JPS63120645A - Laminated molded form - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a molded article in which at least two layers each made of a different resin are laminated. Specifically, it relates to a laminate molded product having at least two layers, a layer made of a specific polyamide resin and a layer made of a polycarbonate resin, and has improved gas barrier properties. Useful as containers for foods, etc.

[Conventional technology]

Hollow molded bodies made of polycarbonate resin are hygienic,
It has excellent properties such as aroma retention, transparency, lightness, and heat resistance, so it is used in baby bottles, pharmaceutical containers, etc. However, polycarbonate resin has the disadvantage of poor gas barrier properties, and is therefore prone to loss of carbon dioxide and intrusion of oxygen, and is not necessarily a desirable material from the viewpoint of preserving contents.

By the way, in the food industry, contents are filled at high temperatures for sterilization purposes, but if a container is used that is made of resin that lacks heat resistance, the shape will change, so a resin with excellent heat resistance is used. That is what is needed. In this respect, polycarbonate resin has a high degree of glass transition, so it is different from other transparent resins (such as polystyrene and acrylic resin).
Although it has advantages over polyethylene terephthalate and the like, it has not been actively used in the past because of its poor gas barrier properties as described above. That is,
Improving this gas barrier property was a problem to be solved by the Todoroki industry.

[Purpose of the invention]

Under these circumstances, the inventors of the present invention have made extensive studies and found that
Layer 9 Made of Polycarbonate Resin When layers made of a specific polyamide resin are laminated, the excellent properties of the polycarbonate hollow molded article are maintained while providing a gas barrier.
The present invention was achieved by discovering that the properties can be improved.

That is, the gist of the present invention is a polyamide forming component 100 to 60 weight tS made from an aliphatic diamine, terephthalic acid and/or isophthalic acid, and a polyamide forming component opθ made from a lactam or an aliphatic diamine and an aliphatic dicarboxylic acid.
% by weight, and a polycarbonate resin layer.

[Structure of the invention] The present invention will be explained in detail below.

The polyamide resin used in the present invention is a polyamide component made of an aliphatic diamine and isophthalic acid and/or terephthalic acid, optionally containing a polyamide component made of 1 lactam and/or an aliphatic diamine and an aliphatic dicarboxylic acid. It is a polyamide resin made by polymerization.

Aliphatic diamines used in the production of such polyamide resins include ethylene diamine, tetramethylene diamine, hexamethylene diamine, octamethylene diamine,
Examples include straight-chain aliphatic diamines such as decamethylene diamine and their methylated, ethylated, and tetragenated derivatives. Furthermore, lactams include caprolactam, lauryllactam, and the like.

Examples of the aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, and derivatives thereof such as methylated, ethylated, and halogenated products.

Such polyamide resin Kj? If the copolymerization composition of lactam and/or aliphatic diamine and aliphatic dicarboxylic acid exceeds 0% by weight, the gas barrier properties will decrease, so such components should be kept at 0% by weight or less. preferably 201f, more preferably 201f
Li'ls or less.

Further, isophthalic acid and terephthalic acid can be used in any ratio, but preferably isophthalic acid/terephthalic acid-7
0720~koo7rθ (weight ratio).

As a method for producing polyamide resins containing such aromatic dicarboxylic acids as main components, a nylon salt consisting of diamine and dicarboxylic acid or an aqueous solution thereof is usually used. Depending on the composition of isophthalic acid and terephthalic acid, it can be produced by a so-called melt polymerization method by adding a lactam depending on the composition, but it can also be produced by a solution method or an interfacial method depending on the composition of isophthalic acid and terephthalic acid.

Using the polyamide resin/concentrated sulfuric acid provided in the present invention, it was measured at 23-°C at a concentration of 17 dl.

Relative viscosity is ηral wm8~3. jdA'/g
Specifically, the polycarbonate resin used in the present invention is produced by reacting one or more bisphenol compounds with a carbonate ester such as phosgene or diphenyl carbonate.

