JPS62187033A - Laminated oritented molded shape - 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 laminated stretch molded product with improved gas barrier properties. Specifically, the present invention relates to a laminated and stretched-molded product obtained by stretching a laminated structure of polyester and thermoliquid crystalline polyester, and is particularly useful as containers for carbonated drinks, beer, and the like.

[Conventional technology]

Polyester, especially polyethylene terephthalate hollow molded bodies, have excellent properties such as hygiene, aroma retention, pressure resistance, and lightness, so they are used for seasonings, carbonated drinks, draft beer, cosmetics, pharmaceutical containers, etc. Pressure is extremely widely used.

[Problem that the invention seeks to solve]

However, even with such excellent 9-polyethylene terephthalate hollow molded bodies, there is only one drawback: insufficient gas barrier properties, and in the future, it will be expanded into fields where it is necessary to prevent loss of carbon dioxide gas and prevention of oxygen intrusion. Therefore, improvement of this gas barrier property is a problem to be solved in this industry.

[Means for solving problems]

Under these circumstances, the inventors of the present invention have studied a hollow molded body with improved gas barrier properties, and as a result, they have arrived at the present invention. That is, the gist of the present invention is to provide a layer consisting of a thermoliquid crystalline polyester formed from an aromatic dicarboxylic acid unit (S), an aliphatic diol unit (B), and a hydroxy aromatic carboxylic acid unit (C); It consists in a laminated stretch-molded product characterized by having one side oriented in a volley direction.

The present invention will be explained in detail below.

The polyester containing a polyethylene terephthalate component used in the present invention means polyethylene terephthalate and a non-thermal liquid crystalline polyester containing polyethylene terephthalate as a main component, and it is preferable that at least 1 k gs mole of the structural unit is ethylene terephthalate. , dicarboxylic acids such as phthalic acid, isophthalic powder, hexahydrophthalic acid, naphthalene dicarboxylic acid, succinic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, etc. in an amount below the tS molar amount of the total acid components. Polyhydric carboxylic acids and the like can be used as the acid component.

Also, in an amount of 10 moles or less of the total alcohol component, %1. Co-propanediol, 1,3-propanediol, 1.
Using glycols such as ψ-butanediol, /, A-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, cyclohexane dimetatool, polyhydric alcohols such as trimethylolpropane, trimethylolpropane, pentaerythritol. is also possible.

The method for producing polyester is usually a so-called one-step reaction in which a known transesterification reaction or direct esterification reaction is performed to obtain a polyester oligomer, followed by a polycondensation reaction.

In this case, the transesterification catalyst may be a known compound such as a calcium compound, a manganese compound, a zinc compound,
Although one or more of the following can be used, a manganese compound is preferable from the viewpoint of transparency.

Moreover, after the transesterification reaction or the esterification reaction is substantially completed, seven or more types of phosphorus compounds may be added as a stabilizer.

Antimony compounds are known as polymerization catalysts.

One or more of germanium compounds, titanium compounds, cobalt compounds, etc. can be used, but antimony compounds, germanium compounds, and titanium compounds are preferably used, and germanium compounds and titanium compounds are more preferably used.

Additionally, additives such as color tone improvers and colorants may be included as necessary during the production of polyester.

The polyester can also be subjected to solid phase polymerization, if necessary. The in-phase polymerization treatment is usually carried out at a temperature of 120° C. to just below the melting point of the polyester for several tens of hours or less.

Preferably, the temperature is -230°C for 5 hours or more.

The intrinsic viscosity of the polyester of the present invention is 0.57 or more, preferably in the range of o, b to box.

On the other hand, the thermoliquid crystalline polyester formed from aromatic dicarboxylic acid units (A), aliphatic diol units (B), and hydroxyaromatic carboxylic acid units (C) used in the present invention can be melt-molded and melt-molded. It is a polyester that sometimes exhibits liquid crystallinity, and the content of dicarboxylic acid units (A) ranges from lO to 10 mol, preferably co-o! Ratio of hydroxy aromatic carboxylic acid unit (C) to the total amount of dicarboxylic acid unit (A) and hydroxy aromatic carboxylic acid unit (C) (C) / (A) + (C)
The ratio is preferably 0 to 90 mol, and the ratio is preferably 0 to 90 mol.

Ratio of hydroxy aromatic carboxylic acid units (C) to the total amount of aliphatic diol units (B) and hydroxy aromatic carboxylic acid units (C) (C) / (B) + (C)
is -0 to 90 mol %, preferably jO to 0 mol %, which is preferably used.

