JPS5954557A - Composite molded vessel made of polyester resin - 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 The present invention &'11 provides a composite molded container made of thermo-rif-formed polyester resin, particularly a bottle body made of biaxially stretched blow-molded 1 ton thermoplastic polyester resin, and provided with a barrier against carbon dioxide gas. 1. In recent years, hollow containers made from thermoplastic polyester resins such as polyethylene terephthalate and its copolymer + 171 fat have been developed. , t() biaxially stretched block lff-formed; I 1. The LR double body has excellent mechanical properties, optical gravity, compatibility, 1:1 quality, and gas barrier properties.
RE, Ministry of Health, etc. 1:,), ll:i /+l+, came to be widely used as containers for foods such as sauces, edible oils, and alcoholic beverages.

[7) Depending on the contents, the barrier properties against carbon dioxide gas and acid gas may be insufficient. I was 1, and I was not able to do it. For example, if you pour the contents of beer or other carbonated drinks into charcoal, which is gasified overnight, carbon dioxide gas will escape from the inside of the bottle, causing a so-called "kinonuke" effect on the taste. There was a problem.

The solution to this problem (~te, lpy' + TJ plastic poly J
From 5°)/. There are burrs on the outer surface of the hollow container.
・In the case of Uchitani, carbon dioxide gas first permeates from the inside of the bottle through the polyester resin layer 2, and the permeation is suppressed by the barrier resin layer. As a result, charcoal gas accumulates at the interface between the polyester resin layer and the barrier t;+-resin layer, and the barrier layer is peeled off from the polyester resin layer. Ha・)
・、Ra」1, nNW +j, ′+ flllll Not only does it jump directly or jji, but also the barrier l < 1st place j fat layer bar') -/=-effect is light minute C・kore] force. I'm sorry for the inconvenience.

The inventor of the tree is the polyester side finger layer and parier +!
L (Ol l's famous charcoal gas permeability, σ in the container) 11-, 1B, and polygosol 44i
As a result of two considerations, we have succumbed to the relationship between the guff strength between the J 11M layer and the barrier A resin layer and the peeling of the barrier +1 resin layer from the polynisdel side resin layer. Providing an adhesive V and a resin layer between both layers 1, - adhesion 1' 1 - The combined strength of the resin layer has a range of T. ′- is the number of hearts, and the present invention was achieved.
did.

The present invention is gas permeable! 51-111-1'L is "Friend 111
However, if there is no peeling between the barrier and the resin layer, there will be some inconveniences. - and father () and -4- Rumo ()), and Zono Yasuji and -fZ, and Koro FJ Ryoji Junior High School 1b Enlarged Middle Zoro - Molded λt made of thermo-EIJ plastic polyester resin. The outside of the container has the adhesive strength (,4K >;';
In the above formula, QI:,,;!θ°(), 0% R H (-Thermoplastic polyester 4xi of container) Carbon dioxide scum permeability of llrf layer (CC/n?・2hrr3+a.tm
).

Electric 2:. 2θ′c. θ% group I
j*. 2'1krrS, atm) P: Pressure inside the molded container at 20'Ij when the container is completely sealed with carbon dioxide gas (kg/cnf) T: Adhesive strength LLCg/inch ( ,;t, JriCJII)]su(
- rh: -, fru.

The following is a detailed description of the invention.

In the present invention, in addition to polyethylene terephthalate alone 11 combined, ethylene de V ivy sheet?
Copolymers containing acid components such as Telenotal it, Isonotal 10, phthalic acid, adipic acid, p-
Human L1 gysibenzoic acid, etc.

Also, 1 minute to 10 ech L/Ngrico,
ITi containing trimethylene glycol, xamethylene glycol, and alcohol (7) or 1)
The copolymer, the song, polybutylene lenticifucrate.

Ptyrene derenotare-1・η (upper p 47' + composition j1) (11-combined product) or a blend of the above can be used.

71<y. 1su1 (7 guests 2:÷(compensation,)・5ii(
1) Vinylidene culture medium laminated on the steel surface of the container.
.

Vinyl chloride IJden 4 [Main component (e.g. +-Xδ′θ~70
As a copolymer with (%), acrylic IJ-1 (-lyl, 7-methacrylo'-tolyl).

Mebultsu'Cree 1.1-Cryly 1., Methyl methacrylate 1., Glythyl 7/Tacrylate.

The combination of vinyl chloride housing / Φ or 2f Φ - 1 - 1 - father is l y V r 7) \, Moshi door / a little 1, this 1 sawa 1,) 1 many things ゛ (above) The ceremony is good.

Present invention 8'+4:÷ti゛, polyester'ti7+I
The resin and beylidene chloride resin are interposed between the resin layer 3 (:'J
6 Jχ adhesion fi1 resin removal of fat layer. , -(-, the above fl1 formula ke/1・"f-j"]b'='<":P"The adhesive strength is 11) is also 11, so A1,(・f-j,
Specifically, I, bow, f, j'; 11 (Material, polyamide (
i11it Umaito.

acetic acid beer) 7J l1ii'; Scratching and cutting of the old surface is removed.1.

