TWI451971B - As a film for thermoforming sheet laminates - Google Patents

Description

作為熱成形板片層積用薄膜之用途Use as a film for thermoforming sheet laminate

本發明關於新穎的用於熱成形板片之層積用薄膜，更詳細地，關於層積在成為熱成形用板片的基底之樹脂板片時的層合適合性優異，對與樹脂板片層合後所得之熱成形板片進行熱成形而得之熱成形體，可賦予優異的光澤性之用於熱成形板片之層積用薄膜。The present invention relates to a novel film for lamination of a thermoformed sheet, and more particularly to a resin sheet which is laminated on a resin sheet which is a base of a sheet for thermoforming, and which is excellent in lamination suitability, and a resin sheet. The thermoformed sheet obtained by lamination is a thermoformed body obtained by thermoforming, and a film for lamination for thermoforming sheets which imparts excellent glossiness can be provided.

目前，於便當容器、托盤、蓋飯容器等食品包裝容器及一般包裝容器中，使用聚烯烴板片，尤其因為微波爐的普及而使用耐熱性高的聚丙烯板片或發泡聚丙烯板片等的樹脂板片。於此等樹脂板片的許多情況中，以提高圖案設計性、賦予高級感為目的，貼合施有印刷的聚丙烯系薄膜。貼合於樹脂板片的聚丙烯系薄膜係使用無拉伸聚丙烯薄膜(以下記載為CPP薄膜)、二軸拉伸聚丙烯薄膜(以下記載為OPP薄膜)。At present, polyolefin sheets are used in food packaging containers and general packaging containers such as containers, trays, and rice bowls, and in particular, polypropylene sheets or foamed polypropylene sheets having high heat resistance are used because of the spread of microwave ovens. Resin sheet. In many cases of such a resin sheet, a polypropylene-based film to which printing is applied is bonded for the purpose of improving pattern design and imparting a high-grade feeling. The polypropylene-based film to be bonded to the resin sheet is a non-oriented polypropylene film (hereinafter referred to as a CPP film) or a biaxially oriented polypropylene film (hereinafter referred to as an OPP film).

上述CPP薄膜由於熱成形性優異，故亦可適應於如深拉容器的熱成形體之製造，但於與板片貼合時若採用可最廉價製造的擠出層合法，由於有層合後CPP薄膜喪失光澤，層合板片熱成形後的熱成形體之表面光澤變差問題，而希望改善它。Since the CPP film is excellent in thermoformability, it can also be applied to the production of a hot-formed body such as a deep-drawn container. However, when it is bonded to a sheet, the extrusion layering method which can be manufactured at the lowest cost is used, since it is laminated. The CPP film loses its luster, and the surface of the thermoformed body after thermoforming of the laminated sheet deteriorates, and it is desired to improve it.

另一方面與CPP薄膜相比，OPP薄膜之層合後及熱成形後的光澤雖然大幅提高，但熱成形條件有限制，得到如一部分的深拉容器之熱成形體時有熱成形性差的問題。On the other hand, compared with the CPP film, the gloss of the OPP film after lamination and after hot forming is greatly improved, but the thermoforming conditions are limited, and the hot formability of a part of the deep drawn container is poor. .

此等熱成形體(容器)一般係藉由真空成形、氣壓成形等的熱成形法來製造。此熱成形方法係在藉由紅外線加熱器等將樹脂板片加熱後，以機械力、真空、氣壓等的外力使該板片緊貼於模具而成形的方法。These hot-formed bodies (containers) are generally produced by a thermoforming method such as vacuum forming or air pressure forming. This thermoforming method is a method in which a resin sheet is heated by an infrared heater or the like, and the sheet is brought into close contact with a mold by an external force such as mechanical force, vacuum, or air pressure.

於將CPP薄膜貼合於樹脂板片，為了改善層合後的光澤及將層合板片熱成形後的容器光澤，有進行以下的檢討。例如，有提案於聚丙烯系樹脂發泡板片的至少一面上，層積聚丙烯系樹脂中摻合有結晶核劑的無拉伸聚丙烯系樹脂薄膜之方法(參照專利文獻1)。此無拉伸聚丙烯系樹脂薄膜的聚丙烯系樹脂，依照專利文獻1的實施例，係聚丙烯均聚物(均聚丙烯)。藉由在聚丙烯均聚物中添加結晶核劑，層積於樹脂板片上，雖然在熱成形後可提高某一程度的光澤，但是表面有白濁感，在此點有改善的餘地。In order to bond the CPP film to the resin sheet, the following review was conducted in order to improve the gloss after lamination and the gloss of the container after thermoforming the laminated sheet. For example, there is a method of laminating a non-stretched polypropylene-based resin film in which a nucleating agent is mixed with a polypropylene-based resin on at least one surface of a polypropylene resin foamed sheet (see Patent Document 1). The polypropylene-based resin of the unstretched polypropylene resin film is a polypropylene homopolymer (homopolypropylene) according to the example of Patent Document 1. By adding a crystal nucleating agent to the polypropylene homopolymer and laminating it on the resin sheet, although a certain degree of gloss can be improved after the thermoforming, the surface has a white turbid feeling, and there is room for improvement in this point.

又，同樣地作為熱成形用的樹脂板片，有提案由在具有特定結晶熔點的2種聚丙烯系樹脂中摻合有結晶核劑的樹脂組成物所成的板片(參照專利文獻2)。再者，有提案在表面層中摻合於特定密度、MFR的丙烯聚合物中用金屬茂觸媒系的乙烯系聚合物、核劑，而且在中間層摻合特定MFR的丙烯．α-烯烴無規共聚物、核劑所成的層積板片(參照專利文獻3)。然而，上述技術雖然提高所得到的熱成形體之光澤，但是有表面白濁感的問題。In the same manner, as a resin sheet for thermoforming, a sheet formed of a resin composition in which a crystal nucleating agent is blended in two kinds of polypropylene resins having a specific crystal melting point is proposed (see Patent Document 2). . Furthermore, it is proposed to incorporate a metallocene catalyst-based vinyl polymer, a nucleating agent in a propylene polymer of a specific density, MFR in a surface layer, and to incorporate a specific MFR propylene in the intermediate layer. A laminated sheet made of an α-olefin random copolymer or a nucleating agent (see Patent Document 3). However, although the above technique improves the gloss of the obtained hot formed body, it has a problem that the surface is cloudy.

一般地，熱成形體例如熱成形後的容器之光澤，於依照JIS K7105的60度鏡面法所測定的光澤值中，若65%以上則是具有光澤感的容器，若為75%以上則可說是更高商品價值的光澤容器。但是，光澤值高的容器，容器表面的白濁感也大，容器表面帶白色地映出而成為看起來混濁的狀態。In general, the gloss of the thermoformed body, for example, a container after thermoforming, is a container having a glossiness when it is 65% or more in a gloss value measured by a 60-degree mirror method according to JIS K7105, and if it is 75% or more, It is a glossy container that is a higher commodity value. However, in the container having a high gloss value, the surface of the container has a large white turbidity, and the surface of the container is white-colored and appears to be turbid.

特別地，將在著色成黑色、紅色等顏色的聚丙烯系板片上貼合有CPP薄膜的熱成形用板片進行熱成形時，或在聚丙烯系板片上貼合有經印刷的CPP薄膜之熱成形用板片進行熱成形時，前述層積薄膜的白濁大者，會發生其著色的顏色或花紋無法鮮明地映出之現象。In particular, when a sheet for thermoforming in which a CPP film is bonded to a polypropylene-based sheet colored in a color such as black or red is subjected to thermoforming, or a printed CPP film is bonded to a polypropylene sheet. When the sheet for thermoforming is subjected to hot forming, the white turbidity of the laminated film is large, and the color or pattern of the colored color cannot be clearly reflected.

[專利文獻l]特開2002-103541號公報[專利文獻2]特開2002-348421號公報[專利文獻3]日本發明專利第3416433號公報[Patent Document 1] JP-A-2002-348421 (Patent Document 3) Japanese Patent No. 3416433

本發明之目的為提供用於熱成形板片之層積用薄膜，其係當作在成為熱成形用板片的基底之樹脂板片上層積的薄膜，層積在樹脂板片上時的層合適合性優異，而且於將層積有此的熱成形板片進行熱成形而得之熱成形體中，表面光澤優異，且可給予白濁小的熱成形體。An object of the present invention is to provide a film for lamination of a thermoformed sheet which is laminated on a resin sheet which is a base of a sheet for thermoforming, and laminated when laminated on a resin sheet. In the thermoformed body obtained by thermoforming a thermoformed sheet obtained by laminating such a laminate, the surface of the thermoformed body is excellent, and a hot formed body having a small white turbidity can be given.

本發明者們為達成上述目的而重複精心研究。結果，發現由在特定丙烯均聚物中加有有機結晶核劑的基層與在丙烯系無規共聚物中加有有機結晶核劑的光澤層以特定厚度所形成的實質上無拉伸的聚丙烯系薄膜，係可完成達成前述課題，終於完成本發明。The present inventors have repeatedly conducted intensive studies to achieve the above object. As a result, it was found that a substantially unstretched polycondensate formed of a base layer to which an organic crystal nucleating agent is added in a specific propylene homopolymer and a gloss layer to which an organic crystal nucleating agent is added in a propylene-based random copolymer is formed with a specific thickness. The acryl-based film can achieve the above problems and finally complete the present invention.

即，解決上述問題的本發明係包含下述事項當作要旨。That is, the present invention for solving the above problems includes the following matters as the gist.

(1)一種用於熱成形板片之層積用薄膜，其係由基層與光澤層所成的無拉伸或低拉伸薄膜，該基層係含有99~99.97質量%的熔點為162℃以上的丙烯均聚物及0.03~1質量%的有機結晶核劑，且具有10μm以上的厚度，該光澤層係形成在該基層的至少一面上，含有99~99.97質量%的丙烯系無規共聚物及0.03~1質量%的有機結晶核劑，且具有1μm以上的厚度。(1) A film for lamination for thermoforming sheets, which is an unstretched or low-stretch film formed of a base layer and a gloss layer, wherein the base layer contains 99 to 99.97% by mass of a melting point of 162 ° C or more. a propylene homopolymer and 0.03 to 1% by mass of an organic crystal nucleating agent having a thickness of 10 μm or more, the gloss layer being formed on at least one side of the base layer and containing 99 to 99.97% by mass of a propylene-based random copolymer And 0.03 to 1% by mass of the organic crystal nucleating agent, and having a thickness of 1 μm or more.

(2)如(1)記載的用於熱成形板片之層積用薄膜，其中光澤層係形成在基層的一面上，於與該光澤層相反側的基層面上，層積有由熔點130℃以上的丙烯系無規共聚物所成的具有1μm以上的厚度之黏著層。(2) The film for lamination of a thermoformed sheet according to (1), wherein the gloss layer is formed on one side of the base layer, and the melting point is laminated on the base layer on the side opposite to the gloss layer. An adhesive layer having a thickness of 1 μm or more formed of a propylene random copolymer of ° C or more.

(3)如(1)或(2)記載的用於熱成形板片之層積用薄膜，其中薄膜的總厚度為15~100μm，基層的厚度係全體的50~90%。(3) The film for lamination of a thermoformed sheet according to (1) or (2), wherein the total thickness of the film is 15 to 100 μm, and the thickness of the base layer is 50 to 90% of the entire thickness.

(4)如申請專利範圍第1至3項中任一項記載的用於熱成形板片之層積用薄膜，其中基層所含有的有機結晶核劑或光澤層所含有的有機結晶核劑之任一者或兩者，係磷酸酯金屬鹽或下述通式(1)所示的醯胺系化合物。(4) The film for lamination of a thermoformed sheet according to any one of claims 1 to 3, wherein the organic crystal nucleating agent contained in the base layer or the organic crystal nucleating agent contained in the gloss layer is Either or both are a phosphate metal salt or a guanamine compound represented by the following formula (1).

