JPH0260929A - Laminated molded product - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a laminate molded product. Specifically, the present invention relates to a transparent laminated resin molded product with improved gas barrier properties.

(Conventional technology and problems) Hollow molded products made of polycarbonate resin are used as baby bottles, pharmaceutical containers, etc. because they have excellent transparency, heat resistance, hygiene, fragrance retention, and light weight. There are, but
Due to poor gas barrier properties, loss of carbon dioxide gas and intrusion of oxygen are likely to occur, making it unfavorable in terms of preserving the contents.

On the other hand, in the food industry, food is filled into containers at high temperatures for sterilization, but if containers made of resin with poor heat resistance are used, the shape will change, so resin materials with excellent heat resistance are required. has been done. In this respect, polycarbonate resin has excellent transparency and a high glass transition temperature, so it can be used as a transparent resin such as polystyrene resin, acrylic resin,
It has an advantage over polyethylene terephthalate, etc.
As mentioned above, it has not been actively used because of its poor gas barrier properties.

The present inventors first improved the gas barrier properties of polycarbonate resin by laminating a certain type of polyamide resin layer on the polycarbonate resin layer (Japanese Patent Laid-Open No. 63
-120645), but there was a problem in that the transparency of this molded product decreased slightly when it was kept in boiling water for a long time.

In view of the above circumstances, the present inventors further investigated and found that when a layer made of polyamide having a specific composition is laminated on a layer of polycarbonate resin, the excellent properties possessed by polycarbonate resin molded products can be maintained. At the same time, the inventors have discovered that the gas barrier properties are improved and that the transparency does not deteriorate even when kept in boiling water for a long time, and the present invention has been achieved. That is, the gist of the present invention is that (a) 20
~90 mol% hexamethylene diamine units and (b)
80 to 10 mol % metaxylylenediamine units and (c) 0 to 49 mol % oxydiacetic acid units and/or 1,3-phenylenedioxydiacetic acid units, based on the total dicarboxylic acid units, and (d) A laminate molded product characterized by laminating a polyamide resin layer containing 100 to 51 mol% of terephthalic acid units and/or isophthalic acid units and a polycarbonate resin layer.

The present invention will be explained in detail below.

The laminate molded product of the present invention is formed by laminating a polyamide resin having a specific composition with a polycarbonate resin.

The above-mentioned polyamide resin contains (a) 20 to 90 mol% hexamethylene diamine units and (b) 80 to 10 mol% metaxylylene diamine units based on the total diamine units, and (based on the total dicarboxylic acid units) te(c)0
~49 mol% oxydiacetic acid units and/or 1,3-phenylenedioxydiacetic acid units and (d) 100-51
It is necessary that it consists of mol% of terephthalic acid units and/or isophthalic acid units.

If the hexamethylenediamine units are less than 20 mol% of the total diamine units, the polymer will be brittle and difficult to mold, and if it is more than 90 mol%, the gas barrier properties will be poor, making it impossible to achieve the desired objective. I can't. A particularly preferable ratio of hexamethylene diamine units is 25 to
It is 85 mol%.

Furthermore, if the metaxylylenediamine unit is less than 10 mol% of all diamine units, the gas barrier properties will be poor, and if it is more than 80 mol%, the polymer will be brittle and difficult to mold, making it difficult to achieve the desired purpose. I can't.

A particularly preferred proportion of metaxylylenediamine units is 15
~75 mol%.

In addition to the hexamethylene diamine units and metaxylylene diamine units described above, other diamine units may be included as long as the gas barrier properties are not impaired. Examples of other diamines include butylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4 (or 2,4,4)-)-limethylhexamethylene diamine, bis-(4, Examples include 4'-aminocyclohexyl)methane, 1,3-bisaminomethylcyclohexane, and the like.

On the other hand, the dicarboxylic acid component that makes up the polyamide resin is
Based on the total dicarboxylic acid units, (c) 0 to 49 mol% oxydiacetic acid units and/or 1,3-phenylenedioxydiacetic acid units; and (d) 100 to 51 mol% terephthalic acid units and/or or isophthalic acid units.

When the oxydiacetic acid units and/or 1,3-phenylenedioxydiacetic acid units are more than 49 mol% of the total dicarboxylic acid units, the glass transition temperature of the polymer decreases,
When drying the polymer, the polymer chips tend to fuse together,
Since drying is required at a low temperature for a long time, it is not preferred in industrial practice. Particularly preferred oxydiacetic acid units and/or 1,3
- The proportion of phenylenedioxydiacetic acid units is 1 to 48 mol%.

