JP2816352B2 - Multi-layer container - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a multi-layered container suitable for food packaging containers and the like. The present invention also relates to a multi-layer container excellent in physical properties such as transparency, heat resistance, impact resistance and gas barrier property.

[Problems to be solved by conventional technology and invention]

Polycarbonate resins are used in various fields because of their excellent mechanical strength, electrical properties, heat resistance, transparency and the like. For example, a multi-layer container composed of a polycarbonate resin layer, a via resin layer, a polyolefin resin layer, an adhesive layer, and the like is used to improve the transparency and heat resistance of the polycarbonate resin, the moldability of polyolefin resin, cost advantages, and the barrier resin. It is used for food containers and the like taking advantage of food preservability and the like.

Such techniques include, for example, JP-B-52-12588, JP-B-62-5063, JP-A-60-179255,
JP-A-61-47253, JP-A-61-222741, and the like are disclosed. In any of the techniques, in order to make use of the transparency of the polycarbonate resin, the polycarbonate resin layer is formed of the outermost layer of a multilayer container. It is used as

However, when the polycarbonate resin is used as the outermost layer of the container in order to make the most of its transparency as described above, the surface slippage is poor, and the containers are connected to each other in an automated process such as a content filling line and a container packing line. blocking,
Troubles such as catching on the line have occurred, and productivity has been significantly reduced, and a solution has been desired.

[Means for solving the problem]

The present inventors have conducted intensive studies to solve these problems, and as a result, by using a polycarbonate-polyorganosiloxane copolymer for the outermost layer of a multilayer structure container, physical properties such as heat resistance and transparency have been improved. It has been found that the slippage of the container is remarkably improved while maintaining, and the trouble of the process hardly occurs. Thus, the present invention has been completed.

That is, the present invention provides a container having a multilayer structure having a gas barrier resin layer, wherein the outermost layer of the container has a polycarbonate-polyorganosiloxane copolymer of 1 to 10
A multi-layer container characterized by comprising a resin comprising 0% by weight and 99 to 0% by weight of a polycarbonate, wherein the amount of the polyorganosiloxane component in the resin is 0.1 to 40% by weight. Is what you do.

The polycarbonate-polyorganosiloxane copolymer used in the present invention is described, for example, in U.S. Pat.
No. 821,325, No. 3,410,634, No. 3,419,635, No.
It is manufactured by a known method according to 3,832,419, 3,189,662 and the like.

Such a polycarbonate-polyorganosiloxane copolymer has the following general formula: (Z in the formula is a single bond, an ether bond,
An alkylene group having 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a sulfonyl group, a sulfoxide group, a carbonyl group, a sulfide group or a formula R ¹ and R ² are a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, and m and n
Is an integer of 1 to 4, and when m is 2 or more, R ¹ may be the same or different, and when n is 2 or more, R ² may be the same And may be different.
1 is 3 to 50. ) A polycarbonate part having a repeating unit represented by the following general formula: (In the formula, R ³ , R ⁴ , and R ⁵ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, which may be the same or different. Is an integer of 0 or an integer of 1 or more.). The degree of polymerization of the polyorganosiloxane moiety is usually 5
~ 300.

The polycarbonate-polyorganosiloxane copolymer has a block composed of a polycarbonate portion having a repeating unit represented by the above general formula (I) and a polyorganosiloxane portion having a repeating unit represented by the above general formula (II). A copolymer having a viscosity average molecular weight of 1
It is from 0,000 to 40,000, preferably from 15,000 to 35,000.

Such a polycarbonate-polyorganosiloxane copolymer is, for example, a polycarbonate oligomer constituting a polycarbonate portion prepared in advance, and a polyorganosiloxane having a reactive group at a terminal constituting a polyorganosiloxane portion, and methylene chloride. , Chlorobenzene, pyridine, and the like, and then an aqueous sodium hydroxide solution of bisphenol is added thereto, and interfacial reaction is performed using triethylamine or trimethylbenzylammonium chloride as a catalyst. Further, a polycarbonate-polyorganosiloxane copolymer produced by a method described in JP-B-44-30108 or JP-B-45-20510 can also be used.

