TWI634007B - Molded body and method of manufacturing same - Google Patents
Molded body and method of manufacturing same Download PDFInfo
- Publication number
- TWI634007B TWI634007B TW103139887A TW103139887A TWI634007B TW I634007 B TWI634007 B TW I634007B TW 103139887 A TW103139887 A TW 103139887A TW 103139887 A TW103139887 A TW 103139887A TW I634007 B TWI634007 B TW I634007B
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- Taiwan
- Prior art keywords
- layer
- sheet
- molded body
- melting point
- pbt
- Prior art date
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010449 novaculite Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000111 poly(butyric acid) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/027—Thermal properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/704—Crystalline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/003—Interior finishings
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Laminated Bodies (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
本發明課題在於提供含有耐熱性及透明性均優異之PBT的成形體。 An object of the present invention is to provide a molded body comprising PBT excellent in heat resistance and transparency.
本發明的成形體係由薄片獲得的成形體，該成形體係具有以聚對苯二甲酸丁二酯(以下稱「PBT」)為主成分的層(以下稱「A層」)、及以PBT以外的聚酯為主成分的層(以下稱「B層」)，該成形體中，A層係位於至少其中一表面，且，滿足以下的(1)及(2)：(1)成形體的A層之GTG分率為0.6以上且1以下；(2)成形體的B層之相對結晶化度為0%以上且5%以下。 In the molding system of the present invention, a molded article obtained from a sheet having a layer mainly composed of polybutylene terephthalate (hereinafter referred to as "PBT") (hereinafter referred to as "A layer") and other than PBT a layer mainly composed of a polyester (hereinafter referred to as "B layer"), wherein the layer A is located on at least one of the surfaces, and satisfies the following (1) and (2): (1) the formed body The GGC fraction of the layer A is 0.6 or more and 1 or less; and (2) the relative crystallization degree of the layer B of the molded body is 0% or more and 5% or less.
Description
本發明係關於透明性、耐熱性優異的成形體及其製造方法。 The present invention relates to a molded article excellent in transparency and heat resistance and a method for producing the same.
聚對苯二甲酸丁二酯(以下簡稱「PBT」)係常通用的工程塑膠之一，因其高結晶性而呈現優異的機械特性、電氣特性、耐藥性、耐熱性等，因而廣泛使用於各種電氣‧電子機器零件、汽車、列車、火車等車輛用內外裝零件、以及其他的一般工業製品製造用材料。又，非晶狀態透明PBT片，具有即便利用玻璃轉移溫度以上的熱處理施行結晶化處理，仍可維持透明性的特徵。著眼於此種PBT除透明性、源自結晶性的耐熱性之外，價格亦較低於其他的工程塑膠，藉由併用其他通用塑膠的聚對苯二甲酸乙二酯(以下簡稱「PET」)，針對食品用成形容器、飲料用杯蓋等要求透明性與耐熱性的容器實用化進行檢討。此種例子在專利文獻1、專利文獻2中有提案：將由PET與PBT摻合而成的薄片施行熱成形，而獲得的透明耐熱容器。又，專利文獻3、專利文獻4中亦有提及PBT與PET的積層薄片、以及由其構成的成形容器。 Polybutylene terephthalate (hereinafter referred to as "PBT") is one of the commonly used engineering plastics. It is widely used because of its high crystallinity and excellent mechanical properties, electrical properties, chemical resistance, heat resistance, etc. It is used in various electrical and electronic parts, automobiles, trains, trains and other vehicles for interior and exterior parts, as well as other general industrial products. Further, the amorphous transparent PBT sheet has a feature of maintaining transparency even when the crystallization treatment is performed by a heat treatment of a glass transition temperature or higher. Focusing on the transparency of this PBT, the heat resistance derived from crystallinity, the price is lower than that of other engineering plastics, and polyethylene terephthalate (hereinafter referred to as "PET") is used in combination with other general-purpose plastics. In consideration of the practical use of containers requiring transparency and heat resistance, such as food molded containers and beverage cup covers. In such an example, Patent Document 1 and Patent Document 2 propose a transparent heat-resistant container obtained by subjecting a sheet obtained by blending PET and PBT to thermoforming. Further, Patent Document 3 and Patent Document 4 also mention a laminated sheet of PBT and PET, and a molded container composed of the same.
專利文獻1：日本專利特開平4-212830號公報 Patent Document 1: Japanese Patent Laid-Open No. Hei 4-212830
專利文獻2：日本專利特開2004-197066號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2004-197066
專利文獻3：日本專利特開平3-189149號公報 Patent Document 3: Japanese Patent Laid-Open No. Hei 3-189149
專利文獻4：日本專利特開平4-070333號公報 Patent Document 4: Japanese Patent Laid-Open No. 4-070333
然而，專利文獻1、專利文獻2所記載的方法，因為與PET的摻合而導致結晶性降低，因而無法充分顯現出源自PBT原本具有結晶性的特性，就實用性層面而言會有耐熱性差的問題。另一方面，專利文獻3、專利文獻4所記載的方法亦非具有充分的耐熱性。 However, the methods described in Patent Document 1 and Patent Document 2 have a decrease in crystallinity due to blending with PET, and thus it is not possible to sufficiently exhibit characteristics inherent in crystallinity derived from PBT, and there is heat resistance in terms of practicality. Poor sex. On the other hand, the methods described in Patent Document 3 and Patent Document 4 do not have sufficient heat resistance.
本發明為解決上述課題，而具有下述構成。即如下述。 The present invention has the following configuration in order to solve the above problems. It is as follows.
1)一種成形體，係由薄片獲得的成形體，該成形體係具有以聚對苯二甲酸丁二酯(以下稱「PBT」)為主成分的層(以下稱「A層」)、及以PBT以外的聚酯為主成分的層(以下稱「B層」)，該成形體中，A層係位於至少其中一表面，且，滿足以下的(1)及(2)：(1)成形體的A層之GTG分率為0.6以上且1以下。 1) a molded body obtained from a sheet having a layer mainly composed of polybutylene terephthalate (hereinafter referred to as "PBT") (hereinafter referred to as "A layer"), and A layer containing a polyester other than PBT as a main component (hereinafter referred to as "B layer"), wherein the layer A is located on at least one of the surfaces, and satisfies the following (1) and (2): (1) forming The GTG fraction of the layer A of the body is 0.6 or more and 1 or less.
(2)成形體的B層之相對結晶化度為0%以上且5%以下。 (2) The relative crystallization degree of the layer B of the molded body is 0% or more and 5% or less.
2)如上述1)所記載的成形體，其中，成形體的B層熔點係較高於成形體的A層熔點；成形體的B層係冷結晶化溫度(Tc)與玻璃轉移溫度(Tg)之差(△Tcg)達35℃以上。 (2) The molded article according to the above 1), wherein the B layer melting point of the molded body is higher than the melting point of the A layer of the molded body; and the B layer of the molded body is a cold crystallization temperature (Tc) and a glass transition temperature (Tg) The difference (ΔTcg) is above 35 °C.
3)如上述1)或2)所記載的成形體，其中，成形體的B層係由以聚對苯二甲酸乙二酯(以下稱「PET」)為主成分的層構成。 The molded article according to the above-mentioned 1), wherein the B layer of the molded article is composed of a layer mainly composed of polyethylene terephthalate (hereinafter referred to as "PET").
4)如上述1)至3)中任一項所記載的成形體，其中，成形體係滿足以下的(1)及/或(2)：(1)成形體的100℃熱收縮率為0%以上且7%以下。 The molded article according to any one of the above-mentioned items 1 to 3, wherein the molding system satisfies the following (1) and/or (2): (1) the 100° C. heat shrinkage rate of the molded body is 0%. Above and below 7%.
(2)成形體的-20℃夏比衝擊強度為0.4MJ/m2以上。 (2) The molded article had a Charpy impact strength of -20 ° C of 0.4 MJ/m 2 or more.
5)如上述1)至4)中任一項所記載的成形體，其中，成形體的積層比率「A層的厚度合計」/「B層的厚度合計」係1/15~1/2之比率。 (5) The molded article according to any one of the above-mentioned items 1 to 4, wherein the laminate ratio of the molded article "total thickness of the layer A" / "total thickness of the layer B" is 1/15 to 1/2 ratio.
6)一種如上述1)至5)中任一項所記載的成形體之製造方法，係依序包括有：對薄片施行預熱的步驟(以下稱「預熱步驟」)、及對薄片施行成形的步驟(以下稱「成形步驟」)的成形體之製造方法，其中， (6) The method for producing a molded article according to any one of the above 1 to 5, comprising the step of preheating the sheet (hereinafter referred to as "preheating step"), and performing the sheeting. a method of producing a molded body of a step of molding (hereinafter referred to as "forming step"), wherein
該薄片係具有A層及B層，且該薄片中，A層係位於至少其中一表面；預熱步驟中，預熱結束時的薄片溫度係「薄片的A層熔點-20」℃以上、且「薄片的A層熔點+20」℃以下。 The sheet has an A layer and a B layer, and the A layer is located on at least one of the surfaces; and in the preheating step, the sheet temperature at the end of the preheating is "the melting point of the A layer of the sheet is -20" ° C or more, and "The melting point of layer A of the sheet is +20" °C or less.
7)如上述6)所記載的成形體之製造方法，其中，上述預熱步驟中，從薄片溫度成為「薄片的B層之Tc-30」℃時起，至預熱結束時為止的平均升溫速度係20℃/秒以上。 (7) The method for producing a molded article according to the above-mentioned item 6, wherein, in the preheating step, the average temperature rise from the time when the sheet temperature is "Tc-30" of the B layer of the sheet to the end of the preheating The speed is 20 ° C / sec or more.
藉由本發明可提供具有耐熱性、且透明性亦優異的成形體。又，本發明亦提供具有耐熱性、且透明性亦優異的成形體之製造方法。 According to the present invention, a molded article having heat resistance and excellent transparency can be provided. Moreover, the present invention also provides a method for producing a molded article having heat resistance and excellent transparency.
本發明所謂「成形體」係指蓋狀、盤子狀、杯狀等具有三維形狀的結構體。成形體的形狀係在三維形狀結構體之前提下，其餘並無特別的限定，較佳係可例如底面部具有多角形形狀的角形容器或圓筒型容器等，例如：盤子、杯、箱子及具有該等的蓋材形狀者。又，本發明成形體的形狀係如前述並無特別的限定，較佳係可例如商品展示包裝用的泡殼包裝等保形工具類等、飲料自動販賣機的顯示用瓶、其他各種包裝用成形體、及表面材等各種工業材料。 The "molded body" in the present invention refers to a structure having a three-dimensional shape such as a lid shape, a plate shape, or a cup shape. The shape of the molded body is raised before the three-dimensional shape structure, and the rest is not particularly limited. For example, it may preferably be an angular container or a cylindrical container having a polygonal shape on the bottom surface, such as a plate, a cup, a box, and the like. Those having the shape of the cover material. In addition, the shape of the molded article of the present invention is not particularly limited as described above, and is preferably, for example, a conformal tool such as a blister package for product display packaging, a display bottle for a beverage vending machine, and various other packaging materials. Various industrial materials such as molded bodies and surface materials.
