JPH03281246A - Multilayer structure and composition used therein - Google Patents

Abstract

PURPOSE:To prevent the interlaminar delamination due to an impact by constitut ing a laminate of a polyamide layer containing an m-xylilenediamine group and a thermoplastic polyester (PES) or polycarbonate (PC) layer containing a specific amount of specific diol and/or dicarboxylic acid with respect to total diol and/or total dicarboxylic acid. CONSTITUTION:This multilayer structure consists of at least two layers of a polyamide (A) layer containing an m-xylilenediamine group and a PES(B1) or PC(B2) layer containing 0.1 - 20 mol.% of diol and/or dicarboxylic acid represented by formula I (wherein X if diol or dicarboxylic acid, R is -SO3Y, -COOY, -OY, -PO(OY)2, -SO3-Z-O3S-, -COO-Z-OOC-, -O-Z-O-, -PO3Z, Y is a monova lent metal and Z is a divalent metal) with respect to total diol and/or total dicarboxyylic acid. A multilayer structure of the composition (C) consisting of 1 - 95 wt.% of the m-xylilenediamine group-containing polyamide resin (A) and 5 - 99 wt.% of the resin (B1) and/or the resin (B2) and unmodified PES {resin (B3)} or unmodified PC {resin (B4)}, more pref., the multilayer structure wherein the resin (B1) or resin (B2) layer is laminated to the composition (C) layer is improved in impact-resistant interlaminar delamination properties to a large extent and a container having good appearance is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Industrial Field of Application The present invention is directed to the prevention of oxygen or carbon dioxide gas, moisture resistance, fragrance retention, flaky <-/< + tourability, and appearance. The present invention relates to multilayer structures, particularly co-injection stretched multilayer structures and compositions, which have good impact resistance and delamination properties (hereinafter referred to as i# delamination properties) for use in containers for beverages, foods, cosmetics, etc.

B. Conventional technology Polyester containers made by stretch blow molding are used in many fields due to their excellent transparency and rigidity.
Because gas barrier properties are not always sufficient, food products can only be stored for a short period of time. In order to improve this drawback, various methods have been proposed in which a polyester is combined with a metaxylylene group-containing polyamide resin having good gas barrier properties to form a multilayer structure. That is, there are coextrusion molding methods, multistage injection molding methods, co-injection molding methods, etc. as methods for manufacturing a preform prior to stretch blowing, and each method has advantages and disadvantages. Among these, co-injection molding has simple equipment;
There is almost no generation of scraps such as trim, and since the metaxylylene group-containing polyamide resin layer is completely covered with a thermoplastic polyester (PES) layer, the metaxylylene group-containing polyamide resin layer and PE
Even though there is no adhesive resin (hereinafter referred to as Ad) layer between the S layer etc. = 3, this method is currently attracting attention because it has the advantage of creating a multilayer container with a good appearance due to the adhesion effect due to atmospheric pressure. . However, when the container is filled with food and subjected to impact such as dropping, delamination occurs between the PET and the metaxylylene group-containing polyamide resin, which poses a major problem in terms of appearance.

C9 Problems to be Solved by the Invention The present invention particularly solves the problem without having an independent adhesive resin layer.
Modified PES or modified polycarbonate) (PC), (
Hereinafter, these will be abbreviated as resin (B). ) and metaxylylene group-containing polyamide resin (A), particularly in a multilayer container obtained by co-injection stretch blow molding, to prevent interlayer delamination due to impact.

D. To solve the problem, the present inventors used a co-injection molding method to create a multilayer structure in which the resin (B) is used as the inner and outer surface layers and the metaxylylene group-containing polyamide resin is used as the intermediate layer that is completely encapsulated by the inner and outer layers. A preform is manufactured, and the parison is heat-stretched and blow-molded to manufacture a container. Impact resistance of the container = 4. To evaluate the impact interlayer delamination, the container is filled with water and dropped onto a concrete floor to determine the presence or absence of delamination. observed. That is, in order to prevent delamination, intensive studies were conducted on a composite of the resin (B) and the metaxylylenediamine group-containing polyamide resin (A). As a result, a modified PES containing 01 to 20 mol% of the diol and/or dicarboxylic acid represented by the following formula (I) as the resin (B) based on the total diol and/or total carboxylic acid.
It has been found that by using (B1) or modified PC (B2), the impact resistance and interlayer delamination properties of the container are greatly improved.

