JPH11198316A - Sheet for pp type ptp - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet for polypropylene type PTP having a wide molding condition range, reduced in curl and excellent in transparency, moistureproofness, impact resistance or the like necessary as PTP packaging. SOLUTION: A PP type sheet consisgts of outer layers with a thickness of 0.005-0.095 mm comprising a polypropylene homopolymer and an intemaediate layer comprising a resin compsn. consisting of 70-95 wt.% an ethylene/propylene random copolymer with a crystalline nucleus content of 0.002-0.3 wt.% and an ethylene content of 0.1-5.0% and 5-30 wt.% pertroleum resin and the thickness of three layers is 0.15-0.45 mm. In this case, when an upper yield point is not present or present within elongation of 200% in a tensile test at 135 deg.C, the first max. point (upper yield point) and first min. point X2 of load satisfy the formula 1<=X1 /X2 <=1.25.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a PTP commonly used for packaging solid preparations in the field of pharmaceutical packaging.
It relates to a polypropylene sheet for (press through pack).

[0002]

2. Description of the Related Art In the field of pharmaceutical packaging, PTP packaging, which is generally used for packaging solid tablets such as tablets and capsules, is mainly made of rigid polyvinyl chloride in terms of transparency, moldability, rigidity, and cost. Is used as a bottom material, the bottom material is formed into a pocket shape, and a solid agent (tablet,
Capsules) and sealed with a lid made of aluminum foil, which was put into practical use and widespread in the early 1960s.

[0003] Most of the contents of tablets, capsules and the like are deteriorated or deformed by absorbing moisture.
This has been dealt with by providing secondary packaging such as pillow packaging with a composite film containing aluminum foil, or by using a sheet in which a rigid polyvinyl chloride sheet is composited with a coating of polyvinylidene chloride resin with excellent moisture resistance. These are expensive and have a problem in cost. In addition, the tendency of polyvinyl chloride resin to be avoided due to the problem of disposal is increasing. Therefore, recently, sheets made of polypropylene resin, which is an olefin-based resin, have been attracting attention for their moisture-proof properties, low cost properties, and easy processability.
It has been used as a TP packaging sheet.

[0004] However, polypropylene as a PTP sheet has a problem in that the range of molding conditions is narrower than polyvinyl chloride, and there is a problem in terms of appearance due to curling of the product or compatibility with an automatic packaging line. These problems are attributable to the fact that polypropylene is a crystalline resin, and attempts have been made to increase the crystallinity of polypropylene in order to improve curl, using a nucleating agent or slow cooling during sheeting. In addition, methods such as annealing the sheet were performed, but the moldability was conversely deteriorated, and was not suitable for actual use. Attempts have also been made to reduce the degree of crystallinity by quenching during sheeting in order to improve the formability. However, in this method, the stiffness of the sheet is significantly reduced, and the sheet cannot be used for practical use. Further, in order to improve moldability, a method of suppressing crystallinity by adding a petroleum resin to a homopolymer of polypropylene has been adopted, but this method has a drawback that impact resistance is significantly impaired. I was In order to improve the impact resistance, a method of adding a thermoplastic elastomer (TPE) has been adopted, but the impact resistance is improved with an increase in the amount of TPE added, but at the same time, the rigidity and the moisture resistance are reduced. was there. As described above, the conventional polypropylene sheet could only partially satisfy the required performance of the PTP sheet such as moldability, low curl property, transparency, rigidity, moisture resistance and impact resistance. .

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made as a result of conducting various studies to solve the above-mentioned problems in the polypropylene-based PTP sheet. An object of the present invention is to provide a polypropylene-based PTP sheet which is wide, has little curl, and is excellent in transparency, rigidity, moisture resistance, impact resistance and the like required for PTP packaging.