而，本發明的成形體係由薄片獲得者。 However, the forming system of the present invention is obtained from a sheet.
再者，本發明的成形體係具有：以PBT為主成分的層(以下稱「A層」)、及以PBT以外的聚酯為主成分的層(以下稱「B層」)，且該成形體中，A層係位於至少其中一表面。此處所謂「以PBT為主成分的層」係指在A層的總成分100質量%中，PBT含有50.1質量%以上且100質量%以下。又，所謂「以PBT以外的聚酯為主成分的層」係指在B層的總成分100質量%中，PBT以外的特定聚酯含有50.1質量%以上且100質量%以下。即，當B層含有PBT以外的複數聚酯時，當B層著眼於某特定的1種聚酯時，該特定的1種聚酯在B層總成分100質量%中，含有50.1質量%以上且100質量%以下。另外，此處所謂「種類」係依照組成而決定。 In addition, the molding system of the present invention has a layer mainly composed of PBT (hereinafter referred to as "A layer") and a layer mainly composed of a polyester other than PBT (hereinafter referred to as "B layer"), and the molding is carried out. In the body, the A layer is located on at least one of the surfaces. Here, "a layer containing PBT as a main component" means that PBT is contained in an amount of 50.1% by mass or more and 100% by mass or less in 100% by mass of the total component of the layer A. In addition, the "polyester which is a main component of the polyester other than PBT" means that the specific polyester other than PBT contains 50.1% by mass or more and 100% by mass or less of 100% by mass of the total component of the B layer. In other words, when the B layer contains a plurality of polyesters other than PBT, when the B layer focuses on a specific one type of polyester, the specific one type of polyester contains 50.1% by mass or more based on 100% by mass of the total B component. And 100% by mass or less. In addition, the "type" here is determined according to the composition.
本發明中，所謂「PBT」係指相對於二羧酸成分合計100莫耳%，對酞酸成分含有80莫耳%以上且100莫耳%以下，且在二醇成分合計100莫耳%中，1,4-丁二醇成分含有80莫耳%以上且100莫耳%以下的聚酯。 In the present invention, "PBT" means 100 mol% based on the total amount of the dicarboxylic acid component, and 80 mol% or more and 100 mol% or less of the tannic acid component, and 100 mol% in total of the diol component. The 1,4-butanediol component contains 80 mol% or more and 100 mol% or less of a polyester.
能當作PBT中之共聚合成分用的二羧酸成分，係可例 如：異酞酸成分、鄰酞酸成分、萘二羧酸成分、二苯基羧酸成分、二苯基磺二羧酸成分、二苯氧基乙烷二羧酸成分、5-間苯二甲酸磺酸鈉成分、酞酸等芳香族二羧酸成分；草酸成分、琥珀酸成分、花生酸成分、己二酸成分、癸二酸成分、二聚酸成分、十二烷二酮酸成分、順丁烯二酸成分、反丁烯二酸成分等脂肪族二羧酸成分；環己烷二羧酸成分等脂肪族二羧酸成分；偏苯三酸成分、及均苯四甲酸成分等多官能基酸成分等。 A dicarboxylic acid component which can be used as a copolymerization component in PBT Such as: isodecanoic acid component, o-nonanoic acid component, naphthalene dicarboxylic acid component, diphenylcarboxylic acid component, diphenylsulfonic acid dicarboxylic acid component, diphenoxyethane dicarboxylic acid component, 5-isophthalic acid An aromatic dicarboxylic acid component such as sodium formate sulfonate or citric acid; an oxalic acid component, a succinic acid component, an arachidic acid component, an adipic acid component, a sebacic acid component, a dimer acid component, a dodecanedione acid component, An aliphatic dicarboxylic acid component such as a maleic acid component or a fumaric acid component; an aliphatic dicarboxylic acid component such as a cyclohexane dicarboxylic acid component; a trimellitic acid component, and a pyromellitic acid component; Functional acid component and the like.
能當作PBT中的共聚合成分用之二醇成分，係可例如：乙二醇成分、丙二醇成分、丁二醇成分、戊二醇成分、己二醇成分、新戊二醇成分及三乙二醇成分等脂肪族二醇成分；雙酚A成分、雙酚S成分等芳香族二醇成分；二乙二醇成分、及聚伸丁二醇成分等。 The diol component which can be used as a copolymerization component in PBT can be, for example, an ethylene glycol component, a propylene glycol component, a butanediol component, a pentanediol component, a hexanediol component, a neopentyl glycol component, and a triethyl group. An aliphatic diol component such as a diol component; an aromatic diol component such as a bisphenol A component or a bisphenol S component; a diethylene glycol component; and a polybutanediol component.
再者，PBT中亦可複數含有該等二羧酸成分及/或二醇成分。 Further, the PBT may contain the dicarboxylic acid component and/or the diol component in plural.
該等之中若考慮兼顧耐熱性與成形性，A層主成分的PBT較佳係以下(A)~(D)中之任一者：(A)不含共聚合成分的PBT同元聚合物；(B)當共聚合成分僅為二羧酸成分的情況，在二羧酸成分全體100莫耳%中，共聚合成分超過0莫耳%且20莫耳%以下的PBT；(C)當共聚合成分僅為二醇成分的情況，在二醇成分全體100莫耳%中，共聚合成分超過0莫耳%且20莫耳%以下的PBT；(D)當共聚合成分係二羧酸成分與二醇成分雙方均含有的情況，相對於二羧酸成分合計100莫耳%與二醇成分合計100莫耳%的總和200莫耳%，共聚合成分合計超過0莫耳%且20莫耳%以下的PBT。 In consideration of heat resistance and moldability, the PBT of the main component of the A layer is preferably any of the following (A) to (D): (A) PBT homopolymer having no copolymerization component (B) When the copolymerization component is only a dicarboxylic acid component, in a total of 100 mol% of the dicarboxylic acid component, the copolymerization component exceeds 0 mol% and 20 mol% or less of PBT; When the copolymerization component is only a diol component, the copolymerization component exceeds 0 mol% and 20 mol% or less of PBT in 100 mol% of the total diol component; (D) when the copolymer component is a dicarboxylic acid In the case where both the component and the diol component are contained, the total amount of 100 mol% of the dicarboxylic acid component and the total of 100 mol% of the diol component are 200 mol%, and the total amount of the copolymer component exceeds 0 mol% and 20 mol. PBT below ear %.
藉由A層主成分係使用(A)~(D)中任一PBT，而保持PBT 的秩序性，所以可輕易地將後述成形體的A層之GTG分率設為0.6以上且1以下。 Maintain PBT by using any PBT in (A)~(D) by the A-layer principal component system Since the order of the order is good, the GTG fraction of the layer A of the molded article described later can be easily made 0.6 or more and 1 or less.
再者，本發明的A層係在以PBT為主成分之前提下，尚亦可含有其他的熱可塑性樹脂，其他的熱可塑性樹脂係可適當地選擇PBT以外的聚酯。而，PBT以外的聚酯中，較佳為可與PBT完全相溶、或熔點較低於PBT、或熔點未定的聚酯。此處所謂「相溶」係指當施行PBT與其他聚酯的熔融混合體之DSC測定時，僅具有1個熔點者。熔融混合體的熔點、與該聚酯的單體熔點及其有無，係可利用與後述成形體的熔點測定條件同樣方法進行確認。 Further, the layer A of the present invention may be removed before PBT is used as a main component, and other thermoplastic resins may be contained. Other thermoplastic resins may be selected from polyesters other than PBT. Further, among the polyesters other than PBT, a polyester which is completely compatible with PBT or has a lower melting point than PBT or an undetermined melting point is preferable. Here, "compatibility" means a case where only one melting point is obtained when DSC measurement of a molten mixture of PBT and other polyesters is carried out. The melting point of the molten mixture and the melting point of the monomer of the polyester and the presence or absence thereof can be confirmed by the same method as the melting point measurement conditions of the molded body to be described later.
A層中所含PBT以外的聚酯較佳係使用例如，從聚對苯二甲酸乙二酯、聚對苯二甲酸/間苯二甲酸乙二酯、聚對苯二甲酸/間苯二甲酸丙二酯、及聚對苯二甲酸(乙二酯/伸環己基二甲酯)所構成群組中選擇至少1者。 The polyester other than the PBT contained in the layer A is preferably used, for example, from polyethylene terephthalate, polyethylene terephthalate/ethylene isophthalate, polyterephthalic acid/isophthalic acid. At least one of the group consisting of propylene glycol and polyethylene terephthalate (ethylenediester/cyclohexyl dimethyl ester) is selected.
PBT以外的其他熱可塑性樹脂在A層中的含有量，相對於A層總成分100質量%，較佳係0質量%以上且49.9%質量%以下。 The content of the thermoplastic resin other than PBT in the layer A is preferably 0% by mass or more and 49.9% by mass or less based on 100% by mass of the total layer A component.
本發明中，所謂「B層主成分的PBT以外之聚酯」係指構成該聚合物的重複單元中含有酯鍵結的聚合物，除前述PBT外的聚合物。其中，較佳係選擇PBT以外的脂肪族聚酯、芳香族聚酯。 In the present invention, the "polyester other than PBT having a main component of the B layer" means a polymer containing an ester bond in a repeating unit constituting the polymer, and a polymer other than the PBT. Among them, aliphatic polyesters and aromatic polyesters other than PBT are preferably selected.
PBT以外的聚酯之脂肪族聚酯，係可例如：由羥羧酸、內酯構成的聚合體；二醇與二羧酸的縮聚體；及該等的共聚合體。 The aliphatic polyester of the polyester other than PBT may, for example, be a polymer composed of a hydroxycarboxylic acid or a lactone; a polycondensate of a diol and a dicarboxylic acid; and such a copolymer.
由羥羧酸、內酯構成的聚合體係可例如：聚二醇酸、聚-L-乳酸、聚-D-乳酸、聚丙酸、聚羥酪酸、聚己內酯等。 The polymerization system composed of a hydroxycarboxylic acid or a lactone may be, for example, polyglycolic acid, poly-L-lactic acid, poly-D-lactic acid, polypropionic acid, polyhydroxybutyric acid, polycaprolactone or the like.
二醇與二羧酸的縮聚體係可例如：聚琥珀酸丁烯酯、聚(琥珀酸丁烯酯/己二酸二丁酯)、聚(己二酸二丁酯/對苯二甲酸丁二 酯)、聚(3-羥丁酸酯/3-羥己酸酯)等。 The polycondensation system of the diol and the dicarboxylic acid may be, for example, polybutyric acid succinate, poly(butenoic acid succinate/dibutyl adipate), poly(dibutyl adipate/butylene terephthalate). Ester), poly(3-hydroxybutyrate/3-hydroxyhexanoate), and the like.
該等之中，就從源自生質、具有生物分解性，且可較廉價取得的觀點，當PBT以外的聚酯係脂肪族聚酯的情況，較佳係聚-L-乳酸或其共聚合聚酯。 Among these, in the case of a polyester-based aliphatic polyester other than PBT, from the viewpoint of being derived from biomass, having biodegradability, and being inexpensively available, it is preferred to use poly-L-lactic acid or a total thereof. Polymerized polyester.
