TWI252163B - Biodegradable film and window pasting case - Google Patents

Abstract

To provide a biodegradable film excellent in heat resistance under a high temperature circumstance in which the film is used and properties for emboss processing for enhancing design quality and capable of being degradable in the natural environment. This biodegradable film comprises a polylactic acid-based polymer and has <= 3% shrinkage factor at 100 DEG C/5 minutes and >= 70 dead fold property.

Description

1252163 V. OBJECT OF THE INVENTION (1) [Technical Field of the Invention] The present invention relates to a biochemical decomposition agent which improves the heat resistance and the relief film, and the workability of the biodegradable film. 'Special film attached to the window box [known technology] See the day t, more use the window opening mouth, however, usually, only open the window of the bag strong # can see the business placed in the box The problem, or the product will protrude from the window hole: the inner product will contaminate some of the plastic film phase with polypropylene, etc.: Situation 'Because &amp;, the box in the material of the window. , or with other papers that are transparent as a substrate for the package, and have insufficient tear strength. 2, π has its water resistance, grease resistance, plastic materials and window openings ^, in order to solve these problems, plastic materials coated with window boxes, clothing, the whole of the composite; Plastic materials, usually in the eye of the eye and less around it. The film is 'for example, it is placed in steam for steam = propylene. However, the heat resistance of polypropylene is excellent, and it is excellent in heat resistance in the temperature environment of the inside. (For the sake of the value, it is embossed by printing. The disadvantage is that in order to improve the so-called embossing processing such as the price of the artist, the trademark of the polypropylene, the name of the product, and the name of the company are used to perform the embossing process on the polypropylene film and the =Z f degree. Use the self-heavy weight, the 'I3' of the windowed box is automatically &lt; relationship, manually assembled. If the box folded by the W box machine can not be erected), observe the sticker 'When using these plastic materials to create wavy, slack, wrinkle, and window parts, you can see that it is special, and its completion is not good. Again, usually plastic

C:\2D-CODE\90-03\89126865.ptd Page 4 1252163 V. Description of invention (2) = The relationship that the material system does not decompose and remains in the environment, and also has a box with a window attached to ° Has a natural destructive problem. "8-2 - Aspects" Regarding plastic materials, when placed in the natural environment: 5 biodegradable plastics are taken from the viewpoint of environmental protection. "One of them is a polylactic acid-based plastic material. "Medium:: The combination of dilactic acid-based materials and paper, to use polylactic acid or straight, and to reconcile the substrate with 3 vegetable fibers (曰特,门^-334448 ^.M,), Λ Λ Λ Λ Λ 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性The film is known as: f = 疋 聚 聚 酸 酸, film, and paper lamination (Japanese shogunate No. 8-252895) is well known. The film disclosed in Japanese Laid-Open Patent Publication No. Hei-4-33-6246 is a weak film having a problem that the portion attached to the window of the packaging container is easily broken. Japanese Patent Application Laid-Open No. Hei 8-25 2895 discloses that the fragile aspect is improved, and the lamination property with paper is good, but it is not easy in the summer, for example, in a high-temperature use environment of 60 degrees Celsius. The heat resistance of iron = and the embossability of the craftsmanship are insufficient. Accordingly, an object of the present invention is to provide a film which is excellent in heat resistance in the high and the field, and which has an effect of improving the embossing process of the singularity of the art. :\2D-CODE\90-O3\89126865.ptd Page 5 1252163 V. Invention Description (3) ^Specially applicable to the biodegradable film of laminated film for packaging box π re-can be provided in the automatic box making Good applicability, loosely produced in the window part of the φ ^ by "wavy, etc., completed in good condition, with a decomposable window in the natural environment. [Means for Solving the Problem] Therefore: The following is the result of a review of the above problems and the invention of the invention. In other words, in the thin production of the present invention. two? The acid-based polymer is formed at a temperature of 100 ° C / 5 minutes. The shrinkage is thin:::...The biodegradability of the characteristic is more than 7〇%, and the biochemical decomposition film of a ί2i ί The extension temperature is 70 to 90 degrees Celsius, and the ρ extension is 5 to 6 times, and in the state of extension, the Celsius &quot;^ old m-10) degree [but the melting point of the Tm-based lactic acid polymer] The temperature is preferably applied to the heat-f-axis stretching film. Further, the biodegradable film described above has an extension temperature of 70 ° to 90 ° and an extension of 1 · 5 to 6 times in the longitudinal direction, and is extended to the lateral direction by an extension temperature of 70 to 80 degrees Celsius. ς c ^ ^ 1 A 1 · 5 to 6 times, in the state of extension, the heat treatment is performed at a temperature of 110 ° C (Tm 1 0 ) degrees [but the melting point of the Tm-based lactic acid polymer] It is preferred to extend the film. The biodegradable film of the present invention having the above configuration is such that it satisfies the above-mentioned results, and it is excellent in heat resistance, and it is not easy to wrinkle with the laminated portion of the paper when it is used in a high temperature environment in summer. The characteristics of the same day, the same day can be 'excellent for the precision of the embossing processability, and has C:\2D-CODE\90-03\89126865.ptd Page 6

