JP4919532B2 - Polyethylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyethylene-based resin composition improved in transparency and flexibility without impairing the properties of the copolymer mentioned below by blending specific tackifier(s) in an ethylene-unsaturated carboxylic acid copolymer or a metal ion-neutralized product thereof. SOLUTION: This polyethylene-based resin composition is characterized by being obtained by blending 100 pts.wt. of an ethylene-unsaturated carboxylic acid copolymer or a metal ion-neutralized product thereof with 0.1-30 pt(s).wt. of at least one tackifier selected from the group consisting of terpene-based resins or hydrogenated products thereof and aromatic hydrogenated resins.

Description

【００４２】
以上の結果から、アイオノマーの種類の如何にかかわらず、選択されたタッキファイアーをブレンドすることで柔軟性、透明性の改良効果があること、そしてアイオノマーだけでなく、酸コポリマーにも同様の効果があることがわかる。
また、透明性の改善には、タッキファイアーの添加量が少なくても十分な効果が得られることがわかる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyethylene-based resin composition having excellent transparency, and more specifically, blending a specific tackifier with an ethylene / unsaturated carboxylic acid copolymer or a metal ion neutralized product thereof. Therefore, it is related with the polyethylene-type resin composition which can improve transparency and a softness | flexibility, without impairing the characteristic of this copolymer.
[0002]
[Prior art]
The ethylene / (meth) acrylic acid copolymer produced by the high pressure polymerization process and the ionomer derived from the copolymer are excellent in processability, chemical resistance, strength, impact resistance, heat seal strength, etc. To packaging materials, sealant layers, molded products, and cover materials for golf balls.
By the way, the flow of PVC removal has accelerated due to recent environmental problems. The ethylene / (meth) acrylic acid copolymer and the ionomer derived from the copolymer are being studied variously as a PVC substitute because they have good scratch resistance and transparency in addition to the above physical properties. On the other hand, soft PVC-like flexibility and higher transparency are often required, leaving room for improvement.
[0003]
On the other hand, many techniques for blending a tackifier with a polyolefin-based material such as polypropylene, polyethylene, and ethylene-vinyl acetate copolymer are known.
For example, Japanese Patent Application Laid-Open No. 58-25341 describes a technique for improving the adhesiveness for stretch wrap by combining an adhesive and a nucleating agent with polyolefin, and by adding an antifogging agent or a nucleating agent, transparency is described. It is also described that becomes better. In addition, in the polypropylene-based material, Japanese Patent Publication No. 7-25959 discloses a film obtained by blending a specific propylene-α-olefin copolymer or a propylene-α-olefin-ethylene copolymer with a hydrocarbon resin, It is described that a film for shrink wrapping excellent in low-temperature shrinkage, transparency and blocking resistance can be obtained by stretching this at least in a uniaxial direction.
[0004]
Furthermore, Japanese Patent Application Laid-Open No. 55-19528 describes a technique for improving adhesiveness and transparency with an LDPE / (LDPE + pressure-sensitive adhesive) structure. Sometimes it is necessary to cool rapidly.
However, there is no known technique for adding a pressure-sensitive adhesive to increase the transparency of the ethylene / unsaturated carboxylic acid copolymer or its metal ion neutralized product, which is the object of the present invention.
[0005]
The present inventors technically intend to expand applications by taking advantage of the excellent physical properties of the above-mentioned ethylene / unsaturated carboxylic acid copolymer or its metal ion neutralized product as it is and further enhancing its transparency. The research has been repeated as an issue. By increasing the transparency of ethylene / unsaturated carboxylic acid copolymer or its metal ion neutralized product, applicable applications include, for example, polychlorination, which has recently been regarded as a social problem with the generation of dioxins associated with incineration. Various types of vinyl molded products, toy applications that make use of the characteristics of dephthalate esters, leather that makes use of adhesiveness and transparency, and wallpaper.
[0006]
The objective of this invention is providing the resin composition which can improve transparency, without impairing the physical property which ethylene / unsaturated carboxylic acid copolymer or its metal ion neutralized material originally has.