Here, the polycarbonate having a repeating unit represented by the above general formula (I) is prepared by a solvent method, that is, in a solvent such as methylene chloride, in the presence of a known acid acceptor and a molecular weight regulator, a dihydric phenol and a carbonate such as phosgene. It can be produced by a reaction with a precursor or a transesterification reaction of a dihydric phenol with a carbonate precursor such as diphenyl carbonate.

Here, the dihydric phenol that can be suitably used includes bisphenols, and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferable. Further, bisphenol A may be obtained by partially or entirely substituting another dihydric phenol. Examples of the dihydric phenol other than bisphenol A include bis (4-hydroxyphenyl) alkane other than bisphenol A, hydroquinone, 4,4′-dihydroxydiciphenyl, bis (4-hydroxyphenyl) cycloalkane,
Bis (4-hydroxyphenyl) sulfide, bis (4
Compounds such as -hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone or bis (3,5-dibromo-4-hydroxyphenyl) Propane, bis (3,5-dichloro-4
And halogenated bisphenols such as (-hydroxyphenyl) propane.

This polycarbonate is made of these dihydric phenols 1
It may be a homopolymer (oligomer) using seeds, or a copolymer using two or more kinds, and furthermore, a heat obtained by using a polyfunctional aromatic compound in combination with the dihydric phenol. It may be a plastic random branched polycarbonate.

The polyorganosiloxane represented by the general formula (II) is, for example, dialkyldichlorosilane and / or
Alternatively, it can be obtained by reacting diaryldichlorosilane with water. Examples of such a polyorganosiloxane monomer include dimethylsiloxane and methylphenylsiloxane.

The polycarbonate-polyorganosiloxane copolymer as described above is blended in the resin composition at a ratio of 1 to 100% by weight, preferably 10 to 100% by weight. Here, if the blending ratio of the co-transporting polymer is less than 1% by weight, no improvement in slipperiness is observed.

Further, in the present invention, a polycarbonate resin is used as necessary.

Here, the polycarbonate resin has a repeating unit represented by the general formula (I), and can be easily produced, for example, by reacting a dihydric phenol with phosgene as described above. Examples of the dihydric phenol include those described above.

The polycarbonate resin used here has a viscosity average molecular weight of 10,000 to 10 from the viewpoint of mechanical strength and moldability.
It is preferably 0,000, and particularly preferably 20,000 to 40,000.

This polycarbonate resin contains 0 to 99 in the resin composition.
% By weight, preferably 0 to 90% by weight.
If the blending ratio of the polycarbonate resin exceeds 99% by weight, no improvement in the slipperiness is observed.

The present invention is characterized in that the outermost layer of the multilayer structure container is formed of a resin composition comprising the above-mentioned polycarbonate-polyorganosiloxane copolymer and a polycarbonate resin.

Further, in the present invention, the amount of polyorganosiloxane in the resin composition is 0.1 to 40% by weight, preferably 0.5 to 40% by weight.
Must be 30% by weight.

Here, if the amount of polyorganosiloxane in the resin composition is less than 0.1% by weight, no improvement in slipperiness is observed, while if it exceeds 40% by weight, a copolymer having a sufficient molecular weight cannot be synthesized. Is also not preferred.

The multilayered container of the present invention has a multilayered structure in which the outermost layer of the container is composed of the above resin composition, and further has a gas barrier resin layer.

Here, as the gas barrier resin constituting the gas barrier resin layer, a conventionally known gas barrier resin may be used, and examples thereof include a saponified ethylene-vinyl acetate copolymer resin, a polyamide resin, and a polyvinylidene chloride resin. Among them, saponified ethylene-vinyl acetate copolymer resin and polyamide resin are preferable.

Further, in the present invention, an inner layer or an adhesive layer can be provided as necessary.

Examples of the resin constituting the inner layer include a polycarbonate resin and a polyolefin resin such as polyethylene and polypropylene.

Further, as a resin constituting an adhesive layer for adhering each of the above layers, for example, carboxylic acid or a salt thereof, a polyolefin modified with an anhydride, an olefin vinyl ester copolymer, or a blend thereof is used.