PBT以外的聚酯之芳香族聚酯係可例如由從對酞酸、2,6-萘二羧酸、異酞酸等之中選擇至少1種酸成分，與從乙二醇、丙二醇、丁二醇、己二醇或聚乙二醇、聚伸丁二醇等聚伸烷基二醇等等之中選擇至少1種二醇成分進行縮聚而獲得者，具體係可例如：聚對苯二甲酸丙二酯(PPT)、聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸己二酯(PHT)、聚萘二甲酸乙二酯(PBN)、聚萘二甲酸丁二酯(PBN)、聚(1,4-伸環己基二亞甲基對酞酸酯)等，此外尚可例如：聚間苯二甲酸/對苯二甲酸乙二酯(PET/I)、聚(乙烯/1,4-伸環己基二亞甲基)等共聚合聚酯等。 The aromatic polyester of the polyester other than PBT may, for example, be selected from at least one acid component selected from the group consisting of citric acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, and the like, and ethylene glycol, propylene glycol, and butyl. Among the diol, hexanediol or polyethylene glycol, polyalkylene glycol such as polybutanediol, and the like, at least one diol component is selected for polycondensation, and specifically, for example, polyparaphenylene Propylenedicarboxylate (PPT), polyethylene terephthalate (PET), poly(trimethylene terephthalate) (PHT), polyethylene naphthalate (PBN), polybutylene naphthalate (PBN), poly(1,4-cyclohexyldimethylene terephthalate), etc., in addition, for example, polyisophthalic acid/ethylene terephthalate (PET/I), poly( A copolymerized polyester such as ethylene/1,4-cyclohexyldimethylene).
該等之中，若考慮能較廉價取得、且A層與B層之層間密接性、及在薄片製膜‧成形中產生的屑等之再利用觀點，PBT以外的聚酯之芳香族聚酯較佳係與PBT間之相溶性高的PET或其共聚合聚酯。 Among these, aromatic polyesters of polyesters other than PBT are considered in view of the re-use viewpoints such as the adhesion between the layers of the A layer and the B layer and the chips generated during the film formation and the formation of the film. It is preferably a PET having high compatibility with PBT or a copolymerized polyester thereof.
本發明成形體的B層中，PBT以外的聚酯較佳係從如上述脂肪族聚酯或芳香族聚酯等聚酯之中選擇至少1種聚酯。又，本發明的B層係含有PBT以外的1種聚酯為主成分，且亦可更進一步含有其他的聚酯。又，本發明的B層係在以PBT以外的聚酯為主成分之前提下，亦可含有其他的熱可塑性樹脂。 In the layer B of the molded article of the present invention, it is preferred that the polyester other than PBT is at least one selected from the group consisting of polyesters such as the above-mentioned aliphatic polyester or aromatic polyester. Further, the B layer of the present invention contains one type of polyester other than PBT as a main component, and may further contain other polyesters. Further, the layer B of the present invention may be removed before the polyester other than PBT is used as a main component, and may contain other thermoplastic resin.
本發明的成形體重點在於：成形體的A層之GTG分率係0.6以上且1以下。其中，G及T係指A層中的PBT之特定立體結構，「G」係間扭結構(gauche structure)的簡稱，「T」係反式結構(trans structure)的簡稱。藉由將GTG分率設為0.6以上且1以下，而可成為具有可實用耐熱性的成形體。成形體的A層之GTG分率較佳係0.65以上、更佳係0.7以上。又，GTG分率較佳係0.9以下、更佳係0.8以下。 The molded article of the present invention is mainly characterized in that the GSG fraction of the layer A of the molded body is 0.6 or more and 1 or less. Among them, G and T refer to the specific three-dimensional structure of PBT in the A layer, the abbreviation of the "G" system gauche structure, and the "T" system trans structure (trans Abbreviation for structure). By setting the GTG fraction to 0.6 or more and 1 or less, it is possible to obtain a molded body having practical heat resistance. The GTG fraction of the layer A of the molded body is preferably 0.65 or more, more preferably 0.7 or more. Further, the GTG fraction is preferably 0.9 or less, more preferably 0.8 or less.
為將成形體的A層之GTG分率設為0.6以上且1以下，可例如後述，A層主成分的PBT係使用前述較佳態樣PBT的方法；或在依序包括有預熱步驟與成形步驟的成形體之製造方法中，將預熱結束時的薄片溫度設為「薄片的A層熔點-20」℃以上、且「薄片的A層熔點+20」℃以下的方法。 In order to set the GTG fraction of the A layer of the molded body to 0.6 or more and 1 or less, for example, the PBT of the main component of the A layer may be a method of using the PBT of the preferred aspect described above; or the preheating step may be included in the order. In the method for producing a molded article in the molding step, the sheet temperature at the end of the preheating is a method of "the melting point of the sheet A layer is -20 ° C" or more, and the "sheet layer A layer melting point is +20" ° C or less.
本發明成形體中，成形體的B層之相對結晶化度係0%以上且5%以下之事，就對成形體能賦予透明性而言係屬重要。成形體的B層之相對結晶化度係可利用後述DSC進行測定。已知多數聚酯會伴隨從非晶狀態的熱結晶化，形成通稱「球晶」的球狀結構三維結晶，隨結晶化的進行，若該球晶尺寸到達可見光波長，會有引發光散射、喪失透明性的問題。例如具有立體錯合物(stereo complex)結晶的特殊聚乳酸，不會因從非晶狀態的結晶化而形成球晶之聚酯、或含有能使球晶尺寸微細化至可見光波長以下的結晶核劑之聚酯，雖可解決上述因球晶造成的透明性降低問題，但因為一般該等聚酯、結晶核劑係屬於高價位，因而就原料成本而言非屬較佳。就從此種理由，當B層主成分的聚酯係使用聚乳酸、PET等具有形成可見光以上尺寸球晶之性質的聚酯時，相對結晶化度設定在0%以上且5%以下則屬重要。成形體的B層之相對結晶化度更佳係0%以上且4%以下、特佳係0%以上且3%以下。 In the molded article of the present invention, the relative crystallization degree of the layer B of the molded article is 0% or more and 5% or less, which is important for imparting transparency to the molded body. The relative degree of crystallinity of the layer B of the molded body can be measured by DSC described later. It is known that most polyesters undergo thermal crystallization from an amorphous state to form a three-dimensional crystal of a spherical structure called "spherulites". As the crystallization progresses, if the spherulite size reaches the visible wavelength, light scattering occurs. Loss of transparency. For example, a special polylactic acid having a stereo complex crystal does not form a spherulite polyester due to crystallization from an amorphous state, or a crystal nucleus capable of refining the spherulite size to a wavelength below visible light. Although the polyester of the agent can solve the above problem of lowering the transparency due to spherulites, since these polyesters and crystal nucleating agents are generally high in price, they are not preferable in terms of raw material cost. For this reason, when a polyester having a property of forming a spherulite having a size of visible light or more, such as polylactic acid or PET, is used as the polyester of the main component of the layer B, it is important to set the degree of crystallization to 0% or more and 5% or less. . The relative crystallization degree of the layer B of the molded body is more preferably 0% or more and 4% or less, and particularly preferably 0% or more and 3% or less.
為能將成形體的B層之相對結晶化度設為0%以上且5% 以下，可例如後述，使成形體的B層熔點較高於成形體的A層熔點，更針對成形體的B層，將冷結晶化溫度(Tc)與玻璃轉移溫度(Tg)之差(△Tcg)設為35℃以上的方法；或在依序包括有預熱步驟與成形步驟的成形體之製造方法中，將預熱結束時的薄片溫度設為「薄片的A層熔點-20」℃以上、且「薄片的A層熔點+20」℃以下的方法。 In order to set the relative crystallization degree of the B layer of the formed body to 0% or more and 5% Hereinafter, for example, the melting point of the B layer of the molded body is higher than the melting point of the layer A of the molded body, and the difference between the cold crystallization temperature (Tc) and the glass transition temperature (Tg) is further made for the B layer of the molded body. Tcg) is a method of 35 ° C or more; or in the manufacturing method of the molded body including the preheating step and the molding step in sequence, the sheet temperature at the end of the preheating is set to "the melting point of the layer A of the sheet -20" ° C The above method and "the melting point of the A layer of the sheet is +20" ° C or less.
本發明的成形體中，當成形體的B層熔點較高於成形體的A層熔點時，成形體的B層之冷結晶化溫度(Tc)與玻璃轉移溫度(Tg)差(△Tcg)較佳係35℃以上。若成形體的B層熔點較高於成形體的A層熔點，且成形體的B層之冷結晶化溫度(Tc)與玻璃轉移溫度(Tg)差(△Tcg)達35℃以上，而可輕易地將成形體的B層之相對結晶化度控制在0%以上且5%以下，結果可輕易地對本發明成形體賦予透明性。成形體的B層之△Tcg更佳係達55℃以上、特佳係65℃。成形體的B層之△Tcg，就從抑制B層結晶化的觀點雖越大越好，但若觸及實質完全抑制成形中結晶化的觀點，上限可認為係110℃。 In the molded article of the present invention, when the melting point of the B layer of the molded body is higher than the melting point of the A layer of the molded body, the difference between the cold crystallization temperature (Tc) of the B layer of the molded body and the glass transition temperature (Tg) (ΔTcg) Good system is above 35 °C. If the melting point of the B layer of the shaped body is higher than the melting point of the A layer of the shaped body, and the difference between the cold crystallization temperature (Tc) of the B layer of the shaped body and the glass transition temperature (Tg) (ΔTcg) is 35 ° C or more, The relative crystallization degree of the layer B of the molded article is easily controlled to 0% or more and 5% or less, and as a result, transparency can be easily imparted to the molded article of the present invention. The ΔTcg of the layer B of the formed body is more preferably 55 ° C or more, and particularly preferably 65 ° C. The ΔTcg of the B layer of the molded article is preferably as large as possible from the viewpoint of suppressing the crystallization of the B layer. However, the upper limit is considered to be 110 ° C from the viewpoint of completely inhibiting crystallization during molding.
另外，將成形體的B層熔點較高於成形體的A層熔點，且將成形體的B層之△Tcg設為35℃以上的方法，可例如：B層主成分係選擇適當聚酯(適當組成與適當聚合度)的方法；或使B層中含有交聯劑、非晶性聚酯的方法等。若觸及成本觀點，則B層主成分的聚酯係選擇聚對苯二甲酸乙二酯或其共聚合聚酯，較佳係將該等聚酯單體在DSC測定中，△Tcg達35℃以上者選用為B層的主成分。 Further, a method in which the melting point of the layer B of the molded body is higher than the melting point of the layer A of the molded body and the ΔTcg of the layer B of the formed body is 35° C. or higher can be selected, for example, from the main component of the layer B to select an appropriate polyester ( A method of appropriately constituting a suitable degree of polymerization; or a method of including a crosslinking agent, an amorphous polyester in the layer B, or the like. If the viewpoint of cost is taken into consideration, the polyester of the main component of the B layer is selected from polyethylene terephthalate or a copolymerized polyester thereof, and it is preferred that the polyester monomers have a ΔTcg of 35 ° C in the DSC measurement. The above is selected as the main component of the B layer.
