WO2016099221A2 - Resin composition for film and unpeel film for rubber - Google Patents

Abstract

The present invention relates to a resin composition for film and an unpeel film for rubber. The present invention advantageously provides a resin composition for film and an unpeel film for rubber such that the problem of a packaging film, when applied as a rubber packaging film, remaining as impurities, if the same is melted without being removed at a rubber mixing temperature of 105°C or less, due to non-melting, is resolved; the same has an excellent effect as an unpeel film even at a lower rubber mixing temperature; and damage to the film can be prevented during storage.

Description

Resin composition for film and unfilled film for rubber

[Reciprocal citation with application (s)]

This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0183711 dated December 19, 2014 and Korean Patent Application No. 10-2015-0181456 dated December 18, 2015. All content disclosed in the literature is included as part of this specification.

The present invention relates to a resin composition for film and an unpeel film for rubber, and more particularly, at a rubber compounding temperature of 105 ° C. or lower when applying a packaging film of rubber. When the packaging film is melted without peeling off, the problem of residual impurities due to unmelting can be eliminated, and the resin composition for film can be prevented from breaking during storage while having an excellent effect as an unpeel film even at a low rubber compounding temperature. And an unpeel film for rubber obtained therefrom.

In general, polyethylene (PE) film has excellent transparency and formability, and is widely used for food packaging, agricultural packaging, electronics, and general industrial packaging. Low-density polyethylene (LDPE) and ethylene-vinylacetate copolymer (EVA) are mainly used in products requiring low processing temperature because of their transparency and film formability as well as lower melting temperature than linear low density polyethylene (LLDPE).

In particular, low density polyethylene (LDPE) or low density polyethylene (LDPE) and ethylene-vinylacetate copolymer (EVA) are used for packaging films of rubber products such as synthetic rubber and EPDM. Since the melting temperature of low-density polyethylene resin is 105 ° C or higher, when the film is blended with rubber without being peeled off (hereinafter referred to as 'unpeel'), the film melts and acts as an impurity in the rubber compound. A process of separately removing the packaging film is required (related prior art information: Korean Patent Registration No. 1019656, Korean Patent Registration No. 0949817, and Korean Patent Publication No. 1995-0008120). In addition, in order to prevent breakage of the packaging film during storage, it is necessary to improve physical properties such as tensile strength and tear strength of the film.

In order to solve the problems of the prior art as described above, the present invention is excellent in the melting effect of the unfilled packaging film at a low rubber compounding temperature of 105 ℃ or less may not act as an impurity in the product, furthermore, An object of the present invention is to provide a resin composition for a film having improved mechanical properties so as to prevent breakage, and an unpeel film for rubber obtained therefrom.

In order to achieve the above object, the present invention is a) a polyolefin resin having a melting temperature (Tm) of 100 ℃ or less; And b) an ethylene-vinyl acetate copolymer having a melting temperature (Tm) of 101 ° C. or less.

The polyolefin resin of a) may be, for example, a polyolefin plastomer.

For example, the polyolefin plastomer may have a molecular weight distribution of 3.5 or less.

The polyolefin plastomer may be, for example, a melt index (190 ° C., 2.16 kgf load) of 0.5 to 20 g / 10 minutes and a density of 0.87 to 0.92 g / cm ³ .

The polyolefin plastomer may be, for example, an ethylene-alpha olefin copolymer.

The alpha olefin content in the ethylene-alpha olefin copolymer may be, for example, 2 to 20 mol%.

The polyolefin resin of a) may be included in 50 to 90% by weight of the total resin composition for film 100% by weight, for example.

The ethylene-vinyl acetate copolymer of b) may include, for example, within 6 to 12% by weight of vinyl acetate monomer.

The ethylene-vinyl acetate copolymer of b) is, for example, 10 to 50% by weight in a total of 100% by weight of the resin composition for film. It can be included within the scope.

Moreover, this invention provides the film manufactured from the resin composition mentioned above.

For example, the film may have a melting temperature (Tm) of 105 ° C. or less.

The film may be, for example, an unpeel packaging film of synthetic rubber.