[0007]
The present invention has been proposed in order to achieve the above object, and by adding a specific tackifier, the transparency of the ethylene / unsaturated carboxylic acid copolymer or its metal ion neutralized product is improved. It has been completed based on the knowledge obtained by the present inventors that it is possible.
[0008]
That is, according to the present invention, ethylene / unsaturated carboxylic acid copolymer or neutralized metal ion thereof, and 0.1 to 30 parts by weight of the terpene resin or hydrogenated resin thereof with respect to 100 parts by weight And at least one tackifier selected from the group consisting of aromatic hydrogenated resins , a polyethylene resin composition for leather , and an ethylene / unsaturated carboxylic acid copolymer or a metal thereof At least one kind of tack selected from the group consisting of an ion neutralized product and 0.1 to 30 parts by weight of the terpene resin or its hydrogenated resin and an aromatic hydrogenated resin with respect to 100 parts by weight There is provided a polyethylene resin composition for wallpaper characterized by comprising a fire .
Moreover, according to this invention, the wallpaper which consists of the leather which consists of the said polyethylene-type resin composition , and the said polyethylene-type resin composition is provided.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, a specific tackifier such as a terpene resin or a hydrogenated resin thereof and an aromatic hydrogenated resin substantially has the physical properties inherent to an ethylene / unsaturated carboxylic acid copolymer or a metal ion neutralized product thereof. This is based on the experimental result found by the present inventors that the transparency can be improved without losing the above.
The fact that only the above-mentioned specific tackifier contributes to the improvement of the transparency with respect to the ethylene / unsaturated carboxylic acid copolymer or the metal ion neutralized product of the present invention is repeated by the present inventors. It was found as a result of the experiment, and it is surprising that it cannot be conceived from the prior art.
[0010]
<Ethylene / unsaturated carboxylic acid copolymer or neutralized metal ion thereof>
The ethylene / unsaturated carboxylic acid copolymer used in the present invention is ethylene, acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, anhydrous It is a copolymer with an unsaturated carboxylic acid such as itaconic acid, among which acrylic acid or methacrylic acid is preferred. The ethylene-unsaturated carboxylic acid copolymer may contain any other monomer.
[0011]
In the ethylene / unsaturated carboxylic acid copolymer, the ethylene component is 70 to 95% by weight, preferably 80 to 95% by weight, and the unsaturated carboxylic acid component is 5 to 30% by weight, preferably 5 to 20% by weight. is there. The ethylene / unsaturated carboxylic acid copolymer has a melt flow rate (MFR) at 190 ° C. and a load of 2160 g of 0.05 to 300 g / 10 minutes, preferably 0.05 to 200 g / 10 minutes.
[0012]
Monomers optionally contained in the ethylene / unsaturated carboxylic acid copolymer include vinyl esters such as vinyl acetate and vinyl propionate, methyl acrylate, ethyl acrylate, isopropyl acrylate, acrylic Examples include n-butyl acid, isobutyl acrylate, isooctyl acrylate, methyl methacrylate, isobutyl methacrylate, dimethyl maleate, diethyl maleate, and the like, carbon monoxide, sulfur dioxide, and the like. The monomer is preferably contained in a proportion of about 0 to 50% by weight.
Such an ethylene / unsaturated carboxylic acid copolymer can be obtained by a method known per se, for example, radical polymerization under high temperature and high pressure.
[0013]
In the present invention, an ionomer in which a part or all of the carboxyl groups of the ethylene / unsaturated carboxylic acid copolymer is converted into a metal salt can also be used. Examples of the metal species constituting the ionomer include monovalent metals such as lithium, sodium, and potassium, and polyvalent metals such as magnesium, calcium, zinc, copper, cobalt, manganese, lead, and iron. A valent metal or zinc is preferred.
[0014]
<Tackfire>
In the present invention, the tackifier added to improve the transparency of the ethylene / unsaturated carboxylic acid copolymer or the metal ion neutralized product thereof is a terpene resin or a hydrogenated resin thereof, and an aromatic hydrogenated resin. Resin.