The multilayer structure container of the present invention may be any container as long as at least the outermost layer of the container is composed of the resin composition described above, and the layer configuration may be various. Usually, it has a three-layer structure in which a gas barrier resin layer is disposed on the inner side of the outermost layer via an adhesive layer, or a five-layer structure in which an inner layer is further disposed via an adhesive layer. It is not limited to those having these structures.

〔Example〕

 Next, the present invention will be described in detail with reference to examples.

In addition, the evaluation of the slipperiness was performed by the following test methods 1 and 2.

Test Method 1 Using the resin constituting the outermost layer of the container, test pieces A and B shown in FIGS. 1 (b) and 1 (c) were formed, respectively (in the figures, the numbers indicate the size of each part (unit: mm) ).), And the coefficient of static friction was measured by the method shown in FIG. In addition, the code | symbol C in a figure is a weight.

 The measurement of the static friction coefficient was performed as follows.

That is, the inclination angle (θ) of the test piece A at which the test piece A starts sliding was determined by continuously changing the inclination angle of the test piece B serving as a sample table, and the static friction coefficient (μ) was calculated from the following equation.

Static friction coefficient μ = tanθ The measurement condition at this time is the speed at which the inclination angle is changed.
2.75 ゜ / S, the contact area between test pieces A and B is 2cm ² ,
The load by the weight C was 500 g.

Test Method 2 Using a multi-layer (five-layer, five-layer) hollow container molding machine (manufactured by Mac International), a polycarbonate-polyorganosiloxane copolymer having the shape shown in FIGS. Layer composed of a mixture of the polymer and polycarbonate resin (hereinafter, referred to as PC resin layer) / adhesive layer / saponified ethylene-vinyl acetate copolymer layer (hereinafter, referred to as EVOH layer) / adhesive layer / polypropylene resin A hollow bottle (capacity: 500 ml) having a five-layer structure (hereinafter, referred to as a PP layer) was prepared, and the coefficient of kinetic friction with the bottle conveyor was measured using the apparatus shown in FIG.

Specifically, 10 bottles 1 filled with water to make the content 500g
The bottles were arranged on the bottle conveyor 2 shown in FIG. 3 and the conveyor 2 was moved at 30 m / min, and the stress applied to the fixed push-pull gauge 4 in contact with the top bottle was measured. The value obtained by dividing this stress by the total weight of the bottle (5000 g) was defined as the dynamic friction coefficient. The bottle conveyor 2 used was a TTDLF type (made of SUS304) manufactured by Mitsubishi Heavy Industries. Reference numeral 3 in the drawing indicates a conveyor guide.

Production Example 1-1 (Production of Reactive Polydimethylsiloxane) A mixture of 100 g of water and 206 g of dioxane was added to 800 g of dimethyldichlorosilane over 2 hours. The resulting mixture was heated with stirring until uniform. The mixture was then stripped under vacuum to a pressure of 12 mm Hg at 202 ° C. The stripped product was then filtered to give a clear oil, 225 g of this oil. Was dissolved in 130 g of dry dichloromethane, 114 g of bisphenol A, 130 g of dry pyridine, 1300 g
To a mixture of dichloromethane. The addition was made with vigorous stirring over 65 minutes. After that, wash with 1000g of sodium hydroxide aqueous solution (0.01N) with alkali, 10
Acid wash with 00g hydrochloric acid (0.01N), water wash with 1000g water,
Performed sequentially. The dichloromethane was removed by evaporation to obtain the desired reactive polydimethylsiloxane having a terminal phenolic hydroxyl group (hereinafter referred to as reactive PDMS).

Production Example 1-2 (Production of Reactive PDMS) Reactive PDMS was obtained in the same manner as in Production Example 1-1, except that the initial 100 g of water was changed to 140 g.

Production Example 1-3 (Production of Reactive PDMS) As reactive PDMS, a double-end reactive silicone oil (KF6002, manufactured by Shin-Etsu Silicone Co., Ltd.) was used.