V. INSTRUCTIONS (4) Decomposing thinness in the natural environment, 3 biodegradable film of laminated film. Especially...applicable to the packaging box and 'this invention is made up of polylactic acid based on the combination of ^ T ^ ^ 5 , , ί ^ 8.0? 71 〇 (Α) and paper (Β), and under The box that extends the film window. In a preferred embodiment of the present invention, at least one of the surfaces of the box 2, the extension film (1) is corona-treated, the above-mentioned phase is pasted, and both sides of the film (A) are stretched. The surface of the above-mentioned window-coated case that has been subjected to corona treatment. The surface of the stretch film (A) has a surface immersion index of 40 to 55 dyn/cmi, and the film (A) and paper (B). For example, a box with a window attached at a temperature of 60 to 8 degrees Celsius is taken as an example. [Embodiment of the Invention] The details of the invention relating to the scope of the patent application of the present invention are as follows. The polylactic acid-based polymer used in the invention of the patent application is based on L_, D_, or DL_lactic acid, and other oxidized tickic acid units are used as a small amount of copolymer to form a knife. Can have a / summer chain extender residue. The polymerization method may be a condensation polymerization method or a ring-opening polymerization method. For example, in the condensation polymerization method, a hydrazine-type n' compound is directly subjected to dehydration condensation polymerization: lactic acid or the like is obtained, and the polylactic acid is passed to the composition. In addition, the % umbrella &amp; method (1 &amp; "1 (16 method)" will be the cyclic dimer of lactic acid

1252163

= C and s day, depending on the necessity, the polylactic acid can be obtained by using a polymerization-adjusted catalyst. The same as % of J temple, the polylactic acid used in the invention of the selection = = should be used. In general, the practical properties such as mechanical properties and heat resistance cannot be found, and when the knife 1 is too small, the viscosity is too high and the formability is poor. When too large, the monomer that is copolymerized with polylactic acid, &gt; butyric acid, 3-rebutyric acid, 2_weiki m = thiobutyric acid, 2-carboxy-3_methylbutyric acid, 2 beauty夂基一3,3二二曱基Continuous 2-dibasic hexanoic acid and other two-functional fats; two-two-methyl lactate, although, pentane, etc. The purpose of acid and hexidine, and the purpose of adjusting various physical properties, can be, day absorbent, slip agent, plasticizer, no;: two fixed: two stabilizers, ^ from the desired strength, etc. Point, ^ ^ color agent, pigment, etc. Reasonable. The extension film has a viewpoint that the film of the 丨 axial extension is extended, etc., and the latter is preferable. / film-seeking, 2-axis stretch film, from physical properties When manufacturing 1-axis stretch film, there are

The roller method has only the extension of the plurality of rollers having different longitudinal speeds in the longitudinal direction. 'Or in the manufacture of the film with only the transverse direction I 2 axis extending by the tenter method, 4 the lateral extension is carried out by the tenter method, the longitudinal extension is carried out by the roller method, and the transverse direction is simultaneously extended by the tenter method. The extension method, or the longitudinal and u ¥2 extension method.

1252163 V. Description of invention (6) Too, in the extended condition, the longitudinal direction is 1. 5~6 times, more suitable 1 ^ 54 ~ 6 times, more preferably 2 ~ 4 · 5 times within the range of 4 · 5 times, the strength of the transverse bismuth film, and the choice of thickness accuracy. In particular, the 2-axis extension is extended in the longitudinal direction and the lateral direction by 2 times, and the extension temperature is 7 摄 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 横向 面积 面积 面积 面积 面积70: Within the range of 〇, the temperature is in the range of 70 to 80 degrees Celsius, and is in the range of 70 degrees to 80 degrees in the horizontal direction, because it is included in the order of 2 fine &quot;,, in the simultaneous 2-axis extension method 70~8〇 The inner extension is the general idea of the car to apply for the law. When the temperature is extended, the thickness of the film produced is::: the magnification and the extension temperature, which is a significant drop after the extension. ;: The unevenness is tied to the printing paper; 1 = often obvious. The scaling up is important. In the invention of the invention, the shrinkage rate at the time of controlling the film is less than 3%: The f rate is a problem in an environment of 100 ° C / 5 °. You Fu: When the income is over 3% and too large, it may be placed when using the cover; the gas; the calculation: the shape of the package used for the house outside the f, and in the use environment, within the In the instrument panel, the shrinkage rate of the film is greater than the predetermined value, and becomes a relatively high temperature. If the film is more than two sides, the part of the window, especially the cross-over win, will shrink and deform. Heat shrinkage, need to hold the film to make it tense. Page 9 C:\2D-CODE\90-03\89126865.ptd 1252163

