KR20050008763A - Synthetic resin container excellent in functional characteristics and production method therefor - Google Patents
Synthetic resin container excellent in functional characteristics and production method therefor Download PDFInfo
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- KR20050008763A KR20050008763A KR10-2004-7019556A KR20047019556A KR20050008763A KR 20050008763 A KR20050008763 A KR 20050008763A KR 20047019556 A KR20047019556 A KR 20047019556A KR 20050008763 A KR20050008763 A KR 20050008763A
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- South Korea
- Prior art keywords
- container
- gas barrier
- synthetic resin
- resin
- barrier material
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- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 24
- 239000000057 synthetic resin Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 230000004888 barrier function Effects 0.000 claims abstract description 33
- 238000000071 blow moulding Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- IEEBOBJWPWIGNW-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione ethene naphthalene-1-carboxylic acid Chemical compound C1(C2=CC=C(C(=O)OCCO1)C=C2)=O.C2(=CC=CC1=CC=CC=C21)C(=O)O.C=C IEEBOBJWPWIGNW-UHFFFAOYSA-N 0.000 claims description 8
- 229920006026 co-polymeric resin Polymers 0.000 claims description 8
- 229920006122 polyamide resin Polymers 0.000 claims description 8
- 229920001225 polyester resin Polymers 0.000 claims description 8
- 239000004645 polyester resin Substances 0.000 claims description 8
- -1 polyethylene terephthalate Polymers 0.000 claims description 8
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 7
- 239000011241 protective layer Substances 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer 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
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/08—Biaxial stretching during blow-moulding
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- B29K2067/003—PET, i.e. poylethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
내열성이 우수하고, 가스배리어성이 높은 합성수지제 용기와 그 제조 방법을 제안한다. 본 발명에 의한 용기는, 모상(母相)에 가스배리어재가 블렌드되며, 가열 처리 공정을 그 사이에 갖는 적어도 2회의 2축 연신 블로우 성형 공정을 거쳐서 제조되는 것이다.The synthetic resin container which is excellent in heat resistance and high gas barrier property, and its manufacturing method are proposed. The container according to the present invention is produced through at least two biaxially stretch blow molding steps having a gas barrier material blended in a mother phase and having a heat treatment step therebetween.
Description
페트병으로 대표되는 합성수지제 용기는, 경량으로 취급이 용이한 점, 또한, 투명성을 확보할 수 있으므로 유리제 용기에 비교하여 손색없는 외관을 나타내는 점, 또한 제조비용적으로도 염가인 점 때문에, 근년, 식품이나 음료, 화장료 또는 약제 등을 수납하는 용기로서 많이 사용되고 있다.The plastic containers represented by PET bottles are light in weight and easy to handle, and because they can secure transparency, they show an inferior appearance compared to glass containers, and because they are inexpensive in manufacturing cost, in recent years, It is frequently used as a container for storing food, beverages, cosmetics, and medicines.
그 반면, 합성수지제 용기는, 용기 본체를 통하여 산소나 탄소 가스가 투과하는 것을 피할 수 없기 때문에, 내용물의 품질을 유지할 수 있는 기간, 소위 "쉘프 라이프(shelf life)"가 유리제 용기에 비교한 경우에 짧다는 결점이 있다.On the other hand, since synthetic resin containers cannot avoid the transmission of oxygen or carbon gas through the container body, when the so-called "shelf life" is compared with the glass containers for a period in which the quality of the contents can be maintained. There is a shortcoming.
또한, 이 종류의 용기는 열에 대한 강도도 작고, 폴리에텔렌테레프탈레이트 수지(PET)로 되는 용기에서는, 85∼87℃ 정도가 상한으로서, 특히, 내용물로서 이러한 상한 온도를 초과하는 액체를 충전하는 경우에는 열수축에 의한 형상 변형을피하기 어려워, 용도 범위를 확대함에는 한계가 있다.In addition, this type of container has a low heat strength, and in a container made of polyetherene terephthalate resin (PET), the upper limit of 85 to 87 ° C is the upper limit, and in particular, the content of filling the liquid exceeding the upper limit temperature as a content. In this case, it is difficult to avoid shape deformation due to heat shrinkage, and there is a limit to expanding the use range.
