Technical field
[0001]The present invention is 4-methyl-1-pentene polymer molded body in which a plurality of parts formed in contact with containing and a method for producing the same.
BACKGROUND
[0002]4-methyl-1-pentene polymer although (polymethyl pentene, etc. and also called PMP) used in various applications, and features excellent stain resistance by the surface tension is very low, the transparency excellent scratch resistance, and taking advantage of the feature of high heat resistance, is also used as a material for food storage containers and tableware.
[0003]
　However, so-called two-color molding or by insert molding or the like, when trying to obtain a molded body designs were fused multiple parts which are formed by 4-methyl-1-pentene polymer, parts thereof are sufficiently that it does not adhere has been pointed out in such strength.
[0004]
　Patent Document 1 double molded article using the composition obtained by adding polypropylene polymethylpentene is disclosed. Specifically, Patent Document 1, after the pre-molded resin molded article comprising a first composition containing a polymethylpentene and polypropylene, the outside of the molded body, polymethyl pentene and polypropylene and / or double molded tableware molded with a second composition containing an inorganic filler. Here, Patent Document 1, there by containing polypropylene in an amount within a specific range in the first composition, also the adhesion of the inner and outer molded body is obtained a good double molded tableware It has been disclosed. In Patent Document 1, by the inclusion of polypropylene and / or inorganic filler in the second composition, also dust with hardly cracks occur in the double molded tableware obtained is unlikely to adhere disclosed It is.
[0005]
　On the other hand, Patent Document 1, in any of these compositions is not disclosed that the inclusion of a combination of two or more of polymethylpentene having different melting points from each other.
CITATION
Patent Document
[0006]
Patent Document 1: JP 2010-89305 JP
Summary of the Invention
Problems that the Invention is to Solve
[0007]
　However, for the double molding method disclosed in Patent Document 1, the present inventors have thought that scratch resistance, and in coloring resistance, there is room for improvement. The present inventors have confirmed that one of the polymethylpentene and polypropylene and molded articles obtained from compositions containing, there is a problem that easily damaged and is also insufficient for discoloration resistance doing. This is the data for the composition X'1 described in the examples below, it is specifically shown in Table 2 below.
[0008]
　The present invention has been made in view of the above circumstances, it is an object to solve the above problems. That is, an object of the present invention is a molded body formed in contact with a plurality of portions containing 4-methyl-1-pentene polymer, excellent adhesive strength of the portion between, and resistance of the molded body scratch resistance, and to provide a coloring resistance of the moldings excellent. Further, it is an object to provide a manufacturing method thereof.
Means for Solving the Problems
[0009]
　Specific means for solving the above problems are as follows.
[0010]
　[1] satisfies the following requirements satisfy (A-a) ~ (A -e) 4- methyl-1-pentene (co) polymer and (A), the following requirements (B-a) ~ (B -e) It includes 4-methyl-1-pentene copolymer (B), the (co) polymer (a) and the copolymer (B) and is 100 parts by weight of total (co) polymer of ( the content of a) is 60 to 95 weight parts, the part made is formed from the composition (X) (1),
　formed in contact with said portion (1), the 4-methyl-1-pentene (co) and a portion comprising the polymer (a) (2),
the molded body having a.
(A-a) 4-methyl-1 content of the constituent units derived from pentene (P) is 100 to 90 mol%, of the carbon atoms 2 ~ 20 alpha-olefin (4-methyl-1-pentene excluding.) the content of constituent unit (AQ) derived from 0 to 10 mol%.
(A-b) an intrinsic viscosity measured at 135 ° C. in decalin [eta] is 1.0 ~ 4.0dl / g.
Melting point measured by (A-c) DSC (T m ) is in the range of 200 ~ 250 ° C..
(A-d) crystallization temperature measured with DSC (T c ) is in the range of 0.99 ~ 220 ° C..
(A-e) density of 820 ~ 850 kg / m 3 is.
(B-a) 4-methyl-1 content of the constituent units derived from pentene (P) is less than 65 mol% 96 mol%, of the carbon atoms 2 ~ 20 alpha-olefin (4-methyl - except 1-pentene.) the content of the constituent unit (BQ) derived from of 35 mol% or less than 4 mol%.
(B-b) an intrinsic viscosity measured at 135 ° C. in decalin [eta] is 0.5 ~ 4.0dl / g.
(B-c) gel permeation chromatography weight average molecular weight measured by (GPC) (Mw) and the ratio a is the molecular weight distribution (Mw / Mn) of 1.0 to the number average molecular weight (Mn) 3.5 it is.
When measured in (B-d) DSC, melting point (T m in the range of) ~ Do 100 ° C. is observed 199 ° C..
(B-e) density of 830 ~ 860 kg / m 3 is.
[0011]
　[2] The structural unit (BQ) are molded body according to a structural unit derived from α- olefin having 2 to 4 carbon atoms [1].
[0012]
　[3] In the composition (X), wherein the content of the (co) polymer (A) is 70 to 90 parts by weight, the molded body according to [1] or [2].
[0013]
　[4] the step (1) to preformed said portion (1), the contact with the part (1), including a step (2) to form the said part (2), [1] - [3 method for producing a molded article according to any one of.
[0014]
　[5] by injection molding, to form said portion (1) and part (2), the production method according to [4].
The invention's effect
[0015]
　According to the present invention, 4-methyl-1 a ​​molded body in which a plurality of parts formed in contact including pentene polymer, excellent adhesive strength of the portion between, and scratch resistance of the molded article , and it can provide a coloring resistance of the moldings excellent.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016]
[1] Figure 1 is the shape of the injection molded article produced in Example illustrates the dimensions. Here, FIGS. 1 (a) and 1 (b) each represents a plan view and a front view of the injection molded article.
DESCRIPTION OF THE INVENTION
[0017]
　Hereinafter will be described specifically for embodiments of the invention in detail, the present invention is not intended to be limited to the following embodiments, within the scope of the object of the present invention is practiced with appropriate modifications be able to.
