JPH05156144A - Resin composition and container - Google Patents

Abstract

PURPOSE:To provide a resin compsn. excellent in oil resistance and flexibility and suitable as a material of a container which is neither deformed nor swollen even by the contents contg. an oil in a high proportion and excellent in squeezability, adhesion by pinch-off, and heat-sealing properties, and to provide the container. CONSTITUTION:At least one amorphous or lowly crystalline resin selected from the group consisting of polyester and polyamide resins each having a glass transition point of about 50 deg.C or higher is blended with at least one resin selected from the group consisting of polyester and polyamide resins each having a glass transition point of about 40 deg.C or lower, thereby giving the objective resin compsn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitable as a constituent material of a container filled with, for example, skin care, hair care, other cosmetics, foods, and the like, and a container formed using this resin composition. It is a thing.

[0002]

BACKGROUND OF THE INVENTION For example, as a constituent material for a single-layer or multi-layer hollow container, there has been proposed a polyolefin-based resin having good extrusion workability and good adhesiveness at a pinch-off portion of a molded container. Further, as a constituent material of at least the inner layer portion of the tubular container, the extrudability is good,
Further, a polyolefin resin having a good heat-sealing property has been proposed. Examples of such polyolefin resins include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, random polypropylene and block polypropylene.

By the way, various proposals have been made for this kind of polyolefin resin because it is inferior in gas barrier property and oil resistance. For example, JP-B-51-43074, JP-B-56-23792 and JP-B-57. -15532 and JP-A-60-49939,
A barrier resin layer such as ethylene-vinyl alcohol copolymer or nylon is provided in the intermediate layer between the innermost layer and the outermost layer made of a polyolefin resin to prevent oxygen gas from entering from the outside, and , A technique for preventing the penetration of oil has been proposed. Even in such a proposed container having a multilayer structure, a polyolefin resin is used as the innermost layer material from the viewpoint of pinch-off adhesiveness and heat sealability.

However, the filler contains various oil components such as skin care, hair care, other cosmetics, foods, and other animal and vegetable oils and fats, their transesterified derivatives, isoparaffins, synthetic oils such as silicone oils. When contained, these oil components permeate the polyolefin-based resin that is the constituent material of the container, and when the container is a single layer of polyolefin-based resin, the phenomenon of oil bleeding to the container surface occurs, and the barrier property Even in the case of a multi-layer container in which the resin is provided in the intermediate layer, the polyolefin-based resin in the innermost layer absorbs oil and swells, causing a phenomenon such as deformation due to the bimetal effect.

In particular, the filler may contain as much as 50 to 60%, and often 80 to 90% of the oil component, and in such a case, the above-mentioned defects are extremely remarkable. Furthermore, recently, due to reasons such as palatability, it is often the case that various flavors such as menthol-based and mint-based flavors, other flavors, vitamin E and various extracts are blended, and these components are also used as the inner layer material of the container. There is a problem in that the expected effect is lost due to a decrease in the compounding effect because phenomena such as permeation, permeation or adsorption into the drug occur and these medicinal components decrease.

Therefore, in order to solve such a problem,
Japanese Examined Patent Publication No. 60-26008 and Japanese Patent Laid-Open No. 21964/1990.
As disclosed in Japanese Patent Laid-Open Publication No. 6-84, it has been proposed to use an ethylene-vinyl alcohol copolymer in the innermost layer of a tubular container, and Japanese Patent Laid-Open Publication Nos.
It has been proposed to use resins such as nylon and polyethylene terephthalate, as disclosed in Japanese Patent Publication No. 92880, Japanese Patent Application Laid-Open No. 62-53817 and Japanese Patent Publication No. 63-50260.

However, in these cases, although the inner layer material has a blocking effect against oil and the like, the pinch-off adhesive property and the heat seal property are inferior, which is not satisfactory at all. Furthermore, when a resin such as ethylene-vinyl alcohol copolymer, nylon or polyethylene terephthalate is used as the material for the inner layer of the container, the container itself has a stiff and hard feel, and a soft squeeze peculiar to the polyolefin resin. It is not possible to expect the properties and squeezability, and the value as a container will be halved by itself.
That is, the goodness of the plastic container is that it is lighter than a glass bottle or a pottery container and less likely to break, and it has the feature that the contents can be easily taken out by squeezing the bottle or squeezing the tube. Such features are halved.

Further, when a container is formed by laminating a resin such as nylon or polyethylene terephthalate and a polyolefin resin, the molding itself is difficult because the optimum processing temperature is different, and the shrinkage rate is forced even if the molding is forced. There is a problem that the container becomes a deformed container due to the difference in

[0009]

DISCLOSURE OF THE INVENTION It is an object of the present invention to have excellent oil resistance, for example, it does not cause deformation or swelling during storage even for oily contents, and is rich in flexibility, squeeze property and squeeze property,
Furthermore, it is to provide a resin composition and a container which are suitable as a constituent material of a container having excellent pinch-off adhesiveness and heat sealability.

The object of the present invention is to select at least one resin selected from the group consisting of non-crystalline or low crystalline polyester resins and polyamide resins having a glass transition temperature of about 50 ° C. or more and a glass transition temperature of about A resin composition characterized by being blended with at least one resin selected from the group consisting of polyester resins and polyamide resins of 40 ° C. or lower (either crystalline or non-crystalline) To be achieved.

A resin selected from the group consisting of non-crystalline or low-crystalline polyester resins and polyamide resins having a glass transition temperature (Tg) of about 50 ° C. or higher, more preferably about 60 ° C. or higher, and a glass transition. Temperature (Tg) is about 40
C. or less, more preferably about 30.degree. C. or less, and even more preferably about 20.degree. C. or less, the ratio of the resin selected from the group of polyester resins and polyamide resins is 1
0 to 95 parts by weight, preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, the latter resin being 90
-5 parts by weight, preferably 80-20 parts by weight, more preferably 70-30 parts by weight.

Further, at least one resin selected from the group of non-crystalline or low crystalline polyester resins and polyamide resins having a high glass transition temperature, and the group of polyester resins and polyamide resins having a low glass transition temperature. At least one resin selected from the above (either crystalline or non-crystalline) is blended, and the temperature dependence of tan δ obtained by dynamic viscoelasticity measurement of this blended resin is This is achieved by a resin composition having two peaks.

Two peaks appearing in the temperature dependence of tan δ obtained by the dynamic viscoelasticity measurement of this blended resin are the dynamic viscoelasticity measurement of an amorphous or low crystalline resin having a high glass transition temperature. Is lower than the peak position appearing in the temperature dependence of tan δ, and higher than the peak position appearing in the temperature dependence of tan δ obtained by dynamic viscoelasticity measurement of a resin having a low glass transition temperature. It is preferable that they are blended so as to be on the temperature side, and tan δ obtained by dynamic viscoelasticity measurement of the blended resin.
It is preferable that one of the two peaks appearing in the temperature dependence of 1 is on the temperature side lower than room temperature, and the other is on the temperature side higher than room temperature.

More preferably, at least one resin selected from the group consisting of non-crystalline or low-crystalline polyester resins and polyamide resins having a glass transition temperature of about 50 ° C. or higher and a glass transition temperature of about 40. A blend of at least one resin selected from the group consisting of polyester resins and polyamide resins (both crystalline and non-crystalline ones) at a temperature of ℃ or below, and measured the dynamic viscoelasticity of this blended resin. It is preferable that the temperature dependence of tan δ obtained by the method has two peaks.

