JP5007105B2 - Resin composition for liquid container and liquid container comprising the same - Google Patents

Description

The present invention relates to a resin composition for a container for storing a liquid, which is excellent in gas barrier properties and transparency, and a liquid storage container comprising the same.

2. Description of the Related Art Conventionally, various types of containers made of polypropylene resin have been used as containers for containing aqueous or oily liquids or gel-like liquids such as ballpoint pen inks and cosmetics. The required properties of these containers are transparency so that the remaining amount of the contents can be confirmed from the outside, and gas barrier properties to prevent deterioration of the contents due to permeation of oxygen, water vapor, etc. and volatilization of the contents. It is mentioned to have. If the gas barrier property is poor, not only will the amount of content decrease over time, but the content will also increase in viscosity, oxidize, solidify, increase in internal pressure, etc., and the quality of the content will deteriorate, shortening the product life. There is a problem.

By the way, although a polypropylene resin is preferably used in terms of chemical stability, solvent resistance, economy, and productivity, it is difficult to combine both transparency and gas barrier properties. A resin having excellent transparency is inferior in gas barrier properties, and conversely, a resin having excellent gas barrier properties is inferior in transparency because of high crystallinity.

  In order to impart gas barrier properties, multi-layer housing members including a resin layer having excellent oxygen barrier properties have been proposed (for example, Patent Documents 1 and 2). However, the multilayer structure has a problem of delamination between layers, and causes a decrease in transparency.

Further, a packaging film having a gas barrier property by coating one surface of a plastic film with an inorganic substance is known (for example, Patent Document 3). However, there are problems such as peeling of the coating layer, generation of cracks, a decrease in transparency, and an increase in cost due to an increase in the lamination process.
JP 2004-25446 A JP 11-239515 A JP 2004-167777 A

The objective of this invention is providing the resin composition excellent in gas barrier property and transparency which does not have the said problem, and a liquid storage container consisting thereof.

The present inventors use a random copolymer of propylene and ethylene and / or α-olefin having a melting point of 125 to 150 ° C. as a polypropylene resin, and this is used as a specific terpene resin hydrogenated derivative, petroleum It discovered that the resin composition excellent in the said characteristic was obtained by mix | blending a resin and / or petroleum resin hydrogenated derivative with a specific ratio.

That is, the present invention
(A) 100 parts by weight of a random copolymer of propylene and ethylene and / or α-olefin having a melting point of 125 to 150 ° C., and (b) 3 to 40 parts by weight of a terpene resin hydrogenated derivative. It is the resin composition for containers containing the ink for writing instruments or cosmetics characterized by the above-mentioned.

  According to a preferred embodiment of the present invention, the resin composition comprises (c) a silicone oil, a fluorosurfactant and / or a paraffin oil having a viscosity (JIS Z 8803) of 20 to 3000 cSt at 25 ° C. 0.03 It further contains ~ 5 parts by weight.

Moreover, this invention provides the container which accommodates the molded object which consists of the said resin composition, especially the ink for writing instruments, and cosmetics.

  Furthermore, this invention provides the writing instrument which has the said ink storage container for writing instruments, and the cosmetics which have the said cosmetics container.

Since the resin composition according to the present invention is excellent in gas barrier properties and transparency, it is useful as a material for liquid housing parts in writing instruments such as ballpoint pens and cosmetics.

Hereinafter, each component of the resin composition according to the present invention will be described.

Component (a) Random copolymer of propylene and ethylene and / or α-olefin having a melting point of 125 to 150 ° C. Component (a) is a random copolymer of propylene and ethylene and / or α-olefin. If it is a copolymer and melting | fusing point is 125-150 degreeC, it will not restrict | limit in particular. Examples of the α-olefin include those having 4 to 8 carbon atoms such as 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.
Among these, a random copolymer of propylene and ethylene is preferable in terms of transparency.

  By using the random copolymer of propylene, the transparency is improved as compared with the case of using homopolypropylene, and when the obtained liquid container is pressed into another member to assemble a ballpoint pen, etc. Cracks due to

It is essential that component (a) has a melting point of 125 to 150 ° C, preferably 130 to 145 ° C. If the melting point is less than the lower limit, the rigidity is remarkably low, which is unsuitable for liquid container applications. When the upper limit is exceeded, the crystallinity becomes very high and the transparency is deteriorated.

