JPS60122148A - Laminate - 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 relates to a one-layer material that is used as a material for various containers and a gas barrier 11 for use as a seal material.

A single container made by laminating an ethylene vinyl alcohol copolymer (ethylene-acid resistant vinyl copolymer kenated product) layer with excellent gas barrier properties on a polyester resin layer is known (Unexamined Japanese Patent Publication) Showa 57-19965613
Public bulletin). This container is starting to attract attention as a container for storing alcoholic beverages, beer, carbonated drinks *S1, Reuse, etc. due to its excellent preservability and aroma retention properties, but due to the poor adhesion between each layer, it At present, a practical laminate cannot be produced because of peeling or peeling during storage after filling with contents.

The present invention has been carried out with the aim of overcoming such conventional drawbacks and obtaining a single laminate, with the aim of improving the properties of the contact between each layer. It was discovered that this can be effectively achieved by interposing a polyester resin as an adhesive layer between each layer.

t tt b H The present invention uses ethylene-vinyl alcohol as well as heat 1 + J plasticity + 1? through an adhesive layer on one side. 11
Laminate the ester resin layer and add JjL・-C, 1 to the laminate.
) The adhesive layer contains (A) 70 to 15 mol% of terephthalic acid 92 AS, 1)) 5 to 80 mol% of isophthalic acid. (Jj, 1: bi(c) 5 ~ 80 moa 1/% 0) carbon source r-number 3 ~ 3 (i 6'l
U) Consists of an aliphatic dicarboxylic acid residue and 1'&u isophthalic acid residue and I'l! I
Total strength of 1 and 11 dicarboxylic acid residues; 30-8
5 mol % acid component and (B) ethylene glycol residue, 1; A laminate characterized by being a copolyester resin comprising a diol component which is a 1,4-butafreol residue is provided in O) and J).

Used as the adhesive of the present invention: 1-Terephthalic acid residues contained in the phester resin 1 form terephthalic acid and its ester-forming properties (such as methyl terephthalate) I''sLstL.

Copolymerization of the terephthalic acid component m 1.1 7 0-15
Mol%, especially 50 to 25 mol% is preferable, and when it exceeds 1070 mol% (functionality as a light agent; (L(1ζ
However, if it is less than 15 mol %, the heat resistance and adhesive function deteriorate, which is not preferable.

Also, isophthalic acid residues include inophthalic acid and its ester-forming derivatives (e.g. dimethyl isofucrate).
formed from.

Specifically, the aliphatic dicarboxylic acid residue having 3 to 36 carbon atoms includes adipinoic acid, azelainoic acid, sebacic acid, dodebuJ nodionoic acid, reinimeric acid, etc.
The esthetics J and Cedar I t1: Derivatives (e.g. dimethyl adipate, 7) <dimethyl tunoate, dimethyl dodecanedioate)-b> and others are used. Particularly preferred are adipic acid, senoacid, 1zdebendioic acid, acyl-L/noic acid, dimethyl hetanoate, and dimethyl dodecanedioate.

Isophthalic acid component and aliphatic dicarboxylic acid component having a carbon division number of 3 to 36
85 mol %, especially 50 to 75 mol % is preferred. The total number of dishes is less than 30%.i. t t &r
;'/'i'l function decreases, and if it exceeds 85 mol%, heat resistance and adhesive function bX low r: SiU
- Not acceptable0 In addition, the amount of copolymerization of the isophthalic acid component is 5 to 80 mol%,
Particularly preferred is 15 to 50 mol%. If it exceeds 80 mol%, the heat resistance and function as an adhesive will deteriorate, which is undesirable, and if it is less than 5 mol%, the function as an adhesive will significantly deteriorate, which is undesirable. Further, the copolymerization amount of the aliphatic dicarboxylic acid component having 3 to 36 carbon atoms is preferably 5 to 80 mol%, particularly 15 to 50 mol%, and if it exceeds 80 mol%, the heat resistance and adhesive function will deteriorate. lowered and unfavorable, 5
If it is less than mol%, its function as an adhesive deteriorates, which is not preferable.