[式中，R¹ 表示由1,2,3-丙烷三羧酸或1,2,3,4-丁烷四羧酸去除全部羧基後所得之殘基；3個或4個R² 係互相相同或不同，各自表示氫原子或碳數1~10的直鏈狀或支鏈狀的烷基；k表示3或4的整數]。 Wherein R ¹ represents a residue obtained by removing all carboxyl groups from 1,2,3-propanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid; and 3 or 4 R ² systems are mutually The same or different, each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms; k represents an integer of 3 or 4.

(5)如(1)~(4)中任一項記載的用於熱成形板片之層積用薄膜，其中在與光澤層相反側的薄膜表面上具有印刷層。(5) The film for lamination of a thermoformed sheet according to any one of (1) to (4) which has a printed layer on the surface of the film opposite to the gloss layer.

(6)一種熱成形用板片，其係在以前述光澤層當作表層的樹脂板片之至少一面上層積有上述(1)~(5)中任一項記載的用於熱成形板片之層積用薄膜。(6) A sheet for thermoforming in which at least one surface of the resin sheet having the gloss layer as a surface layer is laminated on the thermoformed sheet according to any one of the above (1) to (5). The film is laminated.

(7)一種熱成形體，其係由將上述(6)記載的熱成形用板片熱成形而得。(7) A thermoformed body obtained by thermoforming the sheet for thermoforming described in (6) above.

本發明的用於熱成形板片之層積用薄膜，由於層積在成為熱成形用板片的基底之樹脂板片時的層合適合性優異，且係低拉伸薄膜或實質上無拉伸的薄膜，故熱成形條件的限制少，尤其適合於如深拉容器的熱成形體之製造。又，藉由特別規定基層與光澤層的樹脂組成、層厚度，熱成形所得之熱成形體的光澤性優異，而且可得到具有無白濁感的表面之熱成形體。The film for lamination of the thermoformed sheet of the present invention is excellent in lamination suitability when laminated on a resin sheet which is a base of a sheet for thermoforming, and is a low stretch film or substantially no pull. The stretched film has less restrictions on thermoforming conditions and is particularly suitable for the manufacture of hot formed bodies such as deep drawn containers. Further, by specifying the resin composition and the layer thickness of the base layer and the gloss layer, the thermoformed body obtained by thermoforming is excellent in glossiness, and a thermoformed body having a surface having no white turbidity can be obtained.

〔實施發明的最佳形態〕[Best Mode for Carrying Out the Invention]

以下關於本發明，包含其最佳形態，更具體地作說明。Hereinafter, the present invention will be described in more detail with reference to its preferred form.

所謂用於熱成形板片之層積用薄膜，就是在聚丙烯系板片等的樹脂板片之至少一面上層積，與樹脂板片一體化而構成熱成形板片。該熱成形板片係藉由真空成形、氣壓成形等來賦形，使用作為各種容器。The film for lamination of the thermoformed sheet is laminated on at least one surface of a resin sheet such as a polypropylene sheet, and is integrated with the resin sheet to form a thermoformed sheet. The thermoformed sheet is shaped by vacuum forming, pneumatic forming, or the like, and used as various containers.

本發明的用於熱成形板片之層積用薄膜在達成指定效果上極重要的是：其係由以丙烯均聚物當作主成分的基層與以丙烯系無規共聚物當作主成分的光澤層所構成，基層含有99~99.97質量%的熔點162℃以上的丙烯均聚物與0.03~1質量%的有機結晶核劑，具有10μm以上的厚度，而且光澤層含有99~99.97質量%的丙烯系無規共聚物與0.03~1質量%的有機結晶核劑，具有1μm以上的厚度。The film for lamination of the thermoformed sheet of the present invention is extremely important in achieving a specified effect: it is composed of a base layer containing a propylene homopolymer as a main component and a propylene-based random copolymer as a main component. The base layer comprises 99 to 99.97% by mass of a propylene homopolymer having a melting point of 162 ° C or more and 0.03 to 1% by mass of an organic crystal nucleating agent having a thickness of 10 μm or more, and the gloss layer contains 99 to 99.97% by mass. The propylene-based random copolymer and 0.03 to 1% by mass of the organic crystal nucleating agent have a thickness of 1 μm or more.

以往，用於熱成形板片之層積用薄膜一般係使用丙烯的均聚物之無拉伸薄膜，但使用該薄膜來構成熱成形板片，進行熱成形時，所得到的熱成形體之表面光澤及白濁感差。此係因為在藉由加熱溫度將薄膜再熔融而結晶化時，球晶會成長，而發生表面皸裂，表面光澤降低。為了解決此現象，添加結晶核劑的方法係眾所周知，但是茲認為於丙烯均聚物或丙烯均聚物與丙烯-α烯烴無規共聚物或聚乙烯、聚丁烯等的聚烯烴之摻合物中加有結晶核劑時，在熔融後、再結晶化之際，由於丙烯均聚物之結晶化溫度比較高，球晶的尺寸容易變大，故發生白濁感。Conventionally, a film for lamination of a thermoformed sheet is generally a non-stretched film using a homopolymer of propylene. However, when the film is used to form a thermoformed sheet, the obtained hot formed body is subjected to thermoforming. Surface gloss and white turbidity are poor. This is because when the film is crystallized by remelting the film by the heating temperature, the spherulites grow, and surface cracking occurs, and the surface gloss is lowered. In order to solve this phenomenon, a method of adding a crystal nucleating agent is known, but it is considered that a propylene homopolymer or a propylene homopolymer is blended with a propylene-α-olefin random copolymer or a polyolefin such as polyethylene or polybutene. When a crystal nucleating agent is added to the material, the crystallization temperature of the propylene homopolymer is relatively high after melting and recrystallization, and the size of the spherulites tends to increase, so that a white turbidity is generated.

又，將在單獨的丙烯系無規共聚物中加有結晶核劑的薄膜層積到樹脂板片上而進行熱成形時，可改善白濁感。然而，由於薄膜比較柔軟，熱成形時會受到樹脂板片表面的凹凸之影響，故有改善光澤性的餘地。In addition, when a film in which a crystal nucleating agent is added to a single propylene random copolymer is laminated on a resin sheet and thermoformed, the white turbidity can be improved. However, since the film is relatively soft, it is affected by the unevenness on the surface of the resin sheet during thermoforming, so there is room for improvement in gloss.

相對於此，於本發明中，藉由使用由在結晶性高的丙烯均聚物中摻合有結晶核劑的具有特定厚度的基層、與在其至少一面上所形成的在丙烯系無規共聚物中摻合有結晶核劑的具有特定厚度之光澤層所成的層積用薄膜，在與樹脂板片的層積面上配置層積用薄膜的基層，可得到熱成形後的成形體中之白濁感少，且光澤性極優異的成形體。On the other hand, in the present invention, by using a base layer having a specific thickness in which a crystal nucleating agent is blended in a propylene homopolymer having high crystallinity, and a propylene-based random form formed on at least one side thereof A film for lamination formed by a gloss layer having a specific thickness in which a crystal nucleating agent is blended in a copolymer, and a base layer of a film for lamination is disposed on a laminated surface of a resin sheet, whereby a formed body after thermoforming can be obtained. A molded article having a small white turbidity and excellent gloss.

於本發明的用於熱成形板片之層積用薄膜中，基層所用的丙烯均聚物之由差示掃描熱量計所測定的熔點為162℃以上，較佳為163℃以上，更佳為163~170℃的範圍。於基層所用的聚丙烯之熔點低於162℃時，熱成形後的容器之光澤差。In the film for lamination of the thermoformed sheet of the present invention, the melting point of the propylene homopolymer used for the base layer measured by a differential scanning calorimeter is 162 ° C or higher, preferably 163 ° C or higher, more preferably 163~170 °C range. When the melting point of the polypropylene used in the base layer is lower than 162 ° C, the gloss of the container after thermoforming is poor.

又，上述丙烯均聚物在230℃的熔體質量流速(MFR)，若考慮製膜性則較佳為2~50克/10分鐘，更佳為4~20克/10分鐘的範圍。特佳為6~15克/10分鐘的範圍，因為可安定製膜時的厚薄。Further, the melt mass flow rate (MFR) of the propylene homopolymer at 230 ° C is preferably from 2 to 50 g/10 min, more preferably from 4 to 20 g/10 min, in consideration of film formability. It is especially suitable for the range of 6~15g/10min, because it can be customized when the film is thick.

以如上述的丙烯均聚物當作主成分所成的基層之厚度為10μm以上，較佳為12μm以上，特佳為12~80μm的範圍。基層的厚度若低於10μm，則熱成形後的容器之光澤差。The thickness of the base layer formed by using the above propylene homopolymer as a main component is 10 μm or more, preferably 12 μm or more, and particularly preferably 12 to 80 μm. If the thickness of the base layer is less than 10 μm, the gloss of the container after thermoforming is poor.

光澤層所用的丙烯系無規共聚物係丙烯與α-烯烴(包含乙烯)的無規共聚物。作為α-烯烴，較佳為碳數2~10的α-烯烴，具體地較宜使用乙烯、丁烯、戊烯-1、己烯-1、辛烯-1等。丙烯系無規共聚物中的丙烯單位之含有比例為99.7~85質量%，較佳為99~90質量%。再者，前述丙烯系無規共聚物的共聚合組成係可使用後述的核磁共振裝置來測定。The propylene-based random copolymer used for the gloss layer is a random copolymer of propylene and an α-olefin (including ethylene). The α-olefin is preferably an α-olefin having 2 to 10 carbon atoms, and specifically, ethylene, butene, pentene-1, hexene-1, octene-1 or the like is preferably used. The content ratio of the propylene unit in the propylene-based random copolymer is from 99.7 to 85% by mass, preferably from 99 to 90% by mass. Further, the copolymerization composition of the propylene-based random copolymer can be measured by using a nuclear magnetic resonance apparatus to be described later.

作為此等之中的丙烯系無規共聚物，較佳為丙烯-乙烯無規共聚物、丙烯-乙烯-丁烯無規共聚物，更佳為組成分佈窄的丙烯系無規共聚物。作為特佳的丙烯系無規共聚物，可例示由金屬茂觸媒所製造的由凝膠滲透層析術所測定的重量平均分子量(Mw)與數平均分量(Mn)之比(Mw/Mn)為4.5以下的丙烯系無規共聚物。此等丙烯系無規共聚物可各自單獨使用，也可使用2種類以上。The propylene-based random copolymer among these is preferably a propylene-ethylene random copolymer or a propylene-ethylene-butene random copolymer, and more preferably a propylene-based random copolymer having a narrow composition distribution. As a particularly preferable propylene-based random copolymer, the ratio of the weight average molecular weight (Mw) to the number average component (Mn) measured by gel permeation chromatography manufactured by a metallocene catalyst (Mw/Mn) can be exemplified. ) is a propylene-based random copolymer of 4.5 or less. These propylene random copolymers may be used alone or in combination of two or more.

於丙烯系無規共聚物中，較佳為以差示掃描熱量計所測定的熔點為130℃以上，更佳為133℃以上。於低於130℃時，成形後的容器之由於微波爐等的加熱後之耐熱性差。因此，丙烯系無規共聚物的熔點特佳為在133~157℃的範圍。上述丙烯系無規共聚物的熔點係可藉由適宜選擇其製程中所共聚合的單體之種類、比例的眾所周知方法來調整。In the propylene-based random copolymer, the melting point measured by a differential scanning calorimeter is preferably 130 ° C or higher, more preferably 133 ° C or higher. When the temperature is lower than 130 ° C, the formed container is inferior in heat resistance due to heating by a microwave oven or the like. Therefore, the melting point of the propylene random copolymer is particularly preferably in the range of 133 to 157 °C. The melting point of the above propylene random copolymer can be adjusted by a well-known method of appropriately selecting the kind and ratio of the monomers copolymerized in the process.