Further, if the terephthalic acid units and/or isophthalic acid units are less than 51 mol % of the total dicarboxylic acid units, the glass transition temperature of the polymer decreases, which is not preferable for the same reason as above.

A particularly preferred proportion of terephthalic acid units and/or isophthalic acid units is 52 to 99 mol%.

゛In addition to the above (c) oxydiacetic acid unit and/or 1゜3-phenylenedioxydiacetic acid unit and (d) terephthalic acid unit and/or isophthalic acid unit, within the range not impairing the gas barrier properties, It may also contain other dicarboxylic acid units. Examples of dicarboxylic acids include saturated aliphatic dicarboxylic acids such as adipic acid, glutaric acid, succinic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid; phthalic acid, naphthalene dicarboxylic acid; Aromatic dicarboxylic acids such as biphenyldicarboxylic acid are mentioned.

In order to produce the polyamide having the above-mentioned composition, 20 to 90 mol% of hexamethylene diamine and 80 to 10 mol% of metaxylylene diamine are used as diamine components, based on the total diamine, and dicarboxylic diamine is used. As acid components, 0 to 49 mol% of oxydiacetic acid and/or 1,3-phenylenedioxydiacetic acid and 100 to 51 mol% of terephthalic acid and/or isophthalic acid are used, based on the total dicarboxylic acids. Then, '8 melt polymerization may be carried out using a nylon salt or an aqueous solution thereof according to a conventional method. During polymerization, a monobasic acid such as acetic acid or benzoic acid, or a monoacid base such as hexylamine or aniline may be added as a molecular ffi regulator. Also, sodium phosphite, phosphoric acid,
It is also possible to add heat stabilizers such as sodium hypophosphite and hindered phenol, and other polymerization additives.

The polyamide in the present invention has a relative viscosity ηr, 1) of 1.4 to 3.5 dl/gr, particularly 1.6 to 2.7 dl/gr.
l/gr later is preferred.

The polycarbonate resin to be laminated with the above polyamide resin includes at least one type of bisphenol compound,
A variety made by reacting with phosgene or carbonate esters such as diphenyl carbonate can be used.

Specific examples of bisphenol compounds include bis-(4-
hydroxyphenyl)methane, 1,1-bis-(4-hydroxyphenyl)ethane, 1,1-bis-(4-hydroxyphenyl)propane, 2,2-bis-(4-hydroxyphenyl)propane, i.e. bisphenol A; 22
-bis-(4-hydroxyphenyl)butane, 2.2-
Bis-(4-hydroxyphenyl)pentane, 2,2-
Bis-(4-hydroxyphenyl)-3-methylbutane, 2.2binu(4-hydroxyphenyl)hexane,
2,2-bis-(4-hydroxyphenyl)-4-methylpentane, 1,1-bis-(4-hydroxyphenyl)cyclopentane, 1,1-bis-(4-hydroxyphenyl)cyclohexane, bis-( 4-hydroxy-3
-methylphenyl)methane, 1,1-bis-(4-hydroxy-3-methylphenyl)ethane, 2,2-bis-
(4-hydroxy-3-methylphenyl)propane, 2
．． 2-bis-(1-hytomicoxy-3-nitylphenyl)propane, 2,2-bis-(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis-(4-
Hydroxy-3-sec butylphenyl)propane, bis-(4-hydroxyphenyl)phenylmethane, 1.
1-bis-(4-hydroxyphenyl)-1-phenylethane, 1,1-bis-(・1-hydroxyphenyl)
-1-phenylpropane, bis-(4-hydroxyphenyl)diphenylmethane, bis-(4-hydroxyphenyl>dihenzylmethane, 4,4-dihydroxydiphenyl ether, 4,4-dihydoxydiphenyl sulfone, 4,4-dihydroxydiphenyl sulfone) Among them, bisphenol A is particularly suitable.

Polycarbonate resins are manufactured by well-known methods. For example, add at least one of the above bisphenol compounds and an aqueous alkaline solution or an acid acceptor such as pinodine into an inert solvent such as methylene chloride or 1,2-dichloromethane, and react while introducing phosgene at about 0 to +00'C. I do. The reaction rate is increased by adding a tertiary amine such as trimethylamine or triethylamine, or a quaternary ammonium compound such as tetrabutylammonium chloride or penciltributylammonium bromide as a catalyst during the reaction. Further, if necessary, a molecular weight regulator such as phenol or p-tert-butylphenol may be used.

2 (When copolymerizing using one or more bisphenol compounds, two or more bisphenol compounds can be simultaneously reacted with phosgene and polymerized from the beginning, or one bisphenol compound can be reacted with phosgene and the reaction can be carried out to some extent. Any method can be used, such as adding the other bisphenol compound and polymerizing the oligomer, or reacting each bisphenol compound with phosgene separately to form oligomers, and then reacting them to polymerize. .