Here, the melting point is a peak top melting point obtained by a differential scanning calorimeter (DSC). Specifically, using DSC, a sample amount of 10 mg is taken, held at 190 ° C. for 5 minutes, and then −10 ° C. It is a value obtained by crystallization at a temperature decrease rate of 10 ° C./min until it is held at −10 ° C. for 5 minutes and then measured at a temperature increase rate of 10 ° C./min up to 200 ° C.

When the component (a) has an MFR (JIS K 7210, 190 ° C., 2.16 kg load) of 5 to 30 dg / min, the moldability is better, which is preferable.

Component (b): Terpene resin hydrogenated derivative, petroleum resin and / or petroleum resin hydrogenated derivative component (b) imparts functions of transparency and gas barrier properties to the resulting resin composition.

Component (b-1): Terpene resin hydrogenated derivative component (b-1) includes terpene resin obtained by polymerizing α-pinene and β-pinene, terpene phenol resin obtained by reacting phenol and terpene, styrene, etc. Examples thereof include hydrogenated derivatives of terpene resins such as imparted aromatic modified terpene resins.

The component (b-1) preferably has a softening temperature of 120 ° C. or higher from the viewpoints of tackiness, rigidity, elastic modulus, and moldability (particularly mold release property).

Hydrogenated derivatives of terpene resins can be obtained by hydrogenating terpene resins by methods known to those skilled in the art.

A commercial item can also be used as a component (b-1), for example, clearon (hydrogenated terpene resin) by Yashara Chemical Co., Ltd. is mentioned.

Component (b-2): Petroleum resin and petroleum resin hydrogenated derivative Petroleum resin is a resinous substance obtained in various processes in the petroleum refining industry and petrochemical industry, or those processes, particularly a decomposition process of naphtha. It refers to a resin obtained by copolymerization using an unsaturated hydrocarbon obtained in (1) as a raw material. For example, aromatic petroleum resins mainly composed of C5 fraction, copolymerized petroleum resins thereof, and alicyclic petroleum resins can be exemplified. Preferred petroleum resins are aliphatic petroleum resins, aromatic petroleum resins, copolymer petroleum resins, and alicyclic petroleum resins.

Component (b-2) also includes hydrogenated derivatives of the above petroleum resins. The petroleum resin hydrogenated derivative is preferably completely hydrogenated. Those that are partially hydrogenated tend to be inferior in terms of thermal stability and weather resistance.

A hydrogenated derivative of a petroleum resin can be obtained by hydrogenating the above petroleum resin produced by a conventional method by a conventional method.

In particular, petroleum resin hydrogenated derivatives are preferred for molded articles that require heat resistance. More preferably, a hydrogenated derivative of an aliphatic petroleum resin is used, and among these, a hydrogenated derivative obtained by copolymerizing a cyclopentadiene compound is particularly preferable.

The component (b-2) preferably has a softening temperature of 120 ° C. or higher from the viewpoints of tackiness, rigidity, elastic modulus, and moldability (particularly mold release property).

In the resin composition of the present invention, as the component (b), one or more selected from the above-mentioned terpene resin hydrogenated derivatives, petroleum resins, and petroleum resin hydrogenated derivatives may be used. The compounding quantity of a component (b) is 3-40 weight part with respect to 100 weight part of component (a), Preferably it is 10-30 weight part. When the above upper limit is exceeded, the resulting molded article becomes brittle and tackiness is remarkably increased, resulting in poor injection moldability and extrusion moldability. In addition, water repellency and oil repellency are also lowered. Below the lower limit, the transparency and gas barrier properties are not sufficiently improved.

Optional component (c): The silicone oil, the fluorosurfactant and / or the paraffin oil component (c) are optional components and can impart water repellency and / or oil repellency to the resulting resin composition. If the water / oil repellency is good, the content liquid will not adhere to the inner wall of the container when it is molded into a container for containing an aqueous or oily liquid. Can do. This characteristic is particularly advantageous when the content liquid contains a dark color material. In addition, cosmetics with high mobility in the container often have vibrations when carried, and in nail polish etc., if the liquid contents adhere to the cap and the screw part of the container, the liquid solidifies. Therefore, it is advantageous to have water repellency and oil repellency. Furthermore, if the contents remain attached to the inner wall at the time of disposal, it causes environmental pollution, but if it has water and oil repellency, there is no concern.

Component (c-1) Silicone oil Component (c-1) can impart water repellency and oil repellency to the resulting resin composition. Examples of the component (c-1) include dimethyl silicone oil, methylphenyl silicone oil, hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, and amino-modified silicone oil. Epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, and the like. Preferred are dimethyl silicone oil and methylphenyl silicone oil.