That is, the resin composition constituted as described above is excellent in oil resistance, and does not deform or swell during storage, for example, even for contents having a large amount of oil, and is highly flexible and squeeze. It has excellent adhesiveness and squeezing property, as well as pinch-off adhesiveness and heat sealability, and containers made of such resin compositions have various animal and plant properties such as skin care, hair care, other cosmetics, and foods. Oils and fats, their transesterified derivatives, isoparaffins, silicone oils and other synthetic oils, and various flavors such as menthol and mint for flavor and other flavors, and other flavors and vitamin E. It is suitable as a container for those containing various ingredients such as or. In particular, the resin composition of the present invention has good moldability, and has excellent melt adhesion, yet has appropriate flexibility, does not exhibit a stiff feel, and is combined with a polyolefin resin or the like. Excellent container is obtained.

In the present invention, the glass transition temperature (Tg)
Is a differential scanning calorimeter (DSC-manufactured by Seiko Denshi Kogyo Co., Ltd.) of a sample melted at 240 ° C. and then rapidly cooled to 20 ° C.
Type 220) 1 at 30 ° C above melting point
Hold for 0 minutes, then rapidly cool to a temperature 50 ° C lower than the glass transition point and hold for about 10 minutes, then 20 ° C / min
It was measured at the temperature rising rate of. Crystallinity is maintained at a temperature 30 ° C above the melting point for 10 minutes and then 5 ° C above the melting point.
After quenching to 0 ° C lower temperature and holding for about 10 minutes,
A peak based on crystal melting was measured at a temperature rising rate of ° C / min, and judged by the size of the peak area. That is, DSC
In the measurement chart, a resin having a peak area of 20 mJ / g or less is called a low crystalline resin, and a resin having a peak area of 5 mJ / g or less is called an amorphous resin. Moreover, the dynamic viscoelasticity is measured by 24
A sample that was melted at 0 ° C. and then rapidly cooled to 20 ° C. was used for a dynamic viscoelasticity measuring device (RSA-II, manufactured by Rheometric Co., Ltd., frequency 1 Hz, strain 0.1%, measurement temperature −100 to −).
140 ° C., 3 ° C., temperature holding time 1 minute).

The present invention will be described in more detail below. At least one resin selected from the group of non-crystalline or low-crystalline polyester resin and polyamide resin having high Tg, and at least one resin selected from the group of polyester resin and polyamide resin having low Tg Is blended, and the blended resin having two peaks in the temperature dependence of tan δ obtained by the dynamic viscoelasticity measurement of this blended resin has a high Tg resin and a low Tg resin, and It is considered to be separated.

Regarding the temperature dependence of tan δ of the polyester resin or the polyamide resin alone before blending, there is only a single peak at the temperature due to each Tg. Of the two peaks of tan δ of the blended resin, the position of the peak existing on the high temperature side is Tg.
Is caused by the Tg of the polyester resin or the polyamide resin having a high Tg, but by blending with the polyester resin or the polyamide resin having a low Tg, the temperature is shifted to a slightly lower temperature side, and the position of the peak existing on the other lower temperature side is Tg. Low Tg of polyester resin or polyamide resin
However, due to blending with a polyester resin or polyamide resin having a high Tg, the temperature shifts to a slightly high temperature side.

The position of the peak in the temperature dependence of the two tan δ of the blended resin is shifted from the peak position of the resin alone before blending because the polyester resin or polyamide resin having a high Tg and the polyester resin or polyamide having a low Tg. Some transesterification reaction with resin,
It is considered that amide exchange reaction and ester amide exchange reaction are occurring.

Polyester resin and polyamide resin having a high Tg are excellent in molding processability such as extrudability by a screw, but due to their high glass transition temperature (Tg), they exhibit high rigidity near room temperature, and particularly squeeze property. When used in the required container, it gives a stiff feel. On the other hand, a polyester resin or polyamide resin having a low Tg is excellent in flexibility because of its low glass transition temperature (Tg), but has a low melt viscosity and is difficult to be extruded by a screw. Is not good.

However, in the blended resin composition of the present invention, a polyester resin or polyamide resin having a high glass transition temperature (Tg) and a polyester resin or polyamide resin having a low glass transition temperature (Tg) are phase-separated from each other. , The characteristics of each other are complemented with each other, the moldability is good, and the melt adhesion is excellent, so the pinch-off adhesion and heat sealability are good, and also the flexibility is moderate, and the texture is stiff. The excellent container can be obtained even when combined with a polyolefin resin and the like, and the container has excellent oil resistance.

A polyester resin having a high Tg, such as Tg
The polyester resin having a temperature of 50 ° C. or higher uses at least one selected from the group of isophthalic acid, an isophthalic acid derivative and a terephthalic acid or a terephthalic acid derivative as a dicarboxylic acid component, and ethylene glycol and cyclohexanedimethanol as a glycol component. It can be configured by using at least one selected from the group.
A preferable combination of the dicarboxylic acid component and the glycol component is a terephthalic acid-ethylene glycol-cyclohexanedimethanol system or an isophthalic acid-terephthalic acid-ethylene glycol system. The preferred polymerization molar ratio in the system of terephthalic acid-ethylene glycol-cyclohexanedimethanol is 1 terephthalic acid.
For 00, ethylene glycol is 60 to 90, and cyclohexanedimethanol is 40 to 10. Further, a preferable polymerization molar ratio in the system of isophthalic acid-terephthalic acid-ethylene glycol is 100% ethylene glycol.
In contrast, 5-30 for terephthalic acid and 7 for isophthalic acid
0 to 95. In addition to these, small amounts of other components may be used.

A polyester resin having a low Tg, such as Tg
Polyester resins having a temperature of about 40 ° C. or less are terephthalic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid as dicarboxylic acid components. , Cyclopropanedicarboxylic acid,
At least one selected from the group of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid and the former derivative is used, among which succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacine Acid, nonamethylenedicarboxylic acid, using at least one selected from the aliphatic dicarboxylic acid and its derivative group such as decamethylenedicarboxylic acid, ethylene glycol as a glycol component,
At least one selected from the group of diethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, cyclohexanedimethanol, hydroquinone, and resorcin is used, among which diethylene glycol is used. , Propylene glycol, butylene glycol, 1,6-hexanediol, polyethylene glycol, polytetramethylene glycol, cyclohexanedimethanol, at least one selected from the group of aliphatic or alicyclic glycols having 3 or more carbon atoms is used. Can be configured as It can also be constituted by using a hydroxycarboxylic component such as p-oxybenzoic acid. A preferable combination of the dicarboxylic acid component and the glycol component is a polymer composed of a combination of terephthalic acid-isophthalic acid-adipic acid (as required) -butylene glycol, and a preferable copolymerization molar ratio is 30 to 75: 5. 35: 0 to 50: 1
00. In addition to these, small amounts of other components may be used.

A polyamide resin having a high Tg, for example, a polyamide resin having a Tg of about 50 ° C. or higher is succinic acid which is a dicarboxylic acid component of an aliphatic or alicyclic polyamide resin,
Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid,
At least one selected from the group of aliphatic or alicyclic dicarboxylic acids such as decamethylene dicarboxylic acid, cyclopropane dicarboxylic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid and cyclohexane dicarboxylic acid, and trimethylene which is a diamine component. At least one selected from the group of aliphatic or alicyclic diamines such as diamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, polyalkylenepolyamine, polyetherpolyamine and piperazine, and further aromatic polyamide resin Dicarboxylic acid components such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or diamine components of aromatic polyamide resin such as phenylenediamine, m-xylenediamine, benzidine, 4, '- diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'
-Diaminodiphenyl sulfide and 4,4'-diaminodiphenyl sulfone can be used. Further, ε-caprolactam, which is a component of the aliphatic polyamide resin,
ω-aminoenanthlactam, aliphatic lactams such as ω-capryllactam, ω-aminoenanthic acid,
At least one selected from the group of aliphatic amino acids such as 11-aminoundecanoic acid and ε-aminocaproic acid, and at least one selected from the dicarboxylic acid component or the diamine component of the aromatic polyamide resin are used. Can be configured as It can also be constituted by using an aromatic amino acid such as p-aminobenzoic acid which is a component of an aromatic polyamide resin and at least one selected from a dicarboxylic acid component and a diamine component of an aliphatic polyamide resin. In addition to these, other components may be used in small amounts.