발명의 개시Disclosure of the Invention
본 발명의 과제는, 종래의 합성수지제 용기에서의 상술한 문제점을 해소할 수 있는 신규한 용기와, 그 제조 방법을 제안함에 있다.An object of the present invention is to propose a novel container capable of solving the above-mentioned problems in a conventional synthetic resin container and a manufacturing method thereof.
본 발명은 모상(母相: matrix)에 가스배리어재(gas barrier material)를 블렌드하여 되는 합성수지제 용기로서, 상기 용기는 가열 처리 공정을 그 사이에 갖는 적어도 2회의 2축(bi-axial) 연신 블로우 성형 공정을 거쳐 제조된 것임을 특징으로 하는 가스배리어성, 내열성이 우수한 합성수지제 용기이다.The present invention is a synthetic resin container in which a gas barrier material is blended in a matrix, the container having at least two bi-axial stretchings having a heat treatment therebetween. It is a synthetic resin container excellent in gas barrier properties and heat resistance, which is manufactured through a blow molding process.
상기 구성으로 되는 용기에서, 모상은 폴리에틸렌테레프탈레이트 수지로 하고, 가스배리어재로서는 메탁실릴렌(methaxylylene)기 함유 폴리아미드 수지, 비정질 폴리에스테르 수지 및 에틸렌나프탈레이트-에틸렌테레프탈레이트 공중합 수지로 되는 군에서 선택한 적어도 1종으로 하는 것이 바람직하다.In the container having the above constitution, the mother phase is a polyethylene terephthalate resin, and as a gas barrier material, a group consisting of a methacrylic group-containing polyamide resin, an amorphous polyester resin, and an ethylene naphthalate-ethylene terephthalate copolymer resin It is preferable to use at least 1 sort (s) selected.
또한, 본 발명은, 모상에 가스배리어재를 블렌드한 베이스층과, 가스배리어성이 높은 보호층을 교호(交互)로 서로 겹친 다층 구조로 되는 합성수지제 용기로서, 상기 용기는 가열 처리 공정을 그 사이에 갖는 적어도 2회의 2축 연신 블로우 성형 공정을 거쳐 제조된 것임을 특징으로 하는, 가스배리어성, 내열성이 우수한 합성수지제 용기이며, 이 경우에도, 베이스층의 모상은 폴리에틸렌테레프탈레이트 수지로 하고, 가스배리어재는 메탁실릴렌기 함유 폴리아미드 수지, 비정질 폴리에스테르 수지 및 에틸렌나프탈레이트-에틸렌테레프탈레이트 공중합 수지로 되는 군에서 선택한 적어도 1종으로 하는 것이 바람직하다.In addition, the present invention is a synthetic resin container having a multi-layer structure in which a base layer blended with a gas barrier material on a mother layer and a protective layer having high gas barrier properties are alternately overlapped with each other. It is a synthetic resin container excellent in gas barrier property and heat resistance characterized by being manufactured through the at least 2 biaxial stretching blow molding process which hold in between, In this case, the base phase of a base layer is made of polyethylene terephthalate resin, The barrier material is preferably at least one member selected from the group consisting of a methacrylic group-containing polyamide resin, an amorphous polyester resin, and an ethylene naphthalate-ethylene terephthalate copolymer resin.
보호층으로서는, 메탁실릴렌기 함유 폴리아미드 수지, 비정질 폴리에스테르 수지, 에틸렌나프탈레이트-에틸렌테레프탈레이트 공중합 수지 및 에틸렌-비닐알코올 공중합 수지로 되는 군에서 선택한 적어도 1종을 사용할 수 잇다.As the protective layer, at least one selected from the group consisting of a methacrylic group-containing polyamide resin, an amorphous polyester resin, an ethylene naphthalate-ethylene terephthalate copolymer resin and an ethylene-vinyl alcohol copolymer resin can be used.