Further, the diol component is ethylene glycol and/or 1,4-butanediol. In addition, small proportions of other dicarboxylic acid components and diol components can be further polymerized depending on the case. Other dicarboxylic acid components that can be copolymerized include Δltophthalic acid, 2.6-
Naphthalenedicarboxylic acid 1m, 1.5-naphthalenedicarboxylic acid, bis(D-carboxyphenyl)methane, An-1-racendicarboxylic acid M, 4.4-Schif1yldicarboxylic acid, 1,2-bis(phenoxy)ethane-4 , 4'
-dicarboxylic acids, aromatic dicarboxylic acids such as 1,2-bis(2-chlorophenoxy)ethane-4,4-dicarboxylic acid, alicyclic dicarboxylic acids such as hegylyhyde-terephthalic acid, l) - (2- Examples include ester-forming derivatives of A-1-oxycarbonate and/or A-1-oxybenzoic acid. Further, other diol components that can be copolymerized include propylene glycol, neopentyl glycol, 1,5-pencune diol, and 1.

6-hexanediol, decabulene glycol, cyclohexane dimetatool, cyclohexanediyl, or long chain glycols with a molecule ff of 1,400 to 6,000, such as polyethylene glycol, polymethramethylene glycol, etc., and their ester formation Examples include sexual derivatives.

Specific examples of copolymerized polyester resins used as adhesives include polyethylene terephthalate/isophthalate 1 to azibe 1-, polyethylene terephthalate isophthalate sebacate, polyethylene terephthalate isophthalate decanedicarboxylate 1, and
, polybutylene terephthalate isophthalate adipate, polybutylene terephthalate isophthalate sebacate, polybutylene terephthalate isophthalate decanedicarboxylate-1-, and the like.

In addition, these copolymerized polyester resins may be used as a mixture of two or more types, or other polyester resins may be used in combination with 45% of other polyester resins.
You can mix it within the range of w [% or less. Other polyester resins include polyethylene terephthalate, polyethylene terephthalate 1~, isophthale 1~,
poly-1 brene j lenotalate ′) l dibe 1-, borie f-renno lenotalate sebacate, poly 11
- Renrarenotare 1 - Isophthalate adipate 1 of the present invention and copolymerized polynisnol resin j1 (deviating from the composition of 1) used as a neck agent, polyethylene jrenotare 1 - isophthalate adipate (Honko 1! Polybutrene terephthalate, polybutrene terephthalate, polybutrene terephthalate, polybutrene terephthalate, polybutrene terephthalate,
1..Isophthale-1., Polybutylene terenothale-1
-・No'dibe 1-, polybutylene terephthalate/bacate, polybutylene terephthalate 1~・isophthalate adipate (things that deviate from the composition of the Jl, ・1j composite polynisdel resin used as the adhesive of the present invention) , polybutylene derephthalate 1-, isonoclay 1-
・Rebacate (can be used as the adhesive of the present invention)
Examples of the composition of the polymerized polynisder resin include:

The chisel-polymerized polynisder resin used as the adhesive layer of the present invention may optionally contain a crystallization nucleating agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a thickener, a thinner, an antiblocking agent, and a lubricant. One or more types of colorants and the like may be added in an amount of 0.001 to 6.0 parts by weight per 100 parts by weight.

In addition, these copolymerized polyester resins contain 0.5% of 0.
-Chlorophene, '-ol solution measured at 25 DEG C. has a relative stiffness in the range of 1.2 to 2.5, particularly preferably 1.4 to 1.9. Furthermore, the melt viscosity of these copolymerized polynisder resins was measured using a melt indexer (manufactured by Toyo Seiki Co., Ltd.) at
5g) It is preferable that the VFR' (number of grams of polymer flowing out in 10 minutes: g/1QIli11) is 50 or less, and especially 20 or less when forming a frI layer by the Jt extrusion method. It is particularly preferable that there be.