The polycarbonate resin used in the present invention preferably has a viscosity average molecular weight (M) of about 0,000 to about 50,000. The viscosity average molecular weight was determined by using a methylene chloride solution of 6.0 g of polycarbonate resin and 2
This is a value calculated from ηsp measured at 0° C. using the following formula.

ηsp/C=[η](1+K'ηsp)[η]=K
M' In the above formula C: Polymer concentration [η]: Intrinsic viscosity K'
:0.28 K :1.23X 10-
5α: 0.83 M: Indicates average molecular weight.

In the present invention, the method for molding a laminate molded product consisting of the polyamide resin layer and polycarbonate resin layer is as follows: (a) A polyamide resin and a polycarbonate resin are separately charged into a plurality of extrusion molding machines and co-extruded to form a film. A method of laminating in a shape or a sheet shape, or a method of stretching the laminated film or sheet obtained above in the longitudinal direction and/or the stacking direction (b) Using two injection molding machines, the above 2.
Plasticizing the seed resins separately and injecting the two resins almost simultaneously into the same cavity of the mold to create 2 types 2 layers or 2 types 3 layers.
A method of molding a primary molded product in the shape of a bottomed cylinder with a multilayer structure, and then blow molding this secondary molded product to make a multilayer container. A method of forming a pipe-shaped primary molded product of two types and three layers, then welding the lower end to form the bottom of the container, then pressing and deforming the other end to form the mouth, and then blow molding to form a multilayer container. However, the method is not limited to these methods.

In addition, a well-known adhesive made of modified polyolefin resin, α-olefin-vinyl ester copolymer, copolymerized polyamide resin, copolymerized polyester resin, polyurethane resin, etc. may be used between the polyamide resin layer and the polycarbonate resin layer, if necessary. An agent layer may also be provided. Furthermore, a composition comprising a polyamide resin and a polycarbonate resin used in the present invention can also be provided as an adhesive layer.

(Examples) The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

In addition, the oxygen permeability in the examples is determined by MODERNCO in the United States.
Measured at 23℃ and 100%RH using 0X-TRAN 10150A manufactured by NTROLS (unit: cc11CI)
+2·sec-CIllHg).

In addition, the relative viscosity (η,.I) was determined using 98% concentrated sulfuric acid,
The concentration was 1 g/d+, and the measurement was performed at 25°C.

Reference Example 1 (Manufacture into polyamide resin) 80% aqueous solution of hexamethylene diamine 1.45 kg
metaxylylene diamine 1.36 kg oxydiacetic acid 0.27 kgl,
3-phenylenedioxydiacetic acid 0.45 kg Isophthalic acid 2.00 kg Terephthalic acid 0.66 kg Water
6.00
6.0 g of acetic acid was added to a salt aqueous solution consisting of 2.0 kg/cm2, and the mixture was charged into an autoclave equipped with a stirrer, the atmosphere was replaced with nitrogen gas, the temperature was started to rise, and when the pressure reached 2.5 kg/cm2, the valve of the autoclave was opened. and increase the pressure to 2.5k
Concentration was started by distilling off water to maintain the concentration at g/cm2. The temperature continued to rise during the concentration, and when the internal temperature reached 170°C, the autoclave valve was closed and the temperature was further increased. When the pressure reaches 12 kg/cm2, open the autoclave valve again and reduce the pressure to 12 kg/cm2.
Distill the water to maintain it at il! I did the shrinking.

During this concentration, the temperature continued to rise, and when the internal temperature reached 230° C., the pressure was released to atmospheric pressure, and the reaction was carried out for 1 hour.

After the reaction was completed, the molten polymer was extracted from the bottom of the autoclave.

The relative viscosity (ηr01) of the obtained polyamide resin (referred to as polyamide resin A) was 2.0 dl/gr.

Reference example 2 (manufacture of polyamide resin B) 80% aqueous solution of hexamethylene diamine 1.02 kg
Metaxylylene diamine 1.77 kgl
, 3-phenylenedioxydiacetic acid 1.93 kg
Isophthalic acid 1.91 kg water 6
．． 00 kg of acetic acid was added to the aqueous salt solution, and a melt polycondensation reaction was carried out in the same manner as in Reference Example 1 to obtain a polyamide resin (with relative viscosity (η, .+) of 2.1 dl/gr). Polyamide resin B) was obtained.

