JPH07115451B2 - Resin laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin laminate, and more specifically, it has excellent heat resistance,
The present invention relates to a resin laminate which has acid resistance, alkali resistance, hot water resistance, rigidity, and electrical characteristics, as well as excellent gas barrier properties and breaking strength.

[Problems to be Solved by Prior Art and Invention]

Conventionally, various resin laminates have been used as packaging films, sheets, electrical / electronic members, and the like. It is also known that a styrene-based polymer layer is used as a resin layer constituting these resin laminates. However, the styrene-based polymer used here has an atactic structure, and has a high heat resistance. The properties, solvent resistance, hot water resistance and rigidity were not always satisfactory.

The present inventor has conducted intensive studies to solve the above-mentioned drawbacks of the conventional resin laminate and to develop a resin laminate having excellent various physical properties.

[Means for Solving the Problems]

In the process, a styrene polymer having a high syndiotacticity previously developed by the group of the present inventors (JP-A-62-104818) was used as a material, and a specific thermoplastic resin was laminated on it. It was found that the obtained product is a resin laminate having excellent physical properties.

The present invention has been completed based on such findings. That is, the present invention mainly comprises a styrene polymer layer having a syndiotactic structure and a thermoplastic resin layer made of one or more resins selected from polyester resins, polyphenylene sulfide resins, polyamide resins and polycarbonate resins. In addition, the layer thickness ratio of the thermoplastic resin layer and the styrene-based polymer layer is 0.125 to 8
The present invention provides a resin laminate, which is In particular, as a preferred embodiment of this resin laminate, a resin laminate using a styrene-based polymer layer biaxially stretched in advance as the styrene-based polymer layer, a styrene-based polymer layer, and a thermoplastic resin layer A resin laminate obtained by axial stretching can be mentioned.

The styrene-based polymer layer in the resin laminate of the present invention is mainly composed of a styrene-based polymer having a syndiotactic structure as described above. Here, the mainly syndiotactic structure is mainly a stereochemical structure. It has a syndiotactic structure, that is, it has a three-dimensional structure in which phenyl groups and substituted phenyl groups, which are side chains with respect to the main chain formed from carbon-carbon bonds, are alternately located in opposite directions. It is quantified by the nuclear magnetic resonance method ( ¹³ C-NMR method) using body carbon. ^The tacticity measured by the ¹³ C-NMR method is the proportion of a plurality of continuous constitutional units, for example, in the case of two constitutional units, diad, 3
The number of triads can be represented by 5 and the number of pentads can be represented by 5, but the styrene-based polymer mainly having a syndiotactic structure referred to in the present invention is usually 75% or more in diads, preferably 85% or more. , Or 30% or more with pentad (racemic pentad), preferably
Polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (alkoxystyrene), poly (vinyl benzoic acid ester) having 50% or more syndioctacticity, and mixtures thereof, or mainly containing these This refers to a copolymer. A styrene-based polymer having a low syndioctacticity cannot be expected to have desired physical properties desired for the resulting laminate. Here, as the poly (alkylstyrene), there are poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiarybutylstyrene), etc., and as the poly (halogenated styrene), Examples include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene). Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Of these, particularly preferable styrene polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tertiarybutylstyrene), poly (p-chlorostyrene), poly ( Examples thereof include m-chlorostyrene), poly (p-fluorostyrene), and a copolymer of styrene and p-methylstyrene.

The styrene-based polymer used in the present invention is not particularly limited in molecular weight, but preferably has a weight average molecular weight of 10,000 or more, and particularly preferably 50,000 or more. Further, the molecular weight distribution is not limited in width and width, and various kinds can be applied. here,
If the weight average molecular weight is less than 10,000, it may not be possible to obtain a resin laminate having sufficient mechanical strength and heat resistance.

Such a styrenic polymer mainly having a syndiotactic structure is a styrenic polymer, for example, in an inert hydrocarbon solvent or in the absence of a solvent, using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst. It can be produced by polymerizing a monomer (a monomer corresponding to the above styrene-based polymer) (JP-A-62-18).
7708 publication).

On the other hand, the thermoplastic resin forming the thermoplastic resin layer may be appropriately selected from polyester resin, polyphenylene sulfide resin, polyamide resin and polycarbonate resin depending on the use of the resin laminate to be manufactured.
For example, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT),
Further examples include polycarbonate resin, polyphenylene sulfide resin (PPS), and polyamide resin.