Specifically, bisphenol compounds that can be used in the present invention include bis-(4t-hydroxyphenyl)methane, /l/-bis-(4t-hydroxyphenyl)ethane, and bis-(4t-hydroxyphenyl)ethane. ) propane, 2. -1bis-(4t-hydroxyphenyl)propane, bisphenol A, J, 2-bis-(4t-
hydroxyphenyl)butane, co, λ-bis-(Hiro-hydroxyphenyl)pentane, co, cobisu(4t-
hydroxyphenyl)-3-methylbutane, co,2-bis-(terhydroxyphenyl)bexane, λ, λ-bis(terhydroxyphenyl)-termethylpentane, he/-bis-(4t-hydroxyphenyl)cyclopentane, /,/-bis-(terhydroxyphenyl)cyclohexane, bis-(4t-hydroxy-3-methylphenyl)methane, /,/-bis-(4t-hydroxy-3-methylphenyl)ethane, -, corbis-(4t)
-hydroxy-3-methylphenyl)propane, -, Corbis-(4t-hydroxy-3-ethylphenyl)propane, 2,2-bis-(4t-hydroxy-J-1
80propylphenyl)propane, λ, λ-bis-(4
t-hydroxy-j-sea 7'tylphenyl)propane, bis-(hiro-hydroxyphenyl)phenylmethane, /, /-bis-(4t-hydroxyphenyl)-
/-phenylethane, ll/-bis-(terhydroxyphenyl)-/-phenylpropane, bis-(4t-hydroxyphenyl)diphenylmethane, bis-(4t-
hydroxyphenyl)dibenzylmethane, g, 4t'-
Dihydroxydiphenyl ether, a,4t'-dihydroxydiphenyl sulfone, g,4t'-dihydroxydiphenyl sulfide, phenolphthalein and the like can be mentioned, with bisphenol A being particularly preferred.

Specifically, the method of producing a polycarbonate resin from one or more bisphenol compounds and phosgene according to the present invention involves acid-accepting a bisphenol compound in the presence of an inert solvent such as methylene chloride or -1-dichloromethane. Add an alkaline aqueous solution or pyridine as a body and react while introducing phosgene.

When using an alkaline aqueous solution as an acid acceptor, use a tertiary amine such as trimethylamine or triethylamine as a catalyst.
Alternatively, the reaction rate can be increased by using a complex ammonium compound such as nato-2-butylammonium chloride or benzyltributylammonium bromide.

The appropriate reaction temperature is o-100°C.

The catalyst may be added from the beginning, or any method may be used, such as adding it after the oligomer is produced to increase the molecular weight.

In addition, when copolymerizing two or more types of bisphenol compounds, (a) first, they are simultaneously reacted with phosgene and polymerized.

(b) One is first reacted with phosgene, and after a certain amount of reaction, the other is added and polymerized.

(c) React with phosgene separately to form oligomers. React them to polymerize.

-Functional phenols such as phenol, p-tert-butylphenol, etc. may be present.

The polycarbonate resin used in the present invention preferably has a viscosity average molecular weight of /0.000 to to, ooo.

Here, the viscosity average molecular weight (M) is 6. 20 °C using a methylene chloride solution of Oj'/t
It is calculated from ηop measured by the following formula.

qaplo −(η:l C10KIηsp ) [η)
= KMa XI O, ko r K /, ko j X / 0-5 α 0. /3 M indicates average molecular weight.

The method of stretching in the vertical and/or horizontal direction is to plasticize the two types of resin separately using a stand-alone injection molding machine, and then inject the two types of resin almost simultaneously in the same cavity of Venus to form one layer or one layer. A method of forming a bottomed front cylinder with a multi-layered structure of 3 layers of one-yen type/forming a fire-formed product and blow molding this fire-formed product to make a multilayer container, ・ Or using two extruders , after molding a vibrator-like/sub-molded product with two types of λ layers or three types of λ layers, one end is welded to form the bottom of the container, the other end is compressed and deformed to form the mouth, and then blow molded to form a multilayer container. Examples include, but are not limited to, methods for adding modified polyolefin resin, α-olefin-vinyl ester copolymer, A known adhesive layer such as a copolymerized polyamide resin, a copolymerized polyester resin, or a polyurethane resin may be provided. Furthermore, it is also possible to provide a composition comprising a polyamide resin and a polycarbonate resin used in the present invention as an adhesive layer.