[0018]
　Molding of the present invention is formed by forming a later-described 4-methyl-1-pentene (co) polymer (A) and 4-methyl-1-pentene copolymer (B) a composition comprising (X) has a portion (1), in which is formed in contact with said portion (1), and the 4-methyl-1-pentene (co) moiety comprising a polymer (a) (2), a. Here, excellent scratch resistance and discoloration resistance in the molding of the present invention, as confirmed in the examples below, parts (1) and part (2) is 4-methyl-1-pentene (co ) brought about by containing a polymer (a).
[0019]
　In this specification, the term "(co) polymer" and "polymer" is used in the sense encompasses homopolymers and copolymers.
[0020]
　Further, herein, the expression representing the numerical range "x ~ y" (x, y are numbers. However, x ≠ y), unless otherwise noted, x y means" x less than y or more ".
[0021]
　Hereinafter, the components such as is described for use in each portion of the molded article of the present invention.
[0022]
　[Composition formed from (X) formed by portions (1)]
　In the present invention, part (1) is formed from a composition (X). In other words, part (1) can also be viewed as part of the composition (X).
[0023]
　Composition (X) is 4-methyl-1-pentene (co) polymer (A) (hereinafter, simply referred to as "polymer (A)") and 4-methyl-1-pentene copolymer (B) (hereinafter, simply referred to as "copolymer (B)") is a composition comprising a. Here, as one of the characteristics of the composition (X), as described below, 4-methyl-1-pentene (co) in addition to the polymer (A), 4-methyl-1-pentene copolymer ( B) a 4-methyl-1-pentene (co) polymer having a melting point lower than the (a) specific copolymers thereof that are further included. Composition (X) is 4-methyl-1-pentene (co) polymer (A) and 4-methyl-1-pentene copolymer (B) total is 100 parts by weight of the (co) a content of 60-95 parts by weight of the polymer (a), i.e., the content of the copolymer (B) is 5 to 40 parts by weight. Preferably, a 4-methyl-1-pentene (co) polymer 70 to 90 parts by weight the content of (A), i.e. the content of preferably 4-methyl-1-pentene copolymer (B) 10 to 30 parts by weight. 4-methyl-1-pentene (co) polymer and (A) 4-methyl-1-pentene copolymer and (B) by including in the above ratio, part (2) the adhesive strength between the sufficient become.
[0024]
　Hereinafter, 4-methyl-1-pentene (co) polymer (A) (polymer (A)) and 4-methyl-1-pentene copolymer (B), respectively for (copolymer (B)) described to.
[0025]
　
　The polymer (A) satisfies the following requirements (A-a) ~ (A -e).
[0026]
　Requirements (A-a): 100 mol% and the content more than 90 mol% of structural units derived from 4-methyl-1-pentene in the polymer (A) (P) or less, preferably 95 mol% to 100 mol% or less, 4-methyl-1 0 to 10 mol% or more the content of the constituent unit derived from α- olefin having 2 to 20 carbon atoms other than pentene (AQ) or less, preferably 0 mol% or more 5 mol% or less. Here, "mol%" is the polymer (A), the total amount of all the structural units that constitute the polymer (A), i.e., a structural unit (P) derived from 4-methyl-1-pentene, 4 - methyl-1-non-pentene constitutional unit derived from α- olefin carbon atoms 2 ~ 20 (AQ), and 100 mol% of the total amount of the "other structural unit" is capable to be described later using any to.
[0027]
　By the content of the structural unit in the polymer (A) (P) is 90 mol% or more, there is an advantage that the heat resistance of the back-molded body is obtained.
[0028]
　Forming the structural unit (AQ), as is 4-methyl-1-non-pentene carbon atoms 2 to 20 of α- olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene, and the like. The α- olefin constituting the repeating unit (AQ), moderate modulus and flexibility to the layer of composition (X), from the viewpoint of imparting flexibility, carbon atoms 8 to 18 olefin ( such as 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene) are preferred. In a particularly preferred embodiment of the present invention, alpha-olefin to form a structural unit (AQ) is 1-decene.
[0029]
　Polymer (A) is a polymer comprising the above structural unit (P) and the structural units (AQ), In a particularly preferred embodiment of the present invention, the structural units (P) and the structural units (AQ) is a polymer consisting only. However, in the present invention, the polymer (A) is further comprising a structural unit that does not fall in any of the structural units (P) and the structural unit (AQ) is not in any way be eliminated. The structural unit The polymer (A) is within a range not to impair the effects of the present invention, derived from the structural unit (P) and 4-methyl-1-pentene other α- olefins derived from 4-methyl-1-pentene in terms of (AQ) other than the additional structural units (polymer (a), hereinafter sometimes also referred to as "other structural unit". Further, the copolymer (B) that can be incorporated into other to be described later to distinguish between the structural units may also be referred to as "other structural unit (AR)".) may be contained. The content of other structural units, for example, 0 to 10 mol%.
[0030]
　Above Specific examples of the monomer forming the other constituent unit, etc., a monomer for forming another structural unit which may be contained in the copolymer (B) to be described later (i.e., below "other structural unit (BR)") the same as the specific examples and the like of.
[0031]
　The value of the content of each structural unit in the polymer (A) (mol%), similar to the copolymer (B) to be described later, 13 are those as measured by the measurement method using C-NMR.
[0032]
　Requirements (A-b): of the polymer (A), decalin solvent and the intrinsic viscosity measured at 135 ° C. [eta] is 1.0 ~ 4.0 dl / g, preferably 1.0 dl / g a ~ 3.5 dl / g, more preferably 1.0dl / g ~ 3.0dl / g. When the intrinsic viscosity of the polymer (A) [η] is within the above range is preferable in terms of strength of the flowability and molded article during molding.
[0033]
　The intrinsic viscosity [eta] of the polymer (A), using an Ubbelohde viscometer is a value measured by the following method.