A polyamide resin having a low Tg, for example, a polyamide resin having a Tg of about 40 ° C. or lower, is a dicarboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid,
Nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid, using at least one selected from the group of lauric acid, hexamethylenediamine as a diamine component,
At least one selected from the group consisting of heptamethylenediamine, octamethylenediamine, nonamethylenediamine, and decamethylenediamine can be used. Further, it can be constituted by using at least one selected from ω-aminododecanoic acid and 11-aminoundecanoic acid. In addition, terephthalic acid, isophthalic acid,
Succinic acid, glutaric acid, cyclopropanedicarboxylic acid,
Dicarboxylic acid components such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid and cyclohexanedicarboxylic acid, polyalkylenepolyamines, phenylenediamines, m-xylenediamines, benzidines, 4,4'-diaminodiphenylmethanes, 4,4'-diaminodiphenylethers, Diamine components such as 4,4′-diaminodiphenyl disulfide, 4,4′-diaminodiphenyl sulfone and piperazine, ε-caprolactam, ω-
Amino enantolactam, ω-capryllactam, ω-
It may be constituted by using a small amount of a lactam such as decanolactam, or an amino acid such as ω-aminoenanthic acid, ω-aminocaproic acid or p-aminobenzoic acid.

When the resin composition of the present invention is used as a container material, a single layer type container (or container body) can be formed using only this, but it can be formed into multiple layers to form the innermost layer. The blended resin of the present invention may be used. As the layer structure, for example, the following two kinds two layers, three kinds three layers, four kinds five layers and the like can be considered, but if the blend resin of the present invention is used for the innermost layer, any structure is possible. Good.

Outermost layer / Innermost layer Two kinds / two layers Polyolefin resin / blended resin composition of the present invention Two kinds / two layers Blend composition of polyolefin resin and adhesive resin / Blend resin composition of the present invention Three kinds / three layers Polyolefin-based resin / adhesive resin / blended resin composition of the present invention Four-layer / five-layer polyolefin-based resin / adhesive resin / gas barrier resin / adhesive resin / blended resin composition of the present invention Here, polyolefin-based resin As low density polyethylene resin (LDPE), linear low density polyethylene resin (LLDPE), high density polyethylene resin (HDP)
E), homopolypropylene, block polypropylene,
Random polypropylene etc. are mentioned.

Examples of the adhesive resin include α, β-unsaturated acid anhydride modified products, α, β-unsaturated ester modified products, epoxy modified products, and ethylene-vinyl acetate copolymers of the above polyolefin resins. Is mentioned. As the gas barrier resin, ethylene-vinyl alcohol copolymer, M
Examples include X nylon, polyacrylonitrile, and polyvinylidene chloride.

The thickness of the innermost layer in these layer constitutions, that is, the thickness of the blended resin composition of the present invention is preferably 5 μm or more, more preferably 20 μm or more from the viewpoint of oil resistance. The thickness of the gas barrier resin layer is 10
It is preferably 0 μm or less, and more preferably 50 μm or less. The blended resin composition of the present invention can be used in a hollow container by an extrusion blow molding method, or can be used as a laminated sheet with aluminum foil, paper, resin, etc., for a tubular container, pouch, pillow packaging, etc. You can also

What is filled in these containers is
Vegetable oils such as soybean oil, cottonseed oil, corn oil, sesame oil, rapeseed oil, olive oil, camellia oil, castor oil, palm oil, coconut oil, sardine oil, whale oil, bone oil, beef tallow,
Animal fats and oils such as pork fat, sheep fat, horse fat, butter fat, caproic acid and capric acid obtained by hydrolyzing the fats and oils,
Organic acids having 4 to 30 carbon atoms such as lauric acid, oleic acid, linoleic acid, stearic acid, monoglyceride, diglyceride derivatives, synthetic organic acids, liquid paraffin, kerosene, kerosene, naphtha, ligroin, cetene, octene, cetane, octane, Hydrocarbons such as decane, dodecane, octadecane, etc., ester oils such as octyl laurate, dioctyl phthalate, butyl lauryl phthalate, dibutyl phthalate, 2-ethylhexyl laurate, isopropyl palmitate, octyl alcohol, lauryl alcohol, oleyl alcohol, 2 -C4-C30 linear or branched alcohols such as ethylhexyl alcohol and Guerbet alcohol, other mineral oils,
Oily ingredients such as lanolin, petrolatum, beeswax, polypropylene glycol, polyoxyethylene sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan dioleate, propylene glycol monolaurate, glyceryl monostearate Rate, propylene glycol monostearate, ethylene glycol monostearate, polyoxyethylene alkyl phenyl ether, polyoxypropylene alkyl ether, and other surfactants, especially nonionic surfactants with an HLB value of 15 or less, especially strong oiliness Nonionic surfactant with HLB value of 15 or less, baby oil, emollient lotion, moisture lotion, massage lotion, cleansing lotion, etc. Various skin lotions, cosmetic creams, vanishing creams, skin creams such as emollient creams, shaving creams, hair removers, split-hair coat creams, hairdressing oils and other cosmetics, fragrances, cooking oils, salad oils, Italian dressing, French dressing Examples thereof include oily dressings such as, mayonnaise, and household products such as floor waxes, but are not limited thereto.

[0031]

[Examples] Specific examples will be described below.
The invention is not limited to only these examples. [Example 1] terephthalic acid-ethylene glycol-cyclohexanedimethanol (molar ratio 100: 72: 2
8) 50 parts by weight of a non-crystalline polyester resin (A) having a Tg of 81 ° C. and terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio is 47:29:
24: 100) and a Tg of 1.0 ° C. were blended with 50 parts by weight of a polyester resin (B) to obtain a blended resin according to the present invention.

The blended resin according to the present invention is a twin-screw extruder (Labo Plastomill manufactured by Toyo Seiki Seisakusho: Basic device; 30-150 type, measuring head; 2D25-S type, screw; Screw), cylinder set temperature 180-220 ° C, screw rotation speed 8
The mixture was kneaded and extruded under the condition of 0 rpm. The extruded strand-shaped blended resin is immediately cooled in a water tank, cut into pellets by a pelletizer, and then 30 ° C to 50 ° C.
It was vacuum dried for 24 hours. Then, the pellet-shaped blended resin was pressed at 200 ° C., rapidly cooled to 20 ° C. to form a sheet, and the sheet was appropriately cut to measure the dynamic viscoelasticity.

The results of the temperature dependence of tan δ are shown in FIG. The tan δ of each of the resin (B) and the resin (A) is 8
Although a single peak is shown at around 80 ° C and 85 ° C, the tan δ of the blend resin of this example is such that the peak around 23 ° C due to the resin (B) and the peak around 63 ° C due to the resin (A). There are two peaks at. Further, as a result of dyeing the blended resin of this example by a usual method and observing it with a transmission electron microscope, it was found that this blended resin had a sea-island structure and two phases were separated.

Example 2 Terephthalic acid-ethylene glycol-cyclohexanedimethanol (molar ratio 10
0:72:28) consisting of 70 parts by weight of a non-crystalline polyester resin (A) having a Tg of 81 ° C. and terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio 55: 14: 31: 100). Tg is -5.5 ° C
30 parts by weight of the polyester resin (B) was blended to obtain a blended resin according to the present invention.