It is essential that the component (c-1) has a viscosity at 25 ° C. of 20 to 3000 cSt, and preferably 20 to 1000 cSt. If it is less than the said minimum, since volatility is high and a component (a) is deteriorated, it is not preferable. On the other hand, when the upper limit is exceeded, the effect of improving water and oil repellency is low, and the viscosity is too high, making it difficult to handle, and mixing and kneading at the time of producing the composition becomes difficult.

Component (c-2) Fluorine-based surfactant Component (c-2) can impart water repellency and oil repellency to the resulting resin composition. Examples of the component (c-2) include fluoroalkyl (C2-C10) carboxylic acid, N-perfluorooctanesulfonyl glutamate disodium, 3- (fluoroalkyl (C6-C11) oxy) -1-alkyl (C3- C4) Sodium sulfonate, 3- (ω-fluoroalkanoyl (C6-C8) -N-ethylamino) -1-propanesulfonate, N- [3- (perfluorooctanesulfonamido) propyl] -N, N -Dimethyl-N-carboxymethylene ammonium betaine, fluoroalkyl (C11 to C20) carboxylic acid, perfluoroalkyl (C7 to C13) carboxylic acid, perfluorooctanesulfonic acid diethanolamide, perfluoroalkyl (C4 to C12) carboxylic acid lithium , Perfluoroalkyl C4-C12) potassium carboxylate, perfluoroalkyl (C4-C12) sodium carboxylate, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethyl Ammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkyl (C6-C10) ethyl phosphate ester Can be mentioned.

Component (c-3) The paraffin oil component (c-3) can impart water repellency to the resulting resin composition. Examples of the component (c-3) include paraffinic compounds having 4 to 155 carbon atoms, preferably paraffinic compounds having 4 to 50 carbon atoms. Specific examples include butane, pentane, hexane, heptane, and octane. , Nonane, Decane, Undecane, Dodecane, Tetradecane, Pentadecane, Hexadecane, Heptadecane, Octadecane, Nonadecane, Eicosan, Henicosan, Docosan, Tricosan, Tetracosan, Pentacosan, Hexacosan, Heptacosan, Octacosan, Nonacosan, Triacontan, Hentria Contan, Dotoria N-paraffins (linear saturated hydrocarbons) such as contan, pentatriacontane, hexacontane, heptacontane, isobutane, isopentane, neopentane, isohexane, isopentane, neohexane 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2,2,3-trimethylbutane, 3-methylheptane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,4-dimethylhexane, 2 , 2,3-trimethylpentane, isooctane, 2,3,4-trimethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, isononane, 2-methylnonane, isodecane, isoundecane, isododecane, Isotridecane, isotetradecane, isopentadecane, isooctadecane, isonanodecane , Mention may be made of isoeicosane, 4-ethyl-5-isoparaffins methyl octane (branched saturated hydrocarbons) and derivatives thereof and the like saturated hydrocarbons. These paraffins are preferably used in a mixture and are preferably liquid at room temperature.

  Commercially available paraffin oils that are liquid at room temperature include NA Solvent (isoparaffinic hydrocarbon oil) manufactured by Nippon Oil & Fats, PW-90 (n-paraffinic process oil) manufactured by Idemitsu Kosan Co., Ltd., and Idemitsu Petrochemical. Examples thereof include IP-solvent 2835 (synthetic isoparaffinic hydrocarbon, 99.8 wt% or more isoparaffin) manufactured by Sanko Chemical Co., Ltd. (n-paraffinic process oil).

  Moreover, a small amount of unsaturated hydrocarbons and derivatives thereof may coexist in the paraffin oil. Unsaturated hydrocarbons include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2 -Ethylene hydrocarbons such as butene, 1-hexene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 1-nonene, 1-decene, acetylene, methylacetylene, 1-butyne, 2- Examples thereof include acetylene hydrocarbons such as butyne, 1-pentyne, 1-hexyne, 1-octyne, 1-nonine and 1-decyne.

The resin composition of the present invention contains the component (c) as an optional component, and when it is included, at least one selected from the above-described silicone oil, fluorosurfactant and paraffin oil can be used as the component (c). . The amount of component (c) is 0.03 to 5 parts by weight per 100 parts by weight of component (a). Preferably it is 0.05-3 weight part, More preferably, it is 0.1-3 weight part, More preferably, it is 0.5-3 weight part, Most preferably, it is 1-3 weight part. When the upper limit is exceeded, bleeding out occurs and the formability deteriorates. Furthermore, the gas barrier property is also deteriorated. If it is less than the lower limit, the improvement of water repellency and / or oil repellency is insufficient. When component (c) does not contain (c-2) a fluorosurfactant, that is, when component (c) is (c-1) silicone oil and / or (c-3) paraffin oil It is preferable to blend at least 0.1% by weight with respect to 100 parts by weight of component (a).

