JP2006249392A - Propylene-based polymer composition for adhesion and laminated product containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylene-based polymer composition for adhesion, excellent in adhesive properties and further excellent in optical characteristics and drawing properties, and to provide a laminated product containing the same. <P>SOLUTION: This propylene-based polymer composition for adhesion is formed by subjecting 0.001-5 pts.wt. of an unsaturated carboxylic acid and/or its derivative to graft addition to 100 pts.wt. of a composition which contains an isotactic polypropylene (A) in an amount of 50-95 pts.wt. and a propylene-1-butene random copolymer (B) in an amount of 50-5 pts.wt., wherein the copolymer (B) is specified by (i) to (iii) as follows: (i) comprising the propylene-1-butene random copolymer (B) containing units derived from propylene in an amount of 60-90 mol% and units derived from 1-butene in an amount of 10-40 mol%; (ii) having a melting point (Tm) in a range of 40-120°C, when measured by a differential scanning calorimeter; and (iii) having a molecular weight distribution (Mw/Mn) in a range of 1.0-3.0, when measured by gel permeation chromatography (GPC). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polypropylene-based adhesive polymer composition excellent in adhesiveness, optical properties and stretchability, and a laminate using the same.

  Conventionally, polypropylene has been widely used as a thermoplastic molding material excellent in rigidity, heat resistance, transparency and the like. Since this polypropylene is inferior in flexibility, a soft rubber component is usually blended with polypropylene when used as an adhesive polymer composition.

  Thus, when a soft rubber component is blended with polypropylene, a polypropylene-based adhesive polymer composition with improved adhesion can be obtained, but there is a problem that transparency is lowered. In addition, such a polypropylene-based adhesive polymer composition is also desired to be improved in stretching.

For this reason, the appearance of a polypropylene-based adhesive polymer composition having excellent adhesiveness and excellent transparency and stretchability has been desired.
JP-A-9-111069 JP-A-4-300933

  An object of the present invention is to provide a polypropylene-based adhesive polymer composition that is excellent in adhesion and excellent in transparency and stretchability, and a laminate that is excellent in adhesion and transparency.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.

That is, the present invention
A composition 100 comprising 50 to 95 parts by weight of isotactic polypropylene (A) and 50 to 5 parts by weight of a propylene / 1-butene random copolymer (B) defined by the following (i) to (iii): Polypropylene adhesive polymer composition (C) obtained by grafting 0.001 to 5 parts by weight of unsaturated carboxylic acid and / or derivative thereof with respect to weight
(I) a propylene / 1-butene random copolymer (B) containing 60 to 90 mol% of units derived from propylene and 10 to 40 mol% of units derived from 1-butene,
(Ii) The melting point (Tm) measured by a differential scanning calorimeter is in the range of 40 to 120 ° C.,
(Iii) The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) is in the range of 1.0 to 3.0.

  Moreover, this invention is a laminated body which has at least 1 layer containing the said polypropylene-type adhesive polymer composition (C).

  The polypropylene-based adhesive polymer composition (C) of the present invention is a composition having excellent adhesive properties and excellent optical properties and stretching suitability. According to the polypropylene-based adhesive polymer composition (C) of the present invention, it is possible to obtain a molded product having excellent interlayer adhesion, and at the same time, it can be used for a molded product that requires optical characteristics and proper stretching. Become.

  Hereinafter, the present invention will be described in more detail.

The polypropylene-based adhesive polymer composition (C) of the present invention comprises 50 to 95 parts by weight of isotactic polypropylene (A) and propylene / 1-butene random defined by the following (i) to (iii): Polypropylene system comprising 0.001 to 5 parts by weight of an unsaturated carboxylic acid and / or derivative thereof grafted to 100 parts by weight of a composition containing 50 to 5 parts by weight of copolymer (B) The polymer composition for adhesion.
(I) a propylene / 1-butene random copolymer (B) containing 60 to 90 mol% of units derived from propylene and 10 to 40 mol% of units derived from 1-butene,
(Ii) The melting point (Tm) measured by a differential scanning calorimeter is in the range of 40 to 120 ° C.,
(Iii) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1.0 to 3.0.

  Each component will be described below.

  The isotactic polypropylene (A) used in the present invention is a homopolymer of propylene and / or a propylene / α-olefin copolymer.