Of these, polyester resin, polyamide resin, polycarbonate resin, etc. should be selected as the thermoplastic resin when high mechanical strength is required for the obtained resin laminate, and when importance is attached to gas barrier properties. For this, a polyester resin such as PET, a polyamide resin, PPS, or the like should be selected, and if a thermoplastic resin having a low melting point is selected, a resin laminate having a good heat-sealing property can be obtained.

The resin laminate of the present invention includes the above-mentioned styrene-based polymer (SPS) layer mainly having a syndiotactic structure and a thermoplastic resin layer, and the constitution thereof is composed of the SPS layer and the thermoplastic resin layer. It is not limited to a layer, and various forms of lamination including these two layers can be formed. Here, the number of layers and the stacking order are not limited, and may be appropriately determined depending on the situation. For example, SPS layer / thermoplastic resin layer /
A laminated structure of SPS layer, thermoplastic resin layer / SPS layer / thermoplastic resin layer, SPS layer / thermoplastic resin layer / thermoplastic resin layer, etc. can be considered. In these laminated structures, when one laminate has two or more SPS layers or thermoplastic resin layers, they may be the same or different.

Further, the SPS layer and the thermoplastic resin layer of the present invention include the case where they are stretched. Therefore, there are various embodiments depending on the presence or absence of the stretching, and specifically, the stretched SPS layer and the stretched thermoplastic resin layer, the stretched SPS layer and the non-stretched thermoplastic resin layer, the non-stretched SPS layer and the stretched thermoplastic resin layer, and There are combinations such as unstretched SPS layer and unstretched thermoplastic resin layer. Here, when both layers are stretched and when both layers are not stretched, a multi-layer coextrusion method can be used.

Further, in the resin laminate of the present invention, the thickness of the entire layer is not particularly limited, but generally 10 to 500 μm, preferably 2
It is 0 to 200 μm, and the thickness ratio of each layer may be appropriately determined according to the purpose of use, but it is usually selected in the range of thermoplastic resin layer / SPS layer = 0.125 to 8.

As a preferred embodiment of the resin laminate of the present invention, for example, SPS
It consists of three layers of layer / PET layer / SPS layer, and the film thickness is 10-200 μm.
The film thickness ratio of each layer is SPS layer / PET layer / SPS layer = 1 (SPS) /0.125
There is a range of up to 8 (PET) / 1 (SPS), which has excellent heat resistance, acid resistance, alkali resistance and solvent resistance, as well as mechanical strength and gas barrier properties. In addition, it consists of three layers of PPS layer / SPS layer / PPS layer, and the film thickness
~ 200μm, the film thickness ratio of each layer, PPS layer / SPS layer / PPS layer = 1
There is a range of (PPS) /0.125 to 8 (SPS) / 1 (PPS), which is particularly excellent in heat resistance and flame retardancy.

By the way, in producing the resin laminate of the present invention, various methods are conceivable depending on the form and application of the laminate, and ordinary methods may be appropriately combined depending on the situation. Specifically, the following methods can be mentioned. That is, SPS and a thermoplastic resin are co-extruded in multiple layers from a molding machine having a multi-layer die to form a multi-layer cast molding film or multi-layer inflation molding. At this time, in order to increase the adhesive force between the layers, an adhesive layer having affinity with each of the SPS layer and the thermoplastic resin layer is provided as the third component, or either one or both of the SPS layer and the thermoplastic resin is provided. It is also possible to pre-blend an adhesive material. When producing a multilayer cast film, the T-die temperature is set to about 280 to 350 ° C, and
When stretching the extruded sheet, set the chill roll temperature to 90 ° C.
When the draft ratio (ratio of the take-up speed and the extruding speed) is set to 4 or less in addition to the above, a relatively non-oriented amorphous sheet can be obtained, and effective stretching can be facilitated.

In this way, or if necessary, a stretching treatment is then carried out to obtain the desired resin laminate. When a stretched multilayer film is produced by stretching here, as the stretching method, a method such as uniaxial stretching, tubular biaxial stretching, sequential biaxial stretching or simultaneous biaxial stretching may be appropriately selected and used. The conditions for this stretching treatment differ depending on the situation and cannot be unambiguously determined, but usually the stretching temperature is
The temperature may be 80 to 230 ° C., the stretching speed may be 10,000% / min, and the stretching ratio may be set to an area ratio of 3 to 30 times. Further, it is preferable that the stretched multilayer film is subjected to a heat treatment as a post-treatment because sufficient dimensional stability can be obtained. The heat treatment temperature at this time varies depending on the melting point and glass transition temperature of the film to be used, but usually it may be set to 150 to 270 ° C., and the treatment time is about 5 seconds to 20 minutes.

