JP5424547B2 - In-mold label and molded product using the same - Google Patents

Description

  The present invention relates to an in-mold label and a molded article using the same. More specifically, the present invention relates to an in-mold molding label that can be molded even at a low temperature and a molded article using the same.

  In-mold molding is known as a method for producing a resin molded body with a label attached thereto by integral molding. In this method, a label is previously attached to the inside of the mold, and a molding resin such as polyethylene resin or polypropylene resin is melted and directly supplied into the mold, and then molded by injection molding, hollow molding, or the like. A label is attached (Patent Documents 1 and 2).

As a requirement for in-mold molding, it is necessary to strengthen the adhesion between the label and the molded product. Therefore, if the molding temperature of the molded product is low, sufficient adhesion strength cannot be obtained between the molded product and the label. Therefore, it is necessary to set the molding temperature of the molded product high, and the molding temperature of the molded product is extremely limited. The problem that productivity falls is pointed out.
JP 58-069015 A Japanese Patent Laid-Open No. 01-125225

  An object of the present invention is to provide an in-mold molding label that can be molded in-mold even at a low temperature and can cope with a wide range of molding conditions, and a molded product using the same.

  As a result of intensive studies on in-mold molding labels in order to solve the above problems, the present inventors have found that in-mold molding can be performed even at a low molding temperature, and the present invention has been completed.

That is, this invention is specified by the matter described below.
The label for in-mold molding of the present invention is polymerized by a metallocene catalyst system, the melt flow rate is in the range of 0.1 to 40 g / 10 min, the melting point is in the range of 120 to 155 ° C., and the following (1 ) To (3) satisfying a portion insoluble in room temperature n-decane (D _insol ) 90 to 60
A portion soluble in room temperature n-decane that satisfies the following (4) to (6) (D _sol ) 10 to 4% by weight:
The propylene-based random block copolymer (A) is composed of 0% by weight, and the sum of the D _insol and the D _sol is 100% by weight.

(1) The molecular weight distribution (Mw / Mn) determined from GPC of D _insol is 1.0 to 3.5.
(2) Content of skeleton derived from ethylene in D _insol is 0.5 to 8 mol%
(3) Sum of propylene 2,1-insertion bond amount and 1,3-insertion bond amount in D _insol is 0.2 mol% or less (4) Molecular weight distribution (Mw / Mn) determined from GPC of D _sol ) Is 1.0 to 3.5
(5) The intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 1.5 to 4 dl / g.
(6) The content of the skeleton derived from ethylene in D _sol is 15 to 35 mol%.

  The in-mold molding label of the present invention is composed of at least two resin films including a heat seal layer and a print layer, and the heat seal layer is composed of the propylene random block copolymer (A). preferable.

  The heat seal layer is preferably a resin film containing the propylene random block copolymer (A), the inorganic fine powder (B) and / or the organic filler (B ′).

  The molded product of the present invention is characterized by using the label for in-mold molding, and the molded product may be molded by direct blow molding, injection stretch blow molding or injection molding. .

  The molded article may be made of at least one thermoplastic resin selected from the group consisting of polypropylene resin, polyethylene resin, polystyrene resin, polyethylene terephthalate resin, polyamide resin, ABS resin, and polyvinyl chloride resin. preferable.

  INDUSTRIAL APPLICABILITY The present invention can provide an in-mold molding label that can be molded in-mold even at a low temperature and can cope with a wider range of molding conditions, and a molded product using the same.

The label for in-mold molding of the present invention is polymerized by a metallocene catalyst system, the melt flow rate is in the range of 0.1 to 40 g / 10 min, the melting point is in the range of 120 to 155 ° C., and the above (1 ) To (3) satisfying a portion insoluble in room temperature n-decane (D _insol ) 90 to 60
A portion soluble in room temperature n-decane satisfying (4) to (6) above (% _sol ) (D _sol ) 10 to 4
It is characterized by comprising a propylene-based random block copolymer (A) composed of 0% by weight and having a total of 100% by weight of the D _insol and the D _sol .

<Propylene Random Block Copolymer (A)>
The propylene random block copolymer (A) used in the present invention is a propylene block copolymer obtained by copolymerizing propylene and ethylene in the first polymerization step in the presence of a metallocene catalyst system. It is obtained by producing an ethylene random copolymer and subsequently producing a propylene-ethylene random copolymer rubber in the second polymerization step.

  The melt flow rate (MFR) of the copolymer (A) is 0.1 to 40 g / 10 minutes, preferably 1 to 30 g / 10 minutes, and more preferably 3 to 25 g / 10 minutes. MFR was measured according to ASTM D1238 (230 ° C., load 2.16 kg). When the MFR is in the range of 0.1 to 40 g / 10 min, it is preferable from the viewpoint of the film forming property of the label and the expression of adhesion between the in-mold label and the molded product.

  Furthermore, melting | fusing point of this copolymer (A) is 120-155 degreeC, Preferably it is 125-150 degreeC, More preferably, it exists in the range of 130-145 degreeC. When the melting point is in the range of 120 to 155 ° C., it is preferable from the viewpoint of adhesion between the in-mold label and the molded product and imparting the rigidity of the label.

Such a copolymer (A) includes 90-60% by weight of a portion insoluble in room temperature n-decane (D _insol ) mainly composed of the propylene-ethylene random copolymer produced in the first polymerization step. , Composed of a propylene-ethylene random copolymer rubber produced in the second polymerization step as a main component and soluble in room temperature n-decane (D _sol ) of 10 to 40% by weight, and the above D _insol and the above The total with D _sol is 100% by weight. Here, MFR in the propylene random block copolymer (A), melting point, weight fraction of the portion insoluble in room temperature n-decane (D _insol ), weight of the portion soluble in room temperature n-decane (D _sol ) A fraction can be changed according to various molded object uses.

In the propylene random block copolymer (A), the D _insol satisfies the requirements (1) to (3), and the D _sol satisfies the requirements (4) to (6).
(1) The molecular weight distribution (Mw / Mn) determined from GPC of D _insol is 1.0 to 3.5.
(2) Content of skeleton derived from ethylene in D _insol is 0.5 to 8 mol%
(3) Sum of propylene 2,1-insertion bond amount and 1,3-insertion bond amount in D _insol is 0.2 mol% or less (4) Molecular weight distribution (Mw / Mn) determined from GPC of D _sol ) Is 1.0 to 3.5
(5) The intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 1.5 to 4 dl / g.
(6) The content of the skeleton derived from ethylene in D _sol is 15 to 35 mol%.