Other components In addition to the above components, the resin composition according to the present invention includes a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a crystal nucleus within the range not impairing the object of the present invention. Agent, anti-blocking agent, sealant improver, mold release agent such as stearic acid, lubricant such as polyethylene wax, colorant, pigment, inorganic filler (alumina, talc, calcium carbonate, mica, wollastonite, clay), foaming An agent (organic or inorganic), a flame retardant (hydrated metal compound, red phosphorus, ammonium polyphosphate, antimony, silicone) or the like can be blended.

Examples of the antioxidant include 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4- Examples thereof include phenolic antioxidants such as dihydroxydiphenyl and tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, phosphite antioxidants, thioether antioxidants, and the like. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred. As the foaming agent, EXPANSEL is preferable.

The resin composition according to the present invention comprises the above components (a) and (b) and, if necessary, the component (c) and other components, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various types. It can manufacture by melt-kneading at the kneading | mixing temperature of 160-230 degreeC using the kneader of this.

  The resin composition thus obtained contains an aqueous or oily liquid or gel-like liquid such as ink for writing instruments such as ballpoint pens, sign pens, marking pens, brush pens, and cosmetics (eg, nail polish, gloss, eyeliner). It can be suitably used as a container.

EXAMPLES Next, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to a following example. The evaluation methods and raw materials used in Examples and Comparative Examples are as follows.

Evaluation Method (1) Specific gravity: Based on JIS K 7112, measurement was performed using a 1 mm thick press sheet as a test piece.
(2) Flexural modulus: measured according to JIS K 7171. As a test piece, a standard test piece having a length of 80.0 ± 2.0 mm, a width of 10.0 ± 0.2 mm, and a thickness of 4.0 ± 0.2 mm was used.
(3) Injection moldability: Using an injection molding machine with a clamping pressure of 120 tons, a molding temperature of 220 ° C., a mold temperature of 40 ° C., an injection speed of 55 mm / second, an injection pressure of 600 kg / cm ² , and a holding pressure of 400 kg / cm ^2. A sheet of 13.5 × 13.5 × 2 mm was formed with an injection time of 6 seconds and a cooling time of 45 seconds. The presence or absence of delamination, surface layer peeling, deformation, and the presence of a flow mark that significantly deteriorated the appearance was judged by visual observation, and evaluated according to the following criteria.
○: Good (no peeling, deformation and significant flow mark)
X: Poor (there is peeling, deformation or significant flow mark)
(4) Extrudability: A sheet having a width of 50 mm and a thickness of 1 mm was extruded, the drawdown property, surface appearance and shape were observed, and evaluated according to the following criteria.
○: Good (no drawdown, no fish eyes on the surface, good shape)
X: Poor (draw down, fish eyes are seen on the surface, or shape failure is indicated)
(5) Transparency: In accordance with JIS K 7136, the measurement was performed using HGM-2DP manufactured by Suga Test Instruments Co., Ltd. as a measuring device, and using the 2 mm thick sheet prepared in the above (4) as a test piece.

(6) Water vapor barrier property: A cylindrical ink storage container having an outer diameter of 6.8 mm and an inner diameter of 5.4 mm (wall thickness: 0.7 mm) is molded and sufficiently dried, and then the amount is 50% of the container volume. Fill with water, plug and seal. The container was allowed to stand for 10 days in an atmosphere of 50 ° C. and a relative humidity of 30%, and the weight loss (%) from the initial stage was measured. In addition, as a control test, measurement was performed in the same procedure as described above using a container formed only from homopolypropylene (comparative component (a)). Expressed as a number. When the amount of decrease is lower than that of the control test, the numerical value is negative, and when it is high, the numerical value is positive. The minus notation indicates that the water vapor barrier property is superior to that of homopolypropylene alone.