Reference Example 3 (Manufacture of polyamide resin C) Hexamethylene diamine 80% water mtff 2.57
kg Isophthalic acid 1.91
kg・terephthalic acid 0.98
kg water
Acetic acid 11 in a salt solution consisting of 6.00 kg
．． 0 g was added, and a melt polycondensation reaction was carried out in the same manner as in Reference Example 1 to obtain a relative viscosity (ηr*l) of 2.1 dl/
A polyamide resin of gr (referred to as polyamide resin C) was obtained.

Example 1 The polyamide resin layer produced in Reference Example 1 and the polycarbonate resin [manufactured by Mitsubishi Kasei Corporation, Tubarex (registered trademark) 70]
30A] were separately charged into three extrusion molding machines and coextruded to obtain a transparent sheet with a 3N structure in which a polyamide resin layer was sandwiched between two polycarbonate resins. The thickness of the polyamide resin layer was 20 μI, and the thickness of each of the two polycarbonate resin layers was 90 μI. The oxygen permeability of this sheet was as shown in Table 1. In addition, this sheet was heated at 120°C.
When the sheet was treated in boiling water at 2.1 kg/cm2 for 1 hour, no change was observed in the transparency of the sheet.

Example 2 Instead of polyamide resin A used in Example 1,
Using the polyamide resin B produced in Reference Example 2, and otherwise treating in exactly the same manner as in Example 1, a transparent sheet with a 3F+ structure in which the polyamide resin layer was sandwiched between two polycarbonate resins was obtained. The oxygen permeability of the obtained sheet is shown in Table 1.
It was as follows.

In addition, this sheet was heated at 120℃ and 2.1 kg/cm2.
When the sheet was treated in boiling water for 1 hour, no change was observed in the transparency of the sheet.

Comparative Example 1 Instead of polyamide resin A used in Example 1,
Using the polyamide resin C produced in Reference Example 3, and otherwise treating in exactly the same manner as in Example 1, a transparent sheet with a three-layer structure in which the polyamide resin layer was sandwiched between two polycarbonate resins was obtained. The oxygen permeability of this sheet was as shown in Table 1. In addition, this sheet was heated at 120℃ and weighed 2.1 kg/
The sheet became slightly opaque after being treated for 1 hour in boiling water at 2C.

Comparative Example 2 The polycarbonate resin (Tubarex 7030A) used in Example 1 was extruded using an extrusion molding machine to a thickness of 200 mm.
A transparent polycarbonate resin sheet from μ City was obtained. The oxygen permeability of this sheet was as shown in Table 1. Further, when this sheet was treated in boiling water at 120°C and 2.1 kg/cm2 for 1 hour, no change was observed in the transparency of the sheet.

Comparative Example 3 Instead of the polyamide resin used in Example 1,
6 nylon resin [manufactured by Mitsubishi Kasei Corporation, Tsubamitsudo (registered trademark) +030A] was used, and the rest was treated in exactly the same manner as in Example 1 to form a 3N structure in which a 6 nylon resin layer was sandwiched between two polycarbonate resins. An opaque sheet was obtained. The oxygen permeability of this sheet was as shown in Table 1. Furthermore, when this sheet was treated in boiling water at 120°C and 2.1 J/cm2 for 1 hour, the sheet was opaque.

Table 1 (Note) PC: Bolicarbo? -Tresin polyamide]...＼: Hekilyme J diamine/Meta-helylene diamine = 50150 (mo1%) OX Shiji l1
ilii(i/1.3-phenylenediyldiacetate/isophthalic acid/terephthalate=IO/10/(i0/20
(mo1%) Polyamide B: Hexamethylene diamine/
Metaxylylenediamine”35/65 (mo1%)1.
3-phenylene dioxonoacetic acid/Isophthal Q=431
57 (mo1%) Polyamide C: Hexamethylene diamine = lOO (mo1%) Isophthalic #/Terephthalic acid =
66/34 (mo1%) (Effects of the Invention) The laminated molded product of the present invention has a significantly lower oxygen permeability than polycarbonate (Table 1), excellent gas burr, and is produced by treatment in boiling water, so its commercial value is significant. As shown in , it has better properties than resin and also maintains transparency.

Claims (1)

[Claims] (1) Based on total diamine units, (a) 20 to 90 mol % hexamethylene diamine units and (b) 80 to 1
0 mol % metaxylylene diamine units and (c) 0 to 49 mol % oxydiacetic acid units and/or 1,3-phenylenedioxydiacetic acid units, based on the total dicarboxylic acid units, and (d) 100 to 49 mol % oxydiacetic acid units and/or 1,3-phenylenedioxydiacetic acid units. A laminate molded article comprising a layer of polyamide resin comprising 51 mol% of terephthalic acid units and/or isophthalic acid units and a layer of polycarbonate resin.