Hereinafter, the requirements (1) to (6) included in the propylene random block copolymer (A) will be described in detail.
[Requirement (1)]
The molecular weight distribution (Mw / Mn) obtained from GPC (gel permeation chromatography) of a portion (D _insol ) insoluble in room temperature n-decane of the propylene random block copolymer (A) used in the present invention is 1. It is 0 to 3.5, preferably 1.5 to 3.2, and more preferably 2.0 to 3.0. Thus, about the part ( _Dinsol ) insoluble in room temperature n-decane contained in this copolymer (A), molecular weight distribution (Mw / Mn) _{calculated |} required from GPC
) Can be narrowed as described above because a metallocene catalyst system is used as the catalyst. And when Mw / Mn is larger than 3.5, since the low molecular weight component increases, the bleed out of the film occurs, and the transparency after the heat treatment may decrease.

[Requirement (2)]
The content of the skeleton derived from ethylene in the part insoluble in room temperature n-decane (D _insol ) of the propylene random block copolymer (A) used in the present invention is 0.5 to 8 mol%.
Preferably, it is 0.7-6 mol%, More preferably, it is 1.0-4.5 mol%. When the content of the skeleton derived from ethylene in D _insol is less than 0.5 mol%, the copolymer (A)
The melting point (Tm) of the resin becomes high, and the low temperature heat sealability deteriorates. In addition, if the content of the skeleton derived from ethylene in D _insol is more than 8 mol%, the melting point of the propylene random block copolymer (A) becomes low, and the rigidity of the label at high temperature decreases. , Appearance defects such as wrinkling may occur during in-mold molding.

[Requirement (3)]
Sum of 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in a portion (D _insol ) insoluble in room temperature n-decane of the propylene random block copolymer (A) used in the present invention Is 0.2 mol% or less, preferably 0.1 mol% or less. When the sum of the 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in D _insol is more than 0.2 mol%, the random copolymerizability of propylene and ethylene decreases, and as a result The composition distribution of the propylene-ethylene copolymer rubber in the portion soluble in room temperature n-decane (D _sol ) is _broadened , so that the impact resistance is lowered and the transparency is lowered after the heat treatment. Problems may occur.

[Requirement (4)]
The molecular weight distribution (Mw / Mn) obtained from GPC of the portion soluble in room temperature n-decane (D _sol ) of the propylene random block copolymer (A) used in the present invention is 1.0 to 3.
. 5, Preferably it is 1.2-3.0, More preferably, it is 1.5-2.5. As described above, the molecular weight distribution (Mw / Mn) obtained from GPC for the part (D _sol ) soluble in room temperature n-decane of the copolymer (A) can be narrowed as described above. This is because a catalyst system is used. And when Mw / Mn is larger than 3.5, since low molecular weight propylene-ethylene random copolymer rubber increases in D _sol , a bleed component is generated over time, and the transparency of the label deteriorates. Problems such as blocking may occur.

[Requirement (5)]
The intrinsic viscosity [η] in 135 ° C. decalin of the portion (D _sol ) soluble in room temperature n-decane of the propylene random block copolymer (A) used in the present invention is 1.5-4.
dl / g, preferably more than 1.5 dl / g and not more than 3.5 dl / g, more preferably 1.8 to 3.5 dl / g, most preferably 2.0 to 3.0 dl / g. In the production of such a random block copolymer, when a catalyst other than the metallocene catalyst system used in the present invention is used, a propylene random block copolymer (A) having an intrinsic viscosity [η] exceeding 1.5 dl / g (A It is extremely difficult to produce a propylene random block copolymer (A) having an intrinsic viscosity [η] of 1.8 dl / g or more. In addition, the intrinsic viscosity of the intrinsic viscosity D _sol in 135 ° C. decalin [
If η] is higher than 4 dl / g, a very small amount of propylene-ethylene random copolymer rubber is produced as a by-product in the production of propylene-ethylene random copolymer rubber in the second polymerization step. To do. The propylene-ethylene random copolymer rubber produced as a by-product in a minute amount is non-uniformly present in the propylene random block copolymer (A), so that appearance such as reduced impact resistance and fish eyes is generated. Problems may occur.

[Requirement (6)]
The content of the skeleton derived from ethylene in the portion soluble in room temperature n-decane (D _sol ) of the propylene-based random block copolymer (A) used in the present invention is 15 to 35 mol%,
Preferably it is 18-30 mol%, More preferably, it is 20-25 mol%. When the content of the skeleton derived from ethylene in D _sol is lower than 15 mol%, the label adhesion of the propylene random block copolymer is lowered. Further, if the content of the skeleton derived from ethylene in D _sol is higher than 35 mol%, the transparency may be lowered.

The content of normally 17 to 35 mole% of the backbone derived from the room temperature n- decane ethylene in the portion soluble (D _sol), preferably by in the range of 20 to 30 mol%, Transparency is less likely to decrease, and label adhesion is less likely to decrease.

  The propylene random block copolymer (A) used in the present invention is preferably a propylene random block copolymer comprising propylene and a small amount of ethylene in the first polymerization step ([Step 1]) in the presence of a metallocene catalyst. Propylene random block copolymer obtained by producing propylene-ethylene copolymer rubber by copolymerizing propylene and a larger amount of ethylene than the first step in the second polymerization step ([Step 2]) after the production of the polymerization. It is a polymer.

  The metallocene catalyst used in the present invention includes a metallocene compound and at least one compound selected from compounds capable of reacting with an organometallic compound, an organoaluminum oxy compound and a metallocene compound to form an ion pair, A metallocene catalyst comprising a particulate carrier as required, preferably a metallocene catalyst capable of performing stereoregular polymerization such as isotactic or syndiotactic structure. Among the metallocene compounds, the following crosslinkable metallocene compounds exemplified in the international application (WO01 / 27124 pamphlet) by the applicant of the present application are used.

In the general formula [I], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and may be the same or different. Such hydrocarbon groups include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n -Linear hydrocarbon group such as nyl group and n-decanyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group Branched hydrocarbons such as 1-methyl-1-propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl Groups: cyclic saturated hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl; phenyl, tolyl, naphthyl, biphenyl Cyclic unsaturated hydrocarbon groups such as enyl, phenanthryl and anthracenyl groups; saturated hydrocarbon groups substituted with cyclic unsaturated hydrocarbon groups such as benzyl, cumyl, 1,1-diphenylethyl and triphenylmethyl A hetero atom-containing hydrocarbon group such as methoxy group, ethoxy group, phenoxy group, furyl group, N-methylamino group, N, N-dimethylamino group, N-phenylamino group, pyryl group, thienyl group, etc. Can do. Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group.

In the general formula [I], the substituents R ^{5 to} R ¹² may be bonded to adjacent substituents to form a ring. Such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.