1252163 Wet cascading, brushing paper, and mold addition. The agent or the like may be a biochemically decomposable raw rubber or gelatin. The structure is exemplified by film/paper/this report. Before the integration, the bonding force of the Tyran film sheet. Corona treatment of the film of the hot-melt layer of paper, such as ethyl ester, the amount, but the adhesion, the case of the egg, such as the thin electrode of the present invention, the electric surface can be used without the use of surface adhesive 5, the invention (8) Shape. For example, the film may be laminated on a kraft paper or a printing method by dry lamination, and the embossing described above may be carried out in such a state as to be used for lamination, such as an olefin-based, a polyamide-based, a rubber-based adhesive, or the like. . The adhesive used is biodegradable. Regarding carbohydrates such as starch, and the like, the unsulfurized natural rubber or the like is a two-layer structure of a laminate of a film, and the thin layer of the present invention is exemplified, but there is no particular limitation. The film of the present invention is in association with 纟. As a result of the corona treatment, the adhesive can be applied with high adhesion and the adhesive can be easily peeled off from the paper. Well known device. It is necessary to implement the corona surface. a window 1 and a paper (substrate) stacked on a film layer of the upper (outer side) of the film (the substrate of the package of the present invention) It is also known as a paper-based system such as paperboard, and the biodegradability of propylene, etc.

I. The three-layer faint treatment of the film/film of the film is suitable for wetness, and can be used for lifting the sticker used in the past. For example, as shown in Fig. 1, the content can be opened in advance (commercial decomposition) The film 2 is adhered to the window 1 and the substrate 3 is assembled. The film laminated substrate 3 formed by the laminate

C:\2D-CODE\90-03\89126865.ptd Page 11 1252163 V. Invention Description (9) '----, blanking into the expansion diagram shown in ® 1, then, 帛 automatic box making machine or The artificial garment is assembled into a square shape (package) A as shown in FIG. When the automatic box making machine is used, the σ 主 of the main trowel joint of the film laminated substrate shown in the figure is 4, the adhesive is applied, and the folding line 5 is bent and adhered to the state of being folded into two. After that, we will attract the ups and downs and fill it up (commodity). The size and number of the window 1 are not particularly limited, as shown in FIG. 2, the position of the window can be within the Φ of the box, or the box (package box) of the form shown in FIG. ^ It is also possible to be adjacent to both sides; although it is omitted, it may be applied to three or four sides. The related matters concerning the invention of the biodegradable film of the present invention are divided into items and are listed below. 〇) a see-through window made of a biodegradable film made of a polylactic acid-based polymer, having a shrinkage ratio of 3% or less at a temperature of 100 degrees/5 minutes and a full-folding property of 7 degrees or more. The package is coated with a biodegradable film. (2) The biodegradable film is extended to a single direction at a temperature of 7 〇 to 9 摄 in a single direction of 1. 5 to 6 times, and in the state of the extension, with a Celsius 丨 1 〜 degree (Tm-10) degree [However, the melting point of the Tm-based lactic acid-based polymer. The temperature is heat-treated for 3 seconds or more. The one-axis stretch film is a biodegradable film coated with a through-the-box package as described in (丨). (3) The biodegradable film is extended at a temperature of 7 〇 to 9 摄 degrees in the longitudinal direction of the 甸 1 · 纵 1 1 , , , , , , , , , , , , , , , 〇 〇 〇 〇 〇 〇 1 1 1 1 1 1 1 1 1 1 1 1 6 times, in the extended state, using 11 degrees Celsius ~ (Τπι -1 0) degrees [but the melting point of the Tm-based lactic acid polymer. The temperature of the temperature is given to the heat

I

Page 12 C:\2D-C0DE\90-03\89126865.ptd 1252163 V. INSTRUCTIONS (10) - - Two-axis extension for more than 3 seconds. Biodegradable (four) film for box coating. As shown in (1), there is a window with a see-through window =: tf: the box with the window attached to the stomach is, for example, Figure 1, Figure 2, and Figure 3. In the box for the packaging of the paper in the bean, a window is opened to enable遂 size, quantity, etc. and special benefits:; Further, regarding the window spanning on the adjacent two sides, the position of _, and Hungary is in one of the boxes, or in the present invention, control;:;:? Anyone can. The shrinkage rate is 8 degrees Celsius and the rate of undershoot is important. In other words, it is better to be within the range of ~5%. The shrinkage rate in the state of receiving = knife buckle is 〇. 5, when observing the window part, the brother ^, when, and the paper with the window is laminated, etc., the completion is not good. The film is slack, the wavy and wrinkles are greatly shrunk, and the leveling occurs, and =2/heat applied during lamination causes the film to be problematic. The shrinkage rate is caused by the shrinkage of the upper and lower layers of the upper layer and the layered body, so that it is attached to the window portion: 巳c 'the film is slightly finished in the lamination, and the ruthenium, the second relaxation, the wave Shapes and wrinkles, etc., in the case of 80 degrees / 10 minutes, 1 to (four). ☆The more shrinkage rate of the child, in the film and paper cascading), rabbits, avoid the second test after the completion of ί wrinkles, inhibit the static electricity generated in the process, to improve the smoothness of the film, to: '[ It is important to have good slipperiness. The rough method. Then 1 illusion; film f: surface to make the surface ____ or paper contact area,