In addition, an SPS film (stretched or unstretched) and a thermoplastic resin film (stretched or unstretched) are separately prepared in advance, and the resin laminate of the present invention can also be obtained by laminating these films. Can be created. In this lamination, each film surface may be treated by corona treatment, ozone treatment, or the like, or an interlayer adhesive (for example, a dry lamination adhesive such as a curable urethane adhesive) may be used. it can. In addition, the press roll temperature at the time of lamination is about 50 to 100 ° C, and the processing speed is 50 to 1 ° C.
50m / min is suitable.

〔Example〕

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 Syndiotactic polystyrene (SPS) having a weight average molecular weight of 400,000 and a syndiotacticity of 97% in racemic pentad and polyethylene terephthalate (intrinsic viscosity [η] = 0.78 dl / g, trade name: Dianite MA523, Mitsubishi Co-extrusion of Rayon Co., Ltd. (PET) with a cast molding machine having a multi-layer die (T die temperature 300 ° C, take-up speed 1 m / sec)
Then, it was cooled with a cooling roll to form a transparent film.

The combination of film layers is SPS / PET / SPS (thickness 50 μm / 4
00 μm / 50 μm). This film was stretched 3 × 3 times with a table tenter (temperature: 115 ° C.).

The obtained stretched film (thickness 6 μm / 45 μm / 6 μm) was transparent. The evaluation results of the film are shown in Table 1.

Example 2 In the same manner as in Example 1, PET / SPS / PET (thickness 50 μm / 400
(μm / 50 μm) transparent film was prepared and stretched 3 × 3 times with a table tenter. The obtained stretched film (thickness 6 μm / 45 μm / 6 μm) was transparent. The evaluation results of the film are shown in Table 1.

Comparative Example 1 Under the same conditions as in Example 1, atactic polystyrene (weight average molecular weight 30 × 10 ⁴ , trade name: Idemitsu Polystyrene HH
30, Idemitsu Petrochemical Co., Ltd. (aPS) and PET were co-extruded from a multi-layer die to form a transparent film of aPS / PET / aPS. This film was stretched 3 × 3 times with a table tenter.

The obtained stretched film was transparent. The evaluation results of the film are shown in Table 1.

Example 3 In the same manner as in Example 1, SPS / PET (thickness 250 μm / 250 μ
A two-layer cast film of m) was prepared. This film was stretched 3 × 3 with a table tenter, and the obtained stretched film (thickness 28 μm / 28 μm) was transparent. The evaluation results of the film are shown in Table 1.

Comparative Example 2 Under the same conditions as in Example 3, an aPS / PET cast film was prepared and stretched 3 × 3 times.

The resulting film was transparent. The evaluation results of the film are shown in Table 1.

Comparative Example 3 Casting SPS only, transparent raw material (thickness 500 μm)
Was prepared and further stretched 3 × 3 times with a table tenter in the same manner as in Example 1.

The obtained stretched film was transparent. The evaluation results of the film are shown in Table 1.

Comparative Example 4 Only aPS is cast, and it is a transparent material (thickness 500 μm)
Was prepared and further stretched 3 × 3 times with a table tenter in the same manner as in Example 1.

The results of measurement of the obtained stretched film are shown in Table 1.

Comparative Example 5 Only PET is cast, and it is a transparent material (thickness 500 μm)
Was prepared and further stretched 3 × 3 times with a table tenter in the same manner as in Example 1.

The results of measurement of the obtained stretched film are shown in Table 1.

Example 4 Instead of PET, polyphenylene sulfide (intrinsic viscosity [η] = 0.28 dl / g) (PPS) was used, and the T-die temperature was 320.
In the same manner as in Example 1 except that the temperature was set to 0 ° C, SPS / PPS /
Create an SPS film and stretch it 3 times 3 times (Temperature 96 ℃)
did. Both the cast film and the stretched film were transparent.

The results of measurement of the obtained stretched film are shown in Table 1.

Comparative Example 6 Using aPS instead of SPS, an aPS / PPS / aPS film was prepared and stretched 3 × 3 times (temperature 96 ° C.) to obtain a stretched film.

The results of measurement of the obtained stretched film are shown in Table 1.

Example 5 A stretched film was obtained by the same operation as in Example 4, except that the layer combination was PPS / SPS / PPS.

The results of measurement of the obtained stretched film are shown in Table 1.

Example 6 A stretched film was obtained by the same operation as in Example 4 except that a bilayer film of SPS / PPS was prepared.

The results of measurement of the obtained stretched film are shown in Table 1.