In the general formula [I], R ¹ , R ² , R ³ , and R ⁴ substituted on the cyclopentadienyl ring are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 1 to 1 carbon atom
Examples of the hydrocarbon group 20 include the above-described hydrocarbon groups. More preferably, R ³ is a hydrocarbon group having 1 to 20 carbon atoms.

In the above general formula [I], R ^{5 to} R ¹² substituted on the fluorene ring have 1 to 20 carbon atoms.
The hydrocarbon group is preferably. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups listed above. In the substituents R ^{5 to} R ¹² , adjacent substituents may be bonded to each other to form a ring.

In the general formula [I], Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a group 14 element of the periodic table, more preferably carbon, silicon, or germanium, and still more preferably a carbon atom. It is. R ¹³ and R ¹⁴ substituted on Y are preferably a hydrocarbon group having 1 to 20 carbon atoms. These may be the same as or different from each other, and may be bonded to each other to form a ring. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups listed above. More preferably, R ¹⁴ is aryl having 6 to 20 carbon atoms (a
ryl) group. Examples of the aryl group include the above-mentioned cyclic unsaturated hydrocarbon group, a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group, and a heteroatom-containing cyclic unsaturated hydrocarbon group. R ¹³ and R ¹⁴ may be the same or different, and may be bonded to each other to form a ring. As such a substituent, a fluorenylidene group, a 10-hydroanthracenylidene group, a dibenzocycloheptadienylidene group, and the like are preferable.

In the metallocene compound represented by the above general formula [I], the substituent selected from R ¹ , R ⁴ , R ⁵ or R ¹² and R ¹³ or R ^{14 at the} bridging part are bonded to each other to form a ring. May be.
In the above general formula [I], M is preferably a Group 4 transition metal of the periodic table, more preferably Ti, Zr, or Hf. Q is selected from the same or different combinations from a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy. And ethers such as ethane. It is preferable that at least one Q is a halogen atom or an alkyl group.

Such bridged metallocene compounds include diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl). ) (2,
7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (methyl) (Phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrobenzofluorenyl) zirconium dichloride, [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene) Zirconium dichloride (see the following formula [II]) and the like are preferred.

  In the metallocene catalyst used in the present invention, an ion pair reacts with an organometallic compound, an organoaluminum oxy compound, and a transition metal compound used together with the Group 4 transition metal compound represented by the general formula [I]. At least one compound selected from the compounds that form, and a particulate carrier that is used as necessary. These are disclosed in the above-mentioned publication (WO01 / 27124 pamphlet) or JP-A-11-315109. The compounds disclosed in the publication can be used without limitation.

  The propylene random block copolymer (A) in the present invention uses a polymerization apparatus in which two or more reaction apparatuses are connected in series, and continuously performs the following two steps ([Step 1] and [Step 2]). It is obtained by carrying out.

[Step 1] copolymerizes propylene and ethylene at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 1], the propylene-based random copolymer produced in [Step 1] is made the main component of D _{insol by reducing} the amount of ethylene fed relative to propylene.

In [Step 2], propylene and ethylene are copolymerized at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 2], the propylene-ethylene copolymer rubber produced in [Step 2] becomes the main component of D _sol by increasing the amount of ethylene fed to propylene than in [Step 1]. To do.

By doing in this way, requirements (1)-(3) concerning D _insol are adjusted by adjusting polymerization conditions in [Step 1], and requirements (4)-(6) concerning D _sol are [Step 2]. It can be satisfied by adjusting the polymerization conditions.

Further, the physical properties that the propylene random block copolymer (A) used in the present invention should satisfy are often determined by the chemical structure of the metallocene catalyst used. Specifically, requirement (1) molecular weight distribution (Mw / Mn) obtained from GPC of D _insol , requirement (3) 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in D _insol , Requirement (4) molecular weight distribution (Mw / Mn) obtained from GPC of D _sol , and melting point of propylene-based random block copolymer (A) mainly in [Step 1] and [Step 2] By appropriate selection of the metallocene catalyst used, it can be adjusted to meet the requirements of the present invention. The metallocene catalyst preferably used in the present invention is as described above.

Further, the content of the skeleton derived from ethylene in the requirement (2) D _insol can be adjusted by the amount of ethylene feed in [Step 1]. Requirement (5) The intrinsic viscosity [η] of D _sol in 135 ° C. decalin can be adjusted by the feed amount of a molecular weight regulator such as hydrogen in [Step 2]. Requirement (6) The content of the skeleton derived from ethylene in D _sol can be adjusted by the amount of ethylene feed in [Step 2]. Furthermore, by adjusting the amount ratio of the polymer produced in [Step 1] and [Step 2], the composition ratio of D _insol and D _sol and the melt flow of the propylene random block copolymer (A) It is possible to adjust the rate appropriately.

  In addition, the propylene random block copolymer (A) used in the present invention is produced by the propylene-ethylene random copolymer produced in [Step 1] of the above method and [Step 2] of the above method. Propylene-ethylene random copolymer rubbers may be produced separately in the presence of a metallocene compound-containing catalyst and then blended using these physical means.

<Elastomer (C)>
An elastomer (C) can be added to the propylene random block copolymer (A) used in the present invention for the purpose of improving the adhesion between the in-mold label and the molded product.

  As the elastomer (C), ethylene-α-olefin random copolymer (Ca), ethylene-α-olefin / non-conjugated polyene random copolymer (Cb), hydrogenated block copolymer (Cc) ), Propylene-α-olefin copolymer (Cd), other elastic polymers, and mixtures thereof.

  The content of the elastomer (C) in the propylene resin composition containing the propylene random block copolymer (A) and the elastomer (C) varies depending on the properties to be imparted, but is usually 1 to 50% by weight, preferably Is 3 to 30% by weight, more preferably 5 to 25% by weight.

  The ethylene-α-olefin random copolymer rubber (Ca) is a random copolymer rubber of ethylene and an α-olefin having 3 to 20 carbon atoms. In the ethylene-α-olefin random copolymer rubber (Ca), the molar ratio between the structural unit derived from ethylene and the structural unit derived from α-olefin (structural unit derived from ethylene / α- The structural unit derived from olefin) is usually 95/5 to 15/85, preferably 80/20 to 25/75. Moreover, MFR measured by 230 degreeC and the load of 2.16 kg about this ethylene-alpha-olefin random copolymer (Ca) is 0.1 g / 10min or more normally, Preferably it is 0.5-30 g / 10 Within minutes.