又，上述丙烯系無規共聚物在230℃的MFR，若考慮製膜性，則合適為2~50克/10分鐘，較佳為4~20克/10分鐘的範圍。更佳為6~15克/10分鐘的範圍，因為可安定製膜時的厚薄。Further, the MFR of the propylene-based random copolymer at 230 ° C is preferably in the range of 2 to 50 g/10 min, preferably 4 to 20 g/10 min, in consideration of film formability. More preferably, it is in the range of 6 to 15 g/10 minutes because the thickness of the film can be customized.

以如上述的丙烯系無規共聚物當作主成分所成的光澤層之厚度為1μm以上，較佳為2μm以上，特佳為2~10μm的範圍。於光澤層的厚度低於1μm時，白濁感差，而且熱成形後的光澤差。特別地，在成形為深拉容器時，光澤顯著地降低。The thickness of the gloss layer formed by using the propylene-based random copolymer as described above as a main component is 1 μm or more, preferably 2 μm or more, and particularly preferably 2 to 10 μm. When the thickness of the gloss layer is less than 1 μm, the white turbidity is poor, and the gloss after thermoforming is poor. In particular, when formed into a deep drawn container, the gloss is remarkably lowered.

又，於與樹脂板片層積之際，以提高樹脂板片與層積用薄膜之黏著性為目的，在層積薄膜之與光澤層相反的基層面上亦可設置黏著層。又，於基層的兩面上設置光澤層時，可使用一方的光澤層當作黏著層，而且也可在一方的光澤層之表面上設置黏著層。黏著層例如係可藉由層積1μm以上的熔點為130℃以上的丙烯系無規共聚物來形成。於設置黏著層時，其厚度為1μm以上，較佳為2μm以上，特佳為2~10μm的範圍。於黏著層的厚度低於1μm時，有得不到充分的黏著性之虞。構成黏著層的丙烯系無規共聚物係沒有特別的限制，可合適地使用前述光澤層所用的丙烯系無規共聚物。Further, for the purpose of improving the adhesion between the resin sheet and the film for lamination, the adhesive layer may be provided on the base layer of the laminated film opposite to the gloss layer. Further, when a gloss layer is provided on both surfaces of the base layer, one of the gloss layers may be used as the adhesive layer, and an adhesive layer may be provided on the surface of one of the gloss layers. The adhesive layer can be formed, for example, by laminating a propylene-based random copolymer having a melting point of 1 μm or more and a melting point of 130° C. or more. When the adhesive layer is provided, the thickness thereof is 1 μm or more, preferably 2 μm or more, and particularly preferably 2 to 10 μm. When the thickness of the adhesive layer is less than 1 μm, sufficient adhesiveness cannot be obtained. The propylene-based random copolymer constituting the adhesive layer is not particularly limited, and a propylene-based random copolymer used for the above-mentioned gloss layer can be suitably used.

含有此等基層、光澤層及視需要的黏著層之本發明的用於熱成形板片之層積用薄膜之總厚度，只要是可確保前述基層與光澤層的厚度之總厚度即可，並沒有特別的限制，一般為15~100μm，較佳為18~60μm。又，基層的厚度較佳為層積薄膜的總厚之50~90%。於基層的厚度低於總厚的50%時，熱成形後的表面光澤有降低之虞。又，基層的厚度若超過總厚的90%，則有白濁感增加、外觀變差之虞。The total thickness of the film for lamination of the thermoformed sheet of the present invention containing the base layer, the gloss layer and the optional adhesive layer may be any thickness as long as the thickness of the base layer and the gloss layer can be ensured, and There is no particular limitation, and it is usually 15 to 100 μm, preferably 18 to 60 μm. Further, the thickness of the base layer is preferably from 50 to 90% of the total thickness of the laminated film. When the thickness of the base layer is less than 50% of the total thickness, the surface gloss after thermoforming is lowered. Further, when the thickness of the base layer exceeds 90% of the total thickness, the white turbidity is increased and the appearance is deteriorated.

於構成本發明的用於熱成形板片之層積用薄膜之基層及光澤層中，摻合有有機結晶核劑。無機系結晶核劑係未必能改善與樹脂板片層合後及熱成形後的容器之光澤。An organic crystal nucleating agent is blended in the base layer and the gloss layer constituting the film for lamination of the thermoformed sheet of the present invention. The inorganic crystal nucleating agent does not necessarily improve the gloss of the container after lamination with the resin sheet and after hot forming.

作為有機結晶核劑，可舉出二亞苄基山梨糖醇、二甲基亞苄基山梨糖醇等的山梨糖醇系衍生物、松香金屬氯化物、苯甲酸金屬鹽、磷酸酯金屬、前述通式(1)所示的醯胺系化合物等。其中，磷酸酯金屬鹽中的磷酸酯鋁鹽、醯胺系化合物中的前述通式(1)之R² 為氫原子或甲基的醯胺系化合物,例如1,2,3-丙烷三羧酸三環己基醯胺、1,2,3-丙烷三羧酸三(2-甲基環己基醯胺)、1,2,3-丙烷三羧酸三(3-甲基環己基醯胺)、1,2,3-丙烷三羧酸三(4-甲基環己基醯胺)、1,2,3,4-丁烷四羧酸四環己基醯胺、1,2,3,4-丁烷四羧酸四(2-甲基環己基醯胺)、1,2,3,4-丁烷四羧酸四(3-甲基環己基醯胺)、1,2,3,4-丁烷四羧酸四(4-甲基環己基醯胺)等，在熱成形後的光澤提高之效果係最高。Examples of the organic crystal nucleating agent include sorbitol-based derivatives such as dibenzylidene sorbitol and dimethylbenzylidene sorbitol, rosin metal chlorides, metal benzoate salts, and phosphate metal salts. A guanamine-based compound represented by the formula (1). In the phosphate aluminum salt of the phosphate metal salt, the amide compound of the above formula (1) wherein R ² is a hydrogen atom or a methyl group, for example, 1,2,3-propane tricarboxylate Tricyclohexyl decylamine, 1,2,3-propane tricarboxylic acid tris(2-methylcyclohexyl decylamine), 1,2,3-propane tricarboxylic acid tris(3-methylcyclohexyl decylamine) 1,2,3-propanetricarboxylic acid tris(4-methylcyclohexyldecylamine), 1,2,3,4-butanetetracarboxylic acid tetracyclohexyldecylamine, 1,2,3,4- Butane tetracarboxylic acid tetrakis(2-methylcyclohexyldecylamine), 1,2,3,4-butanetetracarboxylic acid tetrakis(3-methylcyclohexyldecylamine), 1,2,3,4- Butane tetracarboxylic acid tetrakis(4-methylcyclohexyldecylamine) and the like have the highest effect of improving gloss after thermoforming.

有機結晶核劑的添加量在基層及光澤層中，相對於99~99.97質量%的聚丙烯成分(基層的丙烯均聚物，光澤層的丙烯系無規共聚物)而言皆為0.03~1質量%，較佳為0.1~0.5質量%，特佳為0.12~0.4質量%的範圍。添加量若低於0.03質量%，則印刷時及與樹脂板片的層合時之尺寸安定性差，而且熱成形後的光澤差。又，有機結晶核劑的添加量若超過1質量%，則由於成形後的光澤性之提高效果已到達頂點，經濟上不利。關於黏著層，有無添加有機結晶核劑係沒有特別的限定。The amount of the organic crystal nucleating agent added is 0.03 to 1 in the base layer and the gloss layer with respect to 99 to 99.97 mass% of the polypropylene component (the propylene homopolymer of the base layer and the propylene random copolymer of the gloss layer). The mass % is preferably from 0.1 to 0.5% by mass, particularly preferably from 0.12 to 0.4% by mass. When the amount is less than 0.03% by mass, the dimensional stability at the time of printing and lamination with the resin sheet is inferior, and the gloss after thermoforming is inferior. In addition, when the amount of the organic crystal nucleating agent added is more than 1% by mass, the effect of improving the gloss after molding has reached the peak, which is economically disadvantageous. Regarding the adhesive layer, the presence or absence of the addition of the organic crystal nucleating agent system is not particularly limited.

於本發明中，上述核劑的添加除了具有提高用於熱成形板片之層積用薄膜的光澤性等之效果，亦發揮提高該薄膜的拉伸彈性模數之效果。即，藉由有機結晶核劑的添加，上述薄膜的行進方向(以下記載為MD方向)之拉伸彈性模數係顯示超過1000MPa之值。因此於本發明中，於樹脂板片上層積用於熱成形板片之層積用薄膜而構成熱成形板片之際，發揮層積時的層合適合性優異之效果。又，如後述地，於形成印刷層之際，由於間距安定性優異，有效於製造定位成形容器。所謂的定位成形容器，就是圖案經常配合一定位置的成形容器。為了進行定位成形，於印刷在層積用薄膜之際要求間距偏差少，而且於層積用薄膜與樹脂板片的層合時亦要求間距偏差少。本發明的用於熱成形板片之層積用薄膜係回應該要求。In the present invention, the addition of the above-mentioned nucleating agent has an effect of improving the glossiness of the film for lamination of the thermoformed sheet, and the effect of improving the tensile modulus of the film. In other words, the tensile elastic modulus of the traveling direction of the film (hereinafter referred to as MD direction) is more than 1000 MPa by the addition of the organic crystal nucleating agent. Therefore, in the present invention, when a film for lamination of a thermoformed sheet is laminated on a resin sheet to form a thermoformed sheet, an effect of excellent lamination suitability at the time of lamination is exhibited. Further, as will be described later, when the printed layer is formed, it is excellent in pitch stability and is effective for producing a positioning molded container. The so-called positioning forming container is a forming container in which the pattern often matches a certain position. In order to carry out the positioning and molding, it is required to have a small variation in pitch when printing on the film for lamination, and it is also required to have a small variation in pitch when laminating the film for lamination and the resin sheet. The film for lamination of the thermoformed sheet of the present invention is required to be returned.

又，於本發明的用於熱成形板片之層積用薄膜中，可按照需要藉由乾層合、擠出層合法等眾所周知的方法來層合聚丙烯、聚乙烯、聚苯乙烯、聚醯胺、聚對苯二甲酸乙二酯等其它可熱成形的薄膜而使用。於此情況下，層合面必須是基層側。Further, in the film for lamination of the thermoformed sheet of the present invention, polypropylene, polyethylene, polystyrene, and poly are laminated by a well-known method such as dry lamination or extrusion lamination as needed. Other thermoformable films such as guanamine and polyethylene terephthalate are used. In this case, the laminated surface must be the base side.

於本發明的用於熱成形板片之層積用薄膜的原料樹脂中，視需要亦可摻合抗靜電劑、防霧濁劑、防黏連劑、抗氧化劑、光安定劑、滑劑、界面活性劑、著色劑、抗菌劑等眾所周知的添加劑。In the raw material resin for the film for lamination of the thermoformed sheet of the present invention, an antistatic agent, an antifogging agent, an anti-blocking agent, an antioxidant, a light stabilizer, a slip agent, or the like may be blended as needed. Well-known additives such as surfactants, colorants, and antibacterial agents.

本發明的用於熱成形板片之層積用薄膜係以無拉伸法所製膜者。若例示代表的方法，可舉出使用T模頭的擠壓成形、使用環狀模頭的吹脹成形法。於上述成形法中，前述用於熱成形板片之層積用薄膜，例如可合適地採用供料頭法或多歧管法的經由T模頭的共擠出法。The film for lamination of the thermoformed sheet of the present invention is formed by a film formed by a non-stretching method. The representative method is exemplified by extrusion molding using a T die and inflation molding using an annular die. In the above-mentioned molding method, the film for lamination for the thermoformed sheet may be, for example, a co-extrusion method via a T die by a feed head method or a multi-manifold method.

於上述使用T模頭的擠壓成形中，若具體顯示，可舉出將構成用於熱成形板片之層積用薄膜的樹脂組成物由各自的擠壓機經由T模頭法擠出熔融物，以可溫度調整的輥或可溫度調整的水槽來冷卻及捲繞的方法，或者，藉由空氣冷卻法或水冷法來冷卻該熔融物及捲繞的方法等。In the extrusion molding using the T die described above, the resin composition constituting the film for lamination of the thermoformed sheet is extruded and melted by a T die method from the respective extruders. The method of cooling and winding with a temperature-adjustable roller or a temperature-adjustable water tank, or a method of cooling the melt and winding by an air cooling method or a water cooling method.