Example 7 A biaxially stretched SPS film and a bisphenol A-type polycarbonate (viscosity average molecular weight 3 × 10 ⁴ , trade name: Idemitsu Polycarbonate A3000, manufactured by Idemitsu Petrochemical Co., Ltd.) (PC) film were combined with a curable urethane adhesive. Was laminated through to prepare a three-layer film of SPS / PC / SPS (thickness 10 μm / 50 μm / 10 μm).

The measurement results of the obtained film are shown in Table 1.

Comparative Example 7 A laminated film of aPS / PC / aPS was prepared under the same conditions as in Example 7, except that the biaxially stretched aPS film was used.

The measurement results of the obtained film are shown in Table 1.

Comparative Example 8 The physical properties of only the PC film (thickness 500 μm) used in Example 7 were examined. The results are shown in Table 1.

Example 8 Nylon (number average molecular weight 24,000, trade name: Unilon, Idemitsu Petrochemical Co., Ltd.) was used as a film for lamination.
(Manufactured by (Ny)) and using SPS / Ny in the same manner as in Example 7 below.
/ SPS three-layer laminated film (thickness 10μm / 50μm / 10μ
m) was created.

The measurement results of the obtained film are shown in Table 1.

Example 9 PET / Ny / SPS was performed in the same manner as in Example 7 using PET, Ny and SPS.
A three-layer laminated film of was prepared.

The measurement results of the obtained film are shown in Table 1.

Example 10 In the same manner as in Example 7, an SPS / Ny two-layer laminate film (thickness 25 μm / 25 μm) was prepared.

The measurement results of the obtained film are shown in Table 1.

Comparative Example 10 Instead of SPS film, aPS film was used, and aPS / Ny
A two-layer laminated film (25 μm / 25 μm in thickness) was prepared.

The measurement results of the obtained film are shown in Table 1.

Comparative Example 11 The physical properties of only the Ny film (thickness 25 μm) were examined. The results are shown in Table 1.

Example 11 Nylon-6 instead of polyethylene terephthalate
(UBE Nylon 1024F, Ube Industries, Ltd.) was used, and the same operation as in Example 1 was performed except that the roll temperature was 180 ° C.

The combination of film layers is SPS / Ny / SPS (thickness 5μm / 10μm / 5
μm). The results are shown in Table 1.

Comparative Example 12 In the same manner as in Example 1, SPS / PET / SPS (thickness 35 μm / 390
(μm / 35 μm) transparent film was prepared and stretched in the same manner as in Example 1. Obtained stretched film (thickness 4μ
m / 45 μm / 4 μm) was transparent. The evaluation result of the film is that the breaking strength is 13 kg / mm ² , the oxygen permeability is 17 cc / m ² , 24 hr ・ atm,
The water resistance was ×, the acid resistance was ○, the alkali resistance was ○, and the organic solvent resistance was ○.

Comparative Example 13 In the same manner as in Example 2, PET / SPS / PET (thickness 35 μm / 390
A transparent film (μm / 35 μm) was prepared and stretched in the same manner as in Example 2. Obtained stretched film (thickness 4μ
m / 45 μm / 4 μm) was transparent. The evaluation result of the film is that the breaking strength is 14 kg / mm ² , the oxygen permeability is 31 cc / m ² , 24 hr ・ atm,
The water resistance was ×, the acid resistance was ○, the alkali resistance was ○, and the organic solvent resistance was ×.

〔The invention's effect〕

As described above, the resin laminate of the present invention has excellent gas barrier properties of a thermoplastic resin while maintaining the effective heat resistance, acid resistance, alkali resistance, hot water resistance, rigidity and electrical characteristics of SPS. Breaking strength etc. are given.

Therefore, the resin laminate of the present invention is expected to be effectively and widely used for general packaging films and sheets, electric / electronic materials, and food packaging films that require heat resistance and body hot water. To be done.

Claims (2)

[Claims] 1. A styrene-based polymer layer mainly obtained by biaxially stretching a styrene-based polymer having a syndiotactic structure and one or more selected from polyester resins, polyphenylene sulfide resins, polyamide resins and polycarbonate resins. And a layer thickness ratio of the thermoplastic resin layer to the styrene-based polymer layer is 0.125 to 8. 2. A styrene-based polymer layer having a syndiotactic structure and a thermoplastic resin layer composed of one or more resins selected from polyester resins, polyphenylene sulfide resins, polyamide resins and polycarbonate resins. A resin laminate, which is obtained by biaxially stretching a laminate having a layer thickness ratio of the thermoplastic resin layer and the styrene polymer layer of 0.125 to 8.