For example, the synthetic rubber may have a blending temperature of 105 ° C. or less.

For example, the film may have a thickness of about 10 μm to about 300 μm.

According to the present invention, there is provided an unpeel film for a film and an unpeel film for rubber, which are excellent in effect as an unpeel film even at a low rubber compounding temperature of 105 ° C. or lower, and which can prevent breakage of the film during storage. It works.

Hereinafter, the present invention will be described in detail.

The resin composition for films of this invention is a) polyolefin resin whose melting temperature (Tm) is 100 degrees C or less, or 70-100 degreeC; And b) an ethylene-vinyl acetate copolymer having a melting temperature (Tm) of 101 ° C. or lower, or 90 to 101 ° C .;

The term " unpeel " refers to the use for rubber compounding processing without unpacking the product after packaging of the synthetic rubber or the like, unless otherwise specified.

The term "melting temperature (Tm)" refers to a value measured by a dynamic scanning calorimeter (DSC) method, unless otherwise specified.

In the present description, the polyolefin plastomizer is a polyolefin having a property that deformation remains after the external force is removed without breaking against the external force, and in the technical field to which the present invention belongs, It may include all referred to as.

The polyolefin resin of a) may be, for example, a metallocene-based polyolefin polymer, and specifically, may be a metallocene-based polyolefin plastomer.

The metallocene-based polyolefin plastomer is prepared, for example, in the presence of a metallocene catalyst composition and has a density of 0.87 to 0.92 g / cm ³ , or a density of 0.89 to 0.90 g / cm ³ and 70 to 100 ° C., or 80 It may be a polyolefin copolymer having a melting temperature of to 100 ℃. If the temperature is lower than the melting temperature, the heat resistance and film properties are lowered and the adhesion is increased, which makes the film difficult to process. If the melting temperature is exceeded, the film is not suitable for an unfilled film for rubber packaging film.

The polyolefin copolymer preferably has a melt index (190 ° C., 2.16 kgf load) of 0.5 to 20 g / 10 min. The melt index suitable for processing varies depending on the film processing method, and the melt index ranges from 0.5 to 3.0 g / 10 min during blow molding, an air blowing film manufacturing method, and cast through a T-Die extruder. In the case of cast molding, the melt index ranges from 3.0 to 20 g / 10 min.

The octene content in the ethylene-octene copolymer is, for example, 2 to 20 mol%, and the molecular weight distribution (Mw / Mn) may be, for example, 3.5 or less, 2.0 to 3.5, 2.0 to 3.4, or 2.0 to 3.3. Within the range, there is an effect of satisfying the physical properties required for the packaging film, especially the unfilled film.

The Mw and Mn can be measured using GPC (Gel Permeation Chromatography) which is a common measuring method.

The metallocene catalyst composition is represented by the following formula 1

[Equation 1]

(In Formula 1,

R ¹ , R ² , R ³ , and R ⁴ are the same as or different from each other, and each independently a hydrogen atom; Alkyl, aryl or silyl radicals having 1 to 20 carbon atoms; Alkenyl, alkylaryl or arylalkyl radicals having 1 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; R ¹ , R ² , R ³ , and R ⁴ may be linked to each other by an alkylidine radical including an alkyl or aryl radical having 1 to 20 carbon atoms to form a ring;

R ⁵ , R ⁶ , and R ⁷ are the same as or different from each other, and each independently a hydrogen atom; Halogen radicals; Or an alkyl, aryl radical, alkoxy, aryloxy, amido radical having 1 to 20 carbon atoms; Two or more of R ⁵ , R ⁶ , and R ⁷ may be linked to each other to form an aliphatic or aromatic ring;

R ⁸ is a hydrogen atom, an alkyl, aryl, alkylaryl or arylalkyl radical having 1 to 20 carbon atoms;

Cy is a substituted or unsubstituted aliphatic or aromatic ring;

M is a Group 4 transition metal;

Q ¹ , Q ² , and Q ³ are each independently a halogen radical; Alkyl or aryl amido radicals having 1 to 20 carbon atoms; Alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals having 1 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.) And a metallocene catalyst and a transition metal.