Production Example 2 (Production of Polycarbonate Oligomer) Bisphenol A (60 kg) was dissolved in a 5% aqueous sodium hydroxide solution of 400 to prepare an aqueous sodium hydroxide solution of bisphenol A. Next, this aqueous sodium hydroxide solution of bisphenol A kept at room temperature was added to 138
Methylene chloride was introduced at a flow rate of 69 / hour through an orifice plate into a tubular reactor having an inner diameter of 10 mm and a length of 10 m, and phosgene was co-flowed into the reactor at 10.7 kg / hour.
Blowing was performed at a flow rate of time, and the reaction was continuously performed for 3 hours. The tubular reactor used here was a double tube, and the cooling water was passed through the jacket to reduce the temperature of the reaction solution discharged to 25 ° C.
Kept. Further, the pH of the discharged liquid was adjusted to indicate 10 to 11. The reaction solution thus obtained is allowed to stand, whereby the aqueous phase is separated and removed, and the methylene chloride phase (220
) And further add methylene chloride 170
Was added and thoroughly stirred to obtain a polycarbonate oligomer (concentration: 317 g /). The polycarbonate oligomer obtained here (hereinafter, referred to as PC oligomer)
Was 3-4.

Production Example 3-1 (Production of PC-PDMS copolymer A) 160 g of the PDMS produced by the reaction obtained in Production Example 1-1 was dissolved in methylene chloride 2 and mixed with PC oligomer 10 obtained in Production Example 2. . Thereto, 26 g of sodium hydroxide dissolved in water 1 and 5.7 cc of triethylamine were added, and the mixture was stirred at 500 rpm for 1 hour at room temperature. Then 5.
A solution of 600 g of bisphenol A in a 2% by weight aqueous sodium hydroxide solution 5, methylene chloride 8 and 81 g of p-tert-butylphenol were added, and the mixture was stirred at 500 rpm for 2 hours at room temperature. Thereafter, methylene chloride 5 was added, followed by water washing with water 5, alkali washing with 0.01N aqueous sodium hydroxide solution 5, acid washing with 0.1N hydrochloric acid 5, water washing with water 5 in order, and finally removing methylene chloride. Thus, a chip-shaped PC-PDMS copolymer A was obtained. The PDMS content of the obtained PC-PDMS copolymer A is
3.5% by weight.

Production Example 3-2 (Production of PC-PDMS copolymer B) In Production Example 3-1, instead of 160 g of the reactive PDMS obtained in Production Example 1-1, the reaction obtained in Production Example 1-2 was used. A PC-PDMS copolymer B was obtained in the same manner as in Production Example 3-1 except that 500 g of soluble PDMS was used. The PDMS content of the obtained PC-PDMS copolymer B was 10% by weight.

Production Example 3-3 (Production of PC-PDMS Copolymer C) In Production Example 3-1, instead of 160 g of the reactive PDMS obtained in Production Example 1-1, the reaction obtained in Production Example 1-2 Using 2.6 g of soluble PDMS and reducing the amount of sodium hydroxide used to 2
A PC-PDMS copolymer C was obtained in the same manner as in Production Example 3-1 except that the amount was changed from 6 g to 50 g. The PDMS content of the obtained PC-PDMS copolymer C was 29% by weight.

Production Example 3-4 (Production of PC-PDMS Copolymer D) 480 g of the reactive PDMS (both terminal reactive silicone oil) obtained in Production Example 1-3 was converted to PC oligomer 9.5 obtained in Production Example 2. Dissolve and stir with triethylamine 1
01 g was slowly dropped. After the dropwise addition, the mixture was stirred for 1 hour, and then washed with acid by adding 0.1N hydrochloric acid 5 to separate an organic phase. Then, a 5.2% by weight aqueous sodium hydroxide solution 5
600 g of bisphenol A dissolved in methylene chloride 8 and 25 g of p-tert-butylphenol
And stirred at 500 rpm for 2 hours at room temperature. After a while
Add methylene chloride 5 and wash with water 5.
Alkaline washing with 0.01N aqueous sodium hydroxide solution, 0.
1 Acidic washing with 5N hydrochloric acid 5 and water washing with water 5 sequentially, and finally methylene chloride is removed.
-PDMS copolymer D was obtained. The obtained PC-PDMS copolymer D
Had a PDMS content of 3.9% by weight.