The ethylene-α-olefin-nonconjugated polyene random copolymer (Cb) is a random copolymer rubber of ethylene, an α-olefin having 3 to 20 carbon atoms, and a nonconjugated polyene. Examples of the α-olefin having 3 to 20 carbon atoms include those described above. As non-conjugated polyethylene, 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene Acyclic dienes such as norbornadiene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1, Examples include chain non-conjugated dienes such as 5-heptadiene, 6-methyl-1,7-octadiene, and 7-methyl-1,6-octadiene; and trienes such as 2,3-diisopropylidene-5-norbornene. . Among these, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are preferably used. In the ethylene-α-olefin-nonconjugated polyene random copolymer (Cb), the structural unit derived from ethylene is usually 94.9 to 0.1 mol%, preferably 89.5 to 40 mol%. Yes, the structural unit derived from α-olefin is usually 5 to 45 mol%, preferably 10 to 40 mol%, the structural unit derived from non-conjugated polyene is usually 0.1 to 25 mol%, Preferably it is 0.5-20 mol%. However, in the present invention, the total of the structural unit derived from ethylene, the structural unit derived from α-olefin, and the structural unit derived from non-conjugated polyene is 100 mol%. The MFR measured at 230 ° C. under a load of 2.16 kg for the ethylene-α-olefin-nonconjugated polyene random copolymer (Cb) is usually 0.05 g / 10 min or more, preferably 0.1-30 g / 10. Within minutes. Specific examples of the ethylene-α-olefin-nonconjugated polyene random copolymer (Cb) include ethylene-propylene-diene terpolymer (EPDM).

  The hydrogenated block copolymer (Cc) is a hydrogenated product of a block copolymer whose block form is represented by the following formula (a) or (b), and the hydrogenation rate is usually 90 mol%. More preferably, the hydrogenated block copolymer is 95 mol% or more.

Examples of the monovinyl-substituted aromatic hydrocarbon constituting the polymerization block represented by X in the above formula (a) or formula (b) include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, and lower alkyl-substituted styrene. And styrene such as vinyl naphthalene or derivatives thereof. These can be used alone or in a combination of two or more. Examples of the conjugated diene constituting the polymer block represented by Y in the formula (a) or (b) include butadiene, isoprene, chloroprene and the like. These can be used alone or in a combination of two or more. n is usually an integer of 1 to 5, preferably 1 or 2. Specific examples of the hydrogenated block copolymer (Cc) include styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and styrene. -Styrenic block copolymers such as ethylene-propylene block copolymer (SEP). The block copolymer before hydrogenation can be produced, for example, by a method in which block copolymerization is performed in an inert solvent in the presence of a lithium catalyst or a Ziegler catalyst. A detailed manufacturing method is described in, for example, Japanese Patent Publication No. 40-23798. The hydrogenation treatment can be performed in an inert solvent in the presence of a known hydrogenation catalyst. Detailed methods are described in, for example, Japanese Patent Publication Nos. 42-8704, 43-6636, and 46-20814. When butadiene is used as the conjugated diene monomer, the ratio of the 1,2-bond amount in the polybutadiene block is usually 20 to 80% by weight, preferably 30 to 60% by weight. A commercial item can also be used as a hydrogenated block copolymer (Cc). Specific examples include Clayton G1657 (registered trademark) (manufactured by Shell Chemical Co., Ltd.), Septon 2004 (registered trademark) (manufactured by Kuraray Co., Ltd.), Tuftec H1052 (registered trademark) (manufactured by Asahi Kasei Co., Ltd.), and the like. Is mentioned.

  The propylene-α-olefin copolymer rubber (Cd) is a random copolymer rubber of propylene and an α-olefin having 4 to 20 carbon atoms. In the propylene-α-olefin random copolymer (Cd), the molar ratio between the structural unit derived from propylene and the structural unit derived from α-olefin (the structural unit derived from propylene / α-olefin). The structural unit derived from is usually 95/5 to 5/95, preferably 80/15 to 20/80. In the propylene-α-olefin random copolymer rubber (Cd), two or more α-olefins may be used, and one of them may be ethylene. Propylene-α-olefin random copolymer rubber (Cd) has an MFR measured at 230 ° C. and a load of 2.16 kg is usually 0.1 g / 10 min or more, preferably in the range of 0.5-30 g / 10 min. Is in.

Elastomer (C) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
In the present invention, the elastomer (C) is usually used in an amount in the range of 0 to 50 parts by weight, preferably 1 to 50 parts by weight, relative to 100 parts by weight of the propylene-based block random copolymer (A). To do.

<Polyethylene resin (D)>
The propylene random block copolymer (A) of the present invention is used together with the elastomer (C) for the purpose of imparting functions such as imparting adhesion between the in-mold label and the molded product and imparting high-speed extrusion film-forming property of the label. Alternatively, polyethylene resin (D) may be added instead of elastomer (C).

For example, when imparting impact resistance while suppressing a decrease in transparency, a density of 0.900 to 0.930 kg / manufactured by copolymerizing ethylene and a C4 or higher α-olefin in the presence of a metallocene catalyst. It is preferred to add m ³ linear low density polyethylene.

As another example, when improving the high-speed extrusion film-forming property of a label, it is desirable to add high-pressure polyethylene. Here, the high-pressure polyethylene is a polyethylene having a long chain branch obtained by radical polymerization of ethylene in the presence of peroxide at a pressure of 100 kg / cm ² or more. The preferred melt flow rate (ASTM D1238, measured at 190 ° C., load 2.16 kg) of the high pressure polyethylene is usually in the range of 0.01-100 g / 10 min, preferably 0.1-10 g / 10 min. . The density (ASTM D1505) is usually 0.900 to 0.940 g / cm ³ , preferably 0.91.
It is in the range of 0 to 0.930 g / cm ³ .

  The content of the polyethylene resin (D) in the propylene-based resin composition containing the propylene-based random block copolymer (A) and the polyethylene resin (D) varies depending on the properties to be imparted, but is usually 0 to 50% by weight. , Preferably 1 to 50 parts by weight, particularly preferably 3 to 30% by weight, more preferably 5 to 25% by weight. A polyethylene resin (D) can also be used individually by 1 type, and can also be used in combination of 2 or more type. However, in the propylene resin composition of the present invention, the above-mentioned elastomer (C) and the polyethylene resin (D) do not simultaneously become 0 parts by weight.

In the case of a propylene-based resin composition comprising a propylene-based random block copolymer (A), an elastomer (C), and a polyethylene resin (D), the amount of the propylene-based random block copolymer (A) is given. Depending on the characteristics, it is usually in the range of 50 to 99% by weight, preferably 70 to 97% by weight, more preferably 75 to 95% by weight. Further, the total amount of the elastomer (C) and the polyethylene resin (D) is usually 1 to 50% by weight, preferably 3 to 30% by weight, further based on 100 parts by weight of the propylene block random copolymer (A). Preferably it is 5-25% of polymerization. In addition, the ratio of an elastomer and polyethylene can be arbitrarily adjusted according to the objective.