또한, 본 발명은 가열 처리를 그 사이에 갖는 2회의 2축 연신 블로우 성형을 행함으로써 합성수지제 용기를 제조함에 있어, 상기 블로우 성형을 할 때, 모상에 가스배리어재를 블렌드한 합성수지로 되는 프리폼(preform)을 사용함을 특징으로 하는, 가스배리어성, 내열성이 우수한 합성수지제 용기의 제조 방법이다.In addition, the present invention is to produce a synthetic resin container by performing two biaxially stretch blow moldings having a heat treatment therebetween. It is a manufacturing method of the synthetic resin container excellent in gas barrier property and heat resistance characterized by using preform).
프리폼으로서는 모상에 가스배리어재를 블렌드한 베이스층과, 가스배리어성이 높은 보호층을 교호로 서로 겹친 다층 구조체로 한 것을 사용할 수 있다.As the preform, a base structure obtained by blending a gas barrier material with a mother phase and a protective layer having a high gas barrier property can be used as a multilayer structure having alternately overlapped with each other.
본 발명은 용기를 투과하는 산소나 탄소 가스 등에 기인한 내용물의 품질 열화를 억제함과 동시에, 그 자신의 내열성을 높인 합성수지제 용기 및 그 제조 방법에 관한 것이다.The present invention relates to a synthetic resin container and a method of manufacturing the same, while suppressing the deterioration of the quality of the contents caused by oxygen, carbon gas, or the like which penetrates the container, and enhances its own heat resistance.
이하, 도면을 참조하여 본 발명을 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to the drawings.
도 1은 본 발명에 따른 용기의 구성도.1 is a block diagram of a container according to the present invention.
도 2는 본 발명에 사용하기에 적합한 프리폼을 나타내는 도면.2 shows a preform suitable for use in the present invention.
도 3a∼3d는 블로우 성형할 때의 각 프로세스에서의 성형체의 외관 형상을 나타낸 도면.3A to 3D are views showing appearance shapes of molded bodies in each process during blow molding;
도 4a, 4b는 본 발명에 따른 용기의 요부를 나타낸 도면.4a, 4b show the main parts of a container according to the invention;
도 5a∼5c는 실시예에서 사용한 용기의 측면, 평면 및 저면을 각각 나타낸 도면.5A to 5C are views showing the side, the plane and the bottom of the container used in the examples, respectively.
발명을 실시하기 위한 최량의 형태Best Mode for Carrying Out the Invention
도 1은 본 발명에 따른 합성수지제의 500ml 내열·내압용기의 외관을 모식적으로 나타낸 것이다. 동 도면에서 참조 숫자 1은 용기 본체, 2는 용기 본체(1)에 일체적으로 마련된 구부(口部)이다.Figure 1 schematically shows the appearance of 500ml heat-resistant and pressure-resistant container of the synthetic resin according to the present invention. In the figure, reference numeral 1 denotes a container body, and 2 denotes a mouth integrally provided in the container body 1.
본 발명에서는, 예를 들면 폴리에틸렌테레프탈레이트 수지를 모상(1a)으로 한 경우, 그 수지 중에 가스배리어재(G)를 블렌드하는 것으로서, 이에 의해 산소 등의 투과가 억제되어 가스배리어성이 개선된다.In the present invention, for example, when a polyethylene terephthalate resin is used as the mother phase 1a, the gas barrier material G is blended in the resin, whereby permeation of oxygen or the like is suppressed, thereby improving gas barrier properties.