[0034]
　After 20mg of polymer (A) is dissolved in decalin 25 ml, using an Ubbelohde viscometer, a specific viscosity η at 135 ° C. in an oil bath sp is measured. The decalin solution was diluted with 5ml of decalin, the specific viscosity η in the same manner as described above sp is measured. This dilution operation was repeated two more times, the concentration eta when the (C) was extrapolated to 0 sp intrinsic viscosity values of / C [eta] (Unit: dl / g) and (see formula below).
[0035]
　　[Eta] = lim (eta sp / C) (C → 0)
　requirements (A-c): the melting point (Tm) of the polymer (A), 200 ~ 250 ℃, preferably from 200 ℃ ~ 245 ℃, more preferably is in the range of 200 ℃ ~ 240 ℃. By melting point of the polymer (A) (Tm) is in the above range, has appropriate elasticity as compared with the case higher than the above range, it is excellent heat resistance as compared with the case lower than the above range .
[0036]
　Requirements (A-d): The crystallization temperature of the polymer (A) (T c ) is, 150 ~ 220 ℃, preferably in 180 ℃ ~ 220 ℃, more preferably in the range of 190 ℃ ~ 220 ℃. Crystallization temperature of the polymer (A) (T c by) is in the above range, the molded body than in the case greater than the above range has an appropriate flexibility, as compared with the case lower than the above range since rigidity and crystallinity is high, it is good releasability.
[0037]
　Melting point (Tm) and crystallization temperature of the polymer (A) (Tc), respectively a differential scanning calorimeter (DSC: Differential scanning calorimetry) using is the value measured by the following method in compliance with JIS K7121 .
[0038]
　Polymer about 5mg to (A), and sealed at room temperature measurement in an aluminum pan Seiko Instruments Co. differential scanning calorimeter (DSC220C type), to 200 ° C. at a rate of 10 ° C. / min from room temperature heating. For complete melting polymer (A), and held at 200 ° C. 5 min, then cooled to -50 ° C. at a 10 ° C. / min. The temperature at which the peak in the cooling process is observed and crystallization temperature (Tc). After holding at -50 ° C. 5 min, subjected to heating for the second time to 200 ° C. at a 10 ° C. / minute rate to a temperature at which the peak in the second time heating is observed and the polymer melting point (Tm). When a plurality of peaks are detected, employing the peak detected at the highest temperature side.
[0039]
　Requirements (A-e): Density is measured in accordance with JIS K7112 (density gradient tube method) of the polymer (A), 820 ~ 850 kg / m 3 is preferably 825 ~ 840 kg / m 3 be , more preferably 830 ~ 835 kg / m 3 is. By density is within this range, the higher the mechanical strength of the molded body than in the case smaller than the range, the impact strength of the molded body tends to be higher than in the case larger than the above range.
[0040]
　Polymer (A), in addition to the above requirements (A-a) ~ (A-e), preferably satisfies one of the requirements below.
[0041]
　Requirements (A-f): of the polymer (A), conforming to ASTM D1238 and 260 ° C., the melt flow rate (MFR) measured at 5.0kg load, which will be described later the copolymer (B) extrusion easy mix on the plane, although it is not particularly limited as long as it can be molded, usually from 0.5g / 10min ~ 200g / 10min, more preferably 1g / 10min ~ 150g / 10min, more preferably from 1g / 10min ~ 100g / it is a 10min. If the MFR is within the above range, the composition (X) easily injection molded.
[0042]
　Requirements (A-g): The molecular weight distribution of the polymer (A) (Mw / Mn) is usually 1.0-7.0, preferably 2.0-6.0. The molecular weight distribution of the polymer (A) (Mw / Mn) is a value calculated by the method described in the examples.
[0043]
　Requirements (A-h): the polymer (A) is preferably a high crystallinity polymer. The high crystallinity polymer, a polymer having an isotactic structure, may be either a polymer having a syndiotactic structure, particularly preferably a polymer having an isotactic structure, also available it is easy. Further, the polymer (A) can be molded composition (X), as long as it has a strength to withstand the intended use, stereoregularity is not particularly limited.
[0044]
　(Method for producing the polymer (A))
　Polymer (A) may be prepared by polymerizing olefins, high molecular weight 4-methyl-1-pentene polymer, prepared by pyrolysis it may be. The polymer (A), solvent fractionation is fractionated by differences in solubility in the solvent, or may be purified by a method such as molecular distillation to fractionation the difference in boiling point.
[0045]
　When producing by polymerization the polymer (A), for example 4-methyl-1-pentene and charged amount of copolymerized to α- olefin optionally, the type of polymerization catalyst, the polymerization temperature, the hydrogen addition amount during the polymerization etc. by adjusting the controls melting point, stereoregularity and molecular weight, and the like. Process for producing by polymerization the polymer (A) may be a known method. Polymer (A), for example, is produced by a method using a Ziegler-Natta catalyst, known catalysts such as metallocene catalysts, preferably may be prepared using Ziegler-Natta catalysts. On the other hand, the polymer (A), as the case may be produced by thermal decomposition of high molecular weight of 4-methyl-1-pentene polymer, by controlling the temperature and time of thermal decomposition, the molecular weight of the desired value to control to.
[0046]
　Polymer (A), in addition to that produced as described above may, for example, manufactured by Mitsui Chemicals, Inc. TPX like, or may be a commercially available polymer.
[0047]
　
　copolymer (B) satisfies the following requirements (B-a) ~ (B -e).
[0048]
　Requirements (B-a): the copolymer (B), 4-methyl-1 constituent unit derived from pentene (P) in a proportion of less than 65 mol% 96 ​​mol%, and 4-methyl-1 having a proportion of 35 mol% or less than 4 mole% structural units derived from 2 or more carbon atoms 20 in the following α- olefin (BQ) of the non-pentene. Here, "mol%" for copolymer (B), the total of all the structural units that constitute the copolymer (B), i.e., a structural unit (P) derived from 4-methyl-1-pentene, a structural unit (BQ) derived from the number 2 or 4-methyl-1 carbon atoms other than pentene 20 in the following α- olefins, total 100 mole% of "other structural unit" below which may optionally be used to.