<Crystal nucleating agent (E)>
A crystal nucleating agent (E) may be added to the propylene random block copolymer (A) or the polypropylene of the present invention, if necessary, for imparting rigidity of the in-mold label.

  Examples of the crystal nucleating agent (E) used in the present invention include sorbitol compounds such as dibenzylidene sorbitol, organophosphate compounds, rosinate compounds, aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and their A metal salt etc. can be mentioned.

  Of these, organophosphate compounds are preferred. The organic phosphate ester compound is a compound represented by the following general formula [III] and / or [IV].

In the above formulas [III] and [IV], R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ are hydrogen atoms or hydrocarbons having 1 to 10 carbon atoms. R ² and R ³ may be the same or different, M is a 1-3 valent metal atom, and n is 1
Is an integer of ˜3, and m is 1 or 2.

Specific examples of the organic phosphate compound represented by the general formula [III] include sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-6-
t-butylphenyl) phosphate, lithium-2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate, lithium-2,2′-methylene-bis (
4-ethyl-6-tert-butylphenyl) phosphate, sodium-2,2′-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2′-butylidene-bis (4 6-di-t-butylphenyl) phosphate, sodium-2,
2′-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2′-t-octylmethylene-bis (4,6-di-t-butylphenyl) phosphate, Calcium-bis- (2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2′-methylene-bis (4,6-di-t- Butylphenyl) phosphate], barium-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2′-methylene-bis (4-methyl-) 6-t-butylphenyl) phosphate, sodium-2,
2′-methylene-bis (4-ethyl-6-tert-butylphenyl) phosphate, sodium-2,2′-ethylidene-bis (4-m-butyl-6-tert-butylphenyl) phosphate, sodium 2,2′-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2′-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2 ′ -Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [ 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate Phosphate], aluminum-tris [2,2′-methylene-bis (4,6-di-t-butylfel) phosphate], aluminum-tris [2,2′-ethylidene-bis (4,6-di-t) -Butylphenyl) phosphate], and mixtures of two or more thereof.

The hydroxyaluminum phosphate compound represented by the general formula [IV] is also an organophosphate compound that can be used, and particularly represented by the general formula [V], in which R ² and R ³ are both tert-butyl groups. Compounds are preferred.

In the formula [V], R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and m is 1 or 2. A particularly preferred organophosphate compound is a compound represented by the general formula [VI].

In the formula [VI], R ¹ is a methylene group or an ethylidene group. Specifically, hydroxyaluminum-bis [2,2-methylene-bis (4,6-di-t-butyl) phosphate] or hydroxyaluminum-bis [2,2-ethylidene-bis (4,6- Di-t-butyl) phosphate]. Specific examples of the sorbitol compound include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4- p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4 -P-ethylbenzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3,2,4
-Di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (pn-propylbenzylidene) sorbitol, 1,3, 2,4-di (pi-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butylbenzylidene) sorbitol, 1,3,2,4-di (ps-butylbenzylidene) ) Sorbitol, 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p -Ethoxybenzylidene) sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidenesorbitol 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4 Examples include -p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol, and the like. In particular, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol or 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol preferable.

  Specific examples of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms and its metal salt that can be used as the crystal nucleating agent (E) in the present invention include succinic acid, glutaric acid, adipic acid, suberic acid, and sebacic acid. And Li salt, Na salt, Mg salt, Ca salt, Ba salt, Al salt, and the like. In addition, aromatic carboxylic acids and metal salts thereof that can be used as the crystal nucleating agent (D) in the present invention include benzoic acid, allyl-substituted acetic acid, aromatic dicarboxylic acids, and group 1 to 3 metal salts of these periodic tables. Specifically, benzoic acid, p-isopropylbenzoic acid, o-tertiary butyl benzoic acid, p-tertiary butyl benzoic acid, monophenylacetic acid, diphenylacetic acid, phenyldimethylacetic acid, phthalic acid, and These Li salt, Na salt, Mg salt, Ca salt, Ba salt, Al salt etc. can be mentioned.

  The crystal nucleating agent (D) used in the present invention is usually 0.05 to 0.00 per 100 parts by weight of the propylene random block copolymer (A) or the propylene resin composition containing the copolymer. 5 parts by weight, preferably 0.1 to 0.3 parts by weight is added.

  If necessary, the propylene resin (P) may be added to the propylene random block copolymer (A) of the present invention or the propylene resin composition containing the polymer. The propylene resin (P) used here is a propylene homopolymer, propylene / ethylene copolymer, propylene / α-olefin copolymer different from the propylene random block copolymer (A) of the present invention. Polymer, propylene / ethylene block copolymer, propylene / α-olefin block copolymer, syndiotactic propylene polymer, atactic propylene polymer, and the like. Here, as the α-olefin, an α-olefin having 4 to 20 carbon atoms can be used.

  The propylene-based random block copolymer (A) of the present invention or the propylene-based resin composition containing the copolymer is within the range not impairing the object of the present invention. It may contain additives such as stabilizers, weathering stabilizers, slip agents, antiblocking agents, petroleum resins, mineral oils and the like.

  After blending each of the above components and, if necessary, various additives using a mixer such as a Henschel mixer, Banbury mixer, or tumbler mixer, the pellets are obtained using a single or twin screw extruder, and then obtained. A molded body can be obtained by various methods such as extrusion molding, injection molding and injection stretch molding using the pellets and the like.

<Resin film>
The in-mold molding label of the present invention is preferably composed of at least two resin films including a heat seal layer and a printing layer.

  The heat seal layer is a resin film made of the propylene random block copolymer (A) and may further contain an inorganic fine powder (B) and / or an organic filler (B ′).

  Since the heat seal layer can be bonded, the heat seal layer is preferably on the outermost layer (the side in contact with the molded product), and the printed layer can be advertised or decorated, so the innermost layer (the reverse of the outermost layer). Side). In addition, the printing layer and the heat seal layer may appropriately use an adhesive in order to improve the adhesive strength.

The above-mentioned printing layer is preferably a resin film which can be printed as a decorative layer and gas barrier properties, light shielding properties, strength enough to peel off the cover material. Preferred examples of the film satisfying these requirements include propylene (co) polymer film, amide (co) polymer film, and ester (co) polymer film represented by polyethylene terephthalate film. The thickness of the in-mold molding label of the present invention including the printing layer is 30 to 250 μm, preferably 35 to 150 μm.