[0015]
Specifically, an alicyclic petroleum resin, a resin obtained by polymerizing a diene component in a petroleum fraction having 4 or 5 carbon atoms after cyclization and dimerization, a resin obtained by polymerizing a cyclized monomer such as cyclopentadiene, an aromatic Examples include resins obtained by hydrogenating aromatic hydrocarbon resins in the nucleus, α-pinene, β-pinene, diterpene polymers, and resins obtained by hydrogenating so-called polyterpene resins. Preference is given to resins hydrogenated with internally hydrogenated resins and polyterpene resins.
The compounding amount of the tackifier with respect to 100 parts by weight of the ethylene / unsaturated carboxylic acid copolymer or its metal ion neutralized product is preferably 0.1 to 30 parts by weight, particularly preferably 0.3 to 20 parts by weight.
[0016]
What should be noted in the present invention is that only the specific tackifier can improve the transparency of the ethylene / unsaturated carboxylic acid copolymer or the metal ion neutralized product thereof. Only this specific tackifier is incompatible with the ionomer aggregation part, and the object of the present invention can be achieved.
[0017]
Incidentally, tackifiers such as rosin, rosin ester, and terpene phenol that have been known as tackifiers before the present application are not compatible with polyethylene parts, but are compatible with polar parts of ionomers and acid copolymers. Due to this compatibility, there is a problem that the agglomeration structure, which is a characteristic of ionomers and acid copolymers, is destroyed, and the scratch resistance and strength inherent in the ethylene / unsaturated carboxylic acid copolymer or its metal ion neutralized product are lowered. .
[0018]
The resin composition of the present invention can contain various additives known per se within a range not impairing the object of the invention.
Examples of such additives include primary antioxidants such as hindered phenols, antioxidants such as phosphorus or sulfur secondary antioxidants, light stabilizers such as HALS (hindered amines), and benzotriazoles. , UV absorbers such as benzophenone UV absorbers, pigments such as inorganic pigments, phthalocyanines and azo pigments, dyes such as oil-soluble dyes, lubricants such as metal soaps, stearic acid and silicone, anti-blocking agents such as silica and oleic amide Agents, foaming agents such as azodicarbonamide, crosslinking agents such as DCP, and phosphorus-based flame retardants.
[0019]
The resin composition of the present invention comprises an ethylene / unsaturated carboxylic acid copolymer or a metal ion neutralized product thereof and the above tackifier, a Banbury mixer, a pressure kneader, a single screw extruder, a twin screw extruder, a roll. Through a process such as melt-kneading with a kneader known per se, etc., and pelletizing as necessary, it is aimed at molding processing means according to the objective such as extrusion molding, injection molding, compression molding, hollow molding, etc. It is a resin molded product. Cross-linking by electron beam irradiation is also possible.
[0020]
【Effect of the invention】
According to the present invention, a specific tackifier is blended with an ethylene / unsaturated carboxylic acid copolymer or a neutralized product thereof, which is inherently excellent in balance of strength, low temperature characteristics, scratch resistance, hardness and the like. Thus, a resin composition with improved transparency can be obtained without substantially impairing the above physical properties. Taking advantage of these properties, this resin composition is a toy application that takes advantage of the properties of dephthalate, various molded products that replace polyvinyl chloride, which has recently been regarded as a social problem in the generation of dioxins associated with incineration. It exhibits excellent aptitude for leather and wallpaper that make use of adhesiveness and transparency.
[0021]
【Example】
Hereinafter, the present invention will be described based on examples, but these examples are intended to disclose preferred embodiments of the present invention and are not limited thereto.
The types of copolymers and tackifiers used in Examples and Comparative Examples, and methods for testing physical properties of the resulting compositions are as follows.