Therefore, this copolyester can be produced by contacting polyester or oligoester with oxycarboxylic acid to form a copolymer oligomer, followed by acetylation and polymerization, and then deacetic acid. I can do it. To explain the production method in more detail, the method for creating such a copolymerized polyester generally involves starting from a raw material polyester or oligoester represented by the general formula 11) (wherein 11 represents an arylene group and Bt represents an alkylene group). However, in order to produce such a raw material polyester +1), a dicarboxylic acid represented by the general formula (2)% (2) and its ester are used. Examples of carboxylic acids include terephthalic acid, methoxyterephthalic acid, ethoxyterephthalic acid, fluoroterephthalic acid, chloroterephthalic acid, methylterephthalic acid, isophthalic acid, phthalic acid, methoxyinphthalic acid, diphenylmethane-hiro, 4! '-Dicarboxylic H, diphenylmethane-, 3,3'-dicarboxylic acid, diphenyl ether-1I, a'-dicarboxylic acid, diphenyl-also a'-dicarboxylic acid, naphthalene-, 6-dicarboxylic acid, naphthalene, j-dicarboxylic acid, naphthalene -! , gettercarboxylic acid, adipic acid, sebacic acid, azelaic acid, speric acid, todecanedicalic acid, J-methylazelaic acid, glitaric acid, Koba/II, cyclohexane-/, 4(-dicarboxylic acid, cyclohexane- l, J
-dicarboxylic acid, cyclopentane-/, J-dicarboxylic acid, and the like. These may be used in combination, and any of those represented by general formula (2) can be used.

The general formula (3) used to produce maku raw material polyester or oligoester (1), HOR”OH・
...Song...(31 Specific examples of diols shown in /, 6-hexanediol, 1.1 code decanediol, cyclohexane-
t,a-diol.

cyclohexane-t, J-diol, cyclohexane-
1, cordiol, cyclopentane-1,J-diol, etc., but these may be used in combination, and any of those represented by general formula (3) can be used.

As the polyester or oligoester represented by the formula (1) used in the present invention, any of those represented by the general formula (1) can be used, but polyethylene tere-7-talate, polybutylene terephthalate, and Those oligomers are preferred, especially polyethylene terephthalate and its oligomers.

Next, the reaction method will be described. The raw material polyester or fclI-i oligoester represented by the general formula (1) and the hydroxyl represented by the general formula (4) (% formula % (4) (in the formula, Bj represents an arylene group) 130~ under normal pressure by contacting with aromatic carboxylic acid
After heating at 350°C to form a copolymerized oligomer, an acetylating agent was added to perform acetylation and polymerization under reduced pressure.

Further, one reaction is completed by deacetic acid removal under vacuum. Also, when contacting polyester or oligoester fl) with hydroxyaromatic carboxylic acid (4), diol (3) and dicarboxylic acid (2)
It is also possible to share.

Examples of the hydroxy aromatic carboxylic acids represented by the general formula (4) include para-hydroxybenzoic acid, + -hydroxy-
3-Chlorobenzoic acid, metahydroxybenzoic acid, Derhydroxy-J,! r-dimethylbenzoic acid, euhydroxy-6-naphthoic acid, l-hydroxy-5-naphthoic acid
ll, t-hydroxy-l-naphthoic acid, Schlinger
Vanillic acid, Hiro-hydroxy-3-methylbenzoic acid, and the like. Although it is preferable to use parahydroxybenzoic acid alone in order to maintain melt anisotropy, the general formula (
Any of the hydroxyaromatic carboxylic acids shown in 4) can be used.

Furthermore, acetic anhydride is typically used as the acetylating agent, but is not necessarily limited to this.

Furthermore, if necessary, a transesterification catalyst, an acetylation catalyst, and a polymerization catalyst may be used.

Furthermore, a small amount of a copolymer component can be introduced into this copolyester according to various purposes.

The copolymerized polyester thus obtained is D9C
Since the melting point (Tm) is relatively low and varies greatly depending on the composition, it is easy to control Tm.

Furthermore, since the temperature dependence of the melt viscosity is small, it is suitable for stable molding.

The method for forming a laminated stretch molded product according to the present invention involves stretching a sheet coextruded using a plurality of extruders in the longitudinal direction and/or horizontal direction to form a film-like laminated stretch molded product. A method of plasticizing two types of resin separately using one injection molding machine, and biaxially stretching blow molding the primary molded product of the two types of wood almost simultaneously in the same mold cavity to make a multilayer container. etc.

As for the biaxial stretching ratio, the preform before biaxial stretching (
It is desirable that the volume ratio of the intermediate (intermediate) and the container after biaxial stretching blowing is at least 3 times, preferably 5 times or more.