其中，成形體的A層熔點、成形體的B層熔點、冷結晶化溫度Tc、玻璃轉移溫度Tg，係指針對成形體使用DSC測定獲得的值。另外，相關薄片的A層熔點、玻璃轉移溫度Tg、薄片的B層熔點、冷結晶化溫度Tc、玻璃轉移溫度Tg亦同樣地，係指針對薄片使用DSC 測定獲得的值。該等測定係根據測定方法項中所記載方法實施。 Here, the melting point of the layer A of the molded body, the melting point of the layer B of the molded body, the cold crystallization temperature Tc, and the glass transition temperature Tg are values obtained by DSC measurement of the molded article. Further, the melting point of the layer A of the relevant sheet, the glass transition temperature Tg, the melting point of the layer B of the sheet, the cold crystallization temperature Tc, and the glass transition temperature Tg are also the same as the use of the DSC for the sheet. The value obtained was determined. These measurements were carried out according to the methods described in the Test Methods section.
本發明成形體的重點在於：具有以PBT為主成分的A層、及以PBT以外的聚酯為主成分的B層，且A層係位於至少其中一表面。所以，成形體的構成係只要A層位於至少其中一者的表面即可，可設定為例如：A層/B層的雙層構成；A層/B層/A層的2種3層構成；A層/B層/A層/B層、A層/B層/A層/B層/A層之類的多層構成。但，若考慮製造成本及成形體保管時的捲曲等問題，成形體的構成較佳係A層/B層/A層的2種3層構成。 The molded article of the present invention is mainly characterized in that it has an A layer mainly composed of PBT and a B layer mainly composed of a polyester other than PBT, and the A layer is located on at least one of the surfaces. Therefore, the configuration of the molded body may be such that, for example, the layer A is located on at least one of the surfaces of the layer A, for example, a two-layer structure of the A layer/B layer; and two three-layer structures of the A layer/B layer/A layer; A multilayer structure such as A layer/B layer/A layer/B layer, A layer/B layer/A layer/B layer/A layer. However, in consideration of problems such as the production cost and the curl during storage of the molded body, the structure of the molded body is preferably two types of three layers of the A layer, the B layer, and the A layer.
本發明的成形體係由薄片獲得的成形體，因而成為本發明成形體材料的薄片較佳係亦是具有：以PBT為主成分的A層、及以PBT以外的聚酯為主成分之B層，且A層係位於至少其中一者的表面。所以，較佳的薄片構成係只要A層位於至少其中一表面即可，可為例如：A層/B層的雙層構成；A層/B層/A層的2種3層構成；A層/B層/A層/B層、A層/B層/A層/B層/A層之類的多層構成。但，若考慮製造成本及薄片保管時的捲曲等問題，薄片的構成較佳係A層/B層/A層的2種3層構成。 In the molding system of the present invention, the molded article obtained from the sheet is preferably a sheet having the PBT as a main component and a layer B containing a polyester other than PBT as a main component. And the A layer is located on the surface of at least one of them. Therefore, a preferred sheet structure is as long as the layer A is located on at least one of the surfaces, and may be, for example, a two-layer structure of the A layer/B layer; two types of three layers of the A layer/B layer/A layer; Multilayer structure such as /B layer/A layer/B layer, A layer/B layer/A layer/B layer/A layer. However, in consideration of problems such as manufacturing cost and curl during storage of the sheet, the configuration of the sheet is preferably two types of three layers of the A layer/B layer/A layer.
成為本發明成形體材料的薄片厚度並無特別的限制，較佳係50μm以上且2000μm以下、更佳係100~1000μm、特佳係150~500μm。 The thickness of the sheet to be a molded article of the present invention is not particularly limited, but is preferably 50 μm or more and 2000 μm or less, more preferably 100 to 1000 μm, and particularly preferably 150 to 500 μm.
成為本發明成形體材料的薄片，為能降低該薄片的製造成本，較佳係相對於薄片全體，含有再利用(回收)原料5~80%。此處所謂「再利用(回收)原料」係指回收經使用完畢薄片、因某種理由無法成為製品的薄片，再細小裁斷該等形成碎片狀，並再度使用為B層的原料。 In order to reduce the manufacturing cost of the sheet, the sheet which is a molded material of the present invention preferably contains 5 to 80% of the recycled (recovered) raw material with respect to the entire sheet. Here, the term "recycling (recycling) raw material" refers to a sheet in which a used sheet is not recovered and which cannot be made into a product for some reason, and is finely cut into pieces, and is again used as a material of the layer B.
再者，相關成為本發明成形體材料的薄片及成形體，就 積層比率並無特別的限定，若考慮薄片的成形性，則「A層的厚度合計」/「B層的厚度合計」較佳係1/15~1/2的比率、更佳係1/10~1/2.5、特佳係1/8~1/3。此處所謂「A層的厚度合計」係當A層僅存在1層的情況，係指該A層的厚度，而當A層存在有2層以上的情況，係指該A層的厚度合計。「B層的厚度合計」亦與A層同樣的涵義。 Further, in relation to the sheet and the molded body which are the molded body materials of the present invention, The laminate ratio is not particularly limited, and in consideration of the formability of the sheet, the "total thickness of the A layer" / "the total thickness of the layer B" is preferably a ratio of 1/15 to 1/2, more preferably 1/10. ~1/2.5, especially good 1/8~1/3. Here, "the total thickness of the A layer" means that the thickness of the A layer is only one layer of the A layer, and the thickness of the A layer is the total thickness of the A layer when there are two or more layers of the A layer. The "total thickness of layer B" also has the same meaning as layer A.
成為本發明成形體材料的薄片，若考慮成形性，則較佳係無配向。此處所謂「無配向」係指依照後述方法測定的面配向係數在0.00~0.05範圍內。因為面配向係數越小則成形性越良好，所以成為本發明成形體材料的薄片之面配向係數，更佳係0.00~0.03、特佳係0.00~0.01。 When the sheet which is a molded material of the present invention is considered to have moldability, it is preferably unaligned. Here, "non-alignment" means that the surface alignment coefficient measured according to the method described later is in the range of 0.00 to 0.05. The smaller the surface alignment coefficient, the better the moldability. Therefore, the surface alignment coefficient of the sheet of the molded article of the present invention is more preferably 0.00 to 0.03 and particularly preferably 0.00 to 0.01.
再者，當本發明的成形體使用為透明容器時，霧度較佳係5%以下。霧度係在與利用表面粗糙、或成形體中所存在的孔隙與球晶，而抑制光穿透情況間具有密接關係，其中霧度受B層結晶化造成的影響較大，藉由將成形體的B層之相對結晶化度設定在5%以下，可將成形體的霧度設定在5%以內。霧度更佳係4%以下、特佳係3%以下。另一方面，若除結晶性以外，尚考慮所存在抑制光穿透的要因，則霧度下限係0.1%。 Further, when the molded article of the present invention is used as a transparent container, the haze is preferably 5% or less. The haze is in close contact with the pores and spherulites present in the formed body, or the spherulites in the formed body, and the light penetration is inhibited, wherein the haze is greatly affected by the crystallization of the B layer, by forming The relative crystallization degree of the B layer of the body is set to 5% or less, and the haze of the molded body can be set to 5% or less. The haze is preferably 4% or less, and particularly preferably 3% or less. On the other hand, in addition to the crystallinity, in consideration of the cause of suppressing light penetration, the lower limit of haze is 0.1%.
本發明的成形體係當使用於進行微波爐加熱的容器等之時，100℃熱收縮率較佳係0%以上且7%以下、更佳係0%以上且5%以下。藉由將100℃熱收縮率設定在該範圍內，而可獲得微波爐加熱等之時的變形較小之成形體，故屬較佳。此處所謂「成形體的熱收縮率」係設為利用後述方法獲得的熱收縮率。為能將成形體的100℃熱收縮率設定為0%以上且7%以下，可例如：A層主成分的PBT係使用前述較佳態樣的PBT之方法；或在依序包括有預熱步驟與成形步驟的成形體 之製造方法中，將預熱結束時的薄片溫度設定為「薄片的A層熔點-20」℃以上、且「薄片的A層熔點+20」℃以下的方法。 When the molding system of the present invention is used in a container for heating a microwave oven or the like, the heat shrinkage ratio at 100 ° C is preferably 0% or more and 7% or less, more preferably 0% or more and 5% or less. By setting the heat shrinkage ratio at 100 ° C within this range, a molded article having a small deformation at the time of heating in a microwave oven or the like can be obtained, which is preferable. Here, the "thermal shrinkage rate of the molded body" is a heat shrinkage ratio obtained by the method described later. In order to set the heat shrinkage rate of the molded body at 100 ° C to 0% or more and 7% or less, for example, the PBT of the main component of the A layer may be a method of using the PBT of the above preferred embodiment; or the preheating may be included in the order. Step and forming step forming body In the production method, the sheet temperature at the end of the preheating is set to "the melting point of the sheet A layer -20" ° C or more, and the "sheet layer A layer melting point + 20" ° C or less.
再者，當本發明的成形體係使用於冷凍容器等之時，-20℃夏比衝擊強度較佳係0.4MJ/m2以上、更佳係0.5MJ/m2以上、特佳係0.7MJ/m2以上。藉由將-20℃夏比衝擊強度設定在該範圍內，當使用為冷凍容器等之時，在進行冷凍運搬時不易導致容器發生龜裂等破損情形，故屬較佳。成形體的-20℃夏比衝擊強度，就從上述觀點雖越高越佳，但就從連續成形時，在成形後的成形體部分之切斷性觀點，可認為上限係2.0MJ/m2。為將成形體的-20℃夏比衝擊強度設定在0.4MJ/m2以上，可例如：A層主成分的PBT係使用前述較佳態樣的PBT之方法；或在依序包括有預熱步驟與成形步驟的成形體之製造方法中，將預熱結束時的薄片溫度設定為「薄片的A層熔點-20」℃以上、且「薄片的A層熔點+20」℃以下的方法。 Further, when the molding system of the present invention is used in a refrigerating container or the like, the Charpy impact strength at -20 ° C is preferably 0.4 MJ/m 2 or more, more preferably 0.5 MJ/m 2 or more, and particularly preferably 0.7 MJ/ m 2 or more. When the Charpy impact strength at -20 ° C is set within this range, when it is used as a refrigerated container or the like, it is preferable that the container is less likely to cause cracks such as cracks during the freezing and transporting. The Charpy impact strength at -20 ° C of the molded article is preferably as high as possible from the above viewpoint. However, from the viewpoint of the cutting property of the molded body after molding, the upper limit is 2.0 MJ/m 2 . . In order to set the Charpy impact strength of the molded body at -20 ° C to 0.4 MJ/m 2 or more, for example, the PBT of the main component of the A layer may be a method of using the PBT of the above preferred embodiment; or the preheating may be included in the order. In the method of producing a molded body in the step and the forming step, the sheet temperature at the end of the preheating is set to "the melting point of the sheet A layer -20" ° C or more, and the "sheet layer A layer melting point + 20" ° C or less.