There is only one thing that can be said about t"L L') (:l'
．． /((, fL. and J1't:, on])・1゛Bird hollow container υ(-light jll(break; b'rost't''↓匡1, depending on the internal pressure generated, Formula (1) above f
I can't choose what satisfies x+.

There is no special method for manufacturing the biaxially stretched polyester resin hollow container, and it is manufactured according to a conventional method. On the outer surface +Mi of this hollow container, the above-mentioned adhesive t (1 resin C and 1 resin vinyl chloride) is laminated, but the lamination method is as follows.

That's λL, (7) Resin emulsion or organic solvent solution Ilb can be applied by tipping method, spray coating method, etc. It may be applied 7 times or more than 2 times, or 7 times. The thickness of the adhesive 1'L resin layer is usually ~5μ, the thickness of the salt f and vinylidene resin layer is usually 5μ.
~30μ is preferable. Then, the adhesive strength should be achieved within the range of the above formula (1).

Each item shown in equation (1) was measured by the following method.

(1) Carbon dioxide permeability (1) Transmittance of polyester resin layer Sampled from the body part of the inner leaf container made of polyester resin alone,
! It cannot be manufactured under the conditions of θ°c1 θ ratio RHσ]! J1 type (
Ministry of International Trade and Industry Product Book
The transmittance of the charcoal 1 gas was measured at , and this value was defined as Ql. (Unit: Co/m's 2'r/hrs, atm
) (11) Transparent vinylidene chloride resin layer (
A hollow container made of polynisder resin was cut out from the body part of a composite container with a vinyl chloride resin layer laminated via an adhesive resin layer on the outer surface of the container. Measure the permeation amount of carbon dioxide gas using a trowel.

This value k Q3 is subtracted from the linear equation by carbon dioxide gas permeation through the vinylidene chloride resin layer +6A. Unit is CC/711'
・−'! K)ir S, atm.

Q2° 1 (2) Adhesive strength (value of T in equation (1)) Vinylidene chloride resin layer is laminated on the outer surface of the polyester resin hollow container through the adhesive resin layer. A 7-inch (2,3-</○I+) piece was cut out from the body of the composite container. Glue it onto a steel plate of 2.0 mm in diameter using an epoxy adhesive based on Ebisu-type epoxy resin.Next, peel off the polyester Ij fat layer at one end of the sample to make a gripping part, and pinch it with this partial clamping tool. , pull it up in the vertical direction (the steel plate is held horizontally), and perform the peeling of the polyester resin layer + Ijlt Kaoru. 4I!111Hf location is pressed with a straight 5 mm roller and sampled 71,1.j No boxwood The steel plate was peeled off.
As # progresses, it moves in the direction of the lateral force.

Peel + -1 jln 1] - At the roller location ゛X1 feed J
j & death so that substantially vertical force rotation is always performed. The adhesive strength is defined as the average tensile force (about t4j, !7/inch) at a peeling rate of 3θan/min. Measurements are made at approximately 2θ°C.

(3) After the pressure-formed container inside the molded container is filled with carbon dioxide gas to the desired gas volume and sealed, the pressure inside the container is adjusted to 20'0 by using a jig with a needle attached to the tip of a pressure gauge. Measure the temperature using the . Unit is kg
/age.

However, the left side of the above equation (1) VC'! The actual adhesive strength (T) is higher than the value given by i9.
If the value is small, the vinylidene chloride resin layer may peel off from the polyester resin layer of the molding container. Therefore, it has excellent carbon dioxide gas barrier properties. Since this does not occur, the adhesion strength must satisfy the above equation (1).

Next, an actual hfu example will be explained. In this example, the loss of 1 charcoal gas is determined by Add a predetermined amount of citric acid and sodium bicarbonate to this water and immediately stopper it.
Carbon dioxide gas is generated by the reaction of both of the above f-hybrid compounds. Carbon dioxide volume and q output when both compounds react completely,
The gas volume fa (■o) at the time of carbon dioxide gas filling is the magnification of this volume to the amount of water. After storing this in a constant temperature room at θ゛C for 2 weeks, the pressure inside the container and the water temperature (
Separately, prepare a water temperature constant container Σ°2, fill it with water, measure the water temperature in the same way (place it in the crystal chamber, check the water temperature in this container), and change the carbon dioxide volume in the pressure car. Sonmyo DC
1-1: Gas container (V+)'a= after the 2nd collar
Find the charcoal 14 ammonium gas loss η (find it from the following formula.

Example/ A bottle body was made from polyethylene terephthalate by biaxial stretch blow molding according to a conventional method. This item has an internal volume of 1000 CC% parison.

The average wall thickness of the body part is 07g. This bottle was made into a bottle by dino-pinging twice in the 1-finger t-fulsion of the adhesive resin shown in the table below, and finally in a hot air drying mold for 10 min. Dry for a minute,
The outer surface of the bottle body was coated with resin, then treated with vinylidene resin (salt).
Coated twice using the emulsion dipping method of Z vinylidene, candy, and the remaining copolymer component methyl acrylate! ,two. Next, dry in a hot air drying mold at θ゛C for ≦θ car, and then dry in a hot air drying mold at 0°C for 2 hours, 2 rows of knee song/work, -0 (I).
Average Jy % T
Yo, 7 wheat 1 queen table C anti-; 1, -4-11 U1 ri,
The average thickness of the vinylidene chloride resin layer was approximately 20 μm.