所得到的層積用薄膜，係由於捲繞時的張力等而成為稍微拉伸程度的低拉伸或實質上無拉伸的薄膜。本發明的層積用薄膜，由於係低拉伸薄膜或實質上無拉伸的薄膜，故熱成形條件的限制少，尤其適合於如深拉容器的熱成形體之製造。The obtained film for lamination is a film which is low-stretched or substantially stretch-free in a slightly stretched state due to tension at the time of winding or the like. Since the film for lamination of the present invention is a low stretch film or a film which is substantially unstretched, the thermoforming conditions are less restricted, and it is particularly suitable for the production of a hot formed body such as a deep drawing container.

本發明的用於熱成形板片之層積用薄膜係可按照用途施予表面處理，進行印刷。表面處理方法係沒有特別的限制，一般以提高與印刷油墨的黏附性為目的，可進行電暈放電處理、火焰處理等。又，施予表面處理的面亦沒有特別的限制，可為一面或兩面。The film for lamination of the thermoformed sheet of the present invention can be subjected to surface treatment according to the use and printed. The surface treatment method is not particularly limited, and for the purpose of improving the adhesion to the printing ink, corona discharge treatment, flame treatment, or the like can be performed. Further, the surface to which the surface treatment is applied is not particularly limited and may be one side or two sides.

如此地經表面處理之本發明的用於熱成形板片之層積用薄膜，係在與光澤層的相反面上形成印刷層。本發明的層積用薄膜，由於印刷間距安定性優異，故可得到精度高的印刷薄膜。於薄膜由光澤層與基層所成時，印刷層係形成在基層面上。又，於薄膜由依順序層積光澤層與基層及黏著層所成時，在黏著層表面上形成印刷層。又，於基層的兩面上形成光澤層時，印刷層係形成在樹脂板片側所配置的光澤層面上。The film for lamination of the thermoformed sheet of the present invention which has been subjected to surface treatment in this manner forms a printed layer on the opposite side to the gloss layer. Since the film for lamination of the present invention is excellent in stability in printing pitch, a printed film having high precision can be obtained. When the film is formed of a gloss layer and a base layer, the printed layer is formed on the base layer. Further, when the film is formed by sequentially laminating the gloss layer, the base layer, and the adhesive layer, a printed layer is formed on the surface of the adhesive layer. Further, when a gloss layer is formed on both surfaces of the base layer, the printed layer is formed on the gloss layer disposed on the resin sheet side.

通常，印刷、層合時薄膜的拉伸張力係50~100N/m，此時的薄膜溫度為60℃以上。為了安定印刷時的間距，薄膜的行進方向(以下記載為MD方向)在23℃的拉伸彈性模數較佳為1000MPa以上，用於熱成形板片之層積用薄膜的薄膜寬度為1000mm寬且在100N荷重時的100℃之尺寸變化率較佳為15%以下。本發明的層積用薄膜，由於添加有機結晶核劑而使得上述薄膜在MD方向的拉伸彈性模數係顯示超過1000MPa之值，印刷及層合適合性優異。因此，將用本發明的層積用薄膜之印刷薄膜與樹脂板片貼合，進行熱成形，可得到表面光澤優異的定位成形容器。Usually, the stretching tension of the film during printing and lamination is 50 to 100 N/m, and the film temperature at this time is 60 ° C or higher. In order to stabilize the pitch at the time of printing, the traveling direction of the film (hereinafter referred to as the MD direction) is preferably 1000 MPa or more at 23 ° C, and the film width for the film for lamination of the thermoformed sheet is 1000 mm wide. Further, the dimensional change rate at 100 ° C at a load of 100 N is preferably 15% or less. In the film for lamination of the present invention, the tensile modulus of the film in the MD direction is more than 1000 MPa by the addition of the organic crystal nucleating agent, and the printing and lamination suitability are excellent. Therefore, the printed film of the film for lamination of the present invention is bonded to the resin sheet and thermoformed to obtain a positioning molded container excellent in surface gloss.

作為上述熱成形板片之基底所用的樹脂板片，可毫無限制地使用熱成形所用的眾所周知者。例如，作為聚丙烯系樹脂，一般使用丙烯的均聚物、以丙烯當作主要構成單位與丙烯以外的α-烯烴之共聚物。具體地，可舉出由丙烯均聚物、丙烯系無規共聚物、丙烯系嵌段共聚物等所成的聚丙烯系板片。As the resin sheet used for the base of the above-mentioned thermoformed sheet, the well-known one for thermoforming can be used without limitation. For example, as the polypropylene-based resin, a homopolymer of propylene and a copolymer of propylene as a main constituent unit and an α-olefin other than propylene are generally used. Specifically, a polypropylene-based sheet made of a propylene homopolymer, a propylene-based random copolymer, a propylene-based block copolymer or the like can be given.

又，作為其它樹脂，可舉出聚乙烯、聚苯乙烯、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等。Further, examples of the other resin include polyethylene, polystyrene, polyethylene terephthalate, and polybutylene terephthalate.

再者，作為前述聚丙烯系板片的形態，有將僅上述聚丙烯系樹脂成形為板片狀者，將聚丙烯系樹脂中摻合有填料的組成物成形成為板片狀(填料含有板片)，使聚丙烯系樹脂發泡而成形成為板片狀者(發泡板片)等。In addition, in the form of the polypropylene-based sheet, only the polypropylene-based resin is formed into a sheet shape, and a composition in which a filler is blended in a polypropylene-based resin is formed into a sheet shape (filler-containing sheet) (Piece), a polypropylene resin is foamed to form a sheet (foam sheet).

於使用將聚丙烯系樹脂中摻合有填料的組成物成形為板片狀者(含填料的板片)時，較佳為使用層積有不含填料的層積板片。於此情況下，藉由在層積板片之不含有填料的層之面上，將層積用薄膜層積，則成形後的光澤變更高。此情況下的熱成形板片之構成，例如係含填料的層/不含填料的層/本發明的用於熱成形板片之層積用薄膜。不含填料的層係可藉由與含填料的層之共擠出法或對含填料的板片之擠出層合法來形成。When a composition in which a filler is blended in a polypropylene resin is formed into a sheet shape (a sheet containing a filler), it is preferred to use a laminated sheet in which a filler is not contained. In this case, by laminating the film for lamination on the surface of the layer on which the filler is not contained in the laminated sheet, the gloss after molding is changed to be high. The composition of the thermoformed sheet in this case is, for example, a layer containing a filler/a layer containing no filler/a film for lamination of a sheet for thermoforming sheets of the present invention. The filler-free layer can be formed by co-extrusion with a filler-containing layer or by extrusion lamination of a filler-containing sheet.

前述樹脂板片的厚度亦沒有特別的限制，但若考慮熱成形性，則較佳為0.2~3mm。The thickness of the resin sheet is not particularly limited, but it is preferably 0.2 to 3 mm in consideration of thermoformability.

又，上述層積方法係可沒有特別限制地使用不顯著改變用於熱成形板片之層積用薄膜的特性之眾所周知的方法。例如，可使用擠出層合法、熱層合法、乾層合法等方法。更具體地，推薦藉由擠壓機將用於形成樹脂板片的樹脂層合於驟冷輥上所固定之本發明的用於熱成形板片之層積用薄膜。於此情況下，驟冷輥的表面較佳為平滑的鏡面輥。Further, the above-described lamination method can be used without any particular limitation, and a well-known method which does not significantly change the characteristics of the film for lamination of the thermoformed sheet can be used. For example, methods such as extrusion lamination, thermal lamination, and dry lamination may be used. More specifically, a film for lamination of the present invention for thermoforming sheets to which a resin for forming a resin sheet is laminated by a press to a chill roll is recommended. In this case, the surface of the chill roll is preferably a smooth mirror roll.

本發明的用於熱成形板片之層積用薄膜，係層積在前述聚丙烯系板片等的樹脂板片上，適用作為用於製造便當容器、托盤、蓋飯容器等的食品容器、一般容器、工業零件容器等的熱成形體之熱成形板片。The film for lamination of the thermoformed sheet of the present invention is laminated on a resin sheet such as the above-mentioned polypropylene sheet, and is suitable as a food container for producing a lunch container, a tray, a rice bowl container, or the like. Thermoformed sheets of thermoformed bodies such as containers, industrial parts containers, and the like.

再者，本發明亦包括於將熱成形板片加熱後，藉由真空成形、氣壓成形、真空氣壓成形等，在模具等的型框內賦形後，進行冷卻而得之熱成形體。Furthermore, the present invention also includes a thermoformed body obtained by heating a thermoformed sheet and then forming it in a mold such as a mold by vacuum forming, air pressure forming, vacuum gas pressure forming, or the like, followed by cooling.

【實施例】[Examples]

以下舉出實施例及比較例來說明本發明，惟本發明不受此等實施例所限定。再者，表1中顯示以下的實施例及比較例中所使用的薄膜之原料樹脂，表2中顯示所使用的結晶核劑。The invention is illustrated by the following examples and comparative examples, but the invention is not limited by the examples. Further, Table 1 shows the raw material resins of the films used in the following examples and comparative examples, and Table 2 shows the used crystalline nucleating agents.

又，表3中顯示實施例及比較例中當作基底的樹脂板片所使用的聚丙烯系板片。Further, Table 3 shows the polypropylene-based sheets used for the resin sheets used as the bases in the examples and the comparative examples.

實施例及比較例中樹脂及薄膜物性等的測定係藉由以下的方法來進行。In the examples and comparative examples, the measurement of the physical properties of the resin and the film was carried out by the following method.

(1)共聚合組成(1) Copolymerization composition

使用核磁共振分光裝置(日本電子(股)製JNM-GSX-270(¹³ C-核共振頻率67.8MHz)，在以下的條件下測定。Using a nuclear magnetic resonance spectroscope (JNM-GSX-270 ( ¹³ C-nuclear resonance frequency: 67.8 MHz) manufactured by JEOL Ltd., the measurement was carried out under the following conditions.

測定模式：¹ H-完全去耦合脈衝寬度：90度脈衝脈衝重複時間：3秒累計次數：10000次溶劑：鄰二氯苯/重苯的混合溶劑(76/24容量%)試料濃度：120mg/2.5ml溶劑測定溫度：120℃Measurement mode: ¹ H-complete decoupling pulse width: 90 degree pulse pulse repetition time: 3 seconds cumulative number: 10000 times solvent: o-dichlorobenzene/heavy benzene mixed solvent (76/24 capacity%) sample concentration: 120 mg/ 2.5ml solvent measurement temperature: 120 ° C

共聚合組成的定量係依照M.kakugo,Y,Naito,K.Mizunuma,T.Miyatake,[Macromolecules,15,1150(1982)]來進行。The basis of the copolymerization composition was carried out in accordance with M. Kakugo, Y, Naito, K. Mizunuma, T. Miyatake, [Macromolecules, 15, 1150 (1982)].

(2)熔體質量流速(MFR)(2) Melt mass flow rate (MFR)

依照JIS K7210，測定230℃的MFR。The MFR at 230 ° C was measured in accordance with JIS K7210.

(3)光澤(gloss)(3) Gloss

依照JIS K7105，以60度鏡面法來測定。It was measured by a 60-degree mirror method in accordance with JIS K7105.

再者，對層積用薄膜、熱成形板片，測定光澤層面。Further, the gloss layer was measured for the film for lamination and the thermoformed sheet.