本發明的成形體之製造方法並無特別的限定，較佳係依序包括有：對薄片施行預熱的步驟(以下稱「預熱步驟」)、及將薄片施行成形的步驟(以下稱「成形步驟」)的成形體之製造方法。依此依序包括有預熱步驟與成形步驟的成形體之製造方法，以下稱為「熱成形方法」。此種製造方法係可例如：真空成形法、真空壓製成形法、塞助成形法、筆直成形法(straight forming method)、自由抽拉成形法(free drawing forming method)、塞環成形法(plug and ring forming method)、骨架成形法(skeleton forming method)等各種成形法。 The method for producing the molded article of the present invention is not particularly limited, and preferably includes a step of preheating the sheet (hereinafter referred to as "preheating step") and a step of molding the sheet (hereinafter referred to as " A method of producing a molded body of the molding step "). The method for producing a molded body having a preheating step and a forming step in this order is hereinafter referred to as "thermoforming method". Such a manufacturing method can be, for example, a vacuum forming method, a vacuum press forming method, a plug assist forming method, a straight forming method, a free drawing forming method, and a plug forming method. Various forming methods such as a ring forming method and a skeleton forming method.
上述各種成形法中，預熱步驟係有間接加熱方式與熱板直接加熱方式。間接加熱方式係利用在遠離薄片的位置處所設置加熱裝置，對薄片施行預熱的方式。熱板直接加熱方式係藉由使薄片與熱 板相接觸而對薄片施行預熱的方式。本發明成形體之製造方法中，預熱步驟較佳亦係使用間接加熱方式或熱板直接加熱方式中之任一方法，更佳係間接加熱方式。 In the above various forming methods, the preheating step is an indirect heating method and a hot plate direct heating method. The indirect heating method uses a heating device provided at a position away from the sheet to preheat the sheet. The hot plate is heated directly by making the sheet and heat The manner in which the sheets are brought into contact to preheat the sheets. In the method for producing a shaped body of the present invention, the preheating step is preferably either an indirect heating method or a hot plate direct heating method, and more preferably an indirect heating method.
本發明成形體之製造方法中，較佳係薄片具有A層及B層，該薄片中，A層係位於至少其中一表面，預熱步驟中當預熱結束時的薄片溫度係「薄片的A層熔點-20」℃以上、且「薄片的A層熔點+20」℃以下。另外，此處所謂「薄片溫度」係指間接加熱方式中，利用在距薄片一定距離處所設置紅外線放射溫度計等溫度檢測機，進行檢測的薄片表面值。又，成形體製造中，通常較佳係預先決定利用預熱應到達的薄片溫度，在該預熱中，利用上述溫度檢測機即時測定薄片溫度的推移，在薄片溫度到達上述應到達的薄片溫度時點，結束預熱步驟，且在2秒以內移往成形步驟。本發明成形體之製造方法中，將上述應到達的薄片溫度設為預熱結束時的薄片溫度。 In the method for producing a molded article of the present invention, it is preferred that the sheet has an A layer and a B layer, wherein the A layer is located on at least one of the surfaces, and the sheet temperature at the end of the preheating in the preheating step is "a sheet A". The melting point of the layer is -20" ° C or more, and "the melting point of the layer A of the sheet is +20" ° C or less. In addition, the term "sheet temperature" as used herein refers to a sheet surface value detected by a temperature detector such as an infrared radiation thermometer provided at a predetermined distance from the sheet in the indirect heating method. Further, in the production of a molded article, it is generally preferred to determine the temperature of the sheet to be reached by the preheating in advance, and in the preheating, the temperature of the sheet is immediately measured by the temperature detector, and the sheet temperature reaches the sheet temperature to be reached. At the time point, the preheating step is ended and moved to the forming step within 2 seconds. In the method for producing a molded article of the present invention, the sheet temperature to be reached is set to the sheet temperature at the end of the preheating.
本發明中，藉由將預熱步驟中當預熱結束時的薄片溫度，設為「薄片的A層熔點-20」℃以上、且「薄片的A層熔點+20」℃以下，而使成形體的A層之GTG分率成為0.6以上且1以下。理由可認為藉由提升A層的PBT之分子運動性，且進行立體結構的形成，而成為具有即便高溫下仍具剛性之耐熱性的成形體。因為GTG分率成為0.6以上且1以下的結構形成，係與分子運動性間具有密接關係，因而直到PBT的結晶熔解正式進行之「薄片的A層熔點+20」℃為止前，預熱結束時的溫度與GTG分率間係具有比例關係，就成為GTG分率更高值的觀點，預熱結束時的薄片溫度更佳係「薄片的A層熔點」以上、且「薄片的A層熔點+10」℃以下，特佳係「薄片的A層熔點+10」℃以上、且「薄片的A層熔點+20℃」以下。 In the present invention, the sheet temperature at the end of the preheating in the preheating step is set to "the melting point of the A layer of the sheet is -20" ° C or higher, and the "melting point of the layer A of the sheet is +20" ° C or less. The GTG fraction of the layer A of the body is 0.6 or more and 1 or less. The reason is considered to be a molded body having heat resistance which is rigid even at a high temperature by enhancing the molecular mobility of the PBT of the layer A and forming a three-dimensional structure. Since the GTG fraction is formed to have a structure of 0.6 or more and 1 or less, and the molecular mobility is in close contact with each other, the preheating is completed until the crystal melting of the PBT is officially performed, "the melting point of the A layer of the sheet is +20" °C. The temperature relationship between the temperature and the GTG fraction is proportional to the higher the GTG fraction. The sheet temperature at the end of the preheating is better than the "layer A melting point" and the "sheet A melting point + When the temperature is below 10 ° C, the "A-layer melting point of the sheet is +10" °C or more, and the "A-layer melting point of the sheet is +20 ° C" or less.
再者，本發明中，藉由將預熱步驟中當預熱結束時的薄片溫度，設為「薄片的A層熔點-20」℃以上、且「薄片的A層熔點+20」℃以下，而可抑制成形時產生成形應變，可成為具有即便高溫下仍能抑制收縮之耐熱性的成形體。 Further, in the present invention, the sheet temperature at the end of the preheating in the preheating step is set to "the melting point of the A layer of the sheet is -20" ° C or higher, and the "melting point of the layer A of the sheet is +20" ° C or less. Further, it is possible to suppress the occurrence of the forming strain at the time of molding, and it is possible to obtain a molded body having heat resistance which can suppress shrinkage even at a high temperature.
再者，本發明中，當薄片的B層熔點係在薄片的A層熔點(熔點：225℃左右)以下時，藉由將預熱結束時的薄片溫度設定為「薄片的A層熔點-20」℃以上、且「薄片的A層熔點+20」℃以下，即便B層主成分的聚酯在預熱中有形成結晶，但在預熱結束時的階段仍會成為該聚酯的熔點以上並進行熔融。所以，可將最終獲得成形體的B層之相對結晶化度設為0%以上且5%以內，結果成為霧度5%以下的透明成形體。 Further, in the present invention, when the melting point of the B layer of the sheet is equal to or lower than the melting point of the layer A of the sheet (melting point: about 225 ° C), the sheet temperature at the end of the preheating is set to "the melting point of the layer A of the sheet - 20 When the temperature of °C or higher and the melting point of the A layer of the sheet is +20°C or lower, even if the polyester of the main component of the B layer forms crystals during preheating, it still becomes the melting point of the polyester at the stage of completion of the preheating. And melted. Therefore, the relative crystallization degree of the B layer of the finally obtained molded body can be set to 0% or more and 5% or less, and as a result, a transparent molded body having a haze of 5% or less can be obtained.
另一方面，本發明中，當薄片的B層熔點較高於薄片的A層熔點時，在上述預熱步驟中，最好將從薄片溫度成為「薄片的B層之Tc-30」℃時起至預熱結束時為止的平均升溫速度，設為20℃/秒以上。此處所謂「平均升溫速度」係指當利用溫度檢測機觀測預熱中之薄片溫度推移時，假設從薄片溫度成為「薄片的B層之Tc-30」℃時起至預熱結束時為止的薄片溫度升溫曲線係直線性，將預熱結束時的薄片溫度、與成為「薄片的B層之Tc-30」℃時的薄片溫度間之溫度差，除以在該溫度區域中升溫所需要時間時的值。 On the other hand, in the present invention, when the melting point of the B layer of the sheet is higher than the melting point of the layer A of the sheet, in the preheating step, it is preferable to change the sheet temperature to "Tc-30" of the B layer of the sheet. The average temperature increase rate from the end of the warm-up period is set to 20 ° C /sec or more. Here, the "average heating rate" means that when the temperature of the sheet during the preheating is observed by the temperature detector, it is assumed that the sheet temperature is "Tc-30 of the B layer of the sheet" and the temperature is up to the end of the warming up. The sheet temperature rise curve is linear, and the temperature difference between the sheet temperature at the end of the preheating and the sheet temperature at the time of "Tc-30 of the B layer of the sheet" is divided by the time required for the temperature to rise in the temperature region. The value of the time.
本發明成形體之製造方法的預熱步驟中，相關將從薄片溫度成為「薄片的B層之Tc-30」℃時起至預熱結束時為止的平均升溫速度設為20℃/秒以上的涵義，詳細如下述。 In the preheating step of the method for producing a molded article of the present invention, the average temperature increase rate from the time when the sheet temperature is "Tc-30" of the B layer of the sheet to the end of the warming is 20 ° C / sec or more. The meaning is as follows.
當薄片的B層熔點較高於薄片的A層熔點時，若在成形體材料的薄片階段，B層主成分的聚酯進行結晶化，則截至預熱結束 為止前，不易使B層主成分的聚酯熔解。所以，為獲得成形體而使用的薄片，前提是B層必需預先使相對結晶化度在0%以上且5%以下的實質非晶狀態。然而，一般非晶狀態的聚酯具有在其玻璃轉移溫度以上起至熔點之間會引發冷結晶化的溫度區域，當使用在較低於PBT熔點(熔點：225℃左右)的溫度區域中具有冷結晶化溫度，諸如PET(冷結晶化溫度：140℃左右)之類的聚酯，使用為B層主成分的情況，若僅單純施行預熱，會進行結晶化，導致所獲得成形體中的B層相對結晶化度較大於5%，且成為透明性低。針對此種問題，本發明藉由將薄片溫度成為「薄片的B層之Tc-30」℃時起至預熱結束時為止的平均升溫速度，設為20℃/秒以上，而相對於B層冷結晶化速度，相對性大幅提升平均升溫速度，發現可抑制截至預熱結束時前的結晶化，將成形體的B層之相對結晶化度設在0%以上且5%以內，且能對成形體賦予透明性。上述平均升溫速度更佳係25℃/秒以上、特佳係30℃/秒以上。平均升溫速度雖越快越佳，但若觸及機械性能，則可認為200℃/秒係上限。 When the melting point of the B layer of the sheet is higher than the melting point of the layer A of the sheet, if the polyester of the main component of the layer B is crystallized at the sheet stage of the shaped body material, the end of the preheating is completed. Until now, it is not easy to melt the polyester of the main component of the B layer. Therefore, the sheet to be used for obtaining a molded body is presumed to have a substantially amorphous state in which the relative crystallization degree is 0% or more and 5% or less in the B layer. However, a polyester in a generally amorphous state has a temperature region which causes cold crystallization between a glass transition temperature and a melting point thereof, and is used in a temperature region lower than a PBT melting point (melting point: about 225 ° C). Cold crystallization temperature, such as PET (cold crystallization temperature: about 140 ° C), when polyester is used as the main component of the B layer, if only preheating is performed, crystallization will occur, resulting in the obtained molded body. The B layer has a relative crystallinity of more than 5% and has low transparency. In order to solve such a problem, the average temperature increase rate from the time when the sheet temperature is "Tc-30 of the B layer of the sheet" to the end of the warm-up period is 20 ° C / sec or more, and is relative to the B layer. The cold crystallization rate and the relative increase in the average temperature increase rate are large, and it is found that the crystallization before the end of the preheating can be suppressed, and the relative crystallization degree of the B layer of the molded body is set to be 0% or more and 5% or less. The molded body imparts transparency. The average temperature increase rate is preferably 25 ° C /sec or more, and particularly preferably 30 ° C / sec or more. The average temperature increase rate is preferably as fast as possible, but if it is in contact with mechanical properties, it is considered to be an upper limit of 200 ° C / sec.