Then, in the same manner as in Example 1, the dynamic viscoelasticity of this blend resin was measured. The results of the temperature dependence of tan δ are shown in FIG. Resin (B) and resin (A)
Each tan δ shows a single peak at around −3 ° C. and 85 ° C., but the tan δ of the blended resin of this example is due to the peak near 13 ° C. due to the resin (B) and the resin (A). Two peaks are seen, such as the peak near 72 ° C.

Further, as a result of dyeing the blended resin of this example by a usual method and observing it with a transmission electron microscope, it is found that this blended resin has a sea-island structure and is separated into two phases. understood. [Example 3] Terephthalic acid-ethylene glycol-cyclohexanedimethanol (molar ratio 100: 72: 2
8) 50 parts by weight of a non-crystalline polyester resin (A) having a Tg of 81 ° C. and terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio 34:21:
45: 100) having a Tg of -19.4 ° C was blended with 50 parts by weight of a polyester resin (B) to obtain a blended resin according to the present invention.

Then, in the same manner as in Example 1, the dynamic viscoelasticity of this blend resin was measured. The results of the temperature dependence of tan δ are shown in FIG. Resin (B) and resin (A)
The tan δ of each of them shows a single peak at around -17 ° C. and 85 ° C., but the tan δ of the blend resin of this example is due to the resin (B) at around -15 ° C. and the resin (A).
There are two peaks such as a peak near 78 ° C. due to

Further, as a result of dyeing the blended resin of this example by a usual method and observing it with a transmission electron microscope, it is found that this blended resin has a sea-island structure and is separated into two phases. understood. Example 4 Tg composed of terephthalic acid-isophthalic acid-ethylene glycol (molar ratio 11: 89: 100)
Of 62 parts by weight of a non-crystalline polyester resin having a temperature of 62 ° C. and a terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio 55: 14: 31: 100) polyester resin having a Tg of −5.5 ° C. ( B) 30 parts by weight were blended to obtain a blend resin according to the present invention.

Then, in the same manner as in Example 1, the dynamic viscoelasticity of this blend resin was measured. The results of the temperature dependence of tan δ are shown in FIG. Resin (B) and resin (A)
The tan δ of each of them shows a single peak at around −3 ° C. and 69 ° C., but the tan δ of the blend resin of this example is due to the peak at around 10 ° C. due to the resin (B) and the resin (A). Two peaks are seen, such as the peak at around 65 ° C.

Further, as a result of dyeing the blended resin of this example by a usual method and observing it with a transmission electron microscope, it is found that this blended resin has a sea-island structure and is separated into two phases. understood. Example 5 Tg composed of terephthalic acid-isophthalic acid-ethylene glycol (molar ratio 11: 89: 100)
Having a Tg of 1.0 ° C., which comprises 60 parts by weight of an amorphous polyester resin (A) having a temperature of 62 ° C. and terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio is 47: 29: 24: 100). 40 parts by weight of the resin (B) was blended to obtain a blended resin according to the present invention.

Then, in the same manner as in Example 1, the dynamic viscoelasticity of this blend resin was measured. The results of the temperature dependence of tan δ are shown in FIG. Resin (B) and resin (A)
The tan δ of each of them shows a single peak at around 8 ° C. and 69 ° C., but the tan δ of the blended resin of this example is due to the peak near 16 ° C. due to the resin (B) and 65 due to the resin (A). Two peaks are seen, such as a peak near ℃.

Further, as a result of dyeing the blended resin of this example by a usual method and observing it with a transmission electron microscope, it is found that this blended resin has a sea-island structure and is separated into two phases. understood. [Example 6] Amorphous polyamide resin (A) 50 made of Novamid X21 (manufactured by Mitsubishi Kasei) and having a Tg of 125 ° C.
Parts by weight, terephthalic acid-isophthalic acid-adipic acid-
Butylene glycol (molar ratio is 47: 29: 24: 10
0) Polyester resin (B) 5 having Tg of 1.0 ° C.
0 part by weight was blended to obtain a blend resin according to the present invention.

Then, in the same manner as in Example 1, the dynamic viscoelasticity of this blend resin was measured. The results of the temperature dependence of tan δ are shown in FIG. Resin (B) and resin (A)
The tan δ of each of them shows a single peak at around 8 ° C. and 135 ° C., but the tan δ of the blended resin of this example has a peak near 10 ° C. due to the resin (B) and 127 due to the resin (A). Two peaks are seen, such as a peak near ℃.

Further, as a result of dyeing the blended resin of this example by a usual method and observing it with a transmission electron microscope, it was found that this blended resin had a sea-island structure and was separated into two phases. understood. [Example 7] Tg of Novamid X21 was 125 ° C.
50 parts by weight of the non-crystalline polyamide resin (A) and 50 parts by weight of a polyamide polyamide resin (B) having a Tg of 24 ° C. composed of Daiamide 471 (manufactured by Daicel Hüls) are blended according to the present invention. A resin was obtained.

Then, in the same manner as in Example 1, the dynamic viscoelasticity of this blend resin was measured. The result of the temperature dependence of tan δ is shown in FIG. 7. Resin (B) and resin (A)
The tan δ of each of them shows a single peak at around 23 ° C. and 135 ° C., but the tan δ of the blended resin of this example has a peak at around 33 ° C. due to the resin (B) and 123 due to the resin (A). Two peaks are seen, such as a peak near ℃.

Further, as a result of dyeing the blended resin of this example by a usual method and observing it with a transmission electron microscope, it is found that this blended resin has a sea-island structure and is separated into two phases. understood. Example 8 Terephthalic acid-ethylene glycol-cyclohexanedimethanol (molar ratio 100: 72: 2
The present invention is obtained by blending 50 parts by weight of an amorphous polyester resin (A) having a Tg of 81 ° C., which is 8), and 50 parts by weight of a copolyamide resin (B) having a Tg of 24 ° C., which is composed of diamide 471. A blended resin was obtained.

Then, in the same manner as in Example 1, the dynamic viscoelasticity of this blend resin was measured. The results of the temperature dependence of tan δ are shown in FIG. Resin (B) and resin (A)
The tan δ of each of them shows a single peak at around 23 ° C. and 85 ° C., but the tan δ of the blended resin of the present example has a peak near 33 ° C. due to the resin (B) and 81 due to the resin (A). Two peaks are seen, such as a peak near ℃.

Further, as a result of dyeing the blended resin of this example by a usual method and observing it with a transmission electron microscope, it is found that this blended resin has a sea-island structure and is separated into two phases. understood. Example 9 Terephthalic acid-ethylene glycol-cyclohexanedimethanol (molar ratio 100: 72: 2
50 g by weight of the amorphous polyester resin (A) having a Tg of 81 ° C. of 8) and a Tg of −0.2 ° C. composed of terephthalic acid-isophthalic acid-butylene glycol (molar ratio 72: 28: 100). A blended resin according to the present invention was obtained by blending 50 parts by weight of the polyester resin (B).

Then, in the same manner as in Example 1, the dynamic viscoelasticity of this blend resin was measured. The result of the temperature dependence of tan δ is shown in FIG. Resin (B) and resin (A)
The tan δ of each of them shows a single peak at around 5 ° C. and 85 ° C., but the tan δ of the blend resin of this example is 45 ° C.
A broad peak can be seen in the vicinity. The blended resin of this example was dyed by a usual method and observed with a transmission electron microscope. As a result, a uniform image was observed.

[Embodiment 10] Sholex 5 as the outermost layer
003 (Showa Denko, HDPE), Admer AT (Mitsui Petrochemical Co., Ltd., adhesive polyolefin) for the middle layer, and the blend resin of Example 1 for the innermost layer,
Flat bottle of 3 types and 3 layers (long diameter 65 mm, short diameter 35 mm,
Inner volume 300ml, outermost layer thickness 450μ in the body
m, the thickness of the intermediate layer is 50 μm, the thickness of the innermost layer is 100 μm)
Was molded.