又，成形容器係以熱成形板片的光澤層面成為容器的內面之方式，藉由(股)淺野研究所製Cosmic成形機FK-0631-20型，在加熱加熱器溫度500~530℃、真空度70mmHg下，真空成形為容器(盤形容器：縱195mm、橫145mm、高度28mm,蓋飯容器：168mmΦ、高度50mm)者進行評價。又，成形時的薄膜表面溫度為175℃。Further, the molded container is a Cosmic molding machine FK-0631-20 type manufactured by Asano Institute, in a manner that the gloss level of the thermoformed sheet is the inner surface of the container, and the heating heater temperature is 500 to 530 ° C. The vacuum was 70 mmHg and vacuum-formed into a container (a disk-shaped container: 195 mm in length, 145 mm in width, 28 mm in height, and a rice container: 168 mmφ, height: 50 mm). Further, the film surface temperature at the time of molding was 175 °C.

又，成形容器的光澤性係由以下3個等級來評價。Moreover, the glossiness of the molded container was evaluated by the following three grades.

○：光澤75%以上△：光澤65%以上、小於75%×：光澤小於65%○: gloss of 75% or more △: gloss of 65% or more and less than 75% ×: gloss is less than 65%

(4)由差示掃描熱量計所測定的熔點及結晶化溫度(4) Melting point and crystallization temperature measured by differential scanning calorimeter

秤量約5~6mg的試料後，封入鋁盤內，藉由差示掃描熱量計(精工電子工業(股)製DSC6200R)，在以20ml/分鐘供給的氮氣流中，升溫到230℃為止，在此溫度保持10分鐘，接著以10℃/分鐘的降溫速度冷卻到20℃為止。然後，以10℃/分鐘的升溫速度升溫到230℃為止，將所得到的吸熱曲線中顯示最大吸熱的峰值溫度當作熔點。又，結晶化溫度係依照JIS K7121，一旦樹脂熔解後，進行冷卻，測定開始結晶化時的溫度。After weighing about 5 to 6 mg of the sample, it was sealed in an aluminum pan and heated to 230 ° C in a nitrogen stream supplied at 20 ml/min by a differential scanning calorimeter (DSC6200R manufactured by Seiko Instruments Inc.). This temperature was maintained for 10 minutes, and then cooled to 20 ° C at a temperature decreasing rate of 10 ° C / minute. Then, the temperature was raised to 230 ° C at a temperature increase rate of 10 ° C /min, and the peak temperature at which the maximum endotherm was displayed in the obtained endothermic curve was taken as the melting point. Further, the crystallization temperature is in accordance with JIS K7121, and once the resin is melted, it is cooled, and the temperature at the start of crystallization is measured.

(5)拉伸彈性模數(5) Tensile modulus of elasticity

在製膜加工時的薄膜行進方向中，由層積用薄膜切出寬度10mm、長度100mm的樣品，以拉伸試驗機(Autograph：(股)島津製作所製)的夾頭固定樣品的兩端。於此情況下，以樣品的長度方向之夾頭間隙成為20mm的方式作調整。以20mm/min的拉伸速度進行拉伸試驗，製作拉伸應力-應變曲線。In the film traveling direction during the film forming process, a sample having a width of 10 mm and a length of 100 mm was cut out from the film for lamination, and both ends of the sample were fixed by a chuck of a tensile tester (Autograph: manufactured by Shimadzu Corporation). In this case, the chuck gap in the longitudinal direction of the sample was adjusted to be 20 mm. The tensile test was carried out at a tensile speed of 20 mm/min to prepare a tensile stress-strain curve.

拉伸彈性模數係用拉伸應力-應變曲線之開頭的直線部，藉由下式來計算。The tensile modulus of elasticity is calculated by the following equation using the straight line at the beginning of the tensile stress-strain curve.

Em=△δ/△ε Em：拉伸彈性模數△δ：直線上2點間的基於樣品原平均截面積的應力之差△ε：相同2點間的應變之差Em=△δ/△ε Em: tensile elastic modulus △δ: difference in stress between two points on the straight line based on the average cross-sectional area of the sample △ ε: difference in strain between the same two points

(6)尺寸變化率(6) Dimensional change rate

在製膜加工時的薄膜行進方向中，由層積用薄膜(厚度25μm)切出寬度100mm、長度100mm的樣品，安裝10N的砝碼，置入經加熱100℃的環境之烘箱內10分鐘，測定在23℃的環境放置2分鐘後的尺寸變化率。In the film traveling direction during the film forming process, a sample having a width of 100 mm and a length of 100 mm was cut out from the film for lamination (thickness: 25 μm), and a 10 N weight was attached thereto, and placed in an oven heated to 100 ° C for 10 minutes. The dimensional change rate after standing for 2 minutes in an environment of 23 ° C was measured.

(7)成形性(7) Formability

與前述光澤之評價同樣地，進行50次的容器成型，目視判定成形品的裂紋(薄膜裂紋)，計算不良率。In the same manner as the evaluation of the gloss, the container was molded 50 times, and the crack (film crack) of the molded article was visually judged, and the defective ratio was calculated.

不良率(%)=(成形品裂紋個數/50)×100Non-performing rate (%) = (number of cracks in molded product / 50) × 100

(8)白濁感(8) White turbidity

對上述(7)記載的成形品之容器內面(光澤層面)，使用Suga試驗機(股)製彩色電腦型式SM-3，測定亨特(Hunter)白色度「W(Lab)」值。The inner surface (gloss layer) of the molded article described in the above (7) was measured using a color computer type SM-3 manufactured by a Suga tester (manufactured by Konica Minolta Co., Ltd.) and a Hunter whiteness "W (Lab)" value was measured.

將層積薄膜的前的聚丙烯系板片之亨特白色度值與各薄膜層積後的成形容器之亨特白色度值作比較及評價。The Hunter whiteness value of the front polypropylene sheet of the laminated film was compared with the Hunter whiteness value of the molded container after lamination of each film.

與層積薄膜前的聚丙烯系板片之亨特白色度相比，各薄膜層積後的成形容器之亨特白色度值愈大，則意味白濁感愈增加，藉由以下3個等級來評價。Compared with the Hunter whiteness of the polypropylene-based sheet before laminating the film, the larger the Hunter whiteness value of the formed container after lamination of each film, the more the white turbidity is increased, and the following three grades are used. Evaluation.

○：(薄膜層積後的成形容器之亨特白色度)-(層積薄膜前的聚丙烯系板片之亨特白色度)=小於2%△：(薄膜層積後的成形容器之亨特白色度)-(層積薄膜前的聚丙烯系板片之亨特白色度)=2%以上、小於5%×：(薄膜層積後的成形容器之亨特白色度)-(層積薄膜前的聚丙烯系板片之亨特白色度)=5%以上○: (Hunter whiteness of the formed container after film deposition) - (Hunter whiteness of the polypropylene-based sheet before lamination film) = less than 2% Δ: (The shape of the formed container after film deposition) Extra whiteness) - (Hunter whiteness of polypropylene-based sheet before lamination film) = 2% or more and less than 5% ×: (Hunt whiteness of a formed container after film deposition) - (Layer Hunter whiteness of polypropylene sheet before film)=5% or more

(9)與板片的黏著性(9) Adhesion to the sheet

對使用上述(3)記載的成形機及模具之成形品，用拉伸試驗機(Autograph：(股)島津製作所製)，以15mm的寬度，在300mm/min的拉伸速度下，進行180°剝離拉伸試驗，藉由以下3個等級來評價樹脂板片與層積用薄膜的黏著強度評價。The molded article of the molding machine and the mold according to the above (3) was subjected to a tensile tester (Autograph: manufactured by Shimadzu Corporation) at a tensile speed of 300 mm/min at a width of 15 mm for 180°. In the peeling tensile test, the adhesion strength evaluation of the resin sheet and the film for lamination was evaluated by the following three grades.

◎：黏著強度1.0N/15mm以上○：黏著強度0.5N/15mm以上、小於1.0N/15mm×：黏著強度小於0.5N/15mm◎: Adhesive strength 1.0N/15mm or more ○: Adhesive strength 0.5N/15mm or more, less than 1.0N/15mm×: Adhesive strength is less than 0.5N/15mm

實施例1Example 1

藉由65mmΦ擠壓機，在99.8質量%當作薄膜用原料樹脂的表1所示之樹脂A(熔點165℃的丙烯均聚物(住友化學公司製FLX80G7))中摻合0.2質量%的表2所示之核劑I，於250℃擠出及丸粒化，將所得到的樹脂當作基層用。藉由65mmΦ擠壓機，在99.8質量%的表1所示之樹脂E(乙烯含量為3.4質量%，熔點為146℃的丙烯-乙烯無規共聚物(日本聚丙烯公司製FW3GT))中摻合0.2質量%的表2所示之核劑I，於250℃擠出及丸粒化，將所得到的樹脂當作光澤層用。接著，將光澤層用樹脂供應給擠壓機A(50mmΦ擠壓機)，將基層用樹脂供應給擠壓機B(75mmΦ擠壓機)，在250℃加熱熔融，以供料頭(feedblock)方式藉由共擠出法由模唇1.2mm的T模頭擠出，邊在40℃的冷卻輥上冷卻固化，邊調整以使得光澤層成為5μm，基層成為20μm，成為計25μm的薄膜，對基層側表面施予電暈放電處理，以使表面張力成為42mN/m後，用捲取機來捲繞，得到用於熱成形板片之層積用薄膜。A resin A (a propylene homopolymer having a melting point of 165 ° C (FLX80G7 manufactured by Sumitomo Chemical Co., Ltd.) shown in Table 1 as a raw material resin for a film of 99.8 mass% was blended with a 0.2 mass% by a 65 mm Φ extruder. The nucleating agent I shown in 2 was extruded and pelletized at 250 ° C, and the obtained resin was used as a base layer. The resin E (ethylene content: 3.4 mass%, propylene-ethylene random copolymer having a melting point of 146 ° C (FW3GT, manufactured by Nippon Polypropylene Co., Ltd.) shown in Table 1 of 99.8 mass% was incorporated by a 65 mm Φ extruder. 0.2% by mass of the nucleating agent I shown in Table 2 was extruded and pelletized at 250 ° C, and the obtained resin was used as a gloss layer. Next, the gloss layer was supplied to the extruder A (50 mm Φ extruder) with a resin, and the base layer was supplied with a resin to an extruder B (75 mm Φ extruder), which was heated and melted at 250 ° C to feed the feed block. The method was extruded by a co-extrusion method from a T-die of a die lip of 1.2 mm, and cooled and solidified on a cooling roll of 40 ° C, and adjusted so that the gloss layer became 5 μm, and the base layer became 20 μm, which became a film of 25 μm. The surface of the base layer side was subjected to corona discharge treatment so that the surface tension became 42 mN/m, and then wound by a coiler to obtain a film for lamination of the thermoformed sheet.

於該薄膜之施有電暈放電處理的面上，邊在250℃擠出厚度0.5mm之加有滑石30質量%的聚丙烯系板片(黑)，邊以40℃的冷卻輥進行固化而得到聚丙烯系熱成形板片。On the surface of the film subjected to the corona discharge treatment, a polypropylene-based sheet (black) having a talc of 30% by mass and a thickness of 0.5 mm was extruded at 250 ° C, and solidified by a cooling roll at 40 ° C. A polypropylene-based thermoformed sheet was obtained.

對所得到的熱成形板片，在薄膜的表面溫度175℃進行真空成形，對容器的光澤、白濁度(亨特白色度)、板片與薄膜的黏著性進行評價，表5中顯示具結果。成形容器的光澤係盤形容器為78%、蓋飯容器為78%，表面光澤為良好者，關於白濁感，薄膜貼合前之聚丙烯系板片的亨特白色度為12%，成形後的容器為幾乎沒有變化的12~13%之無白濁感的容器。The obtained thermoformed sheet was subjected to vacuum forming at a surface temperature of 175 ° C of the film to evaluate the gloss, white turbidity (Hunt whiteness) of the container, and the adhesion of the sheet to the film, and the results are shown in Table 5. . The molded container has a glossy disc-shaped container of 78% and a rice-filled container of 78%, and the surface gloss is good. Regarding the white turbidity, the polypropylene-based sheet before the film-bonding has a Hunter whiteness of 12%, after forming. The container is a 12~13% container with no white turbidity that has almost no change.