이러한 용기를 제조하기 위해서는, 모상(1a)에 대하여 가스배리어재(G)를 블렌드하여 사출 성형이나 압출 성형 등을 거쳐 얻어진, 도 2에 나타내는 것 같은 프리폼(P)(구부를 결정화(백화(白化))한 것)을 사용한다. 이 프리폼(P)을 연신 효과를 발현할 수 있는 온도, 예를 들면 70∼130℃, 더 바람직하게는 90∼120℃ 정도로 가열하고, 50∼230℃, 더 바람직하게는 70∼180℃, 연신 표면적 배율이 4∼22배(더 바람직하게는 6∼15배, 용량으로 완성품보다도 1.2∼2.5배 정도의 오버사이즈)로 하는 조건 하에서, 1회째의 2축 연신에 의한 블로우 성형을 행한다. 다음에, 이렇게 하여 얻어진 블로우 성형품에 110∼255℃, 더 바람직하게는 130∼200℃의 온도 하에서, 완성품보다도 0.60∼0.95배 정도까지 수축시키는 강제적인 가열 처리를 실시하여 내부의 잔류 응력을 제거하고, 60∼170℃, 더 바람직하게는 80∼150℃의 온도 하에서 2회째의 2축 연신에 의한 블로우 성형을 행한다.In order to manufacture such a container, the preform P as shown in FIG. 2 obtained by blending the gas barrier material (G) with respect to the mother phase (1a) and undergoing injection molding, extrusion molding, or the like is crystallized (whitening). Use one)). The preform P is heated to a temperature at which an stretching effect can be expressed, for example, 70 to 130 ° C, more preferably about 90 to 120 ° C, and 50 to 230 ° C, more preferably 70 to 180 ° C, and stretching. Blow molding by the first biaxial stretching is performed under the condition that the surface area magnification is 4 to 22 times (more preferably, 6 to 15 times and an oversize of about 1.2 to 2.5 times the capacity of the finished product). Next, the blow molded article thus obtained is subjected to a forcible heat treatment that shrinks it to about 0.60 to 0.95 times as compared to the finished product at a temperature of 110 to 255 캜, more preferably 130 to 200 캜, thereby removing residual stress in the interior. Blow molding by the second biaxial stretching at a temperature of from 60 to 170 ° C, more preferably from 80 to 150 ° C.
도 3a∼3d는 1.5ℓ 내열 용기의 프리폼의 상태로부터 성형품에 이르기까지 상기 각 단계에서의 외관 형상을 모식적으로 나타낸다. 도면 중 P1은 1차 블로우중간체, P2는 가열 처리 후의 1차 블로우 중간체를 나타낸 것이다.3A to 3D schematically show an appearance shape at each step from the state of the preform of the 1.5 L heat-resistant container to the molded article. In the figure, P 1 represents a primary blow intermediate and P 2 represents a primary blow intermediate after heat treatment.
상기와 같이, 가열 처리를 그 사이에 갖는 적어도 2회의 2축 연신 블로우 성형을 거쳐 제조된 용기는, 그 본체 부분에서의 잔류 응력이 극히 경감되며, 또한, 수지의 밀도가 상승하므로, 외부로부터의 열에 대한 강도가 높아짐(내열성의 개선)과 동시에, 가스배리어성이 더 한층 개선된다.As described above, the container produced through at least two biaxially stretch blow moldings having a heat treatment therebetween is extremely reduced in residual stress in the main body portion, and the density of the resin rises, so that At the same time as the strength against heat (improvement of heat resistance) is improved, the gas barrier resistance is further improved.
도 4a, 4b는 본 발명에 따른 용기의 요부를 확대하여 나타낸 다른 구성예를 나타낸 것이며, 모상(1a)에 가스배리어재(G)를 블렌드한 것을 베이스층(b1)으로 하고, 가스배리어성이 높은 것을 보호층(b2)로 하여 이들을 교호로 서로 겹친 다층 구조(2종 3층, 또는 2종 5층 등)로 할 수 있다. 이 경우, 가스배리어성을 현저히 높일 수 있으므로, 상품의 쉘프 라이프를 더 한층 연장할 수 있게 된다.4A and 4B show another structural example in which the main part of the container according to the present invention is shown in an enlarged manner, and the base layer b 1 is obtained by blending the gas barrier material G with the mother phase 1a. that the high can be a protection layer (b 2) in the multi-layer structure thereof laid one on the other alternately (in two-kind three-layer, or two or five layers, and so on). In this case, since the gas barrier property can be significantly improved, the shelf life of the product can be further extended.