X-R... (1) However, X-diol or dicarboxylic acid R-3O3
Y, C00Y-OY, PO(OY)2, po
aZ Y-monovalent metal Z: divalent metal Furthermore, as a result of intensive studies, the present inventors surprisingly found that metaxylylenediamine group-containing polyamide resin (A
) 1 to 95% by weight and resin (B1) and/or composition (C) consisting of 5 to 99% by weight of resin (B1) and unmodified PES (resin (B3)) or unmodified PC (resin (
B4)), more preferably the composition (C)
It has been found that a multilayer structure in which the resin (B1) or resin (B2) layer is laminated has greatly improved impact resistance and interlayer delamination properties, and a container with a good appearance can be obtained.

The present invention will be explained in more detail below.

In the present invention, the meta-xylylene group-containing polyamide resin (A) refers to metaxylylene diamine or a mixed quinlylene diamine containing para-xylylene diamine in an amount of 80% by weight or less of gold xylylene diamine, and a carbon number of 6.
It is a polymer containing in its molecular chain at least 70 mol % of structural units produced from ~10 α, ω-fatty acid dicarboxylic acids.

Examples of these polymers include homopolymers such as polymethaxylylene adipamide, polymethaxylylene adipamide, polymethaxylylene adipamide, etc., and metagylylene 7/paragylylene adipamide copolymers, metaxylylene/ copolymers such as geramide copolymers, as well as components of these homopolymers or copolymers and aliphatic diamines such as hequinyl diamine, cycloaliphatic diamines such as piperazine, aliphatic diamines such as parabis-(2-aminoethyl)benzene, aliphatic dicarboxylic acids such as terephthalic acid,
Copolymerization of lactams such as ε-caprolactam, γ-aminocarboxylic acids such as nohebutanoic acid, para-aminomethylammonium, Q, aromatic aminocarphonic acids such as aromatic acid, etc. Examples include merging. In the above copolymer, the amount of para-glylylene diamine is 80% or less based on the total xylylene diamine, preferably 70% or less.
The F content is 5% by weight or more, and the amount of structural units formed from quinrylene diamine and aliphatic dicarboxylic acid in the molecular chain is at least 70% by mole, preferably 75% by mole or more. In addition, for example, nylon 6, nylon 6-6, nylon 6 = 10, nylon 1
1. It may contain polymers such as nylon 12 and nylon 6-12, antistatic agents, lubricants, antiblocking agents, stabilizers, dyes, pigments, etc. The relative viscosity of the metaxylylene group-containing polyamide resin (96% sulfuric acid solution (Ig/
100m12), 25℃) is 1.0~5dρ/g1
Furthermore, it is desirable that there be 1.5 to 4 dρ/g.

Among the filter resins (B) used in the present invention, the resin (B1) has ethylene tele and/or isophthalate μ-) as its main constituent units, and contains 60 mol% or more of ethylene tele and/or isophthalate units; Preferably 70 mol%
0.1 to 20 mol%, preferably 1 to 15 mol% of the diol or dicarboxylic acid shown in the above (1) in the molecule based on the total diol and/or diol acid.
It is a modified PES containing mol%. If it is less than 0.1 mol%, the reforming effect will not be sufficient, whereas if it exceeds 20 mol%, the melting activity will increase. As a result, the degree of polymerization cannot be increased, and the strength of the container and 12 decreases. Note that the content of diol or dicarboxylic acid indicated by (+) above is X −R
- If it contains both diols and dicarboxylic acids, it is the value for the total amount of all diols and gold dicarboxylic acid, and if X-R is either diol or dicarboxylic acid, it is the value for all diols or all dicarboxylic acids. be.

■) of x-n is one or two of the above.
More than one group can be included. In addition, R is bonded (1, The dicarboxylic acids shown in R, 29-32, Particularly 2 PJ1-32, such as the following compounds, are suitable.

H00C' R,: SO*Na, COONa, O
Na, PO(ONa)2 Here, the dicarboxylic acid represented by Aromatic dicarboxylic acids such as dicarboxylic acids, uric acid, malonic acid, succinic acid,
Examples include aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. can do.

As the remaining dicarboxylic acids other than X-R used in the present invention, terephthalic acid and/or isophthalic acid are mainly used, but the dicarboxylic acids represented by X described above can also be used, or they can be used in combination. You can also do it.