成為本發明成形體材料的薄片，在不致損及本發明目的之範圍內，亦可含有添加劑。添加劑係可例如：填充劑(玻璃纖維、碳纖維、金屬纖維、天然纖維、有機纖維、玻璃碎片、玻璃珠、陶瓷纖維、陶瓷珠、石綿、矽灰石、滑石、黏土、雲母、絹雲母、沸石、膨潤土、蒙脫石、合成雲母、白雲石、高嶺土、微粉矽酸、長石粉、鈦酸鉀、火山灰微粒(shirasu balloon)、碳酸鈣、碳酸鎂、硫酸鋇、氧化鈣、氧化鋁、氧化鈦、矽酸鋁、氧化矽、石膏、燧石岩(novaculite)、片鈉鋁石或白土等)、紫外線吸收劑(間苯二酚、水楊酸酯、苯并三唑、二苯基酮等)、熱安定劑(受阻酚、氫醌、亞磷酸酯類及該等的取代體 等)、滑劑、脫模劑(二十八酸及其鹽、酯、半酯；硬脂醇、硬脂酸胺及聚乙烯蠟等)、含有染料(苯胺黑等)及顏料(硫化鎘、酞菁等)的著色劑、抗著色劑(亞磷酸鹽、連二磷酸鹽等)、難燃劑(紅磷、磷酸酯、溴化聚苯乙烯、溴化聚伸苯醚、溴化聚碳酸酯、氫氧化鎂、三聚氰胺及三聚氰酸或其鹽、矽化合物等)、導電劑或著色劑(碳黑等)、滑動性改良劑(石墨、氟樹脂等)、抗靜電劑、耐衝擊劑等，可含有該等中之1種或2種以上。 The sheet which is a molded material of the present invention may contain an additive insofar as it does not impair the object of the present invention. The additive may be, for example, a filler (glass fiber, carbon fiber, metal fiber, natural fiber, organic fiber, glass cullet, glass beads, ceramic fiber, ceramic beads, asbestos, ash stone, talc, clay, mica, sericite, zeolite) , bentonite, montmorillonite, synthetic mica, dolomite, kaolin, micronized citric acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide , aluminum silicate, cerium oxide, gypsum, novaculite, dawsonite or clay, UV absorbers (resorcinol, salicylate, benzotriazole, diphenyl ketone, etc.) Heat stabilizer (hindered phenol, hydroquinone, phosphite, and such substituents) Etc.), slip agent, mold release agent (octadecanoic acid and its salts, esters, half esters; stearyl alcohol, stearic acid amine and polyethylene wax, etc.), dyes (aniline black, etc.) and pigments (cadmium sulfide) , phthalocyanine, etc., coloring agent, anti-coloring agent (phosphite, bisphosphonate, etc.), flame retardant (red phosphorus, phosphate, brominated polystyrene, brominated polyphenylene oxide, brominated poly Carbonate, magnesium hydroxide, melamine, cyanuric acid or a salt thereof, cerium compound, etc.), a conductive agent or a coloring agent (carbon black, etc.), a slidability improver (graphite, fluororesin, etc.), an antistatic agent, and a resistant The impact agent or the like may contain one or more of these.
再者，本發明成形體材料的薄片，視需要在不致損及本發明目的之範圍內，亦可添加結晶核劑中之1種或2種以上。結晶核劑例係可例如：滑石等無機系核劑；二苯亞甲基山梨糖醇、苯甲酸鈉、二十八酸鈉等有機系核劑等等。 In addition, one or two or more kinds of crystal nucleating agents may be added to the sheet of the molded material of the present invention as needed within the range which does not impair the object of the present invention. Examples of the crystal nucleating agent may be, for example, an inorganic nucleating agent such as talc; an organic nucleating agent such as dibenzylidene sorbitol, sodium benzoate or sodium octadecoxide; and the like.
為對本發明成形體賦予設計性，配合目的可在成形體材料的薄片表層形成印刷層。印刷層係印製由例如文字、圖形、符號、花紋、其他等構成的所需印刷圖案而形成。就從使該印刷層所使用的油墨、與本發明成形體表層或本發明成形體材料的薄片表層(以下將該等統稱為「表層」)間之接著性呈良好的觀點，亦可對表層在空氣、氮、碳酸氣體環境下，施行電暈處理、電漿處理、臭氧處理、火焰處理等前處理。印刷係可利用例如：凹版印刷、平版印刷、凸版印刷、網版印刷、轉印印刷、橡膠版輪轉印刷、噴墨印刷等公知各種印刷方法形成。又，印刷所使用的油墨係可為水性油墨、亦可為溶劑系油墨等非水性油墨中之任一種。 In order to impart design properties to the molded article of the present invention, a printing layer can be formed on the surface layer of the formed body material for the purpose of blending. The printed layer is formed by printing a desired printed pattern composed of, for example, characters, figures, symbols, patterns, and the like. The adhesion between the ink used in the printing layer and the surface layer of the molded article of the present invention or the surface layer of the molded article of the present invention (hereinafter collectively referred to as "surface layer") is good, and the surface layer may be used. In the air, nitrogen, carbonic acid gas environment, pre-treatment such as corona treatment, plasma treatment, ozone treatment, flame treatment, etc. is performed. The printing system can be formed by various known printing methods such as gravure printing, lithography, letterpress printing, screen printing, transfer printing, rubber plate rotary printing, and inkjet printing. Further, the ink used for printing may be either an aqueous ink or a non-aqueous ink such as a solvent-based ink.
印刷層的厚度並無特別的限制，就從印刷外觀的觀點，較佳係0.1μm~10μm、更佳係0.2μm~3μm、特佳係0.4μm~1μm。 The thickness of the printed layer is not particularly limited, and is preferably from 0.1 μm to 10 μm, more preferably from 0.2 μm to 3 μm, and particularly preferably from 0.4 μm to 1 μm from the viewpoint of printing appearance.
以下，針對本發明成形體之製造方法進行說明。 Hereinafter, a method of producing a molded article of the present invention will be described.
在各個擠出機中，由其中一者進行A層原料的樹脂組成物之熔融擠出，並由另一者進行B層原料的樹脂組成物之熔融擠出，分別利用金網篩網進行異物除去、利用齒輪泵進行流量適性化後，再供應給多歧管噴絲嘴、或在噴絲嘴上部設置的分流器。另外，在上述多歧管噴絲嘴、或分流器中，配合必要的薄膜層構成，設置所需數量、所需形狀的流路。從各擠出機中擠出的熔融樹脂如上述，利用多歧管噴絲嘴或分流器而合流，再從噴絲嘴進行共擠出呈薄片狀。該薄片係利用氣刀或靜電施加等方式，使密接於鑄造鼓輪(casting drum)，經冷卻固化而成為霧度5%以下的無配向薄片。 In each of the extruders, one of the resin compositions of the A-layer raw material is melt-extruded, and the other is subjected to melt extrusion of the resin composition of the B-layer raw material, and the foreign matter is removed by a gold mesh screen. After the flow rate is adapted by the gear pump, it is supplied to the multi-manifold nozzle or the flow divider provided on the upper portion of the spinneret. Further, in the multi-manifold nozzle or the flow divider, a necessary film layer is formed, and a flow path of a desired number and a desired shape is provided. The molten resin extruded from each extruder is joined by a multi-manifold nozzle or a flow divider as described above, and coextruded from the spinneret into a sheet shape. The sheet is adhered to a casting drum by means of an air knife or electrostatic application, and is solidified by cooling to form an unaligned sheet having a haze of 5% or less.
其中，為防止因凝膠、熱劣化物等異物的混入而導致表面粗糙，最好使用50~400篩目之金網篩網。 Among them, in order to prevent surface roughness due to the incorporation of foreign matter such as gel or heat deterioration, it is preferable to use a gold mesh screen of 50 to 400 mesh.
為將依上述所獲得無配向薄片成為成形體，而在上述間接加熱方式中，將預熱結束時的溫度設為「薄片的A層熔點-20」℃以上、且「薄片的A層熔點+20」℃以下施行成形。 In the indirect heating method, the temperature at the end of the preheating is set to "the melting point of the A layer of the sheet -20" ° C or higher, and the melting point of the layer A of the sheet + Forming is carried out below 20 °C.
上述成形步驟中的模具溫度，就從緩和除去因成形所產生應變的觀點，下限較佳係薄片的A層之玻璃轉移溫度以上。另一方面，若觸及模具的脫模性與成形體的冷卻循環，則上限較佳係120℃。成形步驟中的模具溫度更佳係「薄片的A層之玻璃轉移溫度+5」℃以上且100℃以下、特佳係「薄片的A層之玻璃轉移溫度+10」℃以上且90℃以下。 The mold temperature in the above-described molding step is preferably from the viewpoint of ease of removal of strain due to molding, and the lower limit is preferably at least the glass transition temperature of the layer A of the sheet. On the other hand, when the mold release property of the mold and the cooling cycle of the molded body are touched, the upper limit is preferably 120 °C. The mold temperature in the forming step is more preferably "the glass transition temperature of the layer A of the sheet is +5" ° C or more and 100 ° C or less, and particularly preferably, the glass transition temperature of the layer A of the sheet is +10 ° C or more and 90 ° C or less.