A direct blow molding machine having a multi-layer molding head was used for molding, the extruder cylinder temperature of the resin of the outermost layer and the intermediate layer was 150 to 210 ° C., the extruder cylinder temperature of the resin of the innermost layer was 140 to 210 ° C. The molten resin was extruded at 200 ° C. to form a cylindrical parison, which was sandwiched by molds, and then compressed air was blown into the parison to form a flat bottle.

[Example 11] A flat bottle of three types and three layers was molded by using the blend resin of Example 2 instead of the blend resin used in Example 10. [Example 12] The blend resin of Example 3 was used in place of the blend resin used in Example 10, and a flat bottle of three types and three layers was molded.

Example 13 A flat bottle having three layers and three layers was molded by using the blend resin of Example 6 instead of the blend resin used in Example 10. Example 14 The blend resin of Example 7 was used in place of the blend resin used in Example 10, and a flat bottle of three types and three layers was molded.

Example 15 The blend resin of Example 9 was used in place of the blend resin of Example 10, and a flat bottle having three layers and three layers was molded. [Example 16] A three-kind three-layer tubular container was formed by using Mirason 50 (LDPE manufactured by Mitsui Petrochemical Industry Co., Ltd.) as the outermost layer, Admer AT as the middle layer, and the blend resin of Example 8 as the innermost layer. ..

The molding was carried out by using an internal cooling mandrel type coextrusion tube molding machine and extruding each resin at an extruder cylinder temperature of 150 to 180 ° C. to obtain a pipe-shaped molded product of three kinds and three layers having a diameter of 35 mm. .. The thickness of the obtained pipe-shaped molded product was 350 μm for the outermost layer and 50 μm for the intermediate layer.
The innermost layer is 50 μm. This pipe-shaped molded product
It was cut into a length of mm, and the above blended resin was further injected by a vertical injection molding machine to form a head portion with a screw portion at one end to obtain a tubular container having a capacity of about 120 ml.

Example 17 The blended resin of Example 1 was used in place of the blended resin used in Example 16 to form a three-kind three-layer tubular container. [Example 18] Low-density polyethylene / Admer LF (Mitsui Petrochemical Co., Ltd., adhesive polyolefin) / Eval EP-E (Kuraray Co., ethylene-vinyl alcohol copolymer) / Admer AT / Blend of Example 4 A tubular container having five layers and five layers having a layered structure such as a resin was molded.

[Example 19] The blend resin of Example 5 was laminated on a two-layer sheet consisting of a low-density polyethylene layer and an adhesive layer by a T-die extruder to prepare a three-kind three-layer laminated sheet. The thickness of each layer is 40 μm for the low density polyethylene layer, 20 μm for the adhesive layer, and 20 μm for the blend resin layer.

Two sheets of this laminated sheet were stacked with the blend resin inside and heat-sealed in a 10 cm square on three sides to form a pouch-shaped container. Example 20: Sholex 5003 as the outermost layer, Admer AT as the middle layer, and terephthalic acid-ethylene glycol-cyclohexanedimethanol (molar ratio: 10
0:72:28) and 60 parts by weight of a non-crystalline polyester resin having a Tg of 81 ° C. and terephthalic acid-isophthalic acid-butylene glycol (molar ratio 72: 28: 100).
A flat bottle of 3 types and 3 layers (long diameter 65 mm, short diameter 35 mm, internal volume 300 m) using a blended polyester resin with 40 parts by weight of Tg of 21 ° C.
1, the outermost layer thickness of the body portion was 450 μm, the intermediate layer thickness was 50 μm, and the innermost layer thickness was 100 μm.

A direct blow molding machine having a multi-layer molding head was used for molding, and the extruder cylinder temperature of the resin of the outermost layer and the intermediate layer was 150 to 210 ° C., and the extruder cylinder temperature of the resin of the innermost layer was 140 to 210 ° C. The molten resin was extruded at 200 ° C. to form a cylindrical parison, which was sandwiched between molds, and compressed air was blown into the parison to form a bottle.

The blended polyester resin according to the present invention is preliminarily used in a twin-screw extruder, and the cylinder set temperature is 20.
The product was melt-blended at 0 to 280 ° C. and a screw rotation speed of 50 rpm. The product discharged from the discharge port of a twin-screw extruder was rapidly cooled with cooling water, cut with a cutter, and then vacuum-dried at room temperature for one day. .. Example 21 Instead of the blended polyester resin used in Example 20, terephthalic acid-ethylene glycol-cyclohexanedimethanol (molar ratio: 10
0:72:28) having a Tg of 81 ° C. and 50 parts by weight of an amorphous polyester resin and terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio: 55: 1).
The same procedure was performed using a blended polyester resin with 50 parts by weight of a polyester resin having a Tg of −31: 100) of −5.5 ° C. and a flat bottle of three types and three layers was molded.

Example 22 The blended polyester resin of Example 4 was used in place of the blended polyester resin used in Example 20, and a flat bottle of three types and three layers was molded in the same manner. Example 23 Instead of the blended polyester resin used in Example 20, terephthalic acid-isophthalic acid-ethylene glycol (molar ratio 11: 89: 100).
Amorphous polyester resin 50 having Tg of 62 ° C.
Parts by weight and terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio 47: 29: 24: 10
The same procedure was performed using a blended polyester resin containing 50 parts by weight of a polyester resin having Tg of 1.0) and having a Tg of 1.0 ° C., and a flat bottle of three types and three layers was molded.

Example 24 Instead of the blended polyester resin used in Example 20, terephthalic acid-
50 parts by weight of a low crystalline polyester resin having a Tg of 80 ° C. and composed of ethylene glycol-cyclohexanedimethanol (molar ratio 100: 85: 15) and terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio 55:14). : 31: 100) is -5.5.
A blended polyester resin with 50 parts by weight of a polyester resin at 0 ° C. was used, and Mirason 50 was used in place of Shorex 5003 in the same manner to form a flat bottle of three types and three layers.

Example 25 Terephthalic acid-ethylene glycol-cyclohexanedimethanol (molar ratio: 10
90 parts by weight of a non-crystalline polyester resin having a Tg of 81: 0:72:28) and terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio is 55: 1).
4: 31: 100) and a blended polyester resin with 10 parts by weight of a polyester resin having a Tg of −5.5 ° C. were subjected to direct blow molding using a single-layer direct blow molding machine to mold a flat bottle having a capacity of 300 ml.

Example 26 Mirason 50 as the outermost layer, Admer AT as the intermediate layer, and terephthalic acid-ethylene glycol-cyclohexanedimethanol as the innermost layer (molar ratio: 1
00:72:28) having a Tg of 81 ° C. and 75 parts by weight of an amorphous polyester resin and terephthalic acid-isophthalic acid-adipic acid-butylene glycol (the molar ratio is 55:
A 14: 31: 100) Tg of -5.5 ° C and a blended polyester resin with 25 parts by weight of a polyester resin were used to form a three-kind three-layer tubular container.

The molding was carried out by using an internal cooling mandrel type co-extrusion tube molding machine and extruding each resin at an extruder cylinder temperature of 150 to 180 ° C. to obtain a pipe-shaped molded product of three kinds and three layers having a diameter of 35 mm. .. The thickness of the obtained pipe-shaped molded product was 350 μm for the outermost layer and 50 μm for the intermediate layer.
The innermost layer is 50 μm. This pipe-shaped molded product
It was cut into a length of mm, and the above blended polyester resin was further injected with a vertical injection molding machine to form a head portion with a screw portion at one end to obtain a tubular container having a capacity of about 120 ml.