[0049]
　The content of the constituent units (P), is less than 65 mol% 96 ​​mol%, preferably less than 92 mol% 68 mol% or more, more preferably less than 90 mol% 68 mol% or more, particularly preferably is less than 80 mol% or more 88 mol%.
[0050]
　The structural unit content (structural unit (BQ) if is 2 or more the content of the sum of more than the two) of (BQ) is 35 mol% or less than 4 mol%, preferably 8 mole % or less 32 mol% greater than, more preferably not more than 32 mol% greater than 10 mol%, particularly preferably 20 mol% more than 12 mol% or less.
[0051]
　Forming the structural unit (BQ), as the 4-methyl-1-non-pentene carbon atoms 2 to 20 of α- olefins, further reduce the anisotropy of the anisotropic and tear strength of the tensile elongation at break from the viewpoint of, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, 1-octadecene are preferred, carbon atoms 2 ~ 4 alpha-olefins, i.e. ethylene, propylene, more preferably 1-butene, propylene is particularly preferred.
[0052]
　Moreover, the use of those exemplified above as the α- olefin is also improved impact resistance of the resulting molded article.
[0053]
　As α- olefin constituting the repeating unit (BQ), may be used alone or in combination of two or more thereof.
[0054]
　Further, the structural unit (BQ), when the polymer (A) contains a structural unit (AQ), may be the same as the structural unit (AQ), may be different.
[0055]
　Copolymer (B) is within a range not to impair the effects of the present invention, 4-methyl-1 constituent unit derived from pentene (P) and 4-methyl-1 carbon atoms other than pentene 2 to 20 in terms of the structural unit (BQ) other than the additional structural units (copolymer (B) derived from Roh α- olefin, simply sometimes referred to as "other structural unit". Further, the polymer (a) "other structural unit (BR)" for distinction from other structural units that may be included as well may be called.) may be contained. The content of other structural units, for example, 0 to 10 mol%.
[0056]
　These and other structural units (i.e., "other structural unit (BR)") as a monomer for forming a cyclic olefin, an aromatic vinyl compound, a conjugated diene, non-conjugated polyene, functional vinyl compounds, hydroxyl group-containing olefins, halogenated olefins and the like are included.
[0057]
　Cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyene, functional vinyl compounds, hydroxyl group-containing olefins, and as the halogenated olefin, for example, compounds described in paragraphs from 0034 to 0041 of JP-A-2013-169685 be able to.
[0058]
　Examples of the monomer forming the other constituent unit, vinyl cyclohexane, styrene is particularly preferred.
[0059]
　The copolymer (B), if they contain the additional structural units, the other structural units may be contained alone, or be contained two or more.
[0060]
　A specific example of a monomer for forming the above may constitute a polymer (A) "other structural unit (AR)" are also above as specific examples of the monomer corresponding to the "other structural unit (BR)" is the same as that shown.
[0061]
　The value of the content of each structural unit in the copolymer (B) (mol%) is under the following conditions 13 are those as measured by the measuring method using C-NMR.
[0062]
　~ Condition ~
　measuring device: a nuclear magnetic resonance apparatus (ECP500, manufactured by Nippon Denshi Co.)
　Observation nucleus: 13 C (125 MHz)
　Sequence: Single pulse proton decoupling
　Pulse width: 4.7Myu seconds (45 ° pulse)
　repetition time : 5.5 seconds
　number of integrations: 10,000 times or more
　solvent: orthodichlorobenzene / deuterated benzene (volume ratio: 80/20) mixed solvent
　sample concentration: 55 mg / 0.6 mL
　measurement temperature: 120 ° C.
　reference value of the chemical shift : 27.50Ppm
　requirements (B-b): a copolymer of (B), decalin solvent and the intrinsic viscosity measured at 135 ° C. [eta] is 0.5 ~ 4.0 dl / g, preferably was 0.5dl / g ~ 3.5dl / g, more preferably 1.0dl / g ~ 3.5dl / g. When the intrinsic viscosity of the copolymer (B) [η] is within the above range is preferred in terms of moldability.
[0063]
　The intrinsic viscosity [eta] of the copolymer (B) is a value measured in the same manner as the intrinsic viscosity [eta] of the polymer (A).
[0064]
　Requirements (B-c): The molecular weight distribution of the copolymer (B) (Mw / Mn), from the viewpoint of stickiness and appearance of a layer of the composition (X), is 1.0-3.5, preferably it is from 1.1 to 3.0.
[0065]
　The weight average molecular weight of the copolymer (B) (Mw), from the viewpoint of moldability of the composition (X), preferably 1 × 10 4 ~ 2 × 10 6 are, more preferably 1 × 10 4 ~ 1 10 × 6 is.
[0066]
　The weight average molecular weight of the copolymer (B) (Mw) and molecular weight distribution (Mw / Mn) is a value calculated by the method described in the examples.
[0067]
　Requirements (B-d): the melting point of the copolymer (B) (Tm) are either not observed, or in the range of 100 ° C. ~ 199 ° C., or not more preferably be observed, or the range of 110 ° C. ~ 180 ° C. to have, even more preferably within the range of 110 ° C. ~ 160 ° C., particularly preferably in the range of 125 ℃ ~ 150 ℃. This means that in the present invention, as copolymer (B), wherein either the polymer (A) having a melting point lower than, or means that the specific copolymer melting point is not observed, is used.
[0068]
　Melting point of the copolymer (B) (Tm) is a value measured in the same manner as the melting point (Tm) of the said polymer (A).