[0022]
1. Ethylene / unsaturated carboxylic acid copolymer or its metal ion neutralized component
(1) Ionomer (1):
Ethylene 85% by weight / Methacrylic acid 15% by weight, Zn59% neutralized product, MFR 0.6
(2) Ionomer (2):
80% ethylene / 10% methacrylic acid / 10% isobutyl acrylate
Zn 70% neutralized product, MFR 1.3
(3) Ionomer (3):
Ethylene 90% by weight / methacrylic acid 10% by weight, Na50% neutralized product, MFR 1.3
(4) Acid copolymer (1):
90% by weight of ethylene / 10% by weight of methacrylic acid, MFR 35
[0023]
2. Tackifier ingredients
(1) Clearon P105:
Hydrogenated terpene resin (Yasuhara Chemical Co., Ltd., R & B softening point 105 ° C)
(2) Clearon M105:
Terpene resin (Yasuhara Chemical Co., Ltd., R & B softening point 105 ° C)
(3) Archon P100:
Aromatic hydrogenated resin (Arakawa Chemical Co., Ltd., R & B softening point 100 ° C)
(4) Quinton A100:
Aliphatic resin (Zeon Corporation, R & B softening point 100 ° C)
(5) Quinton D100:
Aliphatic-aromatic copolymer resin (manufactured by Nippon Zeon Co., Ltd., R & B softening point 100 ° C.)
[0024]
3. Sample preparation All samples were prepared with a twin screw extruder (screw diameter 30 mm, L / D = 32).
The copolymer component and the tackifier component were introduced into the hopper at the ratio shown in Table 1, and the mixing zone was set to 200 ° C. to perform kneading.
A 50 μm film was prepared using an inflation molding machine (screw diameter 30 mm, processing temperature 210 ° C.). The sample which mix | blended various tackifiers performed inflation molding using the above-mentioned blend. The press sheet was prepared under conditions of preheating at 180 ° C. for 5 minutes, heating at 180 ° C. for 5 minutes, and cooling at 20 ° C. for 5 minutes.
[0025]
4). Evaluation of physical properties The physical properties of each test piece were evaluated by the following methods.
(1) Flexural modulus (MPa)
Measurement was performed in accordance with JIS K7106. The sheet used was 3 mm thick.
(2) Transparency The transparency of a press sheet having a thickness of 1 mm was judged visually.
○: No cloudiness, △: Cloudiness, ×: Opaque
(3) With respect to a film having an optical thickness of 50 μm, haze and transformer were measured in accordance with JIS K7105 and ASTM D1746, respectively.
(4) Tensile properties Breaking force stress (MPa) and elongation at break (%) were measured under the following conditions in accordance with JIS K6760.
Press sheet: 2 mm, pulling speed: 200 mm / min, between marked lines: 25 mm
(5) Abrasion resistance (mg)
Using a press sheet having a thickness of 3 mm, the weight change after 500 rotations of the wear wheel was measured according to JIS A1453, and the wear resistance was evaluated.
[0026]
<Example 1>
Ionomer (1) and Clearon P105 were kneaded at a processing temperature of 200 ° C. using a twin screw extruder in the proportions shown in Table 1, and press sheets of various thicknesses were prepared by the method described above, and bending rigidity (MPa), Transparency, stress at break (MPa), elongation at break (%) and wear resistance were measured. In addition, the optical property was prepared by using a sample kneaded with a twin-screw extruder to produce a 50 μm film using an inflation molding machine under a processing temperature of 210 ° C. and a take-off speed of 3.2 m / min. Measurements were made.
The results are also shown in Table 1.
[0027]
<Example 2>
Various physical properties were measured in the same manner as in Example 1 except that Clearon M105 was used instead of Clearon P105. The results are also shown in Table 1.
[0028]
<Example 3>
Various physical properties were measured in the same manner as in Example 1 except that Alcon P100 was used instead of Clearon P105. The results are also shown in Table 1.
[0029]
<Reference Example 1>
Press sheets of various thicknesses were prepared from the ionomer (1) by the methods described above, and the bending rigidity (MPa), transparency, stress at break (MPa), elongation at break (%), and wear resistance were measured. In addition, the optical property was prepared by using a sample kneaded with a twin-screw extruder to produce a 50 μm film using an inflation molding machine under a processing temperature of 210 ° C. and a take-off speed of 3.2 m / min. Measurements were made.
The results are also shown in Table 1.
[0030]
<Comparative Example 1>
Various physical properties were measured in the same manner as in Example 1 except that Quinton A100 was used instead of Clearon P105. The results are also shown in Table 1.
[0031]
<Comparative Example 1>
Various physical properties were measured in the same manner as in Example 1 except that Quint D100 was used instead of Clearon P105. The results are also shown in Table 1.