Further, in the present invention, when X is a diol, suitable compounds include the following.

R: -SO*Na, -COONa, -0N
a, -PO(ONa)z Here, the diol represented by - aliphatic glycols such as nonanediol, diethylene glycol, triethylene glycol and cyclohexanediol,
Examples include alicyclic diols such as cyclohexanedimethanol, and one or more of these can be used. Among them, ethylene glycol, diethylene glycol, cyclohexanediol, and the like are preferred. In addition, as diols other than X-R used in the present invention, ethylene glycol, diethylene glycol, cyclohexanediol, etc. are mainly used, but the diols indicated by X mentioned above can also be used, and these can also be used in combination. You can also do it.

The molecular weight of these modified PES is determined by sheet molding or
The intrinsic viscosity is 0.60 because it greatly affects the physical properties of the container.
It is desirable that the d ratio is 78 or more, preferably 0.70ρ/g or more. Intrinsic viscosity here means 30°C in a mixed solvent of phenol and tetrachloroethane (1.1 weight ratio).
This is the value measured at Further, heat stabilizers, plasticizers, lubricants, colorants, ultraviolet absorbers, antistatic agents, and the like may be freely used in the modified polyester within a range that does not impede the effects of the present invention.

On the other hand, among the resins (B) used in the present invention, resin (B
2) is a method of transesterifying a carbonic acid diester obtained from a monofunctional aromatic or aliphatic hydroxy compound with a diol compound, that is, in the absence or presence of a transesterification catalyst in an inert gas atmosphere. A method of reacting bisphenol A and diphenyl carbonate under high temperature and reduced pressure, or a method of reacting diolation and phosgene in the presence of an acid binder, i.e., a method of reacting bisphenol A and phosgene in the presence of a solvent with an acid binder (e.g. This is a modified PC obtained by modifying PC with X-R, which is obtained by a method of reacting at around room temperature in the presence of (caustic, caustic, pyridine). PC is a modified PC that is used in a wide variety of fields, and for example, in "Plastic Materials Course [17]" edited by Tachikawa and Sakajiri, PC (Nikkan Kogyo Shimbun, published in 1971) describes its manufacturing method, properties, etc. is known in detail. Modified P used in the present invention
When producing PC, C may be used as a copolymerization monomer such as a dicarboxylic acid or diol compound represented by methylene chain, etc.) by adding a compound represented by X-R. The content of X-H needs to be 0.1 to 20 mol%, preferably 1 to 15 mol%, based on the total diol.

R in the above X-R is -so, y, -COOY, -o
y.

po3z, Y is a monovalent metal, preferably an alkali metal (lithium, sodium, potassium), and Z is a divalent metal, preferably an alkaline earth metal (calcium, magnesium, barium), zinc. Among these, preferred is -8OsNa.

These modified PBS (B1), modified PC resin (B
2) is obtained by laminating the metaxylylenediamine group-containing polyamide resin (A) described above, or by laminating (A) and (
B1) and/or blend (C) of (B1) (
By laminating with B1) or (B1), it is possible to obtain the best multilayer structure, which is the purpose of the present invention. Furthermore, in the present invention, (A) and (B1) and/or (
B1) blend (C) was converted into unmodified PES (Bs)
, unmodified PC (B1) can also be used to form a multilayer structure, which is the object of the present invention.

By the way, regarding the composition (C) formed by blending resin (B1) and/or (B2) with metaxylylenediamine group-containing polyamide resin (A), resin (A)/resin (B1) and/or ( The weight ratio of B1) is 1/9
It is important to satisfy 9 to 9515, preferably 5.
/95 to 70/30. If it is less than 1/99, the effect of improving impact resistance and delaminated properties will not be sufficient, while if it exceeds 9515, it is unfavorable in terms of gas barrier properties.

There are no particular limitations on the blending method of resin (A) and resin (B1) and/or (B1).
There is a method in which the resin (A) and the resins (B1) and/or (B2) are triblended, pelletized using a Banbury Mixer 1 single-screw or twin-screw extruder, and dried. If the blend is non-uniform, or if gels or lumps are generated or mixed during the blend pelletizing operation, there is a high possibility that the effect of improving impact gelatin resistance will deteriorate. Therefore, during the blend pelletizing operation, it is desirable to use an extruder with a high degree of kneading, to nitrogen sole the popper [J, and to extrude at a low temperature. For that reason, resin (B1) or (B2
), it is preferable to increase the types and/or amounts of copolymer components and to use a resin (Bl) or (B2) with a low melting point.