The -Lf-rene-vinylflucol copolymer of the present invention has an ethylene content of 20 to 80 mol%, particularly 25 to 80 mol%.
A saponified ethylene-vinyl acetate copolymer having a degree of saponification of 60 mol % and 90% or more, particularly 95% or more is preferably used. , Ll, this 1-vinyl alcohol copolymer j11. Instead of using German, the gas barrier property can be increased by 1% or 5011%.
Other resins in the range mentioned above, such as polyethylene, ethylene-acrylic acid copolymer, ethylene-acrylic acid copolymer, olefinic polymers such as polypropylene, polyamide resin, etc. It is useful to mix and use.

Thermoplastic fl poly J of the present invention, sural resin (polyconylene terephthalate 1, polyethylene terephthalate isophthalate, polypropylene terephthalate-j~
, polyethylene, ureate, isophthalate, etc. In addition, these thermoplastic polyester resins have a 0.5% O-ri[111], L-Nol solution at 25°C.
The relative Ji'+ degree of 1 when measured at 162 to 2.5, especially 1. : Preferably in the range of 3-2.0.

. If desired, at least one of the 1-dylene-vinyl alcohol copolymer or the polynisder resin used in the present invention may be added with a heat stabilizer, an antioxidant, and an ultraviolet absorber (i!'
ij inhibitor, lubricant J3, coloring 1, etc. - of F or more is 0.001 per 100 parts of polyester 461 fat.
It can be blended within the range of 6.0 parts by weight. In addition, in order to reinforce this laminate, fiber reinforcing materials such as glass fiber, aromatic polyamide base 1, carbon fiber [, = 1 Futon Linter], powder reinforcing materials such as carbon black and white carbon, Add flake reinforcement such as aluminum flakes to 100 parts by weight of polyester resin.
It can be blended within the range of ~100 parts by weight. . Further, inorganic powders such as calcium carbonate, talc, aluminum, kaolin, barium sulfate, and silica may be blended as a filler.

The manufacturing method of the laminate of this light is not particularly limited (
, manufactured by known methods within the scope of forming a multilayer structure.

For example, by coextrusion, dry lamination, lean German delamination, etc.
It is made into a laminate with a shape or a duplex shape. Furthermore, it is made into a cup-shaped, bottle-shaped, or other laminate container by injection molding, blow molding, biaxial stretch blow molding, vacuum forming, compression molding, or the like.

The laminate of the present invention has a
In order to improve the quality, a coating layer of a chlorinated hynyrite copolymer can be provided. The vinylideno chloride copolymer referred to herein means 99 to 65% by weight of vinylideno chloride gfJ,
Acrylic or/and methacrylic monomers 1 to 35
For the total amount of 100 parts by weight of market weight %, other ethylene-based saturated! It is a copolymer consisting of 0 to 11 parts by weight of vinyl chloride/acryloni 1
~Ryl co-copolymer, hinylideno chloride/methoxymethyl acrylate-1-/methylnucuacryle-1-/ethyleno-trichloride-3 (polymer, hinylideno chloride/methyl acrylate/acrylic acid phosphorus copolymer) Examples include merging.

A. The product of the invention has an extremely high adhesive force between each layer.
By taking advantage of the fact that it is easy to produce various types of products that contain a variety of products, we can produce various foods,
It is useful as a container for long-term storage of seasonings, beverages, medicines, chemicals, pesticides, etc.

Invention A will be described below with reference to Examples.

Examples 1 to 2 As a polyester resin, 111 K.J viscosity 1'JI J,
4 ], (1,) 11! ``The first layer of noethylene terephrate, F, 1 Table 1 shows f: Each Ul composition.''
1! F poli ward stell Jilil flit 2nd
layer ((>x71 layer), ethylene-containing (''' jll:(
(14' = A%) 99% ethylene-acid resistant heel 1-11i; body compound (ethylene-hinyl alcohol lu medium negative body) laminated sheet 1 with a two-layer structure as the third layer Molded with 1 extrusion θ, 1 piece (composition ratio: 1st layer, 2nd layer (i''/;: Zi layer), 3rd layer - 5:1
:5, 211th゛・1jl, lmi facing east] IJ N
).

Next, the obtained laminated sheet 1 is iJl, Osr 1
Length 501m, cut +), cut l), contact? +1'C,i
・P (dli IIJ test piece,',: t, /,:
.

Test) The third layer was 29 + u /
A force of 41η (
The contact force is determined by measuring A・(/rm).