(7) Oxygen barrier property: A cylindrical ink storage container having an outer diameter of 6.8 mm and an inner diameter of 5.4 mm (wall thickness: 0.7 mm) was molded and sufficiently dried. Next, the atmosphere in the container was set to 100% oxygen, a sensor was inserted, and the container was sealed with a stopper. The container was allowed to stand for 3 days in an atmosphere of 50 ° C. and a relative humidity of 30%, and the amount of decrease (%) in oxygen concentration from the initial stage was measured with a fluorescent dissolved oxygen meter. In addition, as a control test, measurement was performed in the same procedure as described above using a container formed only from homopolypropylene (comparative component (a)). Expressed as a number. When the amount of decrease is lower than that of the control test, the numerical value is negative, and when it is high, the numerical value is positive. The minus notation indicates that the oxygen barrier property is superior to that of homopolypropylene alone.

(8) Water and oil repellency: After forming a cylindrical ink container having an outer diameter of 6.8 mm and an inner diameter of 5.4 mm (wall thickness: 0.7 mm) and sufficiently drying, the contents shown in Table 1 Put 1-4 each up to 50% of the total capacity of the container, and seal with a stopper. After the storage container is allowed to stand in an atmosphere of 60 ° C. and a relative humidity of 30%, the storage container is moved to a space of 25 ° C. and a relative humidity of 60%. The following criteria evaluated how the liquid contents moved down the wall by moving upside down.
○: Moves quickly and there is no adhesion of the contents.
Δ: The content liquid remains on the wall a little.
×: The liquid content remains on the wall surface, making it difficult to recognize the remaining amount from the outside.

(9) Performance evaluation as a writing instrument (specifications A to C) or cosmetics (specification D)
Specification A: Writing instrument using water-based ink A cylindrical ink container having an outer diameter of 9.2 mm and an inner diameter of 7.1 mm is formed, and a resin ink holder is attached to the container, and the content liquid 1, a ballpoint pen tip made of a hard metal ball and a stainless steel holder was attached to the tip via a joint member with the storage container to obtain an aqueous ballpoint pen.
Except for the ink container, the same member as the water-based ink ballpoint pen UB-150 black (ball diameter 0.5 mm) manufactured by Mitsubishi Pencil Co., Ltd. was used.
Specification B: Writing instrument using water-based gel ink A cylindrical container having an outer diameter of 5.5 mm and an inner diameter of 4.0 mm is formed, filled with the content liquid 2, and made of carbide metal balls and stainless steel. A ballpoint pen tip made of a made holder was attached to the tip via a joint member with the storage container to obtain an aqueous gel ink ballpoint pen.
Except for the container, the same member as the water-based gel ink ballpoint pen UM-100 black (ball diameter 0.5 mm) manufactured by Mitsubishi Pencil Co., Ltd. was used.
Specification C: Writing instrument using oil-based ink A cylindrical storage container having an outer diameter of 3.0 mm and an inner diameter of 1.6 mm is formed and filled with the content liquid 3, and a carbide metal ball and stainless steel are used. A ballpoint pen tip made of a made holder was attached to the tip to make an oil-based ballpoint pen.
Except for the container, the same member as the oil-based ballpoint pen SA-G black (ball diameter 0.7 mm) manufactured by Mitsubishi Pencil Co., Ltd. was used.
Specification D: Cosmetics using nail polish cosmetics A cylindrical storage container having an outer diameter of 15 mm and an inner diameter of 14.5 mm is molded, and this is assembled to the above-mentioned storage container with a screw and is a brush for application. A cosmetic container was formed from the lid body having the above and filled with the content liquid 4 to obtain a nail polish cosmetic.

(9-1) Appearance evaluation The appearance color of the content liquid recognized through the liquid container was evaluated according to the following criteria.
○: Appearance color can be clearly recognized.
X: Appearance color is unclear.

(9-2) For the contents liquid visibility evaluation specifications A to C, after writing about 500 m using a pen body, for specification D, the nail polish cosmetic is vibrated in the vertical direction and allowed to stand for 1 minute, then to the inner wall of the container The following criteria evaluated the adhesion of the content liquid (content liquid visibility).
○: There is no adhesion of the content liquid, and the content liquid amount in the container can be clearly confirmed.
(Triangle | delta): Although the content liquid adheres, the content liquid quantity in a storage container can be confirmed.
X: The content liquid has adhered so that the amount of the content liquid in a storage container cannot be confirmed.

(9-3) Performance evaluation after high temperature storage (high temperature aging)
After storing pens and cosmetics of specifications A to D in an environment of 60 ° C. and 30% relative humidity for 3 months, write a circle with a diameter of 5 cm for specifications A to C. Then, the coating property was evaluated.
○: Can be written or applied smoothly without changing from the initial stage.
Δ: Writability is slightly lowered (ink outflow is slightly lowered) or applicability is slightly lowered (coating unevenness is slightly caused).
X: Writability or applicability deteriorates and normal writing or application cannot be performed.