  The α-olefin is not limited, but preferably includes ethylene having 2 carbon atoms and / or α-olefin having 4 to 20 carbon atoms. These α-olefins may be used alone or in combination of two or more. Also good. Preferred α-olefins in the present invention are ethylene having 2 carbon atoms or α-olefin having 4 to 10 carbon atoms, and in particular, ethylene having 2 carbon atoms or α-olefin having 2 to 8 carbon atoms is particularly preferable. It can be used suitably. Here, the content of the structural unit derived from propylene in the propylene / α-olefin copolymer is at least 50 mol% or more and less than 100%.

  The method for producing isotactic polypropylene (A) is not particularly limited, and can be produced by a known method using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. In addition, a crystalline polymer can be preferably used, and in the case of a copolymer, it may be a random copolymer or a block copolymer. Furthermore, there are no particular restrictions on the stereoregularity and the molecular weight as long as they satisfy the moldability and have a strength that can be used when formed into a molded body. Commercially available resins can be used as they are.

  The isotactic polypropylene (A) preferably used in the present invention is homopolypropylene or a propylene / α-olefin random copolymer. Also, several different isotactic polypropylenes can be mixed and used.

  Further, it may be one obtained by grafting a small amount of maleic anhydride or the like, or after grafting a small amount of maleic anhydride or the like and further modifying the graft monomer with diamine, carbodiimide or the like.

The propylene / 1-butene random copolymer (B) in the present invention is defined by the following (i) to (iii).
(I) 60 to 90 mol% of units derived from propylene and 10 to 40 mol% of units derived from 1-butene,
(Ii) The melting point (Tm) measured by a differential scanning calorimeter is in the range of 40 to 120 ° C.,
(Iii) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1.0 to 3.0.

  The method for producing the propylene / 1-butene random copolymer (B) is not particularly limited, and the propylene / 1-butene random copolymer (B) is produced by a known method using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Can do. Furthermore, there are no particular restrictions on the stereoregularity and the molecular weight as long as they satisfy the moldability and have a strength that can be used when formed into a molded body. Commercially available resins can be used as they are.

  In the present invention, a small amount of maleic anhydride or the like may be grafted as long as the above conditions are satisfied.

  As long as the above conditions are satisfied, a graft monomer may be further modified with diamine, carbodiimide, etc. after grafting a small amount of maleic anhydride or the like.

  The polypropylene-based adhesive polymer composition (C) of the present invention comprises the above-mentioned isotactic polypropylene (A) component in an amount of 50 to 95% by weight and the above-mentioned propylene / 1-butene random copolymer (B) component. Is contained in an amount of 50 to 5% by weight. In the present invention, by setting the composition of the component (A) and the component (B) within the above range, an adhesive polymer composition (C) having excellent interlayer adhesion and excellent optical properties and stretching suitability is obtained. It becomes possible.

  The polypropylene-based adhesive polymer composition (C) of the present invention may be an embodiment in which at least a part of the composition is graft-modified. As the graft monomer, an unsaturated carboxylic acid and / or a derivative thereof can be preferably used. Examples of unsaturated carboxylic acids and / or derivatives thereof include unsaturated compounds having one or more carboxylic acid groups, esters of a compound having a carboxylic acid group and an alkyl alcohol, and unsaturated compounds having one or more carboxylic anhydride groups. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. Moreover, when using unsaturated carboxylic acid and / or its derivative (s) in this invention, it can also be used individually by 1 type and can also be used in combination of 2 or more type. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are suitable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferably used.

  Content with respect to 100 weight part of compositions of unsaturated carboxylic acid and / or its derivative (s) is 0.001-5 weight part normally, Preferably it is 0.01-3 weight part. When the content of the unsaturated carboxylic acid and / or derivative thereof is in the above range, the polyolefin composition of the present invention exhibits high adhesive strength with respect to polyester or ethylene / vinyl alcohol copolymer. The content of the unsaturated carboxylic acid and / or derivative thereof can be easily controlled by, for example, appropriately selecting the grafting conditions.

  In the present invention, when a graft monomer selected from an unsaturated carboxylic acid and / or a derivative thereof is grafted, the method is not particularly limited, and a conventionally known graft polymerization method such as a solution method or a melt-kneading method is employed. be able to. For example, there are a method in which a polymer is melted and a grafting monomer is added thereto for a grafting reaction, or a solution is prepared by dissolving the polymer in a solvent and a grafting monomer is added thereto for a grafting reaction.