在傅立葉轉換紅外線分光裝置Spectrum100(Perkinelmer公司製)中 安裝ATR測定配件，施行成形體的A層之光譜測定。所獲得光譜經施行ATR校正後，將穿透率轉換為吸光度。接著，將891cm-1吸光度與951cm-1吸光度利用直線相連結並設為基線，在891cm-1至951cm-1區域中擷取吸收光譜與基線的差光譜。使用所獲得差光譜中的934cm-1吸光度(以下稱「A934」)、與916cm-1吸光度(以下稱「A916」)，從式1求取GTG分率。 The ATR measuring kit was attached to a Fourier transform infrared spectrometer Spectrum 100 (manufactured by Perkinelmer Co., Ltd.), and the spectrum of the layer A of the molded body was measured. The obtained spectrum was converted to absorbance after being subjected to ATR correction. Next, the absorbance at 891 cm -1 and the absorbance at 951 cm -1 were connected by a straight line and set as a baseline, and a difference spectrum between the absorption spectrum and the baseline was taken in the region of 891 cm -1 to 951 cm -1 . Using the 934 cm -1 absorbance (hereinafter referred to as "A 934 ") and the 916 cm -1 absorbance (hereinafter referred to as "A 916 ") in the obtained difference spectrum, the GTG fraction was obtained from the formula 1.
GTG分率=A916/(A934+A916)…(式1) GTG fraction = A 916 / (A 934 + A 916 )... (Formula 1)
測定條件如下。 The measurement conditions are as follows.
積分次數：8次 Number of points: 8 times
波長間隔：1cm-1 Wavelength interval: 1cm -1
從薄片或成形體削取A層或B層而採取試料5mg，使用微分掃描熱量分析裝置DSCII型(Seiko Instrument(股)製)，依升溫速度20℃/分從20℃升溫至300℃，並保持5分鐘，再依999℃/分急速冷卻至20℃，經保持5分鐘後，再度依20℃/分進行升溫。 A sample of 5 mg was taken from the sheet or the molded body, and a sample of 5 mg was taken, and a differential scanning calorimeter DSCII type (manufactured by Seiko Instrument Co., Ltd.) was used, and the temperature was raised from 20 ° C to 300 ° C at a temperature increase rate of 20 ° C / min. Hold for 5 minutes, and then rapidly cool to 20 ° C at 999 ° C / min. After 5 minutes, the temperature is again increased by 20 ° C / min.
在B層的測定中，將此時所觀測到因結晶化而衍生發熱尖峰的峰頂溫度，設為B層的冷結晶化溫度(Tc)。又，在B層的測定中，將此時所觀測到因熔解而衍生吸熱尖峰的峰頂溫度，設為B層的熔點。又，相關A層亦是同樣地將測定時所觀測到因熔解而衍生的吸熱尖峰之峰頂溫度，設為A層的熔點。 In the measurement of the layer B, the peak top temperature at which the heat generation peak derived by crystallization was observed at this time was taken as the cold crystallization temperature (Tc) of the layer B. Further, in the measurement of the layer B, the peak top temperature at which the endothermic peak derived by the melting was observed at this time was taken as the melting point of the layer B. Further, in the relevant layer A, the peak top temperature of the endothermic peak derived by melting was observed in the same manner as the melting point of the layer A.
其次，成形體的B層之△Tcg測定法係如下述。與熔點、Tc的測定同樣，從在第2次升溫中所觀測到的基線曲線變化，讀取B 層的玻璃轉移溫度(Tg)。 Next, the ΔTcg measurement method of the B layer of the molded body is as follows. As with the measurement of the melting point and Tc, reading B from the change in the baseline curve observed in the second temperature rise The glass transition temperature (Tg) of the layer.
從由該等測定所獲得成形體的B層之Tc及Tg，利用式2求取成形體的B層之△Tcg。 From the Tc and Tg of the layer B of the molded body obtained by the above measurement, ΔTcg of the layer B of the molded body was obtained by the formula 2.
△Tcg=Tc-Tg…(式2) △Tcg=Tc-Tg... (Formula 2)
再者，相關薄片的A層之Tg，亦是與B層同樣，將第2次升溫測定中所獲得的值，設為A層的Tg。 In addition, the Tg of the A layer of the relevant sheet is the same as the layer B, and the value obtained in the second temperature measurement is the Tg of the layer A.
另外，當在成形體的B層的DSC測定中，熔點有存在2個以上的情況，係將所觀測到熔點中的最高值，設為成形體的B層熔點。同樣地，當在成形體的B層之DSC測定中，Tg有存在2個以上的情況，係將所觀測到Tg中的最高值，設為成形體的B層之Tg。又，當在成形體的B層之DSC測定中，Tc有存在2個以上的情況，係將所觀測到Tc中的最低值，設為成形體的B層的Tc。另外，相關薄片的B層熔點、(Tc)、玻璃轉移溫度(Tg)亦同。 In addition, in the DSC measurement of the B layer of the molded body, there are two or more melting points, and the highest value among the observed melting points is the melting point of the B layer of the molded body. In the same manner, in the DSC measurement of the B layer of the molded article, when there are two or more Tg, the highest value of the observed Tg is the Tg of the B layer of the molded body. In addition, when there are two or more Tc in the DSC measurement of the B layer of the molded body, the lowest value of the observed Tc is the Tc of the B layer of the molded body. Further, the B layer melting point, (Tc), and glass transition temperature (Tg) of the relevant sheet are also the same.
再者，當在成形體的A層之DSC測定中，熔點有存在2個以上的情況，係將所觀測到熔點中的最高值，設為成形體的A層熔點。另外，相關薄片的A層熔點亦同。又，相關薄片的A層之玻璃轉移溫度(Tg)，亦是與薄片的B層之玻璃轉移溫度(Tg)同樣地，當Tg有存在2個以上的情況，係將所觀測到Tg中的最高值，設為薄片的A層之Tg。 In addition, when there are two or more melting points in the DSC measurement of the layer A of the molded body, the highest value among the observed melting points is the melting point of the layer A of the molded body. In addition, the melting point of the A layer of the relevant sheet is also the same. Further, the glass transition temperature (Tg) of the layer A of the relevant sheet is also the same as the glass transition temperature (Tg) of the layer B of the sheet, and when there are two or more Tg, the Tg is observed. The highest value is set to the Tg of the A layer of the sheet.
採取從成形體材料的薄片或成形體中僅削取B層的試料5mg，使用微分掃描熱量分析裝置DSCII型(Seiko Instrument(股)製)，依升溫速度20℃/分從20℃升溫至300℃。使用由DSC測定所觀測到的熔解尖 峰面積(Sm)及發熱尖峰面積(Sc)，利用式3計算出相對結晶化度。 5 mg of a sample in which a layer B was cut out from a sheet or a molded body of a molded material, and a differential scanning calorimeter DSCII type (manufactured by Seiko Instrument Co., Ltd.) was used, and the temperature was raised from 20 ° C to 300 at a temperature increase rate of 20 ° C /min. °C. Use the melting tip observed by DSC measurement The peak area (Sm) and the heat peak area (Sc) were calculated by Equation 3 to calculate the relative degree of crystallinity.
相對結晶化度=(Sm-Sc)/Sm×100…(式3)。 Relative crystallinity = (Sm - Sc) / Sm × 100 (Formula 3).
使用測霾計HGM-2DP型(SUGA試驗機公司製)，測定成形體、及成為其材料的薄片之霧度值。另外，成形體的情況，為消除因源自試料的曲折而造成的光散射、穿透距離不均勻性，從具平面性的部分切取試料施行測定。測定係針對1樣品各施行5次，求取5次測定的平均值(平均霧度值)。接著，利用式4求取換算為250μm的值。 The haze value of the molded article and the sheet to be the material thereof was measured using a sputum meter HGM-2DP type (manufactured by SUGA Testing Machine Co., Ltd.). Further, in the case of the molded body, in order to eliminate light scattering and penetration distance unevenness due to the meandering of the sample, the sample was cut out from the flat portion and the measurement was performed. The measurement system was carried out five times for each of the samples, and the average value (average haze value) of the five measurements was obtained. Next, a value converted to 250 μm was obtained by Equation 4.
霧度值=平均霧度值×250(μm)/樣品厚度(μm)…(式4) Haze value = average haze value × 250 (μm) / sample thickness (μm) ... (Formula 4)
另外，樣品厚度係使用度盤規式厚度計(JIS B7503：1997、PEACOCK製UPRIGHT DIAL GAUGE(0.001×2mm)、No.25、測頭5mm 平型)，測定任意選擇的10處，並將平均值設為該樣品的樣品厚度(μm)。 In addition, the thickness of the sample is a gauge gauge (JIS B7503:1997, UPRIGHT DIAL GAUGE (0.001×2mm) made by PEACOCK, No.25, probe 5mm Flat type), 10 randomly selected points were measured, and the average value was set as the sample thickness (μm) of the sample.
以鈉D線(波長589nm)為光源，使用阿貝式折射儀，測定薄片表面的長邊方向折射率(Nx)、寬度方向折射率(Ny)及厚度方向折射率(Nz)，並從式5計算出面配向係數(fn)。 Using a sodium D line (wavelength 589 nm) as a light source, the Abbe refractometer was used to measure the long-side refractive index (Nx), the width-direction refractive index (Ny), and the thickness-direction refractive index (Nz) of the sheet surface. 5 Calculate the face alignment coefficient (fn).
fn=(Nx+Ny)/2-Nz…(式5)。 Fn = (Nx + Ny) / 2 - Nz (Expression 5).
在間接加熱方式中，利用在距薄片30cm距離處設置的紅外線放射溫度計進行測定。 In the indirect heating method, measurement was performed using an infrared radiation thermometer provided at a distance of 30 cm from the sheet.
將蓋型成形體依成形體的底面部朝上方式，在90℃熱風烤箱中放置2分鐘，經試驗後從烤箱中取出並自然冷卻。待冷卻結束後，使用投入熱風烤箱前的初期高度、與投入熱風烤箱後的試驗後高度，依照式6計算出高度維持率，並評價耐熱性。 The lid-shaped formed body was placed in a hot air oven at 90 ° C for 2 minutes in a manner that the bottom surface portion of the molded body was facing upward, and after the test, it was taken out from the oven and naturally cooled. After the completion of the cooling, the initial height before the hot air oven was placed and the height after the test in the hot air oven were used, and the height maintenance ratio was calculated according to Formula 6, and the heat resistance was evaluated.
高度維持率=(初期高度-試驗後高度)/初期高度×100…(式6) Height maintenance rate = (initial height - height after test) / initial height × 100... (Formula 6)
當依式6所獲得高度維持率達70%以上的情況，則評為滿足實用水準的耐熱性。 When the height maintenance rate obtained by the formula 6 is 70% or more, the heat resistance which satisfies the practical level is evaluated.