[Example 27] Mirason 50 (outermost layer side)
-Admer LF-Eval EP-E-Admer AT-blend polyester resin (terephthalic acid-ethylene glycol-cyclohexanedimethanol (molar ratio 10
60 parts by weight of an amorphous polyester resin having a Tg of 81 ° C. and a terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio is 47: 2).
9: 24: 100) and a blended polyester resin with 40 parts by weight of a polyester resin having a Tg of 1.0 ° C.) and a pipe-shaped molded product of five kinds and five layers was obtained in the same manner as in Example 26. The thickness of each layer is 300μ from the outermost layer side.
m, 40 μm, 20 μm, 40 μm, 50 μm.
After this, the pipe-shaped molded product is cut into a length of 130 mm, and Admer AT is further injected with a vertical injection molding machine,
A head with a threaded portion was formed at one end to obtain a tubular container having a capacity of about 120 ml.

Example 28 A two-layer sheet composed of an LDPE layer and an adhesive resin was added to a blended polyester resin (terephthalic acid-isophthalic acid-ethylene glycol (molar ratio 11: 89: 100) and had a Tg of 62 ° C. 40 parts by weight of amorphous polyester resin and terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio: 5
5: 14: 31: 100) having a Tg of −5.5 ° C. and 60 parts by weight of a polyester resin blended polyester resin) were laminated by a T-die extruder to prepare a three-kind three-layer laminated sheet. The thickness of each layer is LD
The PE layer is 40 μm, the adhesive resin layer is 20 μm, and the blended polyester resin layer is 20 μm.

The two laminated sheets were laminated with the blend polyester resin layer side facing inward, and 10 cm in length.
The corners were heat-sealed on three sides to form a pouch-shaped container. [Comparative Example 1] Using Mirason 50, a single-layer flat bottle was molded in the same manner as in Example 10. [Comparative Example 2] A single-layer flat bottle was molded using Sholex 5003 in the same manner as in Example 10.

[Comparative Example 3] A layer structure of Shorex 5003 (outermost layer side) / Admer HB030 (adhesive resin manufactured by Mitsui Petrochemical Co., Ltd.) / Eval EP-E (innermost layer side) was used as in Example 10. A flat bottle was molded in the same manner. [Comparative Example 4] Shorex 5003D (Mitsui Petrochemical Co., Ltd., high-density polyethylene, outermost layer side) / Admer AT / terephthalic acid-isophthalic acid-adipic acid-ethylene glycol-butylene glycol-cyclohexanedimethanol (molar ratio: 147: 29: 24: 72: 1
A flat bottle was molded in the same manner as in Example 10 with a layer structure consisting of a copolyester resin having a Tg of 40 ° C. at 00:28 and the innermost layer side.

[Comparative Example 5] A flat bottle having the layer structure of Sholex 5003 (outermost layer side) / Admar HB030 / Eval EP-E / Admer LF500 / Shorex 5003 (innermost layer side) as in Example 10 Was molded. [Comparative Example 6] Shorex 5003 (outermost layer side) / Admar HB030 / Eval EP-E / Admar LF5
Example 1 using 00 / Himilan 1652 (Ionomer, manufactured by Mitsui DuPont Polychemical Co., Ltd.) (innermost layer side)
A flat bottle was molded in the same manner as in No. 0.

[Comparative Example 7] Shorex 5003 (outermost layer side) / Admer AT / J-125 (polyethylene terephthalate manufactured by Mitsui Pet Co., Tg 78 ° C, intrinsic viscosity [η] 0.77, crystalline) Using the (innermost layer side), a flat bottle was molded in the same manner as in Example 10.

[Comparative Example 8] Terephthalic acid-ethylene glycol-cyclohexanedimethanol (molar ratio: 10
0:72:28) using a noncrystalline polyester resin having a Tg of 81 ° C.
1, the thickness of the body portion was 600 μm).

A direct blow molding machine is used for molding, the extruder cylinder temperature is 220 ° C., the molten resin is extruded to form a cylindrical parison, and the parison is sandwiched by a mold, and then compressed into a parison. Was blown into a bottle. [Comparative Example 9] Terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio: 55: 14: 31: 1)
It was attempted to mold a flat bottle with a direct blow molding machine using a polyester resin having a Tg of 00) of −5.5 ° C. However, a parison could not be formed and the bottle could not be molded.

Comparative Example 10 Using Mirason 50, a single-layer tubular container having a thickness of 450 μm was molded in the same manner as in Example 16. [Comparative Example 11] Mirason 50 (350 μm) (outermost layer side) / Admer LF500 (50 μm) / Eval EP
A tubular container was molded in the same manner as in Example 16 with a layer configuration of -E (50 μm) (innermost layer side).

[Comparative Example 12] Mirason 50 (300 μm)
m) (outermost layer side) / Admer LF500 (40 μm) /
Eval EP-E (20 μm) / Admar LF500
(40 μm) / Mirason 50 (50 μm) (innermost layer side)
A tube-shaped container was molded in the same manner as in Example 16 with the above layer structure.

Comparative Example 13 Mirason 50 (80 μm)
The two single-layer sheets of were laminated and heat-sealed on a 10 cm square on three sides to form a pouch-shaped container. [Characteristics] The oil resistance and flexibility of the blended resins and Mirason 50 obtained in each of the above examples (Examples 1 to 9) were examined, and the results are shown in Table 1.

[Oil resistance]: 2 after melting at 240 ° C.
Test pieces (5 x 23
X 0.5 mm) is cut out, the surface is washed with methanol, precisely weighed, and immersed in isoparaffin at 40 ° C for 24 hours. After that, wipe off the oil on the surface with filter paper, weigh accurately,
Weight change is calculated and evaluated by this. [Flexibility]: A test piece (5 × 23 × 0.5 m) from a hot-pressed sheet that was melted at 240 ° C. and then rapidly cooled to 20 ° C.
m) is cut out and measured with a dynamic viscoelasticity measuring device (RSA-II type, manufactured by Rheometric Co.) (frequency: 1H).
z, measured temperature −100 to 140 ° C., every 3 ° C., temperature holding time 1 minute, strain 0.1%).

Table 1 Oil resistance (%) Flexibility (dyne / cm ² ) Example 1 0.03 1.2 × 10 ¹⁰ Example 2 0.02 1.3 × 10 ¹⁰ Example 3 0.03 4. 9 × 10 ⁹ Example 4 0.03 1.1 × 10 ¹⁰ Example 5 0.04 8.5 × 10 ⁹ Example 6 0.03 7.1 × 10 ⁹ Example 7 0.04 6.3 × 10 ⁹ Example 8 0.03 1.0 × 10 ¹⁰ Example 9 0.02 1.3 × 10 ¹⁰ Mirason 50 9.2 2.8 × 10 ⁹ Also, the above-mentioned examples (Examples 10 to 28 and comparison). Various characteristics of the containers obtained in Examples 1 to 8 and Comparative Examples 10 to 13 were examined, and the results are shown in Tables 2, 3, and 4.

[Pinch-off strength]: A bottle filled with water, sealed, and conditioned in a thermostatic chamber at 5 ° C. for 24 hours or more, and is free from the height of 1 m so that the bottom of the container hits a smooth concrete floor. The sample was dropped, and this was repeated up to 10 times, and the pinch-off portion was indicated by the number of times cracks, pinholes, etc., and cracks occurred.

[Heat-sealing property]: The opening of the container is heat-sealed with a hand sealer (made by Tadashi Yokoyama). The seal heater temperature is 500 ° C., the seal heating time is 9 seconds, and the seal time is 3 seconds. After sealing, heat seal 1
It was cut into a 5 mm wide strip, and a T-shaped peeling test was conducted using an autograph (manufactured by Shimadzu Corporation, AG-500B type) to measure the adhesive strength of the heat-sealed portion.