Raw materials used for resin composition Component (a) Propylene-ethylene random copolymer: J226E (trademark; manufactured by Mitsui Chemicals, Inc.), MFR 20 dg / min (190C, 2.16 kg load), specific gravity 0 .91, Charpy impact strength 5.5 kJ / m ² (23 ° C.), DSC peak top melting point 147 ° C.
Comparative component (a) Homopolypropylene: MA3H (PP) (trademark; manufactured by Nippon Polypropylene), propylene homopolymer, peak top melting point by DSC of 163 ° C., MFR (190 ° C., 2.16 kg load) 10 dg / min, specific gravity 0 90, flexural modulus 2000 MPa
Component (b-1) Hydrogenated derivative of terpene resin: Clearon P-125 (trademark; manufactured by Yasuhara Chemical Co., Ltd.), softening temperature 125 ° C., glass transition temperature 68 ° C.
Component (b-2) Petroleum resin hydrogenated derivative: Imabe P-140 (trademark; manufactured by Idemitsu Petrochemical Co., Ltd.), softening point: 140 ° C., average molecular weight: 910, density: 1.03
Component (c-1) Silicone oil: SH550 (trademark; manufactured by Toray Dow Corning Silicone Co., Ltd.), methylphenyl silicone oil, viscosity (25 ° C.) 125 cSt, specific gravity 1.07
Component (c-2) Fluorosurfactant: EF-102 (trademark; manufactured by Gemco), anionic, specific gravity 2.05, melting point 280 ° C. or higher Component (c-3) paraffin oil: PW-90 (Trademark: Idemitsu Petrochemical Co., Ltd.), paraffin oil

Composition of contents liquid 1-4

Examples 1-14 and Comparative Examples 1-8
Resin compositions of Examples 1 to 14 and Comparative Examples 1 to 8 were produced by melt-kneading the components shown in Tables 2 and 3 at 220 ° C. with a biaxial kneader. Moreover, the evaluation test of said (1)-(8) was done using the obtained resin composition. The results are shown in Tables 2 and 3.

As is apparent from Table 2, the resin composition according to the present invention is excellent in transparency, gas barrier properties and moldability.

On the other hand, as is clear from Table 3, the compositions of Comparative Examples 1 and 3 in which the blending amount of the component (b) exceeds the upper limit of the present invention are markedly tacky and difficult to injection and extrusion. In addition, the water / oil repellency and the flexural modulus are inferior. The composition of Comparative Example 2 in which the amount of component (b) is less than the lower limit of the present invention is slightly inferior in transparency and inferior in gas barrier properties. The compositions of Comparative Examples 4 to 8 where the component (a) is a polypropylene homopolymer are inferior in transparency.

Examples 15-22 and Comparative Examples 9-16
Using the resin compositions obtained in the above examples and comparative examples, writing instruments or cosmetics having the specifications A to D were produced, and the performance evaluation was performed according to the method (9). The results are shown in Tables 4 and 5.

As is apparent from Table 4, the writing instrument and the cosmetics comprising the resin composition of the present invention have excellent appearance due to high transparency, and have no deterioration in performance even after high-temperature storage due to high gas barrier properties. . Further, the content liquid visibility could be further improved by adding the component (c).

  Writing instruments and cosmetics made of the resin composition not having the composition of the present invention have deteriorated appearance due to low transparency or deterioration in high-temperature aging due to low gas barrier properties. Furthermore, deterioration of content liquid visibility due to low water repellency and / or oil repellency was also observed.

  Since the resin composition of the present invention is excellent in gas barrier properties and transparency, it can be advantageously used in liquid containing parts such as ink for writing instruments such as ballpoint pens and cosmetics.

Claims (6)

(A) 100 parts by weight of a random copolymer of propylene and ethylene and / or α-olefin having a melting point of 125 to 150 ° C., and (b) 3 to 40 parts by weight of a terpene resin hydrogenated derivative. A resin composition for containers that contains ink for writing instruments or cosmetics . (C) It further contains 0.03 to 5 parts by weight of a silicone oil, a fluorosurfactant and / or a paraffinic oil having a viscosity (JIS Z 8803) of 20 to 3000 cSt at 25 ° C. The resin composition described in 1. A container containing ink for a writing instrument, comprising the resin composition according to claim 1. A writing instrument comprising the container according to claim 3 . A container for housing cosmetics, comprising the resin composition according to claim 1. A cosmetic comprising the container according to claim 5 .