  The method for producing the polypropylene-based adhesive polymer composition (C) of the present invention is not particularly limited, and a known method can be employed. Examples thereof include a method of melt-kneading the isotactic polypropylene (A), the propylene / 1-butene random copolymer (B), or other components blended as necessary, all at once or sequentially. When the graft modification is performed, the graft modification is performed in the state in which the components (A) and (B) are present at the same time, or one part of the component (A) or (B) is graft modified, and then the graft obtained There is a method of obtaining a modified polyolefin composition by melt-kneading a modified product together with an unmodified resin.

  In the present invention, a method in which one part or all of the isotactic propylene (A) component is graft-modified and then the unmodified component is melt mixed. Examples of the melt kneading method include a method of dry blending the resin composition and then melt kneading with a uniaxial or biaxial screw extruder, a Banbury mixer, a roll, various kneaders, etc. A machine is preferably used. The temperature in the melt-kneading is not particularly limited as long as (A) and (B) are melted, but is usually 160 to 300 ° C., preferably 180 to 250 ° C. is there.

  The polypropylene-based adhesive polymer composition (C) of the present invention can be blended with other resins, elastomers and the like that can be mixed within a range that does not impair the object of the present invention. Even if the blending of other resins and the like is simultaneous with the above-mentioned (A) and (B), mixing after obtaining the propylene-based adhesive polymer composition (C) from (A) and (B). There may be.

  It is possible to add a known process stabilizer, heat stabilizer, heat aging agent, filler, etc. to the polypropylene-based adhesive polymer composition (C) of the present invention within a range not to impair the purpose of the present invention. It is. In the present invention, it is particularly preferable to add a so-called tackifier for the purpose of imparting tackiness. Examples of the substance that imparts tackiness include rosin derivatives, terpene resins, petroleum resins, and hydrides thereof. Among these, hydrogenated terpene resins and hydrogenated petroleum resins are preferable. The tackifier is preferably blended in a proportion of 70 to 95% by weight of the polypropylene-based adhesive polymer composition (C) and 5 to 30% by weight of the tackifier.

Laminate The polypropylene-based adhesive resin composition (C) of the present invention is suitably used as an adhesive layer of a laminate. Various thermoplastic resins such as polyolefin, polyester, polyamide or ethylene / vinyl alcohol copolymer can be used as the resin of the other thermoplastic resin layer constituting the laminate. Among these, ethylene / vinyl alcohol copolymer is used. Polymers are preferably used.

  As the ethylene / vinyl alcohol copolymer, a copolymer containing 20 to 50 mol%, preferably 25 to 48 mol% of a polymerized unit derived from ethylene is desirable. These can be produced by saponifying a corresponding ethylene / vinyl acetate copolymer by a conventional method.

  The laminate of the present invention is preferably one in which an ethylene / vinyl alcohol copolymer layer is laminated on at least one surface of the polypropylene-based adhesive resin composition layer of the present invention.

  The laminate of the present invention can be produced, for example, by melting the composition and resin of each layer and laminating them in a molten state.

    [Example]

(Various measurement methods)
In this example, measurement was performed according to the following method.

[Melting point (Tm)]
An endothermic curve of DSC is obtained, and the temperature at the maximum peak position is defined as Tm. The sample is packed in an aluminum pan, heated to 200 ° C. at 100 ° C./min, held at 200 ° C. for 10 minutes, lowered to −150 ° C. at 10 ° C./min, and then increased at 10 ° C./min. It calculated | required from the endothermic curve at the time of warming.

[Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were measured as follows using GPC-2000 manufactured by Alliance.

  That is, the separation column was TSKgel GMH6-HTx2 + TSKgel GMH6-HTLx2, and the column size was 7.5 mm in diameter and 300 mm in length. The column temperature is 140 ° C., orthodichlorobenzene (manufactured by Wako Pure Chemical Industries) is used as the mobile phase, and 0.025% by mass of BHT (butylhydroxytoluene) (manufactured by Takeda Pharmaceutical Company Limited) is used as an antioxidant. Transferred at 0 ml / min. The sample concentration was 0.1% by mass, and the sample injection amount was 500 microliters. A differential refractometer was used as a detector. Standard polystyrene used was manufactured by Tosoh Corporation.

[Interlayer adhesion of film]
A T peel peel test for the outer layer and the intermediate layer was performed in an atmosphere at 23 ° C.

  The peeling speed was 300 mm / min.

(Substance used)
Substances used in Examples and Comparative Examples are shown below. In addition, unless otherwise indicated, all were prepared by polymerization according to a conventional method.