C:\2D-CODE\90-03\89126865.ptd Page 13 However, the way to do this is to reduce the J:f f wax by the simplest method: method. The second method is the bonding force of the eight, rather than the good machine particles, and the inertness of the extension process is not 1252163. 5. The invention (11) can improve the slipperiness. The thickness is measured by the method described in the approximate manner. It is not too early for money, and it is used in the range below JIS B 0 6 0 1 〇.°S. Average coarse; Ra::: average;; Ra exceeds °.01, not roughened 'high friction coefficient, slipperyness is not ^ Only the surface of the film on the shell is large, the scattering of light on the surface of the film is larger'' In view of the average roughness Ra, the object of the present invention is to make it clear. Regarding the transparency, the turbidity is less than 10%, and the 5% grain-coated box film is used, and although the contents can be seen through, the benefit is good. The turbidity exceeds 10% of the brightness. ..., 忐 eliminate blurry and lack of freshness. It is necessary to suppress the heat shrinkage of the film. Usually, the roll method is heat-treated by stretching in the state of the enamel film; the tenter method is to heat-treat the film by contacting the ruthenium film with a heating roller.埶 π 产 产 、 、 、 、 、 、 、 专 专 专 专 专 I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I Hyun point - two 夂 夂 Μ 以上 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在-A) Thin whitening and impaired transparency. Then rise =, and break.乂上日守,Tao boat begins to melt. The extension sheet (A) used in the present invention has a modulus of elasticity from the viewpoint of the corner of the positron. . ~ 5 〇〇 kgf / appropriate 'and more preferably 2 5 0 ~ 45 ° kg &quot; square mm. The so-called correct ί self-edge angle means that as shown in Figure 3 'fold the film and paper laminate m C: \ 2D-CODE \ 90-03 \ 89126865.ptd page 14 1252163 five, the invention description ( 12) In the form of a box, the sheet itself forms an edge at the window, and / at the two sides of the phase, the desired film cannot form an edge and the corner is folded into a straight line. Soft. This is related to the film's own branch:::The part of the sea is loose, it is wavy and then 'Before the use in the invention, it is corona treated. G: It is still wet with the high film surface of the paper. 19, to;::: The results of the military processing, mention. The sheet processed by the ΐ电军 is easily peeled off from the paper. Corona treatment can be carried out using the conventionally used film on the surface to which the paper is adhered. Yarn and rt electric army cool 疋奵 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : In the figure, the portion of the adhesive is applied or the adhesive is applied, and the portion of the adhesive is applied to the laminate shown in the expanded view: the adhesive is applied. The part is the opposite of the film-to-paper bonding. Therefore, the relationship of applying the adhesive on the film is 'when there is a sticker, when there is an external force, for example, the product is placed in the box, because The impact of the falling of the helmet sound is easy to be made at the interface between the film and the adhesive: peeling. Therefore, when it is required to improve the wettability of the surface when it is required to be stronger, it is corona. The treatment is preferably. From the viewpoint of the above-mentioned adhesion, the stretch film (A) used in the present invention has a wetting index of 40 to 5 5 dyn / cm, and a range of ~Wdyn/cm. The inner portion is more suitable. The solid paper is preferably used. The paper (B) used in the present invention is not particularly limited to paper, printing paper, mold paper, paperboard, etc. &amp; 'can be cowhide m C :\2D-C0DE\90-03\89126865.ptd Page 15 1252163 V. Description of invention (13) ^Extension of invention t The film (A) is dry heat; the layer f method, etc., can be laminated by a known method: the layer is as follows: (4) the dog is exposed to the film with the window portion of the beauty phosphorus, using two degrees Celsius Temperature stack in the range; η.~ Make the film shrink, if the stack::$/the dish is too low, it can't be high. If the dish is too much, then the shrinkage rate will pass:: Μ( Α) Use adhesives and even adhesives to adhere to paper (8). Also use adhesives such as adhesives, amines, rubbers, and urethanes: = 3 splicers and even adhesives. The use of the following 1 = sex: the whole box of the window, is a very small amount from the 丨 = biochemical: solution is appropriate. It belongs to the biodegradable protein shellfish, unsulfurized natural rubber, etc. for example. The layer of the material of the window-attached box of the present invention is composed of a two-layer structure of Α Α)/paper (β), a two-layer structure of a stretch film (Α)/paper (Β)/延牛 () For example, it is not particularly limited thereto. 'The film is formed by laminating a film and paper, for example, as shown in the drawing, and then using an automatic box making machine or Manual operation, as shown in Figure 1. When using the automatic box making machine, from the unfolding diagram shown in Figure n, n is the part of the box after applying the adhesive and then sticking it, which becomes the coating agent as shown in Figure 4. After the state, as shown in Fig. 5, the upper and lower sides are attracted to be folded into a filled product. However, since the erecting situation, the automatic box making and the foot 趁 are at an angle 0 which is similar to that shown in Fig. 5, which is good. The difference between the two ^, the heart. The automatic C:\2D-C0DE\90-03\89126865.ptd Page 16 1252163

1252163 V. Description of invention (15) X ·· Deformation (4) Press for embossing workability, in the size of 3 5 points in the official, w name (Mitsubishi Resin Co., Ltd. 8:: company processing depth of 2mm The mark above is qualified. It is the finished state of the corners. The following two observations are made by visual observation of the relief part, especially the evaluation.