도 4a, 4b에 나타낸 다층 구조로 되는 용기는, 대응하는 다층 구조를 갖는 프리폼을 사용함으로써 성형할 수 있다. 본 발명에서는 2종 3층, 및 2종 5층을 예시하였지만, 적층 구조에 대해서는 특히 한정되지 않고, 용기의 용도에 따라 적합하게 변경할 수 있다.The container which becomes a multilayered structure shown to FIG. 4A, 4B can be shape | molded by using the preform which has a corresponding multilayered structure. In the present invention, two kinds, three layers, and two kinds and five layers are exemplified, but the laminated structure is not particularly limited and can be appropriately changed depending on the use of the container.
모상(1a)을 구성하는 수지는 폴리에틸렌테레프탈레이트 이외에, 폴리부틸렌테레프탈레이트나 폴리에틸렌나프탈레이트 등의 포화 폴리에스테르계 열가소성 합성 수지를 사용할 수 있다.In addition to the polyethylene terephthalate, a saturated polyester-based thermoplastic synthetic resin such as polybutylene terephthalate or polyethylene naphthalate can be used for the resin constituting the mother phase 1a.
이러한 모상(1a)에 블렌드할 수 있는 배리어재로서는, 메탁실릴렌기 함유 폴리아미드 수지로서, 예를 들면 폴리메탁실릴렌아디파미드(poly-m-xylyleneadipamide) 수지(상품명 MXD-6: 미쯔비시 가스 가가쿠제)가 적합하며, 그 이외에, 비정질 폴리에스테르 수지, 예를 들면 테레프탈산, 이소프탈산, 에틸렌글리콜, 및 그 외의 디올 성분체 등의 공중합체나 에틸렌나프탈레이트-에틸렌테레프탈레이트 공중합 수지가 있다.As a barrier material which can be blended in such a mother phase 1a, it is a polysilyl group-containing polyamide resin, for example, a poly-m-xylyleneadipamide resin (brand name MXD-6: Mitsubishi Gas Kaga) Coupe) is suitable, and there are other copolymers such as amorphous polyester resins such as terephthalic acid, isophthalic acid, ethylene glycol, and other diol components, and ethylene naphthalate-ethylene terephthalate copolymer resin.
배리어재의 배합 비율은, 성형성 등을 고려한 경우에 0.5∼10질량%, 바람직하게는 7질량%를 상한으로 함이 바람직한 비율이지만, 리사이클의 관점을 고려하면 5질량% 미만으로 함이 바람직하다.The blending ratio of the barrier material is preferably in the range of 0.5 to 10% by mass, preferably 7% by mass in consideration of moldability and the like, but is preferably less than 5% by mass in view of recycling.
보호층(b2)으로서는, 메탁실릴렌기 함유 폴리아미드 수지, 비정질 폴리에스테르 수지, 에틸렌나프탈레이트-에틸렌테레프탈레이트 공중합 수지 또는 에틸렌-비닐알코올 공중합 수지(EVOH) 등을 사용할 수 있다.As the protective layer (b 2 ), a methacrylic group-containing polyamide resin, an amorphous polyester resin, an ethylene naphthalate-ethylene terephthalate copolymer resin, an ethylene-vinyl alcohol copolymer resin (EVOH), or the like can be used.
도 5a∼5c에 나타낸 것 같은 내열성 각(角) 바틀(bottle, 350㎖, 500㎖)을 제작하기 위하여, PET 수지 단체(單體)의 프리폼을 사용하여 1회의 블로우 성형(싱글 블로우)를 행한 경우와, PET 수지에 배리어재를 블렌드한 프리폼을 사용하여, 가열 처리를 그 사이에 갖는 2회의 블로우 성형(더블 블로우)을 행한 경우에 대하여 비교를 행하였다.One blow molding (single blow) was performed using a preform of a single piece of PET resin to produce a heat resistant bottle (350 ml, 500 ml) as shown in FIGS. 5A to 5C. The case was compared with the case where the two blow molding (double blow) which has heat processing in between was performed using the preform which blended the barrier material to PET resin.