[0032]
<Example 4>
Various physical properties were measured in the same manner as in Example 1 except that ionomer (2) was used instead of ionomer (1). The results are also shown in Table 1.
[0033]
<Reference Example 2>
Press sheets of various thicknesses were prepared from the ionomer (2) by the methods described above, and the bending rigidity (MPa), transparency, stress at break (MPa), elongation at break (%), and wear resistance were measured. In addition, the optical property was prepared by using a sample kneaded with a twin-screw extruder to produce a 50 μm film using an inflation molding machine under a processing temperature of 210 ° C. and a take-off speed of 3.2 m / min. Measurements were made.
The results are also shown in Table 1.
[0034]
<Example 5>
Various physical properties were measured in the same manner as in Example 1 except that the acid copolymer (1) was used instead of the ionomer (2). The results are also shown in Table 1.
[0035]
<Reference Example 3>
Press sheets of various thicknesses were prepared from the acid copolymer (1) by the methods described above, and the bending rigidity (MPa), transparency, stress at break (MPa), elongation at break (%), and wear resistance were measured. . In addition, the optical property was prepared by using a sample kneaded with a twin-screw extruder to produce a 50 μm film using an inflation molding machine under a processing temperature of 210 ° C. and a take-off speed of 3.2 m / min. Measurements were made.
The results are also shown in Table 1.
[0036]
<Example 6>
Ionomer (3), Clearon P105 was kneaded in a ratio of 99: 1 using a twin-screw extruder at a processing temperature of 200 ° C., and press sheets of various thicknesses were prepared by the method described above, bending rigidity (MPa), Transparency, stress at break (MPa), elongation at break (%) and wear resistance were measured. In addition, the optical property was prepared by using a sample kneaded with a twin-screw extruder to produce a 50 μm film using an inflation molding machine under a processing temperature of 210 ° C. and a take-off speed of 3.2 m / min. Measurements were made.
The results are also shown in Table 1.
[0037]
<Example 7>
Various physical properties were measured in the same manner as in Example 6 except that an ionomer (3) and Clearon P105 were kneaded at a ratio of 98: 2. The results are also shown in Table 1.
[0038]
<Example 8>
Various physical properties were measured in the same manner as in Example 6 except that an ionomer (3) and Clearon P105 were kneaded at a ratio of 95: 5. The results are also shown in Table 1.
[0039]
<Example 9>
Various physical properties were measured in the same manner as in Example 6 except that an ionomer (3) and Clearon P105 were kneaded at a ratio of 90:10. The results are also shown in Table 1.
[0040]
<Reference Example 4>
Press sheets of various thicknesses were prepared from the ionomer (3) by the methods described above, and the bending rigidity (MPa), transparency, stress at break (MPa), elongation at break (%), and wear resistance were measured. In addition, the optical property was prepared by using a sample kneaded with a twin-screw extruder to produce a 50 μm film using an inflation molding machine under a processing temperature of 210 ° C. and a take-off speed of 3.2 m / min. Measurements were made.
The results are also shown in Table 1.
[0041]
[Table 1]

[0042]
From the above results, regardless of the type of ionomer, blending selected tackifiers has an effect of improving flexibility and transparency, and not only ionomers but also acid copolymers have similar effects. I know that there is.
In addition, it can be seen that a sufficient effect can be obtained even if the addition amount of the tackifier is small for improving the transparency.

Claims (4)

Ethylene / unsaturated carboxylic acid copolymer or neutralized metal ion thereof, 0.1 to 30 parts by weight of 100 parts by weight of this, terpene resin or hydrogenated resin thereof, and aromatic hydrogenated resin A polyethylene-based resin composition for leather, comprising at least one tackifier selected from the group consisting of: A leather comprising the polyethylene resin composition according to claim 1. Ethylene / unsaturated carboxylic acid copolymer or neutralized metal ion thereof, 0.1 to 30 parts by weight of 100 parts by weight of this, terpene resin or hydrogenated resin thereof, and aromatic hydrogenated resin A polyethylene-based resin composition for wallpaper, comprising at least one tackifier selected from the group consisting of: A wallpaper comprising the polyethylene resin composition according to claim 3 .