  The resin film used in the present invention can use an adhesive when laminating the heat seal layer and the print layer, and can be an adhesive resin such as low-density polyethylene or ethylene-vinyl acetate copolymer, urethane. A water-soluble or water-insoluble adhesive such as a resin, an acrylic resin, an epoxy resin, or a modified polyolefin can be used. Usually, when using a film-like thing, it is 5-20 micrometers in thickness, and when using a liquid thing, it is 1-10 micrometers in thickness. The adhesive is preferably selected as appropriate according to the material of the layer to be bonded.

  Examples of the inorganic fine powder (B) that may be contained in the heat seal layer include fine particles of metal oxides such as alumina, silica, magnesia, and ferrite, or silicates such as talc, mica, kaolin, and zeolite, and barium sulfate. And fine particles such as calcium carbonate. Examples of the organic filler (B ′) that may be contained in the heat seal layer include an epoxy resin, a melamine resin, a urea resin, an acrylic resin, a phenol resin, a polyimide resin, a Teflon (registered trademark) resin, a polyethylene resin, and a polyester. Examples thereof include a filler that is polymerized into fine particles until unnecessary in a solvent that uses a resin such as a resin or a polyamide resin, or a filler that has been cross-linked into fine particles. The content of the inorganic fine powder (B) and / or the organic filler (B ′) that may be contained in the heat seal layer is inorganic fine with respect to 100 parts by weight of the propylene random block copolymer (A). The powder (B) is 1 to 160 parts by weight, preferably 20 to 100 parts by weight, and the organic filler (B ′) is 1 to 160 parts by weight, preferably 20 to 100 parts by weight.

<Molded product>
The molded article using the label for in-mold molding of the present invention is at least one selected from the group consisting of polypropylene resin, polyethylene resin, polystyrene resin, polyethylene terephthalate resin, polyamide resin, ABS resin and polyvinyl chloride resin. The thermoplastic resin is preferably used.

The polypropylene-based resin contains at least 1%, preferably 10% or more, more preferably 50% or more, particularly preferably 75% or more as a constituent unit, and α-olefin as another constituent component. Is ethylene or 4 carbon atoms
To 20 α-olefins, specifically 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene,
1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl- 1-hexene, 4
, 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, and the like. These can also be used individually by 1 type and can also be used in combination of 2 or more type.

  The polyethylene-based resin is not particularly limited as long as it has an ethylene-derived structure as a main component. Specifically, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, other ethylene- α-olefin copolymer, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid copolymer, ethylene / unsaturated carboxylic acid copolymer such as ethylene / methyl methacrylate copolymer and ethylene / unsaturated carboxylic acid ester Examples thereof include copolymers and ionomer resins.

The molded product of the present invention may be molded by direct blow molding, injection stretch blow molding or injection molding.
〔Example〕
EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to the Example which concerns. In addition, the measuring method of the physical property in an Example and a comparative example is as follows.

(M1) MFR (melt flow rate)
MFR was measured according to ASTM D1238 (230 ° C., load 2.16 kg).
(M2) Melting point (Tm)
The measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). The endothermic peak at the third step measured here was defined as the melting point (Tm).

(Measurement condition)
First step: The temperature is raised to 240 ° C. at 10 ° C./min and held for 10 minutes.
Second step: The temperature is lowered to 60 ° C. at 10 ° C./min.

Third step: The temperature is raised to 240 ° C. at 10 ° C./min.
(M3) Amount of room temperature n-decane soluble part (D _sol ) 200 ml of n-decane was added to 5 g of the final product (ie, propylene random block polymer of the present invention) and heated and dissolved at 145 ° C. for 30 minutes. . It was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (hereinafter, n-decane insoluble part: D _insol ) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane (precipitate (A)). The precipitate (A) and acetone were separated by filtration, and the precipitate was dried. Even when the filtrate side was concentrated to dryness, no residue was observed.

The amount of n-decane soluble part was determined by the following formula.
n-decane soluble part amount (wt%) = [precipitate (A) weight / sample weight] × 100
(M4) Mw / Mn measurement [weight average molecular weight (Mw), number average molecular weight (Mn)]
It measured as follows using GPC-150C Plus by Waters. The separation columns are TSKgel GMH6-HT and TSKgel GMH6-HTL, the column size is 7.5 mm in inner diameter and 600 mm in length, respectively, and the column temperature is 140 ° C.
The mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) and BHT (Wako Pure Chemical Industries, Ltd.) 0.025% by weight as an antioxidant, which was moved at 1.0 ml / min. The sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene has molecular weights of Mw <1000 and Mw> 4 × 10 ⁶
Tosoh Co., Ltd. was used, and for 1000 ≦ Mw ≦ 4 × 10 ⁶ , manufactured by Pressure Chemical Co., Ltd. was used.

(m5) Content of skeleton derived from ethylene In order to measure the skeleton concentration derived from ethylene in D _insol and D _sol , 20 to 30 mg of sample was subjected to 1,2,4-trichlorobenzene / heavy benzene (2: 1 ) After dissolving in 0.6 ml of the solution, carbon nuclear magnetic resonance analysis ( ¹³ C-NMR) was performed. Propylene, ethylene and α-olefin were quantitatively determined from the dyad chain distribution. For example, in the case of propylene-ethylene copolymer,

Was obtained by the following calculation formulas (Eq-1) and (Eq-2).

(M6) Intrinsic viscosity [η]
It measured at 135 degreeC using the decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity η _sp was measured in the same manner. This dilution operation was further repeated twice, and the value of η _sp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity.

[Η] = lim (η _sp / C) (C → 0)
(m7) Measurement of 2,1-insertion bond amount and 1,3-insertion bond amount
^{Using 13} C-NMR, the 2,1-insertion bond amount and 1,3-insertion bond amount of propylene were measured according to the method described in JP-A-7-145212.

(M8) Heat sealability of film (minimum heat seal temperature)
The film was sampled to a width of 5 mm, sealed with a sealing time of 1 second and a pressure of 0.2 MPa. The top temperature of the seal bar was varied, the both ends of the film heat-sealed at 70 ° C. were pulled at 300 mm / min, the maximum peel strength was measured, and a diagram plotting the relationship between the top temperature and the heat seal strength was created. . From this plot, the temperature at which the heat seal strength was 1 N / 15 mm was read and taken as the minimum heat seal temperature.

(M9) Young's modulus of film The Young's modulus of a stretched film was measured according to JIS K6781. The tensile speed is 200 mm / min, and the distance between chucks is 80 mm.