[0006]

According to the present invention, there is provided a semiconductor device having a thickness of 0.0
An outer layer made of a homopolymer of polypropylene, having a crystal nucleating agent content of 0.002 to 0.3% by weight, and an ethylene-propylene random copolymer having an ethylene content of 0.1 to 5.0%. Elongation in a tensile test at 135 [deg.] C. of a PP-based sheet having a thickness of 0.15 to 0.45 mm including a middle layer of a resin composition including 70 to 95% by weight and 5 to 30% by weight of a petroleum resin. 200%
Within the range, the upper yield point does not exist, or if it exists, the first maximum point (upper yield point) X ₁ of the load and the first minimum point X ₂
When these are PP-based P satisfying the following formula (1):
It is a sheet for TP. 1 ≦ X ₁ / X ₂ ≦ 1.25 (1) Preferably, the petroleum resin in the intermediate layer is a hydrogenated petroleum resin, and the hydrogenated petroleum resin is a dicyclopentadiene-based petroleum resin or an aromatic petroleum resin, or This is a PP-based PTP sheet that is a hydrogenated product of an aliphatic petroleum resin. Furthermore,
The hydrogenated petroleum resin of the intermediate layer is a hydrogenated product of a copolymer of at least two components selected from dicyclopentadiene-based petroleum resin, aromatic petroleum resin, and aliphatic petroleum resin, or dicyclopentadiene-based petroleum resin. The PP-based PTP sheet is a blend of at least two components selected from a hydrogenated product, a hydrogenated product of an aromatic petroleum resin, and a hydrogenated product of an aliphatic petroleum resin.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The crystal nucleating agent used in the present invention is an organic nucleating agent or a high melting point polymer nucleating agent, which is added for the purpose of imparting rigidity and improving transparency. Crystal nucleating agents include organic nucleating agents, inorganic nucleating agents, and high melting point polymer nucleating agents, but inorganic nucleating agents cannot be used because they hinder transparency. Examples of the organic nucleating agent include sorbitol derivatives, metal salts of dicarboxylic acids, metal salts of aromatic carboxylic acids, and metal salts of organic phosphoric acids. Examples of the high melting point polymer nucleating agent include polyvinylcyclohexane, polyvinylcyclopentane, poly-3-methylpentene-1, poly3-methylbutene-1, and alkenylsilane. These nucleating agents are known, and any one may be used as long as it is other than an inorganic crystal nucleating agent. These nucleating agents are added in an amount of 0.002 to 0.3% by weight. When no nucleating agent is added, the rigidity is significantly reduced. When the addition amount is less than 0.002% by weight, the effect of adding the nucleating agent is not obtained, and the addition amount is 0.3% by weight.
The effect cannot be expected to increase even if it is added in excess of. The above nucleating agent is added to the ethylene-propylene random copolymer. The addition may be performed at the time of polymerization or after the polymerization.

In the present invention, the homopolymer of polypropylene to be used includes any catalyst such as a solvent polymerization method, a bulk polymerization method, a gas phase polymerization method, etc., for example, a titanium trichloride type catalyst, a magnesium chloride supported type. A catalyst, a metallocene catalyst or the like may be used. Further, additives such as a crystal nucleating agent, an antistatic agent, an ultraviolet absorber, a lubricant, and an antioxidant may be added as long as the basic performance is not impaired.

In the present invention, the ethylene-propylene random copolymer used includes any polymerization method such as a solvent polymerization method, a bulk polymerization method and a gas phase polymerization method.
Any catalyst such as a titanium trichloride type catalyst, a magnesium chloride supported type catalyst, a metallocene-based catalyst or the like may be used. Among ethylene-propylene random copolymers, there are those having various ethylene contents, and among them, ethylene-propylene random copolymers having an ethylene content of 0.1 to 5.0% by weight are preferable. If the ethylene content is less than 0.1% by weight, the impact resistance is poor, and if it exceeds 5% by weight, the rigidity and moisture resistance of the sheet are significantly reduced. Further, additives such as a crystal nucleating agent, an antistatic agent, an ultraviolet absorber, a lubricant, and an antioxidant may be added as long as the basic performance is not impaired.

[0010] The petroleum resin used in the intermediate layer of the present invention comprises:
A dicyclopentadiene resin obtained by thermally polymerizing a cyclopentadiene fraction, an aromatic (C9) petroleum resin obtained by cationic polymerization of a C9 aromatic olefin mixture, and an aliphatic (C5) obtained by cationic polymerization of a C5 chain olefin mixture. System) Petroleum resins and copolymers or blends of at least two components selected from these, furthermore, hydrogenated petroleum resins, and blends of at least two components selected from hydrogenated petroleum resins. Among them, a hydrogenated petroleum resin excellent in color tone, odor and stability is preferable, and a dicyclopentadiene-based hydrogenated petroleum resin is more preferable.