PP-1: Isotactic homopolypropylene
(Melt flow rate 5.0, density 0.90 g / cm ³ )
PBR-1: Propylene / 1-butene random copolymer
(Melt flow rate 7.0, density 0.89 g / cm ³ ,
1-butene = 25 mol%, melting point = 80 ° C., Mw / Mn = 2.1)
PBR-2: propylene / 1-butene random copolymer,
(Melt flow rate 7.0, density 0.89 g / cm ³ ,
1-butene = 25 mol%, melting point = 110 ° C.
Mw / Mn = 4.0)
PBR-3: Propylene / 1-butene random copolymer
(Melt flow rate 7.0, density 0.89 g / cm ³ ,
1-butene = 10 mol%, melting point = 130 ° C.
Mw / Mn = 2.5)

Example 1
<Production of Propylene Adhesive Polymer Composition (C)>
(A) 95% by weight of isotactic homopolypropylene (PP-1) having a melt flow rate of 5.0 and a density of 0.90 g / cm ³ ;
(B) 5% by weight of propylene / 1-butene random copolymer (PBR-1) having a melt flow rate of 7.0 and a density of 0.89 g / cm ³ ,
Using a single screw extruder, it was melt-kneaded at 230 ° C. to obtain a propylene-based adhesive polymer composition (C). The resulting propylene-based adhesive polymer composition (C) had a melt flow rate of 6.0 and a density of 0.89 g / cm ³ .

<Production of three-layer laminate>
Each layer having the structure shown below was coextruded under the following conditions to form a three-layer film.

[Middle layer]
As an ethylene / vinyl alcohol copolymer (hereinafter referred to as EVOH), Kuraray Co., Ltd. EVAL (registered trademark) F101A (MFR = 1.0) was extruded at 220 ° C. using a screw having a diameter of 40 mm and an effective length of 1000 mm. did.

[Outer layer and inner layer]
The propylene-based adhesive polymer composition (C) obtained above was extruded at 230 ° C. using a screw having a diameter of 30 mm and an effective length of 750 mm.

[Laminate molding conditions]
The resin extruded for the outer layer, the inner layer, and the intermediate layer is laminated in the order of the inner layer, the intermediate layer, and the outer layer in the feed block. The die temperature is 230 ° C., and the laminate of each resin coextruded into a film having a thickness of about 350 μm is taken up at a speed of 20 m / min while being cooled by a chill roll. The thickness of each layer was outer layer / intermediate layer / inner layer = 40/20/40 μm.

  Table 1 shows the interlayer adhesion of the molded laminate.

(Example 2, Comparative Examples 1-2)
The production of the adhesive polymer composition (C) was carried out in the same manner as in Example 1 except that the composition of the polypropylene-based adhesive polymer composition (C) constituting the outer layer and the inner layer was changed to the composition shown in Table 1. Then, a three-layer laminate was formed. Table 1 shows the physical properties of the resulting propylene-based adhesive polymer composition (C) and the measurement / evaluation results of the molded laminate.

  The polypropylene-based adhesive polymer composition of the present invention is excellent in adhesive properties and optical properties and stretchability.

  In addition, the laminate containing the polypropylene-based adhesive polymer composition of the present invention is excellent in interlayer adhesive force and excellent in optical properties and stretchability. Therefore, it is industrially useful.

Claims (6)

A composition 100 comprising 50 to 95 parts by weight of isotactic polypropylene (A) and 50 to 5 parts by weight of a propylene / 1-butene random copolymer (B) defined by the following (i) to (iii): A polypropylene-based adhesive polymer composition (C) obtained by grafting 0.001 to 5 parts by weight of an unsaturated carboxylic acid and / or derivative thereof with respect to weight.
(I) a propylene / 1-butene random copolymer (B) containing 60 to 90 mol% of units derived from propylene and 10 to 40 mol% of units derived from 1-butene,
(Ii) The melting point (Tm) measured by a differential scanning calorimeter is in the range of 40 to 120 ° C.,
(Iii) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1.0 to 3.0. 2. The polypropylene-based adhesive polymer composition according to claim 1, wherein the unsaturated carboxylic acid is maleic acid. 2. The polypropylene-based adhesive polymer composition according to claim 1, wherein the unsaturated carboxylic acid derivative is maleic anhydride. A laminate having at least one layer comprising the adhesive polymer composition (C) according to claim 1. A laminate comprising at least a layer comprising the adhesive polymer composition (C) according to claim 1 and a layer comprising an ethylene / vinyl acetate copolymer saponified product. A laminated body obtained by stretching the laminated body according to claim 4 in at least one direction.