[0069]
　Requirements (B-e): Density is measured according to JIS copolymer (B) K7112 (density gradient tube method), from the viewpoint of handling property, 830 kg / m 3 ~ 860 kg / m 3 is, preferably 830 kg / m 3 ~ 850 kg / m 3 is.
[0070]
　Copolymer (B) In addition to the above requirements (B-a) ~ (B-e), preferably satisfies the following requirements.
[0071]
　Requirements (B-f): Copolymer (B) of a melt flow rate measured under a load of 2.16kg at in compliance with ASTM D1238 230 ℃ (MFR), at the time of molding of the composition (X) from the viewpoint of fluidity, is preferably 0.1g / 10min ~ 100g / 10min, more preferably from 0.5g / 10min ~ 50g / 10min, more preferably 0.5g / 10min ~ 30g / 10min .
[0072]
　(Manufacturing method of the copolymer (B))
　copolymer (B), the metallocene catalyst system conventionally known, for example, WO 2005/121192, WO 2011/055803, WO it can be synthesized by the method described in 2014/050817 like.
[0073]
　
　composition in (X), the content of the polymer to the total of 100 parts by mass of the polymer (A) and the copolymer (B) (A) is 60 parts by mass or more 95 parts by weight or less, preferably at most 90 parts by mass or more 70 parts by weight.
[0074]
　When the content ratio of the polymer (A) and the copolymer (B) is within this range, molded bodies having excellent adhesive strength of the portion of the molded article obtained is obtained.
[0075]
　Composition (X), the polymer (A) and a composition comprising the copolymer (B), which prevents comprising the copolymer and the polymer (A) and (B) only is not. However, in the present invention, the composition (X) is in a range not impairing the object of the present invention, further the polymer (A) and one to the ingredients does not fall in the copolymer (B) (hereinafter, " other ingredients ") may contain. Such "other ingredients", for example, weathering stabilizer, heat stabilizer, antioxidant, ultraviolet absorber, antistatic agent, slip agent, antiblocking agent, antifogging, nucleating agents, lubricants, pigments , dyes, anti-aging agents, hydrochloric acid absorbers, inorganic or organic fillers, organic or inorganic foaming agent, crosslinking agent, crosslinking aid, or a pressure-sensitive adhesive, softening agent, various additives such as flame retardants, heavy polymer (a) and copolymer (B) other than the resin.
[0076]
　Here, in one preferred and exemplary embodiments of the present invention, the composition (X) consists only of the polymer (A) and the copolymer (B) and the various additives. Among them, as an example of a composition according to a preferred embodiment of the present invention (X), as shown in the examples below, the only and the copolymer (B) and the antioxidant and the polymer (A) composition comprising thereof.
[0077]
　Further, in another aspect of the present invention, the composition (X) consists of the copolymer and the polymer (A) and (B) only.
[0078]
　However, in the present invention, the composition (X), is not intended to exclude embodiments which include the polymer (A) and copolymer (B) other than the resin. That is, in yet another aspect of the present invention, the composition (X), the polymer (A), the copolymer (B), the polymer (A) and copolymer (B) other than the resin it includes the door. In this case, as "polymer (A) and copolymer (B) other than the resin" which may be included in the composition (X), include, for example polypropylene.
[0079]
　In the composition (X), the content of "other component" polymer (A) and preferably the total 100 parts by weight of the copolymer (B) is 50 parts by mass or less, more preferably 30 parts by weight , more preferably not more than 10 parts by mass. In the present invention, as described above, but may also include a "polymer (A) and copolymer (B) other than the resin" as a composition (X) is "other ingredients" , the content thereof is preferably small. Content of the composition may be included in the (X) "polymer (A) and copolymer (B) other than the resin" total 100 weight of the polymer (A) and copolymer (B) 10 parts by mass or less with respect to parts, more preferably 5 parts by mass or less, particularly preferably less than 3 parts by weight.
[0080]
　Composition (X) is obtained by mixing the used optionally as Polymer (A) the copolymer (B) "other components" in the ratio is not particularly restricted but includes mixing method, for example, a method of compounding in a twin-screw extruder, and a method of mixing the pellets with each other by dry blending, and the like.
[0081]
　[(Co) polymer (A) comprising portions (2)]
　the portion (2), said "composition (X) is formed from a comprising the portion (1)" polymer described above in (A) including comprising at. Here, the polymer (A) contained in the part (2), as long as corresponding to the polymer (A), may be the same polymer (A) and contained in the composition (X), Alternatively, it may be different. Further, part (2) may be made of only the polymer (A), in the range that does not impair the effects of the invention, may further comprise other polymers and additives. Further, part (2), like part (1), may be formed from a composition corresponding to the composition (X) (X '). In that case, the composition for forming the portion (2) (X ') is to the composition forming part (1) and (X) may be the same composition, or may be different. Here, in one preferred embodiment of the present invention, part (2) consists of a mixture of an antioxidant polymer (A) or the polymer (A). Further, in another preferred embodiment of the present invention, the portion (2) is 'consists, in a particularly preferred embodiment of which the composition (X composition (X)' a), said portion (1) the composition constituting (X) is a composition of different composition from each other (X1 '). Content of the copolymer (B) in the composition this time (X '), the portion (1) is preferably smaller than the content of the copolymer (B) in the composition forming (X) a. Identical in this case, the copolymer contained in the composition (X ') (B) as long as it corresponds to the copolymer (B), the copolymer contained in the composition (X) and (B) it may be in, or may be different.
[0082]
　[Process for producing a molded article]
　molded body according to the present invention, the portion (1) and said portion (2), that said portion (2) is obtained by forming in a manner in contact with said portion (1) it can.
[0083]
　Here, process for producing a molded article according to the present invention is not limited, as shaping means which may be used to produce the molded body according to the present invention, injection molding, known molding such as lamination molding means, and the like. Molded body according to the present invention, for example insert molding, lamination molding can be molded by two-color molding.
