative and 1,4-butadiene.
  • a copolymer polyester resin consisting of an ester unit with a polyester and having a heat of crystallization that satisfies the following formula (1).
  • Equation (1) He 35.0 (J / g)
  • ⁇ Hc is the calorific value of crystallization when the resin melted at 240 was cooled at a cooling rate of 1/500 at a rate of / 500 by differential thermal analysis. Absolute value of (J / g)
  • the film or sheet in which the molten form is melted is quenched, and once a low crystallinity film or sheet is prepared and aged, the film or sheet is cooled. To heat-treat a room or sheet
  • 70 to 99 mol% of the repeating unit is the teleporter base and the oxial. It consists of an ester unit formed by a kilenoxy group.
  • the material compounds necessary to form the copolymerized polyesters that make up the present invention are described step by step.
  • the raw material compounds required to form the royl group are terephthalic acid and its derivatives, and, to give examples, the dialkyl ester Or one or more species selected from the list or the species. Of these, preferred are terephthalic acid and its dialkyl, and particularly preferred is terephthalic acid. It is dimethyl.
  • Oxial alkylene that forms the polystyrene teleterunit of the copolymerized polyester that constitutes the present invention The group is 1,4-butanedione.
  • the raw material of the common monomer for forming the remaining constituent units of the copolymerized polyester resin of the present invention is polyvalent carbon.
  • One or more species are listed, excluding terephthalic acid and its ester-forming inducer, 1,4-butanediol Of Formed single-position ing and Target.
  • the copolymerized polyester constituting the present invention may be a raw material composed of one or more species selected from the above-mentioned group as a comonomer.
  • the value of the mole fraction ratio for all constituent units of these comonomers is 1 to 30 mol%. I needed this ⁇ ⁇ is there . Especially preferred is 3 to 20 mol%. If the above molar fraction ratio is less than 1 mol%, the crystallizing rate of the copolymerized polyester is too high, so that the present invention is processed. However, it is difficult to prepare a transparent film or sheet, and if it is larger than 30 mol%, the film or sheet will be difficult to prepare. Due to the decrease in crystallinity, mechanical strength ⁇ Physical properties such as air permeability are reduced, and heat resistance is also reduced. I don't like it.
  • polyester copolymer used in the present invention not only satisfies the above requirements but also satisfies the following formula (1). .
  • Equation (1) ⁇ He ⁇ 35.0 (J / g)
  • copolymerized polyesters use the conventionally known condensation reaction or the ester exchange reaction to obtain the interface polycondensation, the fusion polymerization, and the fusion polymerization. It can be manufactured by liquid polymerization. In addition, the obtained resin is subjected to depressurization or heat treatment in the presence of inert gas, by using the solid-phase polymerization method. It is possible that
  • the T-die method or the inflation method can be cited, but it is preferable. This is the T-Dai method. From the viewpoint of moldability and workability, it is desirable that the inherent viscosity of the copolymerized polyester resin be 0.7 or more.
  • the intrinsic viscosity is a value measured in 25: in orthochlorophenol.
  • the thickness of the film or sheet should be about to be favorable, the thickness of the film or sheet should be about to be favorable, the thickness of the film or sheet should be
  • the range of the preferable thickness of the film or sheet is specified by a numerical value, it is 0.01 to 2.5 images, which is more preferable. 0.02 ⁇ : L thigh. Also, after the film or sheet is manufactured by quenching, it may be stretched uniaxially or biaxially so that it becomes the specified thickness. No.
  • ripening is performed after film and sheet preparation. This involves immersing the film or sheet in a heating medium at a specified temperature, such as hot water, or a method of immersing the film or sheet in a dryer at a specified temperature. It is performed by a method that blows wind or a method that uses radiant heat such as infrared rays.
  • Examples of concrete ripening include the method of heating at a temperature near the glass transition point of resin for a certain period of time, and the method of heating to a certain temperature. Heating at a heating rate, a new method Alternatively, there is a method of performing multi-stage heating from room temperature to a certain temperature.
  • the film or sheet After the film or sheet has been aged once, it is further cooled and crystallized by heat treatment to maintain its transparency while maintaining its transparency. After that, the degree of crystallinity of the transparent crystal is kept stable.
  • the CR is 50% or more.
  • the relative crystallinity is a value determined by the DSC measurement method described later. If the relative crystallinity is less than 50%, the gas permeability and heat resistance at high temperatures are remarkably reduced.
  • the degree of crystallinity is not less than 50% and the heat treatment is performed at 120:, the degree of change in the degree of relative crystallinity is small, and the solidification crystallization is performed. This is preferable for practical use, and according to the present invention, such a film or sheet can be provided.
  • the transparency of a film or sheet greatly depends on the smoothness of its surface, high transparency is required when it is required.
  • Press plate or cooling row New First we want to be as smooth as possible.
  • the surface of the film or sheet should be made concave and convex to enhance the transparency. It is possible to lower it. If the haze value of the film or sheet subjected to these treatments exceeds 20%, the advantage based on transparency will be lost. Therefore, the haze value of the transparent film and the sheet of the present invention is less than 20% when the preferable range of the transparency is specified. However, it is not practically desirable to maintain a haze of less than 20% even if the heat treatment is performed in the heat treatment of the present invention. And a seat can be provided.
  • the copolymerized polyester resin used in the present invention is satisfactorily applied within a range that does not impair the effects of the present invention, and other thermoplastic resins are used. If a small amount of fat is used as a supplement, or a known substance commonly added to thermoplastic resin, such as a stabilizer such as an ultraviolet ray absorbent, Antistatic agents, flame retardants, flame retardant aids, coloring agents such as dyes and pigments, lubricants, plasticizers, crystallization promoters, and inorganic fillers are combined. It is, of course, possible.
  • a highly crystalline transparent film or sheet made of a specific resin obtained by the present invention has the following excellent properties. It has the effect.
  • the resin has high heat resistance, and maintains a haze value of 20% or less even under a high temperature condition of about 120 t without a decrease in transparency.
  • the main characteristic value measurement conditions are as follows.
  • the value of the penetration was determined by 1 H-NMR measurement using deuterated trifluoroacetic acid as a solvent.
  • the film or sheet was cut out into a sample for DSC measurement, and the measurement was performed using a DSC device.
  • the calculation of the relative crystallinity (CR) is given by the following equation.
  • the measurement was performed based on
  • Dimethyl terephthalate 305.3 parts by weight, 27,2 parts by weight of 1,4-butanediol 26.2 parts by weight, paradensate glycol The quantity was charged into a reactor equipped with a stirrer and a distilling pipe together with a predetermined amount of the ester exchange catalyst, tetrabutyl titanate. After sufficient nitrogen replacement, the temperature was increased to 160 under normal pressure, and stirring was started. Furthermore, the temperature was gradually raised, and the by-product methanol was distilled off. When the temperature reached 240, the pressure in the reactor was gradually reduced, and stirring was continued for 3.0 hours at a pressure of 0.1 lto to obtain a solid viscosity of 0. Ninety-two copolymerized polyester resins were obtained.
  • polyester resin is pelletized and solid-phase polymerization is performed under a nitrogen stream to obtain a new solid-viscosity of 1.38.
  • ⁇ Polyester of the degree of polymerization was obtained. With respect to the obtained polyester, characteristic evaluations as described above were performed. Table 1 shows the results.
  • Dimethyl terephthalate and 1,4-butanediol are polymerized at the monomer-to-material ratio shown in Table 1 and polybutylene is polymerized. Telephthalate resin (PBT) was obtained. The obtained polyester was subjected to solid-phase polymerization in the same manner as in Production Example 1, and subsequently, its properties were evaluated. Table 1 shows the results.
  • Polyester G As for Polyester G, the film and sheet were melt-formed as in Example 1, and the film and sheet were written. After that, the subsequent processing was not possible.
  • Relative crystallinity (%) 27.1 29.3 29.1 26.3 Heat treatment temperature (100 Same as left Same as left Same as left