Another method is to form a pipe-shaped intermediate material of the Co-type Co layer or Co-species J layer using an extruder, then weld one end to form the bottom of the container, and then press and deform the other end. This method involves biaxial stretching blowing.

In the present invention, the thickness ratio of the layer made of polyester and the layer made of thermoliquid crystalline polyester is preferably such that the polyester layer is Sθ to 9tfb and the thermoliquid crystalline polyester layer is co-jO to the total thickness of the laminated stretch-molded product. It is in the range of 5 to 0.

If the thickness of the thermoliquid crystalline polyester layer is less than 2 inches, the effects of the present invention cannot be achieved, and if it is more than go %, it is more difficult to stretch than when polyester alone is stretched.

In addition, an adhesive layer such as modified polyolefin resin, α-olefin/vinyl ester coelectronic n-former, copolymerized polyamide resin, copolymerized polyester resin, polyurethane resin, etc. may be provided between the thermoliquid crystalline polyester layer and the polyester layer, if necessary. Even if you set it up, you can still pull it.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples.

In addition, measurements of the intrinsic viscosity [η] of the polyester, the logarithmic viscosity ηlnh of the thermoliquid crystalline polyester, and the amount of oxygen permeation in the examples are as follows.

■ Intrinsic viscosity of polyester [η] and logarithmic viscosity of thermoliquid crystalline polyester ηinh The ratio of phenol to tetrachloroethane.

Use a mixed solvent with a weight ratio of 1:1 and a IIk degree of 0.5? /
dt and SOC measurement value■ Oxygen permeation amount Kame0X-TR manufactured by MODERN C0NTR0LS in the United States
Estimated value measured at Ko3C according to AN 1001. unit(/
0-” cc・Crrl/C1ot・sea −
CrrrHf) Example 1 Polyethylene terephthalate oligomer (η1nhO,
10de/f), Ig Hiro? , parahydroxybenzoic acid a
iIIIg- and tin acetate θ, Kohiro? The mixture was placed in a polymerization can equipped with a stirrer, and the gas phase was replaced with nitrogen gas three times.Then, the polymerization can was placed in a Koku OC oil bath and stirred for 1 hour under a nitrogen stream. Next, acetic anhydride 30&? was added and stirred for 1 hour. The bath temperature was raised to 50% SC while distilling acetic acid, and then the acetic acid was completely brought out under a vacuum of 5 Torr.

Supply nitrogen to the polymerization reactor to return it to normal pressure, and add 0% zinc acetate dihydrate. After adding uIIf, the mixture was stirred for 6 hours under a vacuum of O. Torr to complete the polymerization. ηin of this polymer
h was 0.70 dt/l.

Further, when this polymer was cut into flakes and observed under a polarizing microscope equipped with a temperature raising device, it was found that it exhibited optical anisotropy in the molten state in the range of 190 to ytio°C.

In addition, this polymer is % (C) / (B) + (C)
When changing from 6 layer molding to 3 layer molding, Tm
Ha-ko-l! °C~/A 1. ! It changed to C.

Intrinsic viscosity [η] Q, chestnut polyethylene terephthalate resin and the previously obtained thermoliquid crystalline polyester resin, respectively /! After drying under vacuum for a day and a night using QC and l-〇〇, the mixture was co-extruded using a small extruder to obtain a two-layer sheet. The thickness of the thermoliquid crystalline polyester layer was 5 μm, and the baseness of the polyethylene terephthalate layer was aOS: μm.

This sheet is T, M, II, ONG manufactured by HEAVY.
DUTY FILMSTRKTC) IIR was used to simultaneously biaxially stretch the film to a factor of 5 to obtain a stretched film. The oxygen permeability of the obtained film was measured by a predetermined method, and the results shown in Table 1 Example 1 were obtained.

Example A, Comparative Example I Samples were obtained by molding in the same manner as in Example 1 except that the liquid crystalline polyester was used in Example 1 and the thickness with polyethylene terephthalate was changed as shown in Table 1. The results are shown in Table 1.

Compared to polyethylene terephthalate resin alone, thermoliquid crystalline polyester resin laminates have superior gas barrier properties.

Table 1 [Effects of the Invention] According to the present invention, it is possible to obtain a laminated and stretched molded product with particularly excellent gas barrier properties. be.

Claims (1)

[Claims] (1) Aromatic dicarboxylic acid unit (A), aliphatic diol unit (B) and hydroxyaromatic carboxylic acid unit (C)
A laminate stretch-molded product characterized by having a layer made of a thermoliquid crystalline polyester formed from a polyester and a layer made of a polyester containing a polyethylene terephthalate component on at least one side thereof, and oriented in at least one direction. .