In addition, when blending and pelletizing, other additives (plasticizers, heat stabilizers, ultraviolet absorbers, antioxidants, colorants, fillers, other resins, etc.) may be used within the range that does not impede the purpose of the present invention. You are free to do whatever you want. In particular, as a measure to prevent gel formation, hydrotalcite-based compounds, hindered phenol-based, and hindered amine-based heat stabilizers are used at 0.01-
It is suitable to add 1% by weight.

Next, as a method for obtaining a co-injection stretch blow molded container, generally, a container precursor (parison) having a multilayer structure is first obtained, and the parison is reheated and stretch blow molded to produce a container. The multilayer parison is made by melting the resin (B) and the metaxylylenediamine group-containing polyamide resin into a single mold in one or more mold clamping operations using a molding machine having two or more injection cylinders. It can be obtained by injecting (A) or (C) alternately or simultaneously from each injection cylinder at different timings or/and simultaneously through intermittent circular nozzles. For example, the resin (B) injected first is applied to the inner and outer surface layers of the resin (A) or (C) layer injected later, and/or the resin (B) is injected later.
) is injected for the first time inside the inner and outer PES layers, and in some cases, resin (A) or (C) and/or resin (B) is further injected again to form an intermediate layer. (B) A bottomed parison completely encapsulated by the layer (B) can be obtained by a general method, and there are no particular restrictions on the equipment.

Manoko, the multilayer parison can be heated directly to 75 to 100 liters in a hot state or with a heating element such as a block heater or an infrared heater.
．． After being heated to 50°C, it is sent to a stretch blowing process,
After being stretched 1 to 5 times in the vertical direction, it is stretched 1 to 5 times with compressed air, etc.
~4 times blown, resin (B) and 1. /' or the resin (A) or (C) is axially or biaxially stretched to obtain a multilayer stretched blown container.

There are also particular limitations on the equipment in the heating stretching blowing process.
Not Suchino.

Whether or not the stretch blow container is heat treated has a large influence on the impact resistance of the outer layer, and it is more desirable to satisfy the following formula (IV).

(Tp-20) >Tc (IV)
However, Tp: Melting point or softening point (°C) of the resin (B) constituting the layer Tc・Heat treatment temperature of the container (°C) If Tc is greater than Tp-10, the outermost resin (B) layer will soften. However, the strength of the bottle deteriorates, probably because the stretching direction decreases. The heat treatment time may be about 1 to 100 seconds, and the heat treatment method is not particularly limited, but generally, the method is to increase the mold temperature in the blowing process, or heat treatment is performed by applying pressure to the mold again. Examples include a method of heat treatment using hot air or a heat medium. In addition, when taking out a hot bottle after heat treatment, methods include rapidly cooling the heating mold or heating medium, or placing the bottle in a cooling mold again and cooling it in the cooling mold under pressure.

The multilayer structure of the present invention includes metaxylylenediamine group-containing polyamide resin (A), or (A) and (B1).
and/or (B2) blend (C) as the intermediate layer, and the inner and outer layers are resin (B1) and/or (B1) (referred to as base materials 1, 2, etc.) layers, or unmodified PES (B
A preferred example is one in which a layer 3) is provided with an unmodified PC (B4) layer and the intermediate layer is almost completely encapsulated by the inner and outer layers. However, embodiments in which the flange portion is not completely enclosed, such as a thermoformed container made of a multilayer sheet, are not excluded from the present invention. Other configurations include base material I/resin resistance A) or (C)/base material l, base material 1/resin (A) or (C)/base material 2/base material l, base material 1
/ Resin (A) or (C) / Base material 1 / Resin (A) or (C) / Base material I, base material 1 / Resin (A) or (C) / Base material 2 / Resin (A) or ( C)/base material 1, base material 2/base material I/resin (A) or (C)/base material 1/base material 2, and the like. By the way, the base material 1 is resin (B1) or (B1), unmodified PE S (B3) or unmodified P
C (B1), while base material 2 is a resin other than base material 1 (B
1) or (B2), unmodified PES (B3) or unmodified PC (BJ). However, base material 1 or 2
Unmodified PES or unmodified PC is used when the multilayer structure includes a (C) layer.