[Oil resistance]: Oil content in a container [isoparaffin (manufactured by Nippon Oil Co., Ltd.) 82%, glycerin (86% a
q) 15%, 3% highly polymerized silicone in a creamy content], and after tightly capping, temperature 40 ° C., humidity 80
It is stored for 3 months in a constant temperature and humidity chamber. Regarding the preserved products, the deformation of the container and the seepage of oil content were checked. [Squeeze property]: Pressure was applied to the side surface of the empty bottle (almost the center of the flat bottle) at a compression portion having a diameter of 10 mm using an autograph, and the displacement (dent) amount at a pressure of 1 Kgf was used for determination. ..

Table 2 Pinch off strength Squeeze resistance Oil resistance (mm / 1Kgf) Example 10 No cracking 9.5 ◎ to ○ Example 11 No cracking 8.0 ○ to ◎ Example 12 No cracking 7.5 ◎ Example 13 No cracking 6.2 ◎ to ○ Example 14 No cracking 6.7 ◎ to ○ Example 15 No cracking 5.0 ◎ Example 20 No cracking 6.5 ◎ Example 21 No cracking 8.1 ◎ to ○ Example 22 No cracking 8.5 ◎ Example 23 No cracking 10.0 ◎ to ○ Example 24 No cracking 20 <○ to ◎ Example 25 No cracking 7.2 ◎ Comparative example 1 No cracking 20 <× Comparative example 2 No cracking 5.5 △ Comparative Example 3 All cracks at once 3.5 ◎ Comparative Example 4 No cracking Great change with temperature ○ to ◎ Comparative Example 5 No cracking 5.0 △ Comparative Example 6 No cracking 6.5 × Comparative Example 7 Average Cracked twice 2 3.5 Comparative Example 8 Averaged 2 times Cracking 2.5 ◎ Table 3 Seal strength Flexibility Oil resistance (Kgf / 15mm) Deformation, swelling Oil leaching Example 16 4.7 Soft ◎ ~ ○ ◎ Example 17 5.0 Very soft ◎ ~ ○ ◎ Implemented Example 18 4.2 Flexible ◎ to ○ ◎ Example 26 4.2 Flexible ◎ ○ to ◎ Example 27 4.8 Flexible ◎ ◎ Comparative Example 10 5.0 Very flexible XX Comparative Example 11 0.8 Hard ◎ ○ Comparative Example 12 2.8 Somewhat hard ○ ○ Table 4 Heat-sealing property Flexibility Oil resistance (exudation of oil content) Example 19 Good softness ○ Example 28 Good softness ○ Comparative example 13 Good softness × Oil resistance (deformation, swelling) In the column, ◎ indicates no deformation or swelling due to oil, ○ indicates almost no deformation or swelling due to oil, Δ indicates deformation or swelling due to oil, and X indicates deformation or swelling due to oil. Large swelling is observed. In the column of oil resistance (oil content leaching), ○ marks show no bleeding to the surface, Δ marks partially bleed to the surface, and × marks show a lot of bleeding to the surface. There is stickiness. According to this, the resin composition according to the present invention is excellent in oil resistance, for example, does not cause deformation or swelling during storage even for oily contents, and is rich in flexibility, squeeze property and squeeze out. It can be seen that it is suitable as a constituent material of a container having excellent properties, further, pinch-off adhesiveness and heat sealability.

[Brief description of drawings]

FIG. 1 is a graph showing the temperature dependence of tan δ of the blend resin of Example 1.

FIG. 2 is a graph showing the temperature dependence of tan δ of the blend resin of Example 2.

FIG. 3 is a graph showing the temperature dependence of tan δ of the blended resin of Example 3.

FIG. 4 is a graph showing the temperature dependence of tan δ of the blend resin of Example 4.

FIG. 5 is a graph showing the temperature dependence of tan δ of the blend resin of Example 5.

FIG. 6 is a graph showing the temperature dependence of tan δ of the blended resin of Example 6.

FIG. 7 is a graph showing the temperature dependence of tan δ of the blended resin of Example 7.

FIG. 8 is a graph showing the temperature dependence of tan δ of the blend resin of Example 8.

FIG. 9 is a graph showing the temperature dependence of tan δ of the blend resin of Example 9.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 19, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction content]

In particular, the filler may contain as much as 50 to 60%, and often 80 to 90% of the oil component, and in such a case, the above-mentioned defects are extremely remarkable. Furthermore, recently, due to reasons such as palatability, it is often the case that various flavors such as menthol-based and mint-based flavors, other flavors, vitamin E and various extracts are blended, and these components are also used as the inner layer material of the container. There is a problem in that the effect of blending is reduced and the expected effect is lost because phenomena such as permeation, permeation or adsorption to the compound occur, and the amount of these active ingredients decreases.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

A polyester resin having a high Tg, such as Tg
The polyester resin having a temperature of 50 ° C. or higher uses at least one selected from the group of isophthalic acid, an isophthalic acid derivative and a terephthalic acid or a terephthalic acid derivative as a dicarboxylic acid component, and ethylene glycol and cyclohexanedimethanol as a glycol component. It can be configured by using at least one selected from the group.
A preferable combination of the dicarboxylic acid component and the glycol component is a terephthalic acid-ethylene glycol-cyclohexanedimethanol system or an isophthalic acid-terephthalic acid-ethylene glycol system. Then, terephthalic acid - ethylene glycol - preferred copolymerization molar ratio of cyclohexanedimethanol of the system, with respect to terephthalic acid 100, ethylene glycol 60-90, cyclohexanedimethanol is 40 to 10. In addition, the preferred polymerization molar ratio in the system of isophthalic acid-terephthalic acid-ethylene glycol is ethylene glycol 10
0 to terephthalic acid is 5 to 30, and isophthalic acid is 70 to 95. In addition to these, small amounts of other components may be used.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

A polyester resin having a low Tg, such as Tg
Polyester resin having a temperature of about 40 ° C. or less is terephthalic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid as a dicarboxylic acid component. , Cyclopropanedicarboxylic acid,
At least one selected from the group of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid and the former derivative is used, among which succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacine. Acid, nonamethylenedicarboxylic acid, using at least one selected from the aliphatic dicarboxylic acid and its derivative group such as decamethylenedicarboxylic acid, ethylene glycol as a glycol component,
At least one selected from the group of diethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, cyclohexanedimethanol, hydroquinone, and resorcin is used, among which diethylene glycol is used. , Propylene glycol, butylene glycol, 1,6-hexanediol, polyethylene glycol, polytetramethylene glycol, cyclohexanedimethanol, at least one selected from the group of aliphatic or alicyclic glycols having 3 or more carbon atoms is used. Can be configured as It can also be constituted by using a hydroxycarboxylic acid component such as p-oxybenzoic acid. A preferable combination of the dicarboxylic acid component and the glycol component is a polymer composed of a combination of terephthalic acid-isophthalic acid-adipic acid (as required) -butylene glycol, and a preferable copolymerization molar ratio is 30 to 75: 5. 35: 0 to 50:
100. In addition to these, small amounts of other components may be used.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

Polyamide resins having a high Tg, for example, polyamide resins having a Tg of about 50 ° C. or higher are succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid. Acid, cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid,
At least one selected from the group of aliphatic or alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, polyalkylenepolyamine, poly which is a diamine component. At least one selected from the group of aliphatic or alicyclic diamines such as ether polyamine and piperazine,
Furthermore, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, which are dicarboxylic acid components of aromatic polyamide resins, or phenylenediamine, m-xylenediamine, benzidine, 4,4′-diaminodiphenylmethane, which are diamine components of aromatic polyamide resins, and 4 , 4 '
-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide and 4,4'-diaminodiphenyl sulfone can be used. In addition, aliphatic lactams such as ε-caprolactam, ω-aminoenanthlactam, ω-capryllactam which are components of aliphatic polyamide resin, ω-aminoenanthic acid, 11-aminoundecanoic acid, ε-aminocaproic acid At least one selected from the group of aliphatic amino acids as described above and at least one selected from the dicarboxylic acid component or the diamine component of the aromatic polyamide resin can be used. It can also be constituted by using an aromatic amino acid such as p-aminobenzoic acid which is a component of an aromatic polyamide resin and at least one selected from a dicarboxylic acid component and a diamine component of an aliphatic polyamide resin. In addition to these, other components may be used in small amounts.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