〔Example〕

The present invention will be specifically explained below using examples.

The oxygen transmission rate in the example is US MODIRN0ONT.
ROLS 0K-TRAN 10,00 people Shikoj
'c Measured at 100mm RHK. (Unit: ce/cy
n / cd * we ・an Hll) Reference example /
Manufacture of polyamide O hexamethylene diamine? 0% aqueous solution. Ko=r
kgO* ta, o kgO isophthalic acid /, ritkgOfV7tal@
0. Add acetic acid//, 01 to a salt aqueous solution consisting of 'Prkg, charge it to a reaction tank with a stirrer, and after replacing it with sufficient nitrogen, heat and pressurize until the system pressure reaches /rkg/-. After reaching /l"kg/aNc, the system internal pressure was 2>; / / kg15i, and the mixture was stirred while releasing the pressure to start the first reaction. During this time, the internal temperature was gradually increased (2/θ℃) After 4 hours, almost no water was distilled out, and at this point the internal temperature was 1!Jθ°C.

After further pressure release, the system pressure finally reached 700vtHl13
After the pressure was reduced until the pressure was reduced, the pressure was returned and the molten polymer was extracted from the bottom of the reaction tank.

This polymer had aliphatic diamine and isophthalate ratios of -0/.

This polyamide resin is referred to as (a).

Reference Example Co Polyamide Production Q Hexamethylene diamiphta 0 Aqueous solution
Q water
Ta, o kgO isophthal@ /
, Ribu~0 Terephthalic acid θ, Ri/l
Add acetic acid / /, 01 to a salt aqueous solution consisting of cgOcaglolactam 0.77 and 9, charge it to a reaction tank with a stirrer, replace it with sufficient N, and then add /rkg/c
Heat and pressurize until the system pressure reaches dK, u,/rkg.
After reaching /-, the polymerization reaction was started by stirring while releasing the system pressure so that it became /Icg/I:Ill.

During that time, the internal temperature rose slowly from 7'C.
After a while, almost no water was distilled out, and at this point the internal temperature was 1.
10°C was specified.

After the pressure was further released and the system pressure was finally reduced to 700 wHJfi, the molten polymer was extracted from the bottom of the reaction tank (1) where the pressure was returned.

This polymer contains polyamide components from aliphatic diamine and isophthalic acid and terephthalic acid. It was a polyamide resin containing 71% by weight of the lactam polyamide component, and the relative viscosity ηrel was -10.

This Boriad resin is referred to as (b).

Polyamide resin (a) and polycarbonate resin (manufactured by Mitsubishi Kasei@, product name - Novarex 70) obtained in Example/Reference Example/
jOA) was separately charged into three extruders and co-extruded,
A transparent sheet having a three-layer structure in which a polyamide resin layer was sandwiched between λ polycarbonate resin layers was obtained.

Is the thickness of each polycarbonate layer different? The Qμm polyamide layer was 20μm.

The oxygen permeability of this sheet was measured by the method described above and was found to be as shown in Table 7 below.

Example In Example /, the polyamide resin (1) manufactured in Reference Example - was used instead of the polyamide resin (a) manufactured in Reference Example /.
)) The same operation as in Example 1 was carried out except that 20% of the transparent sheet was used, and the oxygen permeability of the obtained transparent sheet was as shown in Table 1.

Comparative Example/A transparent sheet having a thickness of 10Qμ was obtained by extrusion using the polycarbonate resin prepared in Example/. The oxygen permeability of this sheet was as shown in Table 1.

The comparative sheet was slightly opaque, and the oxygen permeability was on average.

〔Effect of the invention〕

The laminate molded product of the present invention has excellent gas barrier properties, and Table 71C
As shown, the oxygen permeability is extremely lower than that of conventional polycarbonate resins, and its commercial value is high.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - Others/names

Claims (1)

[Claims] (1) Polymerizing 100 to 60% by weight of a polyamide-forming component from an aliphatic diamine, terephthalic acid and/or isophthalic acid, and 0 to 40% by weight of a polyamide-forming component from a lactam or an aliphatic diamine and an aliphatic dicarboxylic acid. A laminated molded product made by laminating a polyamide resin layer and a polycarbonate resin layer.