The softening point of petroleum resin is 50 to 16
0 ° C. is preferable, and more preferably 100 to 16 ° C.
The molecular weight is 0 ° C., and the molecular weight is preferably 3000 or less, more preferably 1000 or less. If the softening point of the petroleum resin is less than 50 ° C., there is a problem of elution, and if it exceeds 160 ° C., there is a problem that moldability deteriorates. If the molecular weight of the petroleum resin exceeds 3,000, there is a problem that moldability deteriorates.

The intermediate layer has a nucleating agent content of 0.002 to 0.5.
It is composed of 3% by weight, 70-95% by weight of an ethylene-propylene random copolymer having an ethylene content of 0.1-5.0%, and 5-30% by weight of a petroleum resin. It is 25% by weight, more preferably 15 to 20% by weight. When the blending amount of the petroleum resin is less than 5% by weight, the moldability of PTP is deteriorated, and
Exceeding the weight percentage is not preferable in terms of cost and hygiene.

The thickness of the polypropylene-based PTP sheet of the present invention is 0.15 to 0.45 mm, preferably 0.20 to 0.40 mm, and more preferably 0.1 to 0.40 mm.
23 to 0.35 mm. If the thickness is less than 0.15 mm, the stiffness of the sheet is weakened, the curl is increased, and the appearance is poor. On the other hand, if the thickness exceeds 0.45 mm, the sheet becomes hard and the push-through property deteriorates. The thickness of the outer layer of the present invention is 0.005 to 0.095 mm, more preferably 0.01 to 0.06 mm. If the thickness of the outer layer is less than 0.005 mm, there is a problem of elution of the petroleum resin from the intermediate layer, which is not preferable. Also, 0.095m
If it exceeds m, the moldability deteriorates, which is not preferable.

In a tensile test at 135 ° C. of the polypropylene-based PTP sheet according to the present invention, when the first maximum point (upper yield point) X ₁ and the first minimum point X ₂ of the load are defined as X _{1 /} X ₁
X2 is 1 to 1.25, preferably 1 to 1.25, and more preferably there is no upper yield point. When X ₁ / X ₂ exceeds 1.25, the moldability deteriorates, which is not preferable as a PTP sheet.

The method for producing a three-layer sheet in the present invention is not particularly limited, but is a co-extrusion method in which the resin is melt-extruded by several extruders and led to a multilayer die or a feed block to form a sheet. It is used in combination with a dry lamination method, an extrusion lamination method in which a single-layer sheet or film forming each layer is laminated using an appropriate adhesive, and a combination of these methods.

[0016]

EXAMPLES (Examples 1 to 5 and Comparative Examples 1 to 3) The following raw materials were melt-extruded from a multi-layer coextrusion die (three-layer multi-manifold die), and the layer configuration having a thickness of 0.30 mm was polypropylene / polypropylene + A three-layer sheet composed of petroleum resin / polypropylene was prepared. The thickness of each layer was 0.015 / 0.27 / 0.015 mm.

The raw materials used are as follows. <For outer layer> PP-1: polypropylene homopolymer (MFR = 2.
0) (no crystal nucleating agent added) <For intermediate layer> ・ PP-2: Ethylene-propylene random copolymer (MFR = 0.5) ・ Petroleum resin-1: Dicyclopentadiene-based hydrogenated petroleum resin ・ Petroleum resin -2: Aliphatic hydrogenated petroleum resin-Petroleum resin -3: Aliphatic petroleum resin (non-hydrogenated)-Crystal nucleating agent: Gerol D (Nippon Rika Co., Ltd. (dibenzylidene sorbitol)) The formulation is as shown in Table 1.

(Comparative Example 4) The composition of the outer layer and the intermediate layer was the same as in Example 2, and a three-layer sheet having a thickness of each layer of 0.1 / 0.1 / 0.1 mm was prepared in the same manner as in Example 1. did. (Comparative Example 5) A propylene homopolymer (MFR = 0.5) was used in place of PP-2 of Example 2, and the other procedures were the same as in Example 2.