〇 Δ X The corners also maintain a normal shape. The embossed parts are deformed and have poor finishes and shapes. (5) Melting point The melting is carried out in accordance with JIS-K7121, and the state is carried out in a standard state. The heating temperature is 10 °C / min. The measurement is performed using the DSC%? point made by Bajin Jelma. That is, after the film test piece 1〇1]]§ is adjusted, during the period of the nitrogen flow rate of 25 ml/min, the temperature is raised to 20 degrees Celsius in the period of time, such as the mountain two...and ▼... 丄v 'the 'knife is also placed &gt; The DSC curve appearing in the U room does not read the endothermic peak, and the temperature at that time is used as the melting point. (6) Turbidity Measured in accordance with J I S K 7 1 0 5 . Lord-y scholars are brothers and sisters. The smaller the value, the higher the transparency. (7) Surface roughness The measurement was carried out in accordance with the method described in J I S B 0 601. Using the surface roughness tester (SE-3F) manufactured by Otaru Research Institute, the center line average roughness Ra and the ten point average roughness (Rz) were obtained. The tip of the stylus of the measuring device has a radius of 2 μm, a load of 30 mg, a measuring length of 8 mm, and a cutoff value of 〇· 〇 8 mm. (8) Surface wetting index

C:\2D-CODE\90-03\89126865.ptd Page 18 1252163 V. Description of the invention (16) Measured according to J IS K 6 788. (9) Lamination suitability A3 size cardboard having a small window was uniformly applied to the adhesive at a predetermined position. Then, a film cut into A3 was pressure-bonded by a manual roller. The adhesive used was Tektronix A-991/Heike Ned a-; [9 (mixed in a ratio of 15/1) (product of Takeda Music Industrial Co., Ltd.). The laminate was immediately dried in an oven at a temperature of five degrees Celsius for one minute. Then, the appearance of the film and the adhesion of the paper to the film were observed. For the wrinkles caused by shrinkage, the laminate has a curler' and the easy peeler is represented by X, and the upper one is indicated by 〇. y (1 0) After the completion of the window part (9), observe the window part, and note that there are slacks, waves and wrinkles, and no one is marked as 〇. ~ (11) The automatic box-making property is manufactured in (9), and the laminate which has been aged at 38 degrees Celsius for 48 hours or more is cut into the developed view of Fig. 1, and the adhesive is applied to the applied adhesive agent ^^, as shown in the figure. As shown in 4, the fold becomes the state of two. The adhesive system used is the same as that of the user, and the aging is performed at 38 degrees Celsius for 48 hours or more. Then, it is erected as shown in Fig. 6(a), and then as shown in Fig. 6(b). Exceeding the load by hand from the opposite direction and biasing to 45 degrees. Then, as shown in Fig. 6 (c), the measurement angle Θ is used to evaluate the state of the box e when the load is not applied. When the value is below 20 degrees, the good state is denoted by 〇, and when it is equal to or greater than one, it is denoted by X. Yikou ‘ 2〇 (1 2) drop test

1252163 V. INSTRUCTIONS (17) A 150 g piece of wood is placed in a box manufactured in (11) and sealed. Drop it on a concrete floor from a height of one meter. Observe the deformation of the box caused by the impact of the next shot, especially the deformation of the adhesive portion. In the case where the adhesive portion is completely peeled off, it is marked as X, and at least if the 7-dry state is recorded as △, and if there is no abnormality, it is marked as 〇. [Example 1] The ratio of the L-lactic acid component to the D-lactic acid component was 9 8 : 2 of polylactic acid having a molecular weight of about 220,000 (melting point: 158 ° C), and the average particle size was about 25 μm.颗粒 二 ( ( ( ( ( ( ( ( ( ( ( ( ( ( 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士It is melted and mixed at about 2 degrees Celsius, extruded into a thin strip, and cut into pellets while being cooled. The granule was used as the main batch, and after drying again, 10% of the same dried polylactic acid was mixed, placed in a 40 mm diameter biaxial extrusion machine, and extruded into a sheet shape at a set temperature of 210 degrees Celsius. It is rapidly cooled and solidified by a rotating cooling cylinder to produce a substantially amorphous sheet. The prepared sheet is heated while being heated by an infrared heater while being in contact with the warm water circulating roller, and is extended by 2.6 times in the longitudinal direction between the circumferential speed difference rollers at a temperature of 75 degrees Celsius, and then the longitudinal direction is extended. The extending sheet is gripped by a clip and guided to the tenter, and is heated to a vertical direction of the film 'with a temperature of 75 degrees Celsius _ extended 2. 6 times and then heat treated at 135 degrees Celsius for about 20 seconds to make a 25 micron thick. film. The film produced was uniformly coated with a polyurethane-based solvent-based adhesive (Heke Lake A- 9 70/Heike Ned A-19=15/1, Takeda Pharmaceutical Co., Ltd.