These results are summarized in Table 1.

Ratio -1 (k to Example 1 5) A laminate was molded using the same IJ method as in Example 1 using the copolymerized polyester resin of each composition shown in Table 1 as the second layer (adhesive layer). , a laminate consisting of polyethylene terephthalate and ethylene-hinyl alcohol J (j@aggregate) without using a second layer (adhesive layer) was molded.

The adhesive force was measured in the same manner as in Example 1, and the results were
It is shown in the table.

Examples 13.14.1 et al., 17.11) A copolymerized polyester resin having the composition shown in Table 2 was used as the polyester resin for the first layer of polyethylene terephthalate clay+-fe having a relative viscosity of 1.41 (J+Yll, as shown in Table 2). 2B (adhesive layer)
, x tyreno content is 30 mol% -
A 3-layer H1 laminated bottle (with an internal volume of 500 ml) having an ethylene-acid-resistant vinyl compound (coalescence)) as the third layer (outer layer) was made by biaxial elongation blowing. (component ratio 1st layer: 3rd layer: 40:1:2, second layer thickness average 8μ).

Next, the resulting bottle was heat-treated (aged) at 0°C for 3 hours, and then visually tested to see if any peeling occurred between each layer, and then the bottle was removed from the body of the bottle. 1lJIQ+y*, length 5U #II
& Determine the fit.1. :.

These results are shown in Table 2.

Example 15.18.20, 21 Polyethylene terephthalate 1- with relative viscosity lx o and 81 was used as the polyester resin in the first layer (Jj and 1-Ejuμ4), as shown in Table 2. Polymerized polyester resin is used as the second and fourth layer (adhesive layer), and ethylene-vinyl acetate copolymer kenonide with ethylene content of 30 mol% and kenization degree of 99% is used as the third layer (adhesive layer). 211 5-layer laminated bottle (inner volume 500 leakage l) with
! Molded by stretch blow molding method (composition ratio 1st
Layer: 21st m, 3rd Jim: 4th layer: 5th layer-2:
1:2:1:35, second layer thickness is 8μ on average].

Next, the resulting laminated bottle was heat treated (aged) at 90'C for 3 hours, and then visually tested to see if any peeling occurred between the layers, and then the bottle body was heated to 11].
A test piece with a length of 0 ma1 and 500 mm was cut out, and the adhesive strength was determined in the same manner as in Example 1.

These results are shown in Table 2.

Comparative Examples 6 to 13 Two-layer structure and three-layer structure were molded in the same manner as in Examples 13 and 15 using a copolymer resin having the composition shown in Table 2 as an adhesive layer, and without an adhesive layer. A laminated bottle with a five-layer structure was evaluated in the same manner as in Example 13, and the results are shown in Table 2.

As is clear from the results in Tables 1 and 2, the laminate of the present invention has a large contact force between each layer, and does not peel off when loaded.

Procedure Amendment Portfolio (Method) 59, 3. 23, 1972, Director General of the Patent Office, Kazuo Wakasugi, 1, Indication of the Case, 1982 Patent Application No. 228! 'i55 Bow 2, name of the invention laminate 5 person making the amendment 4 date of amendment order February 2811, 1982 (dispatch 11) 5 number of inventions increased by the amendment U 6 target type of the amendment engraving (% - 1 tsubutsu f-rishi)

Claims (1)

[Scope of Claims] A laminate in which a thermoplastic polyester resin layer is laminated on at least one side of a gas barrier layer mainly composed of an ethylene-vinyl alcohol copolymer via an adhesive layer, wherein the adhesive HD CatA) ta170~ 15 mol% terephthalic acid residues, 1]l 5-80 mol% isophthalic acid residues h
(and (C) consisting of 5 to 80 mol % aliphatic dicarbono acid residues having 3 to 36 carbon atoms, and the total z1 of the isophthalic acid residue and the aliphatic dicarboxylic acid residue is 30 to 85 mol %) A laminate characterized in that it is a copolymerized polyester resin consisting of an acid component, (B) an ethylene glycol residue, and a leol component, which is a 1,4-butanediol residue. .