[0084]
　Here, the order of forming the portion (1) and said portion (2), and the specific molding method employed in forming the respective said portion (1) and said portion (2) are, in particular the present invention is not limited. However, in any of the illustrated forming method wherein also, preformed part (1), in a state in contact with the part (1), to form a portion (2), preferable in terms of increasing the adhesion strength . That is, embodiments in a preferred embodiment of the present invention, process for producing a molded article according to the present invention, the contact forming the portion (1) by molding the composition (X), the partial (1) in, and molding the polymer (a) or a composition comprising the polymer (a), and a step of forming the portion (2). In the preferred and exemplary embodiments of the present invention, process for producing a molded article of the present invention, a primary injection step of forming the portion (1) with the composition (X) by injection molding, then the portion ( in a manner in contact with the 1) by injection molding the polymer (a) or a composition comprising the polymer (a), and a secondary injection step of forming the portion (2). In one preferred embodiment of the present invention, the secondary injection step is to insert the portion (1) obtained in advance the primary injection step to injection mold for forming a green body, then part (2) the polymer or composition constituting the can be done by injection molding to the injection mold. However, in the present invention, partially performs the primary injection step using deformation or exchangeable injection mold, then by deforming or replace the part of the injection mold, resulting in the primary injection step It performs the step of providing a cavity shape corresponding to the portion (2) adjacent to the obtained partial (1), Thereafter, the polymer or composition constituting the portion (2) by injection molding to the cavity it may perform the secondary injection step.
[0085]
　Molding temperature is generally 200 ~ 350 ° C., preferably in the range from 220 ~ 350 ° C..
[0086]
　[Shape of the molded body]
　contact surface portion (1) and part (2) is may be a curved surface be planar. Molding of the present invention, as long as they do not impair the effects of the invention, part (1) and part (2) may also contain other portions other than. Resulting molded article, the shape is not particularly limited, for example, plate-like, film-like, container-like, cylindrical, rod-like. It is bonded part (1) and part (2). The strength of the adhesive is adjusted according to the application of the molded article.
[0087]
　[Moldings applications]
　molded article of the present invention may in particular use is not limited, used in applications where general olefin resin is applied. Poly-4-methylpentene-based resin is preferably used in applications that are conventionally used, more preferably, tableware, food storage containers, daily necessities, is suitably used as a release film.
Example
[0088]
　Will be further specifically described by the present invention embodiment, the present invention as long as not exceeding its gist is not limited to the following examples.
[0089]
　[Measurement method of physical properties]
　illustrates a method used to determine various physical properties of each polymer obtained in this example are shown below.
[0090]
　(1) Composition
　described above 13 by the measuring method according to C-NMR, it was determined the composition of the polymer.
[0091]
　(2) the intrinsic viscosity [eta]
　using an Ubbelohde viscometer, the method described above to determine the intrinsic viscosity measured in 135 ° C. in decalin solvent [eta].
[0092]
　(3) a weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
　Liquid chromatograph: a Waters Co. ALC / GPC 150-C plus type (suggested refractometer detector integral type) manufactured by Tosoh Corporation as a column GMH6 the -HT 2 present and GMH6-HTL 2 present × × connected in series, using o- dichlorobenzene as the mobile phase medium, a flow rate of 1.0 ml / min, followed by gel permeation chromatography (GPC) at 140 ° C. . The resulting chromatogram, by known methods, by analyzing using a calibration curve using standard polystyrene samples was determined weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn).
[0093]
　(4) Melt flow rate
　(MFR) of conforming to ASTM D1238 and 260 ° C., was determined melt flow rate (MFR) measured at 5.0kg load. However, measurement of MFR of the following polymer (B) (i.e., below the polymer B-1 and B-2) is the measurement conditions, 230 ° C., was performed by changing the 2.16kg load.
[0094]
　(5) Density
　was determined density in conformity with JIS K7112 (density gradient tube method).
[0095]
　(6) the melting point (Tm), crystallization temperature
　(Tc) in compliance with JIS K7121 was measured by the method was determined from the peak temperature.
[0096]
　[4-methyl-1-pentene polymer (A)]
　in accordance with the polymerization method described in Comparative Example 7 and Comparative Example 9 of WO 2006/054613, 4-methyl-1-pentene, 1-decene, hydrogen by changing the ratio, to give 4-methyl-1-pentene copolymer a-1 and a-2. That is, 4-methyl-1-pentene copolymer A-1 and A-2 are both, anhydrous magnesium chloride, 2-ethylhexyl alcohol, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane and tetrachloride It will be obtained by using the solid titanium catalyst obtained by reacting a titanium as a polymerization catalyst.
[0097]
　The obtained 4-methyl-1 each pentene copolymer A-1 and A-2, with respect to the 4-methyl-1-pentene copolymer 100 parts by weight of phenolic stabilizers as heat stabilizer agent Irganox1010 0.15 parts by weight (manufactured by BASF), a sulfur-based stabilizer DLTP "YOSHITOMI" (manufactured by Mitsubishi Chemical Corporation) and 0.30 parts by mass after dry-blended, mixed by thermoplastics Co. biaxial extruder It was obtained having physical properties as shown in Table 1 4-methyl-1-pentene polymer a-1 and a-2, respectively.
[0098]
　Such 4-methyl-1-pentene polymer A-1 and A-2 obtained in is strictly compositions because they contain a phenolic stabilizer and a sulfur type stabilizer traces. However, the amount of these stabilizers are traces, the influence of the physical properties due to the presence of these stabilizers can be estimated that the negligible thoroughly. Therefore, in the following description, the 4-methyl-1-pentene polymer A-1 and A-2, and be treated as the polymer, respectively "polymer A-1" and "polymer A-2" It will be referred to.
[0099]
　Also shows the obtained polymer A-1 and polymer A-2 of the measurement results of various physical properties in Table 1.