(M10) Haze of film (HAZE)
Measured according to ASTM D-1003.
Moreover, in order to evaluate the change of transparency with time, haze measurement was similarly performed on a film after heat treatment at 80 ° C. for 4 days.

(M11) Cross-cut peel test In-mold molded product label surface is cut in a grid pattern at intervals of 2 mm, and vertical and horizontal incisions reaching the molded product body are made. I made my eyes. After that, after sticking an adhesive tape (Nichiban Co., Ltd., “Cellotape (registered trademark)” 24 mm width, industrial use) on the surface of the molded product at 25 ° C., it is peeled off vigorously, and the in-mold label is peeled off together with the tape. Evaluated. The case where there was no peeling was rated as ◯ (good), and the case where there was one or more peeling was rated as x (defective).

[Production Example 1]
(1) Production of solid catalyst carrier 300 g of SiO ₂ was sampled in a 1-liter branch flask and 800 m of toluene.
l was added to make a slurry.

Next, the slurry was transferred to a 4-liter flask having a volume of 5 liters, and 260 ml of toluene was added.
2830 ml of methylaluminoxane (hereinafter MAO) -toluene solution (Albemarle 10 wt% solution) was introduced into the solution, and the mixture was stirred at room temperature for 30 minutes. The temperature was raised to 110 ° C. over 1 hour, and the reaction was carried out for 4 hours. After completion of the reaction, it was cooled to room temperature. After cooling, the supernatant toluene was extracted and replaced with fresh toluene until the replacement rate reached 95%.

(2) Production of solid catalyst component (support of metal catalyst component on carrier)
In a glove box, diphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-di-t) synthesized in accordance with the description of WO2004 / 08775 in a 5-liter four-necked flask was prepared. -Butylfluorenyl) zirconium dichloride (M1) was weighed 2.0 g. The flask was taken out of the glove box, 0.46 liters of toluene and 1.4 liters of MAO / SiO ₂ / toluene slurry prepared in the above (1) were added under nitrogen, and the mixture was stirred for 30 minutes to carry.

The obtained diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (
The 2,7-t-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% substituted with n-heptane to a final slurry volume of 4.5 liters. This operation was performed at room temperature.

(3) Production of prepolymerized catalyst 202 g of the solid catalyst component prepared in (2) above, 109 ml of triethylaluminum, and 100 liters of heptane were introduced into an autoclave with a stirrer having an internal volume of 200 liters, and the internal temperature was maintained at 15 to 20 ° C. 2020 g of ethylene was introduced and reacted with stirring for 180 minutes.

  After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 2 g / liter. This prepolymerized catalyst contained 10 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, the catalyst slurry produced in the above (3) is used as a solid catalyst component, 3.6 g / hour, triethylaluminum 2 .2 g / hour was continuously fed, and polymerization was performed in a full liquid state in which no gas phase was present in the tubular polymerizer. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.11 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 61 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-1). The resulting propylene random block copolymer (A-1) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-1) are shown in Table 1.

[Production Example 2]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 3.6 g / hour as a solid catalyst component. Triethylaluminum (2.2 g / hour) was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerization reactor. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization reactor, propylene is 10 kg / hour, hydrogen is 0.1% in the gas phase.
It supplied so that it might become mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 54 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-2). The resulting propylene random block copolymer (A-2) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-2) are shown in Table 1.

[Production Example 3]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 2.7 g / hour as a solid catalyst component. 1.6 g / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerizer. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.4 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.4 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.4 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. Propylene was supplied to the polymerization vessel at a rate of 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.2 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 61 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-3). The resulting propylene random block copolymer (A-3) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-3) are shown in Table 1.

[Production Example 4]
(1) Preparation of Solid Titanium Catalyst Component 952 g of anhydrous magnesium chloride, 4420 ml of decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution, 213 g of phthalic anhydride was added, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

After cooling the homogeneous solution thus obtained to 23 ° C., 750 ml of this homogeneous solution was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 52.2 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. Held on. Subsequently, the solid part was collected by hot filtration, and the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.

After the heating, the solid part was again collected by hot filtration, and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.
The solid titanium catalyst component prepared as described above was stored as a hexane slurry, and a part of the catalyst was dried to examine the catalyst composition. The solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP.

(2) Preparation of prepolymerization catalyst 56 g of transition metal catalyst component, 8.0 g of triethylaluminum, and 80 liters of heptane were introduced into an autoclave with a stirrer having an internal volume of 200 liters, and the internal temperature was kept at 5 ° C. and 560 g of propylene was inserted for 60 minutes. The reaction was carried out with stirring. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane and prepared by adding heptane so that the transition metal catalyst component concentration was 0.7 g / liter. This prepolymerized catalyst contained 10 g of polypropylene per 1 g of the transition metal catalyst component.

(3) Main polymerization A tubular polymerizer having an internal volume of 58 liters was supplied with 30 kg / hour of propylene, 0.4 kg / hour of ethylene, 300 Nliter / hour of hydrogen, 0.4 g / hour of catalyst slurry as a solid catalyst component, triethylaluminum 2 0.7 g / hour and 1.8 g / hour of dicyclopentyldimethoxysilane were continuously fed, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerizer. The temperature of the annular reactor was 65 ° C., and the pressure was 3.6 MPa / G. The catalyst in this reaction is a ZN catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 15 kg / hour, ethylene at 0.3 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 15.0 mol%. Polymerization was performed at a polymerization temperature of 63 ° C. and a pressure of 3.4 MPa / G.

  The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 liters, and the slurry was gasified and subjected to gas-solid separation. After that, a polypropylene homopolymer powder was sent to a 480 liter gas phase polymerization vessel, and ethylene / Propylene block copolymerization was performed. Propylene, ethylene, hydrogen so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.30 (molar ratio), hydrogen / (ethylene + propylene) = 0.068 (molar ratio). Was fed continuously. Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 1.2 MPa / G to obtain a propylene random block copolymer (A-4).

The resulting propylene random block copolymer (A-4) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-4) are shown in Table 1.
[Production Example 5]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.

(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 57 kg / hour, hydrogen is 2.5 Nliters / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component at 5.0 g / For 2.3 hours, 2.3 g / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 2.6 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization reactor, propylene was supplied at 50 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.4 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 60 ° C. and a pressure of 2.5 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters and further polymerized. To the polymerization reactor, propylene was supplied at 11 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.4 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 59 ° C. and a pressure of 2.4 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-ethylene random copolymer (R-1). Obtained propylene-ethylene random copolymer (R-1) at 80 ° C.
And dried in vacuum. The properties of the resulting propylene-ethylene random copolymer (R-1) are shown in Table 1.