Obtained bottle V (-1, θ gas volume of carbon dioxide gas? Filling) - 1 - Measurement of loss of carbon dioxide scum in water placed in the bottle in the same manner as described in section Carbon dioxide gas η (result 47f of 2θH01 normal pressure of the acid scum in the child's life is the water volume times Ti; 7.)
).

Saved at 20°C at 7F + 1F. , after storage for 2 weeks, vinylidene chloride resin (p v
d, a omitted - [ru] layer peeling 1; I ■ state ke observation (
~is. Measurement of soil carbon dioxide gas permeability, adhesive strength, pressure inside molded mold A7 [2, results shown in Table 7/7f-].

In Table 2, the peeling status of the vinylidene chloride resin layer in (2) below is measured as follows: The ratio of the area to the total surface area of the bottle) was taken as the peeling+i+i situation.

In addition, Table 7 (described below) shows adhesive resin layers 1 to 6.
4) was coated directly onto the outer surface of a PET bottle by dipping a polyvinyl chloride-lidene resin t' without coating with an adhesive resin.

Fill in -/ +-j+1 The polyurethane resin of the adhesive resin is Toyo Morn 1- ((Adco manufactured by 4J)) Hri 0
The acrylic sphere resin is a 10% concentration of Movinyl 2gθ, which is an acrylic acid ester resin manufactured by Hegist Synthetic Co., Ltd. and has an active ingredient of Movinyl 2gθ.

The ethylene-convex vinyl monate copolymer resin is a 10% concentration one manufactured by Denki Kagaku Kogyo Co., Ltd. (fnka EV Atex H20/L manufactured by Ze0), and the polyester resin is manufactured by Dainippon Ink 1 #mile/l Fine Dell. Tsukusu E S l, ,
It has a 7θ concentration of 5θ.

Table/Experiment number-! Nos. 3 and 3 are composite molded containers according to the present invention, which have the formula (1) defined in the present invention, with no peeling of the 1° VdC layer and little loss of carbon dioxide gas. Experimental number and 3-d*m adhesive layer, then the island's [-vinylidene resin layer? Although they are laminated, the pressure inside A2 is high, and in this adhesive layer, the value of the 71st side of equation (1) is higher than the value of T<ilJ2satisfaction11"), and I couldn't do it.

Example The content is responsible for /θθθCC, and the parison is still there.

Table M VC of a biaxial stretch blow-molded polyethylene terephthalate bottle with an average wall thickness of the body part θ and 0 mm
The adhesive resin layer was coated in the same manner as in Example 1 shown in Table 2, and then an emulsion of vinylidene chloride resin (combined with vinylidene chloride and mol% of the remaining methyl acrylate) was added by dipping method. After coating, it was dried in a hot air dryer at θ゛C for two minutes, and then aged for another 2 hours in a hot air dryer at θ゛C. The average thickness of the adhesive resin layer of the obtained bottles was as follows.

The average thickness of the vinylidene chloride resin layer is approximately /θμ −ζ
Two Atsu Noko.

The resulting bottle contained 3.0 gas volume fi. Please fill the carbon dioxide gas capacity with θ gas capacity %! 0'Q
It was stored in a constant temperature room. Then, the peeling status of the vinylidene chloride resin layer after being incubated for 2 hours was observed. In addition, carbon dioxide gas permeability, adhesive strength, pressure inside the bottle, etc. were measured using the methods described above. As for the adhesive resin in Table 2, the same brand of product as explained in Table 1 was used.

In Table 2, Experiment No. 3, RI and O are related to the present invention, and are a) a molded container that satisfies formula (I);
No peeling of the PVdO layer occurred. Experiment No. 23 was coated with the same adhesive 44 resin and the same film thickness as Experiment No. 23, but the gas capacity of the carbon dioxide gas filled in the bottle was too large, and formula (1) was satisfied. 'A'l 1' of the %PV d C layer;

What has been explained above and mentioned in the second embodiment relates to uninvented examples for aiding the beating process.

Without being limited to the illustration, it is possible to take any variation of flf within the gist of the invention.

Claims (1)

[Claims] Does the outer surface of a biaxially stretch blow-molded thermoplastic polyester resin container have an adhesive strength that satisfies the following formula (1)?
Therefore, a thermoplastic τV polyester resin composite molded container 1.5-P(Q, Q2)≦T (1) is formed by adhering the vinylidene chloride resin layer through the adhesive resin layer.
"For the second formula, Ql: , 2θ'c1θ coefficient RH of the thermoplastic polyester resin layer of the container (CO/, i
t・217-hrs, atm) 1l Q2: , 2.0'c, 0%RH
r 8 , a ℃m) P: Monthly force inside the container at 2θ゛C when the molded container is filled with carbon dioxide gas and sealed (
+<g7J)T: Adhesive strength [1q/inch (2°3-)]