1252163 V. INSTRUCTIONS (18) Manufactured to be 1 micron thick and dried in a thickness of 60 in a windowed oven for 3 minutes. The punching post is crimped and attached to: the upper layer, and the above-mentioned polylactic acid-based film roll laminated material; the second temperature aging small (four) window box. The measurement of the physical property value and practicability of the film produced is shown in Table 3. The physical properties of the film and the method of returning to A are as shown in Table i. Practicality of the package [Example 2] The ratio of the L-lactic acid component to the D_lactic acid component is 98:2, the polylactic acid of 182,200,000 (melting point: 158 degrees Celsius), and the average particle size of the knife = Fuji Granular sulphur dioxide produced by Silesian Chemical Co., Ltd. (commodity 5 Lia 4 3 0) 1 weight fraction is dried separately to remove moisture, then 'release' into the diameter of 4Omm in the same direction two-axis extrusion machine, set in about It is melted and mixed at a temperature of 2 degrees Celsius, extruded into a thin strip, and cooled and cut into pellets and granules. The pellet is used as the main batch. After drying again, the same dried polylactic acid is mixed by 1%. Into the diameter of 4 〇 mm in the same direction of the two-axis extrusion machine, with a set temperature of 2 1 0 degrees Celsius The sheet-like shape is cooled and solidified by a rotating cooling cylinder to produce a substantially amorphous sheet. The door is made to be heated by an infrared heater while being in contact with the warm water circulating roller. The circumferential speed difference roller is extended by 2.6 times in the longitudinal direction at a temperature of 77 degrees Celsius. Then, the longitudinally extending sheet is gripped by a clip and guided to a tenter, and the vertical direction of the film flow is '72 degrees Celsius. The temperature is extended by 2.8 times and then heat treated at 135 degrees Celsius for about 20 seconds, longitudinally and horizontally.

C:\2D-CODE\90-O3\89126865.ptd Page 21 1252163

A 5% relaxation heat treatment was carried out to produce 2 5 micro-half &gt;# using the film in the same manner as in the example. Box of windows. In the same conditions as in the case of the example i, the utility of the "clothing + augmented layer material and the box with the window attached (package box) is checked, and the physical properties of the film and the film are as follows. ^, ,,, ° The results are shown in the table [Comparative Example 1] A polylactic acid (melting point: 48 degrees Celsius) of a ratio of L-lactic acid component to D_lactic acid component of 200,000, and a sub-amount of about about Fuji Silicia Chemical The granularity produced by the company is 2 = particle size of about 2 · 5 micron. 43 0 ) 1 weight is separately dried and fully emulsified 7 stone eve ^ commodity name: 矽 diameter 40mm in the same direction two-axis extrusion machine, After setting the &amp; waterjet, put it into the blending, mix it into a thin strip and extrude it, and let it cool; it: 200 °C and melt the pellet as the main batch, after drying again, cut into pellets Polylactic acid mixed 10%, placed in the same direction with a diameter of 4〇mm—extruded into a sheet shape at the above-mentioned set temperature of 210 degrees Celsius, and in the form of a cold curing in a broadcaster. Crystalline sheet. The special cooling cylinder is used to contact the sheet made of hot water circulating roller heater Heating, in the longitudinal direction of the circumferential speed difference roller and extending by 2.6 times with infrared, and then, the longitudinally extending sheet is heated to a tenter with a temperature of 77 degrees Celsius to the film. a, with the child holding and guiding, and the universal direction is extended by 2.8 times with Celsius, and then heat-treated at a temperature of 115 degrees Celsius, which is about 4.7 degrees Celsius. The film was fabricated in the same manner as in the examples. The film was examined under the same conditions as in Example 1 and the material was attached and the film was attached with β.

1252163

Box with window (package box) [. M properties were used, and the results thereof are shown in the table [Comparative Example 2] The use of a 15 μm two-vehicle extension was carried out, and the remainder was a hybrid polypropylene film instead of a polylactic acid-based film case. The physical properties of the laminated material and the window-covered box (package box) were examined by the method of the same example as in the case of j 1 to inspect the physical properties of the film and as a window attached [Table 1] and the result was And is shown in Table 1.