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Une pellicule ou feuille transparente en polyester ayant une excellente transparence, utile comme matériau d'emballage, a un degré relatif de cristallinité égale ou supérieur à 50 % et peut retenir une valeur de voile égale ou inférieure à 20 % même lorsqu'elle est thermiquement traitée à 120 °C. On la produit par moulage par fusion d'une résine de copolyester, dans laquelle 70 à 99 % molaires des unités répétitives comprennent des unités esters composées d'acide téréphtalique ou d'un dérivé de celui-ci capable de former des esters, ainsi que de 1,4-butanediol. En ce qui concerne la quantité de chaleur requise pour la cristallisation, la résine de copolyster satisfait les critères de la formule (I): ΔHc « 35.0 (J/g), dans laquelle ΔHc est une valeur absolue de la quantité de chaleur (J/g) requise pour une cristallisation à une température en réduction lorsque l'on refroidit une résine fondue à 240 °C à une vitesse de réduction de la température égale à -500 °C/min selon une analyse thermique différentielle. On forme une pellicule ou une feuille avec ladite résine de copolyester, on la refroidit rapidement afin de réduire son degré de cristallinité, puis on vieillit et traite thermiquement la pellicule ou la feuille ainsi obtenue.
PCT/JP1990/001569 1989-12-05 1990-12-04 Pellicule ou feuille transparente en polyester WO1991008103A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019910700813A KR920700894A (ko) 1989-12-05 1990-12-04 투명 폴리에스테르 필름 또는 시트 및 그 제조방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1/316083 1989-12-05
JP31608389 1989-12-05

Publications (1)

Publication Number Publication Date
WO1991008103A1 true WO1991008103A1 (fr) 1991-06-13

Family

ID=18073064

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1990/001569 WO1991008103A1 (fr) 1989-12-05 1990-12-04 Pellicule ou feuille transparente en polyester

Country Status (2)

Country Link
KR (1) KR920700894A (fr)
WO (1) WO1991008103A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4982778A (fr) * 1972-12-12 1974-08-09
JPS517079A (ja) * 1974-07-09 1976-01-21 Teijin Ltd Toomeiboriesuteruseikeihinno kaishitsuhoho
JPS56146723A (en) * 1980-04-16 1981-11-14 Kuraray Co Ltd Preparation of film
JPS61277422A (ja) * 1985-05-31 1986-12-08 Kuraray Co Ltd ポリエステルフイルムの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4982778A (fr) * 1972-12-12 1974-08-09
JPS517079A (ja) * 1974-07-09 1976-01-21 Teijin Ltd Toomeiboriesuteruseikeihinno kaishitsuhoho
JPS56146723A (en) * 1980-04-16 1981-11-14 Kuraray Co Ltd Preparation of film
JPS61277422A (ja) * 1985-05-31 1986-12-08 Kuraray Co Ltd ポリエステルフイルムの製造方法

Also Published As

Publication number Publication date
KR920700894A (ko) 1992-08-10

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