What is filled in these containers is
Vegetable oils such as soybean oil, cottonseed oil, corn oil, sesame oil, rapeseed oil, olive oil, camellia oil, castor oil, palm oil, coconut oil, sardine oil, whale oil, bone oil, beef tallow,
Animal fats and oils such as pork fat, sheep fat, horse fat, butter fat, caproic acid and capric acid obtained by hydrolyzing the fats and oils,
Organic acids having 4 to 30 carbon atoms such as lauric acid, oleic acid, linoleic acid, stearic acid, monoglyceride, diglyceride derivatives, synthetic organic acids, liquid paraffin, kerosene, kerosene, naphtha, ligroin, cetene, octene, cetane, octane, Hydrocarbons such as decane, dodecane, octadecane, etc., ester oils such as octyl laurate, dioctyl phthalate, butyl lauryl phthalate, dibutyl phthalate, 2-ethylhexyl laurate, isopropyl palmitate, octyl alcohol, lauryl alcohol, oleyl alcohol, 2 -C4-C30 linear or branched alcohols such as ethylhexyl alcohol and Guerbet alcohol, other mineral oils,
Oily ingredients such as lanolin, petrolatum, beeswax, polypropylene glycol, polyoxyethylene sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan dioleate, propylene glycol monolaurate, glyceryl monostearate , Propylene glycol monostearate, ethylene glycol monostearate, polyoxyethylene alkyl phenyl ether, polyoxypropylene alkyl ether, and other surfactants, especially nonionic surfactants with a strong HLB value of 15 or less, baby Oil, emollient lotion,
Various skin lotions such as moisture lotion, massage lotion, cleansing lotion, skin cream such as make-up cream, vanishing cream, emollient cream, shaving cream, hair remover, split hair coat cream, hair styling oil and other cosmetics, fragrance field , Oily dressings such as cooking oil, salad oil, Italian dressing, and French dressing, mayonnaise, and household products such as floor wax, but are not limited thereto.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

Further, as a result of dyeing the blended resin of this example by a usual method and observing it with a transmission electron microscope, it is found that this blended resin has a sea-island structure and is separated into two phases. understood. Tg of Example 6 NOVAMID X21 (manufactured by Mitsubishi Chemical Industries, Ltd.)
Polyester having a Tg of 1.0 ° C., which is composed of 50 parts by weight of an amorphous polyamide resin (A) having a temperature of 125 ° C. and terephthalic acid-isophthalic acid-adipic acid-butylene glycol (molar ratio is 47: 29: 24: 100). The blended resin according to the present invention was obtained by blending 50 parts by weight of the resin (B).

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Further, as a result of dyeing the blended resin of this example by a usual method and observing it with a transmission electron microscope, it was found that this blended resin had a sea-island structure and was separated into two phases. understood. [Example 7] 50 parts by weight of an amorphous polyamide resin (A) having a Tg of Novamid X21 of 125 ° C and diamide 4
71 (manufactured by Daicel Hüls) was blended with 50 parts by weight of a copolyamide resin (B) having a Tg of 24 ° C. to obtain a blend resin according to the present invention.

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Claims (11)

[Claims] 1. At least one resin selected from the group consisting of a non-crystalline or low-crystalline polyester resin and a polyamide resin having a glass transition temperature of about 50 ° C. or higher, and a polyester having a glass transition temperature of about 40 ° C. or lower. A resin composition obtained by blending at least one resin selected from the group consisting of a resin and a polyamide resin. 2. 10 to 95 parts by weight of a resin selected from the group of non-crystalline or low crystalline polyester resins and polyamide resins having a glass transition temperature of about 50 ° C. or higher and a glass transition temperature of about 40 ° C. or lower. The resin composition according to claim 1, wherein 90 to 5 parts by weight of a resin selected from the group consisting of the polyester resin and the polyamide resin is blended. 3. A group of at least one resin selected from the group of amorphous or low crystalline polyester resins and polyamide resins having a high glass transition temperature, and a group of polyester resins and polyamide resins having a low glass transition temperature. A resin composition comprising at least one resin selected from among the above, and having two peaks in the temperature dependence of tan δ obtained by the dynamic viscoelasticity measurement of the blended resin. .. 4. Two peaks appearing in the temperature dependence of tan δ obtained by the dynamic viscoelasticity measurement of the blend resin are measured by the dynamic viscoelasticity measurement of an amorphous or low crystalline resin having a high glass transition temperature. Tan obtained
On the temperature side lower than the peak position appearing in the temperature dependence of δ, and on the temperature side higher than the peak position appearing in the temperature dependence of tan δ obtained by dynamic viscoelasticity measurement of a resin having a low glass transition temperature. A blend as described above, characterized in that
~ The resin composition according to claim 3. 5. A blend such that one of two peaks appearing in the temperature dependence of tan δ obtained by dynamic viscoelasticity measurement of a blended resin is at a temperature lower than room temperature and the other is at a temperature higher than room temperature. The resin composition according to claim 3 or 4, wherein the resin composition is a resin composition. 6. A polyester resin having a high glass transition temperature, wherein at least one selected from the group of isophthalic acid and terephthalic acid is used as the dicarboxylic acid component, and ethylene glycol and cyclohexanedimethanol are selected as the glycol component. The resin composition according to any one of claims 1 to 3, which is configured by using at least one selected from the following. 7. A polyamide resin having a high glass transition temperature is a component of an aliphatic or alicyclic polyamide resin, and further an aromatic dicarboxylic acid, an aromatic diamine, or an aromatic lactam which is a component of an aromatic polyamide resin. The resin composition according to any one of claims 1 to 3, wherein the resin composition comprises at least one selected from the group consisting of aromatic amino acids. 8. A polyester resin having a low glass transition temperature is a dicarboxylic acid component containing terephthalic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid, cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, using at least one selected from the group of cyclohexanedicarboxylic acid, As glycol component, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1,
6-hexanediol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol,
The resin composition according to any one of claims 1 to 3, which is constituted by using at least one selected from the group of cyclohexanedimethanol. 9. A polyamide resin having a low glass transition temperature is a dicarboxylic acid component containing adipic acid, pimelic acid,
Suberic acid, azelaic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid, using at least one selected from the group of lauric acid, hexamethylenediamine, heptamethylenediamine as a diamine component,
At least one selected from the group consisting of octamethylenediamine, nonamethylenediamine, and decamethylenediamine, or at least one selected from ω-aminododecanoic acid and 11-aminoundecanoic acid. The resin composition according to any one of claims 1 to 3, wherein the resin composition is constituted by using the resin composition. 10. At least one resin selected from the group consisting of non-crystalline or low-crystalline polyester resins and polyamide resins having a glass transition temperature of about 50 ° C. or higher,
A container, wherein a blended resin containing at least one resin selected from the group consisting of polyester resin and polyamide resin having a glass transition temperature of about 40 ° C. or lower is used as a resin material for the innermost layer. 11. A group of at least one resin selected from the group of amorphous or low crystalline polyester resins and polyamide resins having a high glass transition temperature, and a group of polyester resins and polyamide resins having a low glass transition temperature. Ta obtained by dynamic viscoelasticity measurement, which is obtained by blending with at least one resin selected from among
A container characterized in that a blend resin having two peaks in the temperature dependence of nδ is used as a resin material for the innermost layer.