[0100]
　[4-methyl-1-pentene copolymer (B)]
　 - Polymer B-1 of Synthesis -
　made of SUS autoclave stirring with blades thoroughly purged with nitrogen capacity 1.5 L, of 300ml n- hexane (dry nitrogen atmosphere, which had been dried over activated alumina), and then was charged at 23 ° C. 4-methyl-1-pentene 450 ml, 1.0 mmol / ml toluene triisobutyl aluminum (TIBAL) the solution was 0.75ml charged, and stirring was started.
[0101]
　Then heated to an internal temperature of the autoclave became 60 ° C., a total pressure (gauge pressure) was pressurized with propylene so that 0.19 MPa.
[0102]
　Then, previously prepared, 1mmol of methylaluminoxane in terms of Al, and 0.01mmol of diphenylmethylene (1-ethyl -3-t-butyl - cyclopentadienyl) (2,7-di -t- butyl - fluorenyl) of a toluene solution 0.34ml containing zirconium dichloride was introduced with pressurized nitrogen into the autoclave to initiate the polymerization reaction. During the polymerization reaction, the internal temperature of the autoclave was temperature adjusted to 60 ° C..
[0103]
　After 60 minutes from polymerization initiation, methanol 5ml with pressurized nitrogen into the autoclave, after the polymerization reaction was stopped and depressurized and the inside of the autoclave to atmospheric pressure. After depressurizing, the reaction solution, while stirring the reaction solution was added acetone to give a polymerization reaction product containing a solvent. Then, under reduced pressure the polymerization reaction product containing the resulting solvent and dried at 130 ° C. 12 hours, as copolymer (B), to obtain a powdery polymer B-1 of 44.0 g.
[0104]
　The measurement results of the polymer B-1 of various physical properties are shown in Table 1.
[0105]
　 - Synthesis ~ of Polymer B-2
　to 1.5 liter capacity stirred SUS autoclave with wings which was sufficiently purged with nitrogen was 750ml charged with 4-methyl-1-pentene at 23 ° C.. Into the autoclave, a 1.0 mmol / ml toluene solution of triisobutyl aluminum (TIBAL) and stirring was started and 0.75ml charged.
[0106]
　Then, the autoclave was heated to an internal temperature of 60 ° C., the total pressure was pressurized with propylene so that 0.13 MPa (gauge pressure). Subsequently, 1mmol methylaluminoxane which had been preliminarily prepared in terms of Al, diphenylmethylene (1-ethyl -3-t-butyl - cyclopentadienyl) (2,7-di -t- butyl - fluorenyl) zirconium dichloride the toluene solution 0.34ml pressed into the autoclave with nitrogen containing 0.01 mmol, the polymerization was initiated. During the polymerization reaction, the temperature was adjusted to the autoclave internal temperature is 60 ° C.. After the polymerization After 60 minutes, the methanol 5ml stop pressed polymerized in nitrogen to an autoclave depressurized autoclave to atmospheric pressure. It poured with stirring acetone to the reaction solution.
[0107]
　The resulting 100 ° C. The powdered polymer containing solvent was dried under reduced pressure for 12 hours to give a copolymer of 36.9g of (B-2). Table 1 shows the measurement results of various physical properties.
[0108]
　[Polymer (A) and copolymer (B) other than the polymer (C-1)]
　is a Prime Polymer Co., Ltd. made of polypropylene, Prime Polypro J105G (homopolypropylene, MFR9.0g / 10 min (230 ° C., 2.16kg load) hereinafter also referred to as "polymer C-1".) was used.
[0109]
[Table 1]

[0110]
　[Composition (X) (X1 ~ X8) and other compositions (X'1 and A-3) of Preparation]
　
　and the polymer A-1 to 90 parts by weight polymer after dry blending B-1 and 10 parts by weight, and mixed by thermoplastics manufactured a biaxial extruder to obtain a composition X1.
[0111]
　Similarly, to obtain each composition under the compounding conditions shown in Table 2.
[0112]
　That is, the composition X2, X5 and X6 are the type and amount of the polymer (A), as well, except that the kind and amount of the polymer (B), were respectively changed to those described in Table 2, each was obtained in the same manner as composition X1.
[0113]
　The compositions X3, X4, X7 and X8 are the type and amount of the polymer (A), as well as the type and amount of the polymer (B), after having changed to those described in Tables 2 further, except that lithopone (white pigment consisting of a mixture of barium sulfate and zinc sulfide) was added in amounts shown in Table 2, were obtained respectively in the same manner as composition X1.
[0114]
　
　composition X'1 is a polymer A-1 and 90 parts by weight, instead of the polymer B-1 to 10 parts by mass, heavy a combined a-1 100 parts by mass, except for using the polymer C-1 5.3 part by weight similarly to composition X1.
[0115]
　The compositions A-3 has a Polymer A-1 90 parts by weight, instead of the polymer B-1 to 10 parts by mass, the polymer A-1 was used 100 parts by weight, further, the lithopone 43 except for the additional part by weight similarly to composition X1.
[0116]
　Preparation of injection-molded square plate, Evaluation
　and resulting composition X1 ~ X8, A-3 and X'1, polymer A-1, the polymer C-1, scratch resistance, coloring resistance evaluation, and transparency (haze) was prepared injection angle plate for evaluation. Using an injection molding machine (Meiki Ltd. M-70B), the molding temperature 295 ° C., mold temperature of 60 ° C., a screw rotation speed of the metering 260 rpm, a molding cycle 60s, thickness 2 mm, width 120 mm, length 130mm to prepare an injection molded angle plate.
[0117]
　The obtained injection molded angle plate were evaluated in the following. The evaluation results are also shown in Table 2.
[0118]
　
　was performed a scratch test on the obtained injection-molded square plate. Shinto Scientific Co., used a reciprocating friction wear tester, hurt jig sapphire (0.5 R), load 2 kg, speed of 500 mm / min, were carried out at a stroke 50 mm. The scratch depth was measured using a surface roughness shape measuring device (product of Tokyo Seimitsu Co. SURFCOM 1400D). Stylus 5Myuemufai, measured length 2.0 mm, adopts the average value of the measured speed of 0.3 mm / s, 3-point measurement was evaluated on the following criteria.