Regarding the thickness of the parison, the total thickness is 2 to 5 mm, and the total thickness of resin (A) or (C)H is lO to 100 μ.
-The thinner the resin (A) or (C) layer for boat fishing, the more
) or (C) The smaller the number of layers, and the closer they are to the outer layer side, the more easily delamination occurs due to impact from the container. In addition, the total thickness of the container body is generally 100 to 3000μ,
Can be used depending on the purpose. Also, at this time, resin (A
) or (C) The total thickness of the layer is 2 to 200μ, preferably 5 to 100μ.

Although it is not particularly necessary to provide an interlayer adhesive between the resin (A) or (C) layer and the base material in the multilayer structure of the present invention, the provision of this is not prohibited.

This will be further explained in the examples below, but as a result of this,
The present invention is not limited in any way.

L-Support Ran Example 1 70 parts by weight of metaxylylene group-containing polyamide (A) using polymethaxylylene adipamide (metaxylylene/baraxylylene weight ratio 9515), 10 mol% of isophthalic acid, and sodium sulfonate based on the total dicarboxylic acid. 30 parts by weight of modified isophthalic acid terephthalate (B1) were charged into a twin-screw extruder, and pelletized and dried under N2 at a tip temperature of 260°C to obtain a composition (C). On the other hand, resin (B1)'' and (7
A modified polyethylene terephthalate having an intrinsic viscosity of 0.71 ρ/g and containing 5 mol % of sodium sulfonate modified isophthalic acid based on the total dicarboxylic acid was obtained. Next, using the composition (C) and the resin (B1)'', Nisshin ASB
Co-injection stretch blow molding equipment (50HT type 750mQ,
A co-injection stretched blow bottle was made using 2 pieces. At this time, the resin (B1)' sub-extruder tip temperature is 260°C, the composition (C) side extruder tip temperature is 270°C, and the hot runner block part 2 where the resin (B1)' and the composition (C) are joined.
Co-injection stretch blow molding was carried out at 60°C, and the average thickness of the body was 190μ for the inner layer resin (B1) and 20μ for the intermediate layer composition (C).
A multilayer co-injection stretch blow-molded bottle was obtained with μ and outer layer resin (B1) of 90 μ. By the way, is there a mold in the body of this bottle so that impact delamination is likely to occur? Vertical 50mm x Width 15mm 5 Thickness 1. Omm, 2.0mm and 4.0
A roughness of mm was provided. Filling the multilayer container with water,
The body was repeatedly dropped 30 times from a height of 1 m under normal pressure with the body horizontal, but no delamination occurred.

Examples 2 to 18, Comparative Examples 1 to 3 Bottles were obtained under the same conditions as in Example 1 except as shown in Table 1.

Table 1 shows the results. Shown below.

The following margin is JP-A-3 281246 (7) Mu 1! J Marriage F8 Effects of the Invention According to the present invention, in a multilayer structure obtained by multilayer molding, especially co-injection stretch blow molding, when an impact is applied to the empty, normal pressure filling, or high pressure filling, It is possible to obtain a multilayer structure (container, etc.) with good appearance and good gas barrier properties without interlayer delamination.

Claims (4)

[Claims] (1) Metaxylylenediamine group-containing polyamide (A)
layer, and a thermoplastic polyester containing 0.1 to 20 mol% of diol and/or dicarboxylic acid represented by the following formula (I) based on the total diol and/or dicarboxylic acid (
B_1) or a multilayer structure consisting of at least two layers of polycarbonate (B_2). X-R...(I) However, X: Diol or dicarboxylic acid R: -SO_3Y, -COOY, -OY, -PO(OY)_2, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas , tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, -PO_3Z Y: Monovalent metal Z: Divalent metal (2) 1 to 95% by weight of the resin (A) according to claim 1 and 5 to 99% of the resin (B_1) and/or the resin (B_2)
A multilayer structure consisting of at least two layers: a composition (C) layer consisting of % by weight and a resin (B_1) or resin (B_2) layer. (3) 1 to 95% by weight of the resin (A) according to claim 1 and 5 to 99% of the resin (B_1) and/or the resin (B_2)
A multilayer structure consisting of at least two layers: a composition (C) layer consisting of % by weight and a thermoplastic polyester (B_3) or polycarbonate (B_4) layer. (4) 1 to 95% by weight of the resin (A) according to claim 1 and 5 to 99% of the resin (B_1) and/or the resin (B_2)
The composition consists of % by weight.