實施例2~3Example 2~3

除了以光澤層成為2μm，基層成為23μm的方式調整，變更為計25μm(實施例2)，以光澤層成為10μm，基層成為15μm的方式調整，變更為計25μm(實施例3)以外，與實施例1完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。於實施例2中，成形容器的光澤係盤形容器為77%，蓋飯容器為76%，表面光澤為良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為幾乎沒有變化的12~13%之無白濁感的容器。於實施例3中，成形容器的光澤係盤形容器為79%，蓋飯容器為79%，表面光澤為良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為沒有變化的12%之完全無白濁感的容器。In addition to the case where the gloss layer is 2 μm and the base layer is 23 μm, it is changed to 25 μm (Example 2), and the gloss layer is adjusted to 10 μm, and the base layer is adjusted to 15 μm, and is changed to 25 μm (Example 3). In Example 1, film formation, lamination, thermoforming, and evaluation were carried out in exactly the same manner. The results are shown in Table 5. In Example 2, the gloss container of the molded container was 77%, the rice container was 76%, and the surface gloss was good. Regarding the white turbidity, the Hunter whiteness of the polypropylene sheet before the film bonding At 12%, the formed container was a 12-1% non-white turbid container with almost no change. In Example 3, the gloss container of the molded container was 79%, the rice container was 79%, and the surface gloss was good. Regarding the white turbidity, the Hunter whiteness of the polypropylene sheet before the film bonding At 12%, the formed container was a 12% non-white turbid container with no change.

實施例4Example 4

除了以實施例1的光澤層用樹脂當作表1中所示的樹脂H(乙烯含量為4.2質量%,熔點為135℃的金屬茂觸媒系丙烯-乙烯無規共聚物(日本聚丙烯公司製WFW4))以外，完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。成形容器的光澤係盤形容器為82%，蓋飯容器為81%，表面光澤為極良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為幾乎很少變化的12~13%之無白濁感的容器。The resin for the gloss layer of Example 1 was used as the resin H shown in Table 1 (metallocene catalyst-based propylene-ethylene random copolymer having an ethylene content of 4.2% by mass and a melting point of 135 °C) Film formation, lamination, thermoforming, and evaluation were carried out in the same manner except for WFW4)). The results are shown in Table 5. The gloss container of the molded container was 82%, the rice container was 81%, and the surface gloss was excellent. Regarding the white turbidity, the polypropylene whiteness of the film before the film bonding was 12%, forming The latter container is a 12 to 13% white turbid container with almost no change.

實施例5~6Example 5~6

除了以光澤層成為2μm，基層成為23μm的方式，調整實施例4的光澤層與基層之厚度，變更為計25μm(實施例5)，以光澤層成為10μm，基層成為15μm的方式，調整調整實施例4的光澤層與基層之厚度，變更為計25μm(實施例6)以外，與實施例1完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。於實施例5中，成形容器的光澤係盤形容器為81%，蓋飯容器為81%，表面光澤為極良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為幾乎沒有變化的13%之無白濁感的容器。於實施例6，成形容器的光澤係盤形容器為84%，蓋飯容器為82%，表面光澤為良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為沒有變化的12%之完全無白濁感的容器。The thickness of the gloss layer and the base layer of Example 4 was adjusted to be 25 μm (Example 5), and the gloss layer was 10 μm, and the base layer was 15 μm, and the adjustment and adjustment were carried out, except that the gloss layer was 2 μm and the base layer was 23 μm. Film thickness, laminate, thermoforming, and evaluation were carried out in the same manner as in Example 1 except that the thickness of the gloss layer and the base layer of Example 4 was changed to 25 μm (Example 6). The results are shown in Table 5. In Example 5, the glossy container of the molded container was 81%, the rice container was 81%, and the surface gloss was excellent. Regarding the white turbidity, the polypropylene plate before the film bonding was Hunter White. The degree was 12%, and the formed container was a container having no white turbidity of 13% with almost no change. In Example 6, the glossy container of the shaped container was 84%, the rice container was 82%, and the surface gloss was good. Regarding the white turbidity, the whiteness of the polypropylene sheet before the film bonding was 12%, the formed container was a 12% non-white turbid container with no change.

實施例7Example 7

除了以實施例4的基層用樹脂當作表1中所示的樹脂B(熔點164℃的丙烯均聚物(SUNALLOMER公司製PC600A))以外，完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。成形容器的光澤係盤形容器為82%，蓋飯容器為82%，表面光澤為極良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為幾乎很少變化的12~13%之無白濁感的容器。The film formation, lamination, thermoforming, and the like were carried out in the same manner except that the resin for the base layer of Example 4 was used as the resin B (the propylene homopolymer having a melting point of 164 ° C (PC600A manufactured by SUNALLOMER Co., Ltd.) shown in Table 1). Evaluation. The results are shown in Table 5. The molded container has a glossy disc-shaped container of 82% and a rice-filled container of 82%, and the surface gloss is excellent. Regarding the white turbidity, the polypropylene-based sheet before the film-bonding has a Hunter whiteness of 12%. The latter container is a 12 to 13% white turbid container with almost no change.

實施例8Example 8

除了於實施例4的光澤層及基層中所添加的核劑I之添加量為0.1質量%以外，完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。成形容器的光澤係盤形容器為80%，蓋飯容器為80%，表面光澤為極良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為幾乎很少變化的12~13%之無白濁感的容器。Film formation, lamination, thermoforming, and evaluation were carried out in the same manner except that the amount of the nucleating agent I added to the gloss layer and the base layer of Example 4 was 0.1% by mass. The results are shown in Table 5. The gloss container of the molded container is 80%, the rice container is 80%, and the surface gloss is excellent. Regarding the white turbidity, the polypropylene whiteness of the film before the film bonding is 12%, forming The latter container is a 12 to 13% white turbid container with almost no change.

實施例9~10Example 9~10

除了以實施例4的光澤層用樹脂當作表1中所示的樹脂F(乙烯含量為3.2質量%,丁烯含量為1.5質量%,熔點為137℃的丙烯-乙烯-丁烯三元無規共聚物(日本聚丙烯公司製FW4BT))(實施例9)，以光澤層用樹脂當作表1中所示的樹脂G(乙烯含量為2.2質量%,丁烯含量為6.8質量%,熔點為133℃的丙烯-乙烯-丁烯三元無規共聚物(PRIME聚合物公司製F794NV))(實施例10)以外，完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。實施例9、10之成形容器的光澤係盤形容器皆為78%，蓋飯容器皆為78%，表面光澤為良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為幾乎很少變化的12~13%之無白濁感的容器。Except that the resin for the gloss layer of Example 4 was used as the resin F shown in Table 1 (propylene content of 3.2% by mass, butene content of 1.5% by mass, and melting point of 137 ° C of propylene-ethylene-butene ternary Synthetic copolymer (FW4BT manufactured by Nippon Polypropylene Co., Ltd.) (Example 9), the resin for the gloss layer was used as the resin G shown in Table 1 (the ethylene content was 2.2% by mass, the butene content was 6.8% by mass, and the melting point was Film formation, lamination, thermoforming, and evaluation were carried out in the same manner except that the propylene-ethylene-butylene ternary random copolymer (F794NV manufactured by PRIME Polymer Co., Ltd.) (Example 10) of 133 ° C was used. The results are shown in Table 5. The gloss containers of the molded containers of Examples 9 and 10 were all 78%, and the rice container was 78%, and the surface gloss was good. Regarding the white turbidity, the polypropylene plate before the film bonding was Hunter. The whiteness is 12%, and the formed container is a 12 to 13% white turbid container with almost no change.

實施例11Example 11

藉由65mmΦ擠壓機，在99.8質量%的表1所示的樹脂A中摻合0.2質量%的表2所示的核劑I，於250℃擠出及丸粒化，將所得到的樹脂當作基層用。藉由65mmΦ擠壓機，在99.8質量%的表1所示的樹脂H中摻合0.2質量%的表2所示的核劑I，於250℃擠出及丸粒化，將所得到的樹脂當作光澤層用。使用表1所示的樹脂E單體當作黏著層樹脂。將光澤層用樹脂供應給擠壓機A(50mmΦ擠壓機)，將基層用樹脂供應給擠壓機B(75mmΦ擠壓機)，將黏著層用樹脂供應給擠壓機C(50mmΦ擠壓機)，在250℃加熱熔融，以供料頭方式藉由共擠出法由模唇1.2mm的T模頭擠出，邊在60℃的冷卻輥上冷卻固化，邊調整以使得光澤層成為5μm，基層成為15μm，黏著層成為5μm，成為計25μm的薄膜，對黏著層側表面施予電暈放電處理以使表面張力成為42mN/m以外，與實施例4完全同樣地進行層合、熱成形及評價。表5中顯示結果。成形容器的光澤係盤形容器為81%，蓋飯容器為80%，表面光澤為極良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為幾乎很少變化的12~13%之無白濁感的容器。0.29% by mass of the nucleating agent I shown in Table 2 was blended into the resin A shown in Table 1 by a 65 mm Φ extruder, and extruded and pelletized at 250 ° C to obtain the obtained resin. Used as a base layer. 0.29% by mass of the nucleating agent I shown in Table 2 was blended into the resin H shown in Table 1 by a 65 mm Φ extruder, and extruded and pelletized at 250 ° C to obtain the obtained resin. Used as a gloss layer. The resin E monomer shown in Table 1 was used as the adhesive layer resin. The gloss layer was supplied to the extruder A (50 mm Φ extruder) with resin, the base layer was supplied with resin to the extruder B (75 mm Φ extruder), and the adhesive layer was supplied with resin to the extruder C (50 mm Φ extrusion) Machine, heated and melted at 250 ° C, extruded by a T-die of a die lip of 1.2 mm by a co-extrusion method, cooled and solidified on a cooling roll of 60 ° C, and adjusted so that the gloss layer becomes 5 μm, the base layer was 15 μm, the adhesive layer was 5 μm, and the film was 25 μm, and the surface of the adhesive layer was subjected to corona discharge treatment so that the surface tension was 42 mN/m, and lamination and heat were carried out in the same manner as in Example 4. Forming and evaluation. The results are shown in Table 5. The gloss container of the molded container is 81%, the rice container is 80%, and the surface gloss is excellent. Regarding the white turbidity, the polypropylene whiteness of the film before the film bonding is 12%, forming The latter container is a 12 to 13% white turbid container with almost no change.

實施例12~13Examples 12 to 13

除了以基層成為18μm，黏著層成為2μm的方式，調整實施例11的基層與黏著層之厚度，變更為計25μm(實施例12)，以光澤層成為8μm，基層成為12μm的方式，調整實施例11的基層與黏著層之厚度，變更為計25μm(實施例13)以外，與實施例11完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。於實施例12中，成形容器的光澤係盤形容器為81%，蓋飯容器為80%，表面光澤為極良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為幾乎沒有變化的12~13%之無白濁感的容器。於實施例13中，成形容器的光澤係盤形容器為80%，蓋飯容器為79%，表面光澤為極良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為幾乎很少變化的12~13%之無白濁感的容器。The thickness of the base layer and the adhesive layer of Example 11 was adjusted to be 25 μm (Example 12), and the gloss layer was 8 μm, and the base layer was 12 μm, and the example was adjusted, except that the base layer was 18 μm and the adhesive layer was 2 μm. Film formation, lamination, thermoforming, and evaluation were carried out in the same manner as in Example 11 except that the thickness of the base layer and the pressure-sensitive adhesive layer of 11 was changed to 25 μm (Example 13). The results are shown in Table 5. In Example 12, the glossy container of the molded container was 81%, the rice container was 80%, and the surface gloss was excellent. Regarding the white turbidity, the polypropylene plate before the film bonding was Hunter White. The degree was 12%, and the formed container was a 12-1% non-white turbid container with almost no change. In the thirteenth embodiment, the gloss container of the molded container was 80%, the rice container was 79%, and the surface gloss was excellent. Regarding the white turbidity, the polypropylene plate before the film bonding was the Hunter white. The degree is 12%, and the formed container is a 12 to 13% white turbid container with almost no change.