[Production Example 6]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerizer having an internal volume of 58 liters, propylene is 57 kg / hour, hydrogen is 2.5 Nliters / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component. For 2.3 hours, 2.3 g / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerizer. The temperature of the tubular reactor was 30 ° C., and the pressure was 2.7 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization reactor, propylene was supplied at 50 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 3.9 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.28 mol%. Polymerization was performed at a polymerization temperature of 60 ° C. and a pressure of 2.6 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters and further polymerized. To the polymerization reactor, propylene was supplied at 11 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 3.9 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.28 mol%. Polymerization was performed at a polymerization temperature of 59 ° C. and a pressure of 2.5 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-ethylene random copolymer (R-2). Obtained propylene-ethylene random copolymer (R-2) at 80 ° C.
And dried in vacuum. The properties of the resulting propylene-ethylene random copolymer (R-2) are shown in Table 1.

With respect to 100 parts by weight of the propylene random block copolymer (A-1) produced in Production Example 1, 0.1 part by weight of thermal stabilizer IRGANOX 1010 (trademark of Ciba Geigy Corp.), thermal stabilizer IRGAFOS 168 (Ciba Geigy ( (Trademark) 0.1 parts by weight and 0.1 parts by weight of calcium stearate were mixed with a tumbler, and then melt-kneaded with a twin screw extruder to prepare a pellet-shaped polypropylene resin composition. About the said polypropylene resin composition, the 30-micrometer-thick cast film was formed into a film with T-die extruder [product number GT-25A, product made from Plastic Engineering Laboratory]. Table 2 shows the physical properties of cast film molded articles having a thickness of 30 μm.

(Melting and kneading conditions)
Same-direction biaxial kneader: Part number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 180 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 400rpm
(Film forming conditions)
25 mmΦT die extruder: Part No. GT-25A, manufactured by Plastic Engineering Laboratory Co., Ltd. Extrusion temperature: 230 ° C
Chill roll temperature: 30 ° C
Take-off speed: 8.5 m / min Cast film thickness: 30 μm
<In-mold molding>
The polypropylene resin composition was cast into a film having a thickness of 70 μm using a T-die extruder [product number GT-25A, manufactured by Plastic Engineering Laboratory Co., Ltd.] to produce an in-mold label. Using an injection molding machine (NV50ST / clamping 50 tons, vertical arrangement type) manufactured by Niigata Co., Ltd., the mold for injection molding is a flat plate with a molded product size of 130 mm wide, 150 mm long and 2 mm thick. After fixing the label on the surface of the female mold attached to the lower fixed plate side, and then clamping the split mold, polypropylene (manufactured by Prime Polymer Co., Ltd., Prime Polypro J715M (MFR: 9 g / 10 minutes)) was injection molded. After the molten resin injected into the mold was cooled and solidified and the label was fused, the mold was opened to obtain a PP injection molded product with the label attached. Table 2 shows the adhesion data of the in-mold label.

(Label filming conditions)
25 mmΦT die extruder: Part No. GT-25A, manufactured by Plastic Engineering Laboratory Co., Ltd. Extrusion temperature: 230 ° C
Chill roll temperature: 30 ° C
Take-off speed: 3.0 m / min Label film thickness: 70 μm
(In-mold molding conditions)
Injection molding machine: NV50ST manufactured by Niigata Steel Co., Ltd.
Injection temperature: 190 ° C
Mold temperature: 40 ℃

  In Example 1, it carried out similarly except having used the propylene random block copolymer (A-2) manufactured by manufacture example 2 instead of the propylene random block copolymer (A-1). Table 2 summarizes the film properties and in-mold label adhesion.

[Comparative Example 1]
In Example 1, it carried out similarly except having used the propylene random block copolymer (A-3) manufactured by manufacture example 3 instead of the propylene random block copolymer (A-1). Table 2 summarizes the film properties and in-mold label adhesion.

[Comparative Example 2]
In Example 1, it carried out similarly except having used the propylene random block copolymer (A-4) manufactured by manufacture example 4 instead of the propylene random block copolymer (A-1). Table 2 summarizes the film properties and in-mold label adhesion.

[Comparative Example 3]
In Example 1, it carried out similarly except having used the propylene random copolymer (R-1) manufactured by manufacture example 5 instead of the propylene random block copolymer (A-1). Table 2 summarizes the film properties and in-mold label adhesion.

[Comparative Example 4]
In Example 1, it carried out similarly except having used the propylene random copolymer (R-2) manufactured by manufacture example 6 instead of the propylene random block copolymer (A-1). Table 2 summarizes the film properties and in-mold label adhesion.

  The in-mold molding label of the present invention and a molded product using the same are suitably used for various molded body applications such as an injection molded body, a direct blow molded body, and an injection stretch blow molded body.

Claims (6)

Polymerized by a metallocene catalyst system,
The melt flow rate (MFR: 230 ° C., 2.16 kg) is in the range of 0.1 to 40 g / 10 minutes,
The melting point is in the range of 120-155 ° C.,
The portion insoluble in room temperature n-decane satisfying the following (1) to (3) (D _insol ) 90 to 60% by weight and the portion soluble in room temperature n-decane satisfying the following (4) to (6) (D _sol And 10 to 40% by weight, comprising a propylene random block copolymer (A), wherein the total of the D _insol and the D _sol is 100% by weight. label.
(1) The molecular weight distribution (Mw / Mn) determined from GPC of D _insol is 1.0 to 3.5.
(2) Content of skeleton derived from ethylene in D _insol is 0.5 to 8 mol%
(3) The sum of 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in D _insol is 0.2 mol% or less. (4) Molecular weight distribution determined from GPC of D _sol (Mw / Mn ) Is 1.0 to 3.5
(5) The intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 1.5 to 4 dl / g.
(6) The content of the skeleton derived from ethylene in D _sol is 15 to 35 mol%. Consists of at least two layers of resin film including a heat seal layer and a print layer,
The label for in-mold molding according to claim 1, wherein the heat seal layer is made of the propylene random block copolymer (A).   The heat seal layer is a resin film containing the propylene random block copolymer (A), an inorganic fine powder (B) and / or an organic filler (B '). Or the label for in-mold shaping | molding of 2.   A molded product comprising the in-mold molding label according to claim 1.   The molded article according to claim 4, which is formed by direct blow molding, injection stretch blow molding or injection molding.   The molded article is composed of at least one thermoplastic resin selected from the group consisting of polypropylene resin, polyethylene resin, polystyrene resin, polyethylene terephthalate resin, polyamide resin, ABS resin, and polyvinyl chloride resin. The molded article according to claim 4 or 5.