Comparative example _J__ 2 10. 0 8. 0 1. 0 0. 5 95. 0 1T2.0 X 〇 Ο 1 X丨 -------J

[Example 3] The L-lactic acid component and the d-lactic acid 忐80,000 聚聚朝萨, the other sub-identified knife ratio of 95 · · 5 its molecular weight is about the granular dioxide dioxide produced by the company The Changshi Silesia fraction is separately (4) fully removed from the water (sub-judgment sub-(four)) 1 weight strip and extruded, cooled and melted and combined, into a fine batch, after drying again, the same granular. The granule is taken as the main, put into the diameter of 40 off (five) direction two-axis squeeze the above 5% lactic acid mixed 10% ~ i money to set the temperature Celsius

1252163 V. INSTRUCTIONS (21) ^ In the form of a sheet, it is rapidly cooled and solidified by a rotating cooling cylinder to produce a sheet of two or two sheets. The prepared sheet is heated in contact with the warm water cycle and heated by an infrared heater, and is extended by 3.0 times between the circumferential speed difference rollers to a longitudinal σ of 75 degrees, and then the longitudinally stretched sheet is stretched. Use the clip to decapitate the animal, m ^ ^ and then to the tenter, to the vertical direction of the film flow, with 75 ° Celsius, w μ,, R .. ^ and then, the extension extends 3 · After 0 times, it was heat-treated at 120 ° C for about 15 seconds to make a film of 15 μm thick by making, raw, Γ川, 蒋制, 生夕^. A 矣 浔 浔 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视The corona treatment of the surface is shown in Table 2. The ancient _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The ancient = t ίί method determines the physical properties of the film produced. In addition, the above-mentioned ... day &gt; = member of the box. Lamination characteristics and box-adaptability at this time The results of 1 field 1H β and the like are shown in Table 2. Further, the heat shrinkage rate was measured by the above method in addition to the warm water bath instead of the warm water bath of 100 °C. [Example 4] A film was produced in the same manner as in Example 3, in accordance with the method of Example 3 described in Table 2 below.

The physical properties, lamination characteristics and ‘adhesiveness of the film made by tanning and + ^ ^ lL jin were measured by the above method. The results of these are shown in Table 2. X, the heat shrinkage rate was measured by the above method except that a warm water bath of 80 degrees Celsius was used instead of the warm water bath of 1 degree Celsius. [Example 5]

1252163 V. The invention (22) The ratio of the L-lactic acid component to the D-lactic acid component is %: 2, the polylactic acid having a molecular weight of about 220,000, and the average particle diameter of about 2. 5 μm. The shape of the dioxide dioxide (trade name: Seychela (4)) ^ is: m to dry enough to remove the water, 'put into the diameter of 4 〇 同 in the same direction, set at about 200 degrees Celsius and blending, It is set as a thin strip and is set to be cooled. At the same time, it is cut and squirted. J is a salty granule. The granule is used as the main batch of rice: after drying, the bell is dried and the above polylactic acid is mixed by 1%% η Λ Λ4 〇_In the same direction, the two-axis extrusion machine solidifies the substantially amorphous sheet with a rotating cooling cylinder at a set temperature of Celsius and &amp;倍倍, The longitudinal extension is extended to the longitudinal temperature between the circumferential speed difference rollers, and the longitudinal temperature is extended by 2.6 times. The sheet was held by a J-clip and guided to a tenter, and the film was stretched 2.8 times to a temperature of 72 ° C., and then heat-treated at 135 ° C for about 15 seconds to produce a film of 15 μm thick. The film was measured by the method described above, and the physical properties, lamination property, and the suitability of the film produced were evaluated. The results of these are shown in Table 2. X, the heat shrinkage rate was measured by the above method, except that a warm water bath of 80 ° C was used instead of the warm water bath of Celsius.

I

[Comparative Example 3] The film described in Table 2 was produced in the same manner as in Example 3. The physical properties, lamination property, and box-adhesive properties of the produced film were measured and evaluated by the above method. The results of these are shown in Table 2. χ, the heat shrinkage rate is to use a warm water bath of 80 degrees Celsius instead of a warm water bath of 1 degree Celsius.

1252163 V. Inventive Note (23), measured according to the above method. [Comparative Examples 4 to 7] A film was produced in the same manner as in Example 3 except for the conditions described in Table 2. In Comparative Example 4, granular cerium oxide having an average particle diameter of 6.0 μm (manufactured by Fuji Silisia Chemical Co., Ltd., trade name: Sevilla 7 7 0) was used. The film was measured by the above method to evaluate the physical properties of the film produced, the lamination characteristics, and the suitability of the package. The results of these are shown in Table 2. In addition, the heat shrinkage rate is to use a warm water bath of 80 degrees Celsius instead of a warm water bath of 100 degrees Celsius.