Production Example 3-5 (Production of PC-PDMS copolymer E) As PC-PDMS copolymer, Macrolon manufactured by Bayer AG
Type 1207 was used. PDMS content of this is 4.8% by weight
Met. In addition, PDMS of all the above PC-PDMS copolymers
Content was measured by H NMR.

Examples 1-4 and Comparative Example 1 PC-PDMS produced in Production Example 3-1 as a resin for the outer layer
Copolymer A and polycarbonate are the former / latter = 100/0
A resin (PC resin) mixed at a weight ratio of 1/1/99 was used as the outer layer resin.

Also, as a gas barrier resin layer, saponified ethylene-vinyl acetate copolymer (EVAL 105B manufactured by Kuraray Co., Ltd.)
(EVOH) and a polypropylene resin (PP) for the inner layer.

Further, between the outer layer and the intermediate layer and between the inner layer and the intermediate layer, as the adhesive layer, maleic anhydride-modified polypropylene (manufactured by Idemitsu Petrochemicals Co., Ltd., Polytack H-6300) was used. Using a resin as a raw material, a PC-based resin layer / adhesive layer / gas barrier resin layer (EVOH layer) using a multilayer hollow container molding machine (MAC-5S-S, five types of five-layer hollow container molding machine, manufactured by Mac International) ) / Adhesive layer / PP layer as shown in FIG.

The thickness of each layer is as follows: PC resin layer: 20 μm, adhesive layer: 5 μm
m, EVOH layer: 10 μm, PP layer: 360 μm, total thickness 400 μm
The volume of the hollow bottle was 500 ml.

With respect to the hollow bottles as described above, the static friction coefficient and the dynamic friction coefficient were measured by the test methods 1 and 2, respectively. First result
It is shown in the table.

Examples 5 to 16 and Comparative Example 2 In Example 1, using the PC-PDMS copolymers BE produced in Production Examples 3-2 to 3-5, polycarbonate (made by Idemitsu Petrochemical Co., Ltd., Tufflon A2500)
A hollow bottle and a test piece were prepared and tested in the same manner as in Example 1 except that the resin for the outer layer was used. The results are shown in Table 1.

[Effects of the Invention] In the multilayered container of the present invention, since the outermost layer has good slippage, troubles due to catching in an automatic filling line or the like hardly occur.

Moreover, the multilayer structure container of the present invention has excellent physical properties such as transparency, heat resistance, impact resistance and gas barrier properties.

Therefore, the multilayer structure container of the present invention can be effectively used as a food packaging container or the like.

[Brief description of the drawings]

FIG. 1 (a) is an explanatory view showing a method of measuring a static friction coefficient by a test method 1 in an embodiment of the present invention. FIGS. 1 (b) and 1 (c) show test pieces A and It is explanatory drawing which shows the shape of B. 2 (a) to 2 (d) are drawings showing the shape of the hollow bottle used in Test Method 2 in the example of the present invention. FIG. 2 (a) is a plan view, and FIG. ) Is a front view, FIG. 2 (c) is a right side view, and FIG. 2 (d) is a bottom view. FIG. 3 is a schematic plan view of a test apparatus used in test method 3 in the embodiment of the present invention. In the drawing, reference symbol A indicates test pieces A and B indicates test pieces B and C.
Indicates a weight, 1 indicates a hollow bottle, 2 indicates a conveyor, 3 indicates a conveyor guide, and 4 indicates a push-pull gauge.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁶ , DB name) B32B 27/00-27/42 B65D 1/00-1/48 C08L 67/00-69/00

Claims (1)

(57) [Claims] 1. A container having a multilayer structure having a gas barrier resin layer, wherein the outermost layer of the container has a polycarbonate-polyorganosiloxane copolymer content of 1 to 100% by weight.
And a resin comprising 99 to 0% by weight of polycarbonate, wherein the amount of the polyorganosiloxane component in the resin is 0.1%.
A multi-layered container comprising a resin of 1 to 40% by weight.