實施例14Example 14

除了以實施例11的黏著層樹脂當作在99.8質量%的表1所示的樹脂H中加有0.2質量%的核劑I之樹脂以外，與實施例11完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。成形容器的光澤係盤形容器為82%，蓋飯容器為81%，表面光澤為極良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為沒有變化的12%之完全無白濁感的容器。Film formation and lamination were carried out in the same manner as in Example 11 except that the adhesive layer resin of Example 11 was used as a resin containing 0.2% by mass of the nucleating agent I in 90% by mass of the resin H shown in Table 1. , thermoforming and evaluation. The results are shown in Table 5. The gloss container of the molded container was 82%, the rice container was 81%, and the surface gloss was excellent. Regarding the white turbidity, the polypropylene whiteness of the film before the film bonding was 12%, forming The resulting container was a 12% non-white turbid container with no change.

實施例15Example 15

除了以光澤層成為10μm，基層成為40μm的方式，調整實施例1的光澤層與基層的厚度，變更為計50μm以外，與實施例1完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。成形容器的光澤係盤形容器為85%，蓋飯容器為83%，表面光澤為極良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為沒有變化的12%之完全無白濁感的容器。Film formation, lamination, thermoforming, and evaluation were carried out in the same manner as in Example 1 except that the thickness of the gloss layer and the base layer of Example 1 were changed to 10 μm in the case where the gloss layer was 10 μm and the thickness of the base layer was changed to 40 μm. The results are shown in Table 5. The gloss container of the molded container is 85%, the rice container is 83%, and the surface gloss is excellent. Regarding the white turbidity, the polypropylene whiteness of the film before the film bonding is 12%, forming The resulting container was a 12% non-white turbid container with no change.

實施例16Example 16

在97.5質量%當作薄膜用原料樹脂的表1所示的樹脂A中摻合2,5質量%的表2所示的核劑II，將所得到的樹脂當作基層用。於97,5質量%的表1所示的樹脂H中摻合2.5質量%的表2所示的核劑III，將所得到的樹脂當作光澤層用。接著，除了將光澤層用樹脂供應給擠壓機A(50mmΦ擠壓機)，將基層用樹脂供應給擠壓機B(75mmΦ擠壓機)以外，與實施例1完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。成形容器的光澤係盤形容器為71%，蓋飯容器為70%，表面光澤係稍微良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為沒有變化的12%之完全無白濁感的容器。In the resin A shown in Table 1 which is a raw material resin for a film of 97.5 mass%, 2,5 mass% of the nucleating agent II shown in Table 2 was blended, and the obtained resin was used as a base layer. To the resin H shown in Table 1 at 97,5 mass%, 2.5% by mass of the nucleating agent III shown in Table 2 was blended, and the obtained resin was used as a gloss layer. Next, film formation was carried out in the same manner as in Example 1 except that the gloss layer resin was supplied to the extruder A (50 mm Φ extruder), and the base layer resin was supplied to the extruder B (75 mm Φ extruder). Lamination, thermoforming and evaluation. The results are shown in Table 5. The gloss container of the molded container was 71%, the rice container was 70%, and the surface gloss was slightly good. Regarding the white turbidity, the polypropylene whiteness of the film before the film bonding was 12%, forming The resulting container was a 12% non-white turbid container with no change.

實施例17Example 17

於實施例1的薄膜之施有電暈放電處理的面上，邊在250℃擠出厚度0.4mm之加有30質量%滑石的聚丙烯系板片(朱紅)，邊以40℃的冷卻輥進行固化而得到聚丙烯系熱成形板片。On the surface of the film of Example 1 which was subjected to the corona discharge treatment, a polypropylene-based plate (red) having a thickness of 0.4 mm and added with 30% by mass of talc was extruded at 250 ° C, and a cooling roll of 40 ° C was used. Curing was carried out to obtain a polypropylene-based thermoformed sheet.

對所得到的熱成形板片進行真空成形，對容器的光澤、白濁度(亨特白色度)、板片與薄膜的黏著性進行評價，表5中顯示具結果。成形容器的光澤係盤形容器為78%、蓋飯容器為78%，表面光澤為良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為22%，成形後的容器為幾乎沒有變化的22~23%之無白濁感的容器。The obtained thermoformed sheet was subjected to vacuum forming, and the gloss, white turbidity (Hunt whiteness) of the container, and adhesion of the sheet to the film were evaluated, and the results are shown in Table 5. The molded container has a glossy disc-shaped container of 78% and a rice-filled container of 78%, and the surface gloss is good. Regarding the white turbidity, the polypropylene-based sheet before the film-bonding has a Hunter whiteness of 22%. The container is a container with no white turbidity of 22 to 23% with almost no change.

實施例18Example 18

藉由65mmΦ擠壓機，在94質量%當作薄膜用原料樹脂的表1所示之樹脂A(熔點165℃的丙烯均聚物(住友化學公司製FLX80G7))中摻合6質量%的表2所示之核劑IV，於250℃擠出及丸粒化，將所得到的樹脂當作基層用。藉由65mmΦ擠壓機，在94質量%的表1所示之樹脂E(乙烯含量為3.4質量%,熔點為146℃的丙烯-乙烯無規共聚物(日本聚丙烯公司製FW3GT))中摻合6質量%的表2所示之核IV，於250℃擠出及丸粒化，將所得到的樹脂當作光澤層用。接著，將光澤層用樹脂供應給擠壓機A(50mmΦ擠壓機)，將基層用樹脂供應給擠壓機B(75mmΦ擠壓機)，在250℃加熱熔融，以供料頭方式藉由共擠出法由模唇1.2mm的T模頭擠出，邊在40℃的冷卻輥上冷卻固化，邊調整以使光澤層成為5μm，基層成為20μm，成為計25μm的薄膜，對基層側表面施予電暈放電處理，以使表面張力成為42mN/m後，用捲取機來捲繞，得到用於熱成形板片之層積用薄膜。A resin of A (melting point 165 ° C propylene homopolymer (FLX80G7 manufactured by Sumitomo Chemical Co., Ltd.) shown in Table 1 as a raw material resin for a film of 94% by mass was blended into a 6 mass% table by a 65 mm Φ extruder. The nucleating agent IV shown in 2 was extruded and pelletized at 250 ° C, and the obtained resin was used as a base layer. The resin E (ethylene content: 3.4 mass%, propylene-ethylene random copolymer having a melting point of 146 ° C (FW3GT, manufactured by Nippon Polypropylene Co., Ltd.) shown in Table 1 of 94% by mass was blended by a 65 mm Φ extruder. 6% by mass of the core IV shown in Table 2 was extruded and pelletized at 250 ° C, and the obtained resin was used as a gloss layer. Next, the gloss layer was supplied to the extruder A (50 mm Φ extruder) with a resin, and the base layer was supplied with a resin to an extruder B (75 mm Φ extruder), which was heated and melted at 250 ° C, by means of a feed head. The coextrusion method was extruded from a 1.2 mm T die of a lip, cooled and solidified on a cooling roll of 40 ° C, adjusted so that the gloss layer became 5 μm, and the base layer became 20 μm, which became a film of 25 μm, and the base side surface After the corona discharge treatment was carried out so that the surface tension became 42 mN/m, the film was wound by a coiler to obtain a film for lamination of the thermoformed sheet.

於該薄膜之施有電暈放電處理的面上，以250℃擠出厚度0.5mm之添加有30質量%滑石的聚丙烯系板片(黑)，邊以40℃的冷卻輥進行固化而得到聚丙烯系熱成形板片。On the surface of the film subjected to the corona discharge treatment, a polypropylene-based sheet (black) to which 30% by mass of talc was added was extruded at a thickness of 0.5 mm at 250 ° C, and solidified by a cooling roll at 40 ° C. Polypropylene thermoformed sheet.

對所得到的熱成形板片，在薄膜的表面溫度175℃進行真空成形，對容器的光澤、白濁度(亨特白色度)、板片與薄膜的黏著性進行評價，表5中顯示具結果。成形容器的光澤係盤形容器為79%，蓋飯容器為78%，表面光澤為良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為沒有變化的12%之無白濁感的容器。The obtained thermoformed sheet was subjected to vacuum forming at a surface temperature of 175 ° C of the film to evaluate the gloss, white turbidity (Hunt whiteness) of the container, and the adhesion of the sheet to the film, and the results are shown in Table 5. . The molded container has a glossy disc-shaped container of 79% and a rice-filled container of 78%. The surface gloss is good. Regarding the white turbidity, the polypropylene-based sheet before the film-bonding has a Hunter whiteness of 12%. The container was a 12% non-white turbid container with no change.

實施例19Example 19

除了以實施例18的光澤層用樹脂當作表1中所示的樹脂H(乙烯含量為4.2質量%,熔點為135℃的金屬茂觸媒系丙烯-乙烯無規共聚物(日本聚丙烯公司製WFW4))以外，完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。成形容器的光澤係盤形容器為82%，蓋飯容器為81%，表面光澤為極良好者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為沒有變化的12%之無白濁感的容器。The resin for the gloss layer of Example 18 was used as the resin H shown in Table 1 (metallocene catalyst propylene-ethylene random copolymer having an ethylene content of 4.2% by mass and a melting point of 135 ° C (Japan Polypropylene Co., Ltd.) Film formation, lamination, thermoforming, and evaluation were carried out in the same manner except for WFW4)). The results are shown in Table 5. The gloss container of the molded container was 82%, the rice container was 81%, and the surface gloss was excellent. Regarding the white turbidity, the polypropylene whiteness of the film before the film bonding was 12%, forming The resulting container was a 12% non-white turbid container with no change.

比較例1Comparative example 1

除了於實施例1的各層之原料樹脂中不添加有機結晶核劑以外，與實施例1完全同樣地進行製膜、層合、熱成形及評價。Film formation, lamination, thermoforming, and evaluation were carried out in the same manner as in Example 1 except that the organic crystal nucleating agent was not added to the raw material resins of the respective layers of Example 1.

表5中顯示結果。成形容器的光澤係盤形容器為16%，蓋飯容器為15%，表面光澤為差者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為15%之有白濁感的容器。The results are shown in Table 5. The gloss container of the molded container is 16%, the rice container is 15%, and the surface gloss is poor. Regarding the white turbidity, the polypropylene whiteness of the polypropylene sheet before film bonding is 12%, after forming. The container is 15% white turbid.

比較例2Comparative example 2

除了於實施例1的各層之原料樹脂中有機結晶核劑的添加量為0.02質量份以外，與實施例1完全同樣地進行製膜、層合、熱成形及評價。Film formation, lamination, thermoforming, and evaluation were carried out in the same manner as in Example 1 except that the amount of the organic crystal nucleating agent added to the raw material resin of each layer of Example 1 was 0.02 parts by mass.

表5中顯示結果。成形容器的光澤係盤形容器為16%，蓋飯容器為17%，表面光澤為差者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為15%之有白濁感的容器。The results are shown in Table 5. The gloss container of the molded container was 16%, the rice container was 17%, and the surface gloss was poor. Regarding the white turbidity, the polypropylene whiteness of the polypropylene sheet before film bonding was 12%, after forming. The container is 15% white turbid.

比較例3Comparative example 3

除了代替實施例1之基層所用的樹脂A，使用表1所示的樹脂C(熔點16l℃的丙烯均聚物(住友化學公司製FLX80G1))以外，與實施例1完全同樣地進行製膜、層合、熱成形及評價。Film formation was carried out in the same manner as in Example 1 except that Resin C (a propylene homopolymer having a melting point of 16 l ° C (FLX80G1 manufactured by Sumitomo Chemical Co., Ltd.)) shown in Table 1 was used instead of the resin A used in the base layer of Example 1. Lamination, thermoforming and evaluation.

表5中顯示結果。成形容器的光澤係盤形容器為62%，蓋飯容器為60%，表面光澤為差者。The results are shown in Table 5. The gloss container of the shaped container was 62%, and the rice container was 60%, and the surface gloss was poor.