In addition, it was measured in accordance with the above method. [Table 2 ]

EXAMPLES Comparative Example 3 4 5 3 4 5 6 7 D% 5 5 2 2 5 5 5 5 Melting point (°C) 146 146 166 -166 H6 146 H6 146 Average particle size of spent particles (/im) — 2.5 2.5 2.5 2.5 6.0 0.9 2.5 2.5 Heat treatment temperature (°C) 120 115 135 105 135 120 120 120 Heat burying time (seconds) 15 15 15 20 20 15 15 15 Corona treatment on both sides. Both sides are two sides r two sides two p. One-sided, no heat shrinkage (%). 3. 1 4. i 1.5 19.0 0.4 3. 1 3. 1 3. 1 TD 3.2 4.8 0.6 14.0 0.3 3.2 3.2 3.2 Turbidity (%) 〇3 〇2 〇5 〇1 X 11 0 i 〇3 〇3 Surface index 0 0 0 0 0· 1 0 0 0 Wet finger _ (dyn/cm) 51 51 51 51 47 43 51 36 Laminated special 1 〇〇〇X 〇X 0 〇 X case with window part 〇〇〇 〇〇〇 〇〇〇 Automatic box making 〇〇〇X 〇〇〇_〇_j| Drop test 〇〇〇〇〇 〇 X _ Total evaluation increase X • XXXX

[Effects of the Invention] The invention relating to the scope of the patent application of the present invention is a polylactic acid polymerization having a predetermined heat shrinkage ratio and having a predetermined complete folding property as described above.

C:\2D-CODE\90-03\89126865.ptd Page 26 1252163 V. Description of the invention (24) The relationship between the biodegradable film formed by the body is excellent in the heat of the high-temperature use environment, and the artistic property is improved. The embossing processability is also excellent, and the film has the advantage of being decomposable in the natural environment. Moreover, the biodegradable film has the above-described characteristics and can be applied to a laminated film for a packaging box, and the film is provided with excellent heat resistance in an environment of use, and is excellent in craftsmanship and has a natural environment. Decomposable packaging box with window. Furthermore, according to the present invention, it is possible to provide an automatic box making machine with good adaptability, which can eliminate the slack, wrinkle and wavy shape attached to the window, and has a good finished state, and has a decomposing window in the natural environment. The boxer. φ [Description of component number] 1,6 Window 2 Biodegradable film (full laminate) 3 Film laminate substrate 4 Coating adhesive portion 5 Folding line 7 Suction direction 8 Pulling direction 9 Load direction A, B Case Reference

C:\2D-CODE\90-03\89126865.ptd Page 27 1252163 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a developed view of a windowed box showing the state of use of a biodegradable film. Fig. 2 is a perspective view showing a window-mounted case showing the state of use of the biodegradable film. Fig. 3 is a perspective view showing another form of a box with a window in which the biodegradable film is used. Fig. 4 is a view showing the unfolded view of Fig. 1 in which the adhesive is applied to a part of the adhesive and adhered to the state of being folded into two. Fig. 5 is a view showing a case in which a box folded in two is sucked up and erected to fill a content (commodity). Figure 6 (a) - (c) is a diagram showing the experimental method for automatic box making.

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Claims (1)

&quot;7 ^ 々丨V~π丨· u - One of the heat treatments at a temperature of 110 ° C (Tm-10) degrees [but Tm lactic acid polymer melting point] In the case of the stretched film, the stretched film has a surface average roughness Ra of 0.01 or more and 0.08 or less and a surface wetting index of 4 to 55 dyn/cm. 2. A biochemically decomposable film comprising: a polylactic acid-based polymer, having a shrinkage ratio of 3% or less at 100 ° C / 5 minutes, and a complete folding property of 70% or more, the biochemical The decomposable film is extended by 1 to 5 times in the longitudinal direction at an extension temperature of 70 to 90 degrees Celsius, and is extended by 1 to 5 to 6 times in the lateral direction at an extension temperature of 7 to 80 degrees Celsius. In the state of the biaxially stretched film which is heat-treated at a temperature of 110 degrees Celsius (Tm-ΙΟ) degree (but the melting point of the Tm-based lactic acid-based polymer), the surface roughness Ra of the stretched film is 0.11. Above 〇·08 and below, the surface wetting index is 4〇~ 5 5dyn/cm 〇3 · A kind of box with window attached, which consists of: made of polylactic acid polymer, at 80 degrees / 10 minutes Celsius The shrinkage ratio is 〇·5 to 5%, and the laminate having the turbidity of 1 〇/〇 or less of the stretched film (A) and the paper (B) has a window capable of seeing the inside of the box, and the stretched film ( A) The average surface roughness is “above 〇〇1 and above 0·08, and the surface wetting index is 4〇~““” (4). Item of paste box 3 has a window, the system including at least one surface treated by corona surface of the film extension (A) of the medium. 1252163 _ Case No. 89126865_Yearly 曰 Amendment _ VI. Scope of application for patents 5. If the box with window is attached to the third item of the patent application, the surface of both of the above-mentioned stretched film (A) is corona treated. 6. For the box with the window attached to the third paragraph of the patent application, the above-mentioned stretch film (A) and paper (B) are laminated at a temperature of 60 to 80 degrees Celsius. C:\Total file\89\89126865\89126865 (replace)-2.pt C Page 30