[0119]
　○: scratch depth is 20μm or less.
　×: scratch depth is more than 20μm.
[0120]
　
　was visually observed and the resulting injection-molded square plate was evaluated by the following criteria.　　　
　○: the other side of the high seat transparency can be clearly observed.　　　
　△: a little the other side of the sheet is not cloudy vaguely be confirmed.
　×: other side of the seat low transparency can not be visually.
[0121]
　
　The obtained injection molded angle plate, the commercial ketchup and cooking canola oil immersed in the test solution were mixed at a mass ratio of 90:10, after 20 hours holding at 90 ° C., washed with water did. Then, it was visually observed and evaluated according to the following criteria.
[0122]
　○: coloring is not observed.
　△: they are lightly colored.
　×: it is strongly colored.
[0123]
　[Preparation of molded article]
　was prepared injection molded for adhesion evaluation. Shows the shape of the injection molded body, the dimensions in Figure 1. In Figure 1, an injection molding body (10) consists of parts 1 (11) and part 2 (12). First, as the primary injection, the polymer or composition constituting part 1, using an injection molding machine (Meiki Ltd. M-70B), the molding temperature 280 ° C., a mold temperature of 50 ° C., a screw rotation speed of the metering 260 rpm, a molding cycle 50s, injection molded in an injection mold for part 1 formed to obtain a part 1 (11). Then as a secondary injection, a portion 1 obtained by the primary injection were inserted into an injection mold for forming a green body, the polymer or composition constituting part 2, the same as when used to form the portion 1 in the molding conditions and injection-molded into the injection mold (in this process, part 2 (12) are formed), to prepare an injection molded body (10).
[0124]
　
　In the primary injection and the secondary injection, to obtain a molded body using each polymer or composition shown in Table 3.
[0125]
　[Evaluation of molded article]
　The obtained molded article was subjected to the following measurement and evaluation. The measurement and evaluation methods are shown below. The results are shown in Table 3.
[0126]
　
　The ends of the resulting molded article held by sandwiching the right hand and left thumb and forefinger, respectively, to evaluate the adhesion of the halves pieces each other by applying a twisting with both hands. It was evaluated by the following criteria.
[0127]
　○: that adhere well to not take even twist strongly.
　△: it would take the adhesive surface and the twist strongly.　　　
　×: half pieces to each other is a non-evaluation does not adhere.
[0128]
[Table 2]

[0129]
[table 3]

[0130]
　[Comparison Examples and Comparative Examples]
　From Table 3, Example whereas molded article was obtained, Comparative Example 1-5, the half pieces each other does not adhere, i.e. partial (1) and in contact shaped body having a portion formed (2) Te was obtained. From Table 2, X1 ~ X7 corresponding to the composition X used in the present invention, be compared to compositions X'1 which does not correspond to the composition X, is excellent in scratch resistance and discoloration resistance It can be seen. Furthermore, it can be seen that excellent transparency for compositions X1, X2, X5, X6.
DESCRIPTION OF SYMBOLS
[0131]
10 injection molded articles were produced in ... Example
11 ... part
1 12 ... part 2

The scope of the claims

[Requested item 1]Following requirement (A-a) ~ satisfy (A-e) 4-methyl-1-pentene (co) polymer and (A), satisfying the following requirements (B-a) ~ (B -e) 4- methyl 1-comprises pentene copolymer (B), a (co) polymer (a) and the copolymer (B) total is 100 parts by weight of the (co) polymer (a) content is 60-95 parts by weight, the composition and partial (1) comprising formed from (X),
　formed in contact with said portion (1), the 4-methyl-1-pentene (co) a moiety comprising a polymer (a) (2),
the molded body having a.
(A-a) 4-methyl-1 content of the constituent units derived from pentene (P) is 100 to 90 mol%, of the carbon atoms 2 ~ 20 alpha-olefin (4-methyl-1-pentene excluding.) the content of constituent unit (AQ) derived from 0 to 10 mol%.
(A-b) an intrinsic viscosity measured at 135 ° C. in decalin [eta] is 1.0 ~ 4.0dl / g.
Melting point measured by (A-c) DSC (T m ) is in the range of 200 ~ 250 ° C..
(A-d) crystallization temperature measured with DSC (T c ) is in the range of 0.99 ~ 220 ° C..
(A-e) density of 820 ~ 850 kg / m 3 is.
(B-a) 4-methyl-1 content of the constituent units derived from pentene (P) is less than 65 mol% 96 mol%, of the carbon atoms 2 ~ 20 alpha-olefin (4-methyl - except 1-pentene.) the content of the constituent unit (BQ) derived from of 35 mol% or less than 4 mol%.
(B-b) an intrinsic viscosity measured at 135 ° C. in decalin [eta] is 0.5 ~ 4.0dl / g.
(B-c) gel permeation chromatography weight average molecular weight measured by (GPC) (Mw) and the ratio a is the molecular weight distribution (Mw / Mn) of 1.0 to the number average molecular weight (Mn) 3.5 it is.
When measured in (B-d) DSC, melting point (T m in the range of) ~ Do 100 ° C. is observed 199 ° C..
(B-e) density of 830 ~ 860 kg / m 3 is.
[Requested item 2]
　The structural unit (BQ) are molded body according to claim 1 is a structural unit derived from α- olefin having 2 to 4 carbon atoms.
[Requested item 3]
　In the composition (X), the (co) content of the polymer (A) is 70 to 90 parts by weight, the molded body according to claim 1 or 2.
[Requested item 4]
　And step (1) to preformed said portion (1), the contact with the part (1), and step (2) to form the said portion (2)
including, any of claims 1 to 3, one method for producing a molded article according to claim.
[Requested item 5]
　By injection molding, to form said portion (1) and part (2) The process of claim 4.