比較例4Comparative example 4

除了代替實施例1的基層所用的樹脂A，使用表1所示的樹脂D(熔點157℃的丙烯均聚物(日本聚丙烯公司製FB3EBT))以外，與實施例1完全同樣地進行製膜、層合、熱成形及評價。The film formation was carried out in the same manner as in Example 1 except that the resin D used in the base layer of the first embodiment was used, except that the resin D (the propylene homopolymer having a melting point of 157 ° C (FB3EBT manufactured by Nippon Polypropylene Co., Ltd.) shown in Table 1) was used. , lamination, thermoforming and evaluation.

表5中顯示結果。成形容器的光澤係盤形容器為60%，蓋飯容器為60%，表面光澤為差者。The results are shown in Table 5. The gloss container of the shaped container was 60%, and the rice container was 60%, and the surface gloss was poor.

比較例5Comparative Example 5

除了代替實施例1的光澤層所用的樹脂E，使用表1所示的樹脂A(熔點165℃的丙烯均聚物(住友化學公司製FLX80F7))以外，與實施例1完全同樣地進行製膜、層合、熱成形及評價。Film formation was carried out in the same manner as in Example 1 except that Resin A (a propylene homopolymer having a melting point of 165 ° C (FLX80F7 manufactured by Sumitomo Chemical Co., Ltd.)) shown in Table 1 was used instead of the resin E used in the gloss layer of Example 1. , lamination, thermoforming and evaluation.

表5中顯示結果。成形容器的光澤係盤形容器為60%，蓋飯容器為60%，表面光澤為差者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為21%之有白濁感的容器。The results are shown in Table 5. The gloss container of the molded container is 60%, the rice container is 60%, and the surface gloss is poor. Regarding the white turbidity, the polypropylene whiteness of the polypropylene sheet before film bonding is 12%, after forming. The container is 21% white turbid container.

比較例6Comparative Example 6

除了以光澤層成為0.5μm，基層成為24,5μm的方式，調整實施例4的光澤層與基層之厚度，成為計25μm的以外，與實施例4完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。成形容器的光澤係盤形容器為62%，蓋飯容器為61%，表面光澤為差者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為19%之有白濁感的容器。Film formation, lamination, and thermoforming were carried out in the same manner as in Example 4 except that the gloss layer was 0.5 μm and the base layer was 24 μm. The thickness of the gloss layer and the base layer of Example 4 was adjusted to be 25 μm. And evaluation. The results are shown in Table 5. The molded container has a glossy disc-shaped container of 62%, and the rice-filled container has a surface gloss of 61%. The surface gloss is poor. Regarding the white turbidity, the polypropylene-based sheet before the film-bonding has a Hunter whiteness of 12%. The container is 19% white turbid.

比較例7Comparative Example 7

除了以光澤層成為20μm，基層成為5μm的方式，調整實施例4的光澤層與基層之厚度，成為計25μm的以外，與實施例4完全同樣地進行製膜、層合、熱成形及評價。表5中顯示結果。成形容器的光澤係盤形容器為62%，蓋飯容器為61%，表面光澤為差者。Film formation, lamination, thermoforming, and evaluation were carried out in the same manner as in Example 4 except that the gloss layer was 20 μm and the base layer was 5 μm. The thickness of the gloss layer and the base layer of Example 4 was adjusted to be 25 μm. The results are shown in Table 5. The gloss container of the shaped container was 62%, and the rice container was 61%, and the surface gloss was poor.

比較例8Comparative Example 8

除了代替實施例1的基層所用的樹脂A，使用表1所示的樹脂E(乙烯含量為3.4質量%,熔點為146℃的丙烯-乙烯無規共聚物(日本聚丙烯公司製FW3GT))以外，與實施例11完全同樣地進行製膜、層合、熱成形及評價。In addition to the resin A used in the base layer of the first embodiment, a resin E (having an ethylene content of 3.4% by mass and a propylene-ethylene random copolymer having a melting point of 146 ° C (FW3GT, manufactured by Nippon Polypropylene Co., Ltd.)) shown in Table 1 was used. Film formation, lamination, thermoforming, and evaluation were carried out in exactly the same manner as in Example 11.

表5中顯示結果。成形容器的光澤係盤形容器為62%，蓋飯容器為61%，表面光澤為差者。The results are shown in Table 5. The gloss container of the shaped container was 62%, and the rice container was 61%, and the surface gloss was poor.

比較例9Comparative Example 9

除了代替實施例1的光澤層所用的樹脂E，使用摻合有表1所示之樹脂C90質量%及樹脂I(乙烯含量為89.4質量%,己烯含量為10.6質量%,熔點為110℃的金屬茂觸媒系乙烯系無規共聚物(住友化學公司製FV402))10質量%者，代替基層所用的樹脂A，使用樹脂E(乙烯含量為3.4質量%,熔點為l46℃的丙烯-乙烯無規共聚物(日本聚丙烯公司製FW3GT))以外，與實施例1完全同樣地進行製膜、層合、熱成形及評價。In place of the resin E used in place of the gloss layer of Example 1, a resin C of 90% by mass and a resin I (having an ethylene content of 89.4% by mass, a hexene content of 10.6% by mass, and a melting point of 110 ° C) were used. The metallocene catalyst-based ethylene-based random copolymer (FV402 manufactured by Sumitomo Chemical Co., Ltd.) was used in an amount of 10% by mass in place of the resin A used in the base layer, and a resin E (propylene content of 3.4% by mass and melting point of 146 ° C) was used. Film formation, lamination, thermoforming, and evaluation were carried out in the same manner as in Example 1 except that the random copolymer (FW3GT, manufactured by Nippon Polypropylene Co., Ltd.) was used.

表5中顯示結果。成形容器的光澤係盤形容器為60%，蓋飯容器為60%，表面光澤為差者、關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%，成形後的容器為21%之有白濁感的容器。The results are shown in Table 5. The gloss container of the molded container is 60%, the rice container is 60%, the surface gloss is poor, and the whiteness of the polypropylene sheet is 12%. The container is 21% white turbid container.

比較例10Comparative Example 10

於比較例5的薄膜之施有電暈放電處理的面上，邊在250℃擠出厚度0.4mm之加有30質量%滑石的聚丙烯系板片(朱紅)，邊以40℃的冷卻輥進行固化而得到聚丙烯系熱成形板片。On the surface of the film of Comparative Example 5 which was subjected to the corona discharge treatment, a polypropylene-based plate (jujube) to which 30% by mass of talc was added at a thickness of 0.4 mm was extruded at 250 ° C, and a cooling roll of 40 ° C was used. Curing was carried out to obtain a polypropylene-based thermoformed sheet.

對所得到的熱成形板片進行真空成形，對容器的光澤、白濁度(亨特白色度)、板片與薄膜的黏著性進行評價，表5中顯示具結果。成形容器的光澤係盤形容器為60%，蓋飯容器為60%，表面光澤為差者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為22%，成形後的容器為30~32%之有白濁感的容器。The obtained thermoformed sheet was subjected to vacuum forming, and the gloss, white turbidity (Hunt whiteness) of the container, and adhesion of the sheet to the film were evaluated, and the results are shown in Table 5. The gloss container of the molded container is 60%, the rice container is 60%, and the surface gloss is poor. Regarding the white turbidity, the polypropylene whiteness of the polypropylene sheet before film bonding is 22%, after forming. The container is 30 to 32% of a container with a white turbidity.

比較例11Comparative Example 11

除了於實施例18的各層之原料樹脂中有機結晶核劑的添加量為0.01質量份以外，與實施例l完全同樣地進行製膜、層合、熱成形及評價。Film formation, lamination, thermoforming, and evaluation were carried out in the same manner as in Example 1 except that the amount of the organic crystal nucleating agent added was 0.01 parts by mass in the raw material resin of each layer of Example 18.

表5中顯示結果。成形容器的光澤係盤形容器為16%，蓋飯容器為15%，表面光澤為差者，關於白濁感，薄膜貼合前的聚丙烯系板片之亨特白色度為12%、成形後的容器為15%之有白濁感的容器。The results are shown in Table 5. The gloss container of the molded container is 16%, the rice container is 15%, and the surface gloss is poor. Regarding the white turbidity, the polypropylene whiteness of the polypropylene sheet before the film bonding is 12%, after forming. The container is 15% white turbid.

表4中彙總顯示以上實施例及比較例中所得的用於熱成形板片之層積用薄膜的層構成。又，表5中彙總顯示此等實施例及比較例的結果。The layer constitution of the film for lamination of the thermoformed sheet obtained in the above Examples and Comparative Examples is collectively shown in Table 4. Further, the results of the examples and comparative examples are collectively shown in Table 5.

Claims (5)

一種作為熱成形板片層積用薄膜之用途，該薄膜為由基層與光澤層所成的無拉伸或低拉伸薄膜，該基層係含有99~99.97質量%的熔點為162℃以上的丙烯均聚物及0.03~1質量%的有機結晶核劑，且具有10μm以上的厚度，該光澤層係形成在該基層的至少一面上，含有99~99.97質量%的丙烯系無規共聚物及0.03~1質量%的有機結晶核劑，且具有1μm以上的厚度。 The invention relates to a film for laminating a thermoformed sheet, which is a non-stretched or low-stretch film formed by a base layer and a gloss layer, wherein the base layer contains 99 to 99.97% by mass of propylene having a melting point of 162 ° C or higher. a homopolymer and 0.03 to 1% by mass of an organic crystal nucleating agent having a thickness of 10 μm or more, the gloss layer being formed on at least one side of the base layer, containing 99 to 99.97% by mass of a propylene-based random copolymer and 0.03 ~1% by mass of the organic crystal nucleating agent and having a thickness of 1 μm or more. 如申請專利範圍第1項之作為熱成形板片層積用薄膜之用途，其中光澤層係形成在基層的一面上，於與該光澤層相反側的基層面上，層積有由熔點130℃以上的丙烯系無規共聚物所成的具有1μm以上的厚度之黏著層。 The use of the film for thermoforming sheet laminate according to claim 1, wherein the gloss layer is formed on one side of the base layer, and the base layer on the opposite side of the gloss layer is laminated with a melting point of 130 ° C. An adhesive layer having a thickness of 1 μm or more formed by the above propylene random copolymer. 如申請專利範圍第1或2項之作為熱成形板片層積用薄膜之用途，其中薄膜的總厚度為15~100μm，基層的厚度係全體的50~90%。 The use of the film for laminating a thermoformed sheet according to claim 1 or 2, wherein the total thickness of the film is 15 to 100 μm, and the thickness of the base layer is 50 to 90% of the total. 如申請專利範圍第1項之作為熱成形板片層積用薄膜之用途，其中基層所含有的有機結晶核劑或光澤層所含有的有機結晶核劑之任一者或兩者，係磷酸酯金屬鹽或下述通式(1)所示的醯胺系化合物： 式中，R¹ 表示由1,2,3-丙烷三羧酸或1,2,3,4-丁烷四羧酸去除全部羧基後所得之殘基；3個或4個R² 係互相相同或不同，各自表示氫原子或碳數1~10的直鏈狀或支鏈狀的 烷基；k表示3或4的整數。The use of the film for thermoforming sheet laminate in the first aspect of the patent application, wherein the organic crystal nucleating agent contained in the base layer or the organic crystal nucleating agent contained in the gloss layer or both are phosphate esters. a metal salt or a guanamine compound represented by the following formula (1): Wherein R ¹ represents a residue obtained by removing all carboxyl groups from 1,2,3-propanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid; and 3 or 4 R ² systems are identical to each other; Or different, each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms; k represents an integer of 3 or 4. 如申請專利範圍第1項之作為熱成形板片層積用薄膜之用途，其中在與光澤層相反側的薄膜表面上具有印刷層。The use of the film for thermoforming sheet laminate as in the first aspect of the patent application, wherein a printed layer is provided on the surface of the film opposite to the gloss layer.