각각의 블로우 성형에 의해 얻어진 용기의 산소 투과량 비율(산소 투과 비율) 및 쉘프 라이프에 대하여 조사한 결과를 표 1 및 표 2에 각각 나타낸다.Table 1 and Table 2 show the results of the oxygen permeation rate (oxygen permeation rate) and shelf life of the containers obtained by the respective blow moldings.
싱글 블로우의 성형 조건:Molding conditions for single blow:
-금형 온도(본체): 110℃Mold temperature (the body): 110 degrees Celsius
-블로우 압력: 3.92MPaBlow pressure: 3.92 MPa
-연신 스피드: 42cm/sElongation: 42cm / s
더블 블로우의 성형 조건:Molding condition of double blow:
1회째의 2축 연신 블로우 성형First biaxial stretch blow molding
-금형 온도(본체): 165℃Mold temperature (main body): 165 ° C
-블로우 압력: 2.35MPaBlow pressure: 2.35 MPa
-연신 스피드: 40cm/sElongation speed: 40cm / s
2회째의 2축 연신 블로우 성형Second biaxial stretching blow molding
-금형 온도(본체): 104℃Mold temperature (main body): 104 degrees Celsius
-블로우 압력: 3.92MPaBlow pressure: 3.92 MPa
표 1: (350㎖ 각 바틀)Table 1: (350ml each bottle)
표 2: (500㎖ 각 바틀)Table 2: (500ml each bottle)
표 1 및 표 2로부터 명백한 바와 같이, 본 발명에 따른 용기에 있어서는, 산소 투과량을 크게 저감할 수 있으며, 상품의 쉘프 라이프를 현저히 연장할 수 있음이 확인되었다.As apparent from Table 1 and Table 2, it was confirmed that in the container according to the present invention, the oxygen permeation amount can be greatly reduced, and the shelf life of the product can be significantly extended.
또한, 내열성에 대해서는, 싱글 블로우에 의해 제조된 용기에서는, 내용물의 온도가 85∼87℃ 정도에서 형상 변형이 생긴데 대하여, 본 발명에 따른 용기에 있어서는, 90∼93℃ 정도까지 형상 변형이 생기지 않고, 내열성에 관해서도 현저한 개선을 보였다.In addition, about the heat resistance, in the container manufactured by the single blow, the shape deformation generate | occur | produces at the temperature of about 85-87 degreeC, but in the container which concerns on this invention, shape deformation does not occur about 90-93 degreeC. In addition, it also showed a remarkable improvement in terms of heat resistance.
이상의 기재로부터 명백한 바와 같이, 본 발명에 의하면, 내열성은 물론이고, 가스배리어성을 높일 수 있으므로, 용기의 용도의 확대를 꾀할 수 있을 뿐만 아니라, 내용물의 품질을 장기에 걸쳐 유지할 수 있다,As is apparent from the above description, according to the present invention, not only heat resistance but also gas barrier properties can be improved, not only the use of the container can be expanded, but also the quality of the contents can be maintained for a long time.
또한, 본 발명이 상기 실시예에 한정되는 것이 아니고, 많은 변형 태양으로 실시할 수 있음은 말할 것도 없다.In addition, this invention is not limited to the said Example, Needless to say that it can implement in many modified aspects.
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| US8343604B2 (en) | 2008-03-31 | 2013-01-01 | Yoshino Kogyosho Co., Ltd. | Synthetic resin container with high barrier properties |
| KR101227299B1 (en) * | 2005-08-05 | 2013-01-29 | 기린비루 가부시키가이샤 | Sealed container with resealability |
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| JP2000289099A (en) * | 1999-04-05 | 2000-10-17 | Toppan Printing Co Ltd | Composition of blow molding resin and molded container |
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| KR101227299B1 (en) * | 2005-08-05 | 2013-01-29 | 기린비루 가부시키가이샤 | Sealed container with resealability |
| US8343604B2 (en) | 2008-03-31 | 2013-01-01 | Yoshino Kogyosho Co., Ltd. | Synthetic resin container with high barrier properties |
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