從成形體中切取150mm×10mm尺寸的測定用樣品片。另外，在後述實施例中雖從成形體底部進行切取，但該樣品係可從成形體的任何部位切取。將該樣品片在23℃、相對濕度60%的環境中放置30分鐘，於該環境下，在樣品長邊方向依約100mm間隔標註2個標記，使用Nikon公司製萬能投影機(Model V-16A)，測定該標記的間隔，並將該值設為「A」。接著，將樣品在施加3g荷重的狀態下，懸吊於齒輪烤箱中，於100℃環境中放置30分鐘。接著，於23℃、相對濕度60%環境中進行1小時冷卻、調濕後，測定先前所標註的標記間隔，並將其設為「B」。此時，利用下式(i)求取熱收縮率。試驗次數設為3，採用平均值。 A sample piece for measurement having a size of 150 mm × 10 mm was cut out from the molded body. Further, in the examples described later, the sample was cut out from the bottom of the molded body, but the sample was cut out from any portion of the molded body. The sample piece was allowed to stand in an environment of 23 ° C and a relative humidity of 60% for 30 minutes. In this environment, two marks were placed at intervals of about 100 mm in the longitudinal direction of the sample, and a universal projector (Model V-16A manufactured by Nikon Corporation) was used. ), measure the interval of the mark, and set the value to "A". Next, the sample was suspended in a gear oven under a state where a load of 3 g was applied, and left in an environment of 100 ° C for 30 minutes. Subsequently, the mixture was cooled and conditioned for 1 hour in an environment of 23° C. and a relative humidity of 60%, and then the previously marked mark interval was measured and set to “B”. At this time, the heat shrinkage ratio was obtained by the following formula (i). The number of tests was set to 3, and the average value was used.
熱收縮率(%)=100×(A-B)/A…(i)。 Heat shrinkage ratio (%) = 100 × (A - B) / A (i).
從成形體切取50mm×10mm尺寸的測定用樣品片。將該樣品片利用冷凍機冷卻至-20℃。從冷凍機中取出的樣品，將樣品的長條(50mm)側固定於東洋精機製作所製夏比衝擊試驗器(容量：10kg‧cm、鎚重量：1.019kg、鎚的空持上舉角度：127度、軸心至重心的距離：6.12cm)，於23℃、相對濕度60%環境下施行測定。試驗次數設為10，採用平均值。該等平均值除以樣品的截面積(樣品厚度×10mm)，並換算為MJ/m2單位。 A sample piece for measurement having a size of 50 mm × 10 mm was cut out from the molded body. The sample piece was cooled to -20 ° C using a freezer. The sample taken out from the freezer was fixed to the Charpy impact tester manufactured by Toyo Seiki Co., Ltd. (capacity: 10 kg‧cm, hammer weight: 1.019 kg, weight of the hammer): 127 The distance from the axis to the center of gravity: 6.12 cm) was measured at 23 ° C and 60% relative humidity. The number of tests was set to 10 and the average value was used. These average values were divided by the cross-sectional area of the sample (sample thickness x 10 mm) and converted to MJ/m 2 units.
使用Leica Microsystems(股)製金屬顯微鏡LeicaDMLM，針對薄膜截面依倍率100倍條件照相拍攝穿透光，測定成形體及薄片各層的層厚度。 The layer thickness of each of the formed body and the sheet was measured by using a Leica DMLM, a metal microscope manufactured by Leica Microsystems, to photograph the through-light of the film section at a magnification of 100 times.
利用實施例進行具體例示，惟本發明併不僅侷限於該等實施例。 Specific examples are given by way of examples, but the invention is not limited to the embodiments.
本發明的成形體之製造例、實施例及比較例所使用的原料，如下述。另外，實施例、比較例中依下述簡稱記載。 The raw materials used in the production examples, examples, and comparative examples of the molded article of the present invention are as follows. In addition, in the examples and comparative examples, the following abbreviations are described.
PBT-A：聚對苯二甲酸丁二酯(熔點225℃) PBT-A: polybutylene terephthalate (melting point 225 ° C)
PBT-B：(聚對苯二甲酸/聚間苯二甲酸)丁二酯(熔點205℃對酞酸：異酞酸=90莫耳%：10莫耳%) PBT-B: (polyterephthalic acid/polyisophthalic acid) butadiene ester (melting point 205 ° C for citric acid: isophthalic acid = 90 mol %: 10 mol %)
PBT-C：(聚對苯二甲酸/聚間苯二甲酸)丁二酯(熔點170℃對酞酸：異酞酸=70莫耳%：30莫耳%) PBT-C: (polyterephthalic acid/polyisophthalic acid) butane (melting point 170 ° C for citric acid: isophthalic acid = 70 mol %: 30 mol %)
PET-A：聚對苯二甲酸乙二酯(熔點250℃) PET-A: polyethylene terephthalate (melting point 250 ° C)
PET-B：聚對苯二甲酸乙二酯(熔點250℃) PET-B: Polyethylene terephthalate (melting point 250 ° C)
PET-C：聚對苯二甲酸/間苯二甲酸乙二酯)(熔點205℃對酞酸：異酞酸=82.5莫耳%：17.5莫耳%) PET-C: Poly(terephthalic acid/ethylene isophthalate) (melting point 205 ° C for citric acid: isophthalic acid = 82.5 mol %: 17.5 mol %)
PLA-A：結晶性聚L-乳酸(Nature Works製「Ingeo」4032D；D體量=1.4mol%、熔點=168℃、Tg=58℃) PLA-A: Crystalline poly-L-lactic acid ("Ingeo" 4032D, manufactured by Nature Works; D body amount = 1.4 mol%, melting point = 168 ° C, Tg = 58 ° C)
實施例、比較例所使用的測定方法，係如同上述〔物性的測定方法及效果的評價方法〕中所記載。 The measurement methods used in the examples and the comparative examples are as described in the above [Methods for Measuring Physical Properties and Methods for Evaluating Effects].
在擠氣式擠出機(1)中投入A層原料之經預先施行真空乾燥處理過的PBT-A(100質量%)，一邊將真空排氣部施行脫氣，一邊依250℃施行熔融混練並擠出，使用100篩目的金網篩網過濾聚合物，再供應給2種3層積層式的多歧管噴絲嘴。又，在擠氣式擠出機(2)中投入B層原料之經預先施行真空乾燥處理過的PET-A(100質量%)，一邊將真空排氣部施行脫氣，一邊依280℃施行熔融混練並擠出，利用不同於擠出機(1)的其他流路，使用100篩目的金網篩網過濾聚合物後，再從噴絲嘴溫度設定為270℃的T型模頭噴絲嘴進行共擠出呈薄片狀，在所擠出的薄片二端部使用針狀尖銳針軋裝置，併用靜電施加方式及氣室(air chamber)方式，使靜電密接於冷卻至20℃的鑄造鼓輪而冷卻固化，即獲得未延伸薄片。 In the squeezing extruder (1), PBT-A (100% by mass) which was subjected to vacuum drying treatment in advance of the A-layer raw material was introduced, and the vacuum venting portion was degassed while performing melt-kneading at 250 ° C. Extrusion was carried out, and the polymer was filtered using a 100 mesh gold mesh screen and supplied to two 3-layer laminated multi-manifold spinnerets. In addition, PET-A (100% by mass) which has been subjected to vacuum drying treatment in the B layer raw material in the squeezing extruder (2) is subjected to degassing at 280 ° C while degassing the vacuum exhaust unit. Melt-kneading and extruding, using a different flow path from the extruder (1), using a 100-mesh gold mesh screen to filter the polymer, and then setting the T-die nozzle from the nozzle temperature to 270 ° C The co-extrusion was carried out in the form of a sheet, and a needle-shaped sharp needle rolling device was used at both ends of the extruded sheet, and electrostatically adhered to a casting drum cooled to 20 ° C by an electrostatic application method and an air chamber method. The film is cooled and solidified to obtain an unstretched sheet.
所獲得薄片係250μm，厚度構成係A層/B層/A層=1/8/1。 The obtained sheet was 250 μm, and the thickness was composed of A layer/B layer/A layer=1/8/1.
接著，以所獲得薄片為材料，使用淺野研究所製FKS真空壓製成形機，施行間接加熱方式的真空壓製成形。成形時，使用 開口部132mm×183mm、底部112mm×160mm、深度25mm的蓋狀模具，依加熱器溫度600℃、壓空壓力3kg/cm2、模具溫度60℃的條件施行成形。所獲得成形體的結果如表1所示，屬於具有透明性；耐熱性者。又，呈現100℃熱收縮率小、-20℃夏比衝擊強度較大的值。 Next, the obtained sheet was used as a material, and a vacuum compression molding machine by indirect heating was used using a FKS vacuum press molding machine manufactured by Asano Research Institute. At the time of molding, a lid-shaped mold having an opening of 132 mm × 183 mm, a bottom portion of 112 mm × 160 mm, and a depth of 25 mm was used, and molding was carried out under the conditions of a heater temperature of 600 ° C, a pressure air pressure of 3 kg/cm 2 , and a mold temperature of 60 °C. The results of the obtained molded body are shown in Table 1, and belonged to those having transparency and heat resistance. Further, it exhibited a value at which the heat shrinkage rate at 100 ° C was small and the Charpy impact strength at -20 ° C was large.
實施例2~17、比較例1~7係除將A層、B層的樹脂、擠出機(1)、擠出機(2)所使用的原料，變更為如表1或表2所示，且將成形條件變更如表1所示之外，其餘均與實施例1同樣地獲得薄片及成形體。所獲得薄片及成形體的物性如表1或表2所示。 In Examples 2 to 17, and Comparative Examples 1 to 7, the materials used in the resin of the A layer and the B layer, the extruder (1), and the extruder (2) were changed as shown in Table 1 or Table 2. The sheet and the molded body were obtained in the same manner as in Example 1 except that the molding conditions were changed as shown in Table 1. The physical properties of the obtained sheet and the molded body are shown in Table 1 or Table 2.
準備將實施例1所獲得之薄片經細小裁斷而形成碎片狀的原料30%。除以該原料及PET-A原料70%為B層原料之外，其餘均與實施例1同樣地獲得薄片及成形體。所獲得薄片及成形體的物性如表1所示 The sheet obtained in Example 1 was finely cut to form a chip-shaped raw material of 30%. A sheet and a molded body were obtained in the same manner as in Example 1 except that the raw material and the PET-A raw material were 70% of the material of the B layer. The physical properties of the obtained sheet and molded body are shown in Table 1.
Claims (7)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03189149A (en) * | 1989-12-19 | 1991-08-19 | Sekisui Chem Co Ltd | Multi-layer sheet and molded container |
| JPH0470333A (en) * | 1990-07-02 | 1992-03-05 | Toray Ind Inc | Polyester sheet for molding and polyester molded body |
| TW200524731A (en) * | 2003-05-09 | 2005-08-01 | Mitsubishi Plastics Inc | Emboss-designed sheet and metal plate covered with emboss-designed sheet |
| JP2010070581A (en) * | 2008-09-16 | 2010-04-02 | Toray Ind Inc | Polyester film |
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- 2014-11-13 WO PCT/JP2014/080040 patent/WO2015072500A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03189149A (en) * | 1989-12-19 | 1991-08-19 | Sekisui Chem Co Ltd | Multi-layer sheet and molded container |
| JPH0470333A (en) * | 1990-07-02 | 1992-03-05 | Toray Ind Inc | Polyester sheet for molding and polyester molded body |
| TW200524731A (en) * | 2003-05-09 | 2005-08-01 | Mitsubishi Plastics Inc | Emboss-designed sheet and metal plate covered with emboss-designed sheet |
| JP2010070581A (en) * | 2008-09-16 | 2010-04-02 | Toray Ind Inc | Polyester film |
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| WO2015072500A1 (en) | 2015-05-21 |
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