The results of evaluating the obtained sheets of Examples 1 to 5 and Comparative Examples 1 to 5 by the following methods are shown in Tables 2 and 3, respectively. Although all the evaluations are satisfied for Examples 1 to 5, Comparative Examples 1 and 4 have poor pocket thickness uniformity, Comparative Example 2 has poor impact resistance, and n-heptane extraction results are reported by the Ministry of Health and Welfare 20 Does not conform to the issue. Comparative Example 3 is inferior in rigidity, and Comparative Example 5 is inferior in impact resistance. Example 2,
X1 and X2 of Comparative Examples 2 and 3 do not exist. That is, there is no upper yield point.

The evaluation method is as follows. X1 / X2: shape and dimensions shown in FIG. 2 (6.3 m width)
m) at 135 ° C, 1000 mm / m
It was measured by a tensile test at a constant speed of in. The first maximum point (upper yield point) of the load within 200% elongation is X
1. The first minimum point is X2. (FIG. 1) PTP moldability: In a PTP molding machine (FBP-M2 manufactured by CKD Co., Ltd.), a tablet type (diameter 10)
mmφ, depth 5 mm), and the molding temperature range was determined by comprehensive evaluation of the mold followability to the molding die, the unevenness of the appearance of the pocket top, and the thickness of the top. The mold followability and the uneven appearance of the top were visually evaluated, and the thickness of the top was obtained by measurement with a dial gauge. The uniformity of the thickness distribution of the molding pocket was divided into two parts by a cutter blade and determined by a photograph of a cross section. The curl after punching is molded under the best conditions in the above evaluation of the molding temperature range, without filling the contents, sealing with aluminum foil at 180 ° C., slitting at 130 ° C., width 37 mm, 94mm length, 5m corner
The molded product punched to mR was placed on a flat surface, and the warpage of the molded product 10 minutes after punching was measured. The six molded articles were measured at six locations beside each molding pocket, and the average value was determined for evaluation. As the aluminum foil, a hard aluminum foil having a thickness of 20 μm and a maleated polypropylene having a thickness of 5 μm applied thereto was used. -Transparency; JIS-K-7105 for the internal haze of the sheet
It measured based on. -Flexural rigidity: measured according to JIS-K-7106. -Impact resistance: by a method in accordance with JIS-K-7211,
The Dupont impact value at 23 ° C. was measured. -N-heptane extraction; measured according to Ministry of Health and Welfare Notification No.20.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

The PP-based PTP sheet of the present invention improves the formability and impact resistance of polypropylene-based sheets, which have been problems of the prior art, and is widely used as a PTP sheet. Useful as a replacement for vinyl.

[Brief description of the drawings]

FIG. 1 is an example of a tensile test result at 135 ° C. of the present invention.

FIG. 2 is a plan view of a test piece in a tensile test.

Claims (5)

[Claims] 1. An outer layer made of a homopolymer of polypropylene having a thickness of 0.005 to 0.095 mm, a nucleating agent content of 0.002 to 0.3% by weight and an ethylene content of 0.1.
~ 5.0% ethylene-propylene random copolymer 7
The thickness of three layers consisting of an intermediate layer of a resin composition comprising 0 to 95% by weight and 5 to 30% by weight of a petroleum resin is 0.15 to
In a 0.45 mm PP-based sheet, an upper yield point does not exist within an elongation of 200% in a tensile test at 135 ° C., or if it exists, a first maximum point of load (upper yield point) X ₁ , a first yield point when the minimum point X _2, PP-based PTP sheet, characterized in that they satisfy the following formula (1). 1 ≦ X ₁ / X ₂ ≦ 1.25 (1) 2. The PP-based PTP sheet according to claim 1, wherein the petroleum resin of the intermediate layer is a hydrogenated petroleum resin. 3. The PP according to claim 2, wherein the hydrogenated petroleum resin of the intermediate layer is a hydrogenated product of a dicyclopentadiene-based petroleum resin, an aromatic petroleum resin, or an aliphatic petroleum resin.
System PTP sheet. 4. The hydrogenated petroleum resin of the intermediate layer is a hydrogenated product of a copolymer of at least two components selected from dicyclopentadiene petroleum resin, aromatic petroleum resin, and aliphatic petroleum resin. 2. The PP-based PTP sheet according to 2. 5. The hydrogenated petroleum resin of the intermediate layer is at least two components selected from hydrogenated dicyclopentadiene petroleum resin, hydrogenated aromatic petroleum resin, and hydrogenated petroleum resin. 3. A blend of
The PP-based PTP sheet described in the above.