The metallocene catalyst composition may further include at least one cocatalyst selected from compounds represented by the following Chemical Formulas 2, 3, and 4, for example.

[Formula 2]

^{- [Al (R 9) -O} ] a -

(In Formula 2, R ⁹ is each independently a halogen radical; a hydrocarbyl radical having 1 to 20 carbon atoms; or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more.)

[Formula 3]

Al (R ¹⁰ ) ₃

(In Formula 3, R ¹⁰ is each independently a halogen radical; a hydrocarbyl radical having 1 to 20 carbon atoms; or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen);

[Formula 4]

_{^{[LH] + [ZA 4]}} - or _{^{[L] + [ZA 4]}} -

(In Formula 4, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is each independently one or more hydrogen atoms are halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy Or an aryl or alkyl radical of 6 to 20 carbon atoms substituted with a phenoxy radical.

The polyolefin resin of a) may be included, for example, in the range of 50 to 90% by weight, or 60 to 80% by weight of the total 100% by weight of the resin composition for the film. It can provide an excellent effect.

The ethylene-vinyl acetate copolymer of b) may be, for example, a copolymer in which the vinyl acetate monomer is included in the range of 6 to 12 wt%, or 6 to 9 wt%.

The ethylene-vinyl acetate copolymer of component b) may be prepared by a polymerization process by a high pressure radical method using an oxygen or a peroxide initiator. For example, b) the ethylene-vinyl acetate copolymer may be polymerized under an appropriate temperature and pressure after the ethylene monomer and the vinyl acetate monomer are added to the tubular reactor and oxygen or a peroxide-based initiator is added. The content of the ethylene monomer may be adjusted according to the b) vinyl acetate content of the above-mentioned b) ethylene-vinyl acetate copolymer.

The ethylene-vinyl acetate copolymer of b) may be included, for example, within a range of 10 to 50% by weight, or 20 to 40% by weight, in a total of 100% by weight of the resin composition for film. Stability may be lowered, and when the content exceeds the content range, physical properties such as tensile strength, tearing strength, and impact strength of the film may be lowered.

For example, the composition may have a melting temperature (Tm) of 100 ° C. or less, or 80 to 100 ° C.

According to this invention, the film manufactured from the resin composition mentioned above is provided.

The film is generically made in the form of a thin film, and may include all that are commonly called sheets, wraps, and the like.

For example, the film may have a melting temperature (Tm) of 100 ° C. or less, or 80 to 100 ° C.

As a specific example, the film may be an unpeel packaging film of synthetic rubber such as EPDM. The synthetic rubber is not otherwise specified, and may be a synthetic rubber compoundable at 105 ° C. or lower, or 80 to 105 ° C.

For example, the film may have a thickness of 10 to 300 μm, or 20 to 100 μm, and has excellent packaging properties within this range.

The processing of the film is not specific to this, but when the blown film processing method is described as an example, the film is expanded and stabilized in the horizontal / vertical direction before the molten resin is cooled and cooled, thereby producing a stable film. The shaking of the bubble can be evaluated by the bubble stability that the so-called tube bubble shakes left and right while the film thickness is generated, the film processed in this case is excellent in the bubble stability.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Examples 1 to 6, Comparative Examples 1 to 3 and Control Examples 1 to 2

As a resin composition for the film was formulated in the component and content ranges shown in Table 1 below and extruded into a film having a thickness of 50 ㎛ with an extruded blow molding method to prepare a specimen.

The raw materials used in the above examples and comparative examples are as follows:

* POP1 : A product manufactured according to the contents of Korean Patent Laid-Open No. 2012-0090927, which is prepared using the metallocene catalyst of Formula 1, and has a melt index (190 ° C., 2.16 kgf load) of 1.2 g / 10 minutes and a density of It is a metallocene-based polyolefin plastomer of 0.903 g / cm ³ and melting temperature (Tm) of 96 ° C. It is sold by LG Chem under the LF100 brand name.

* POP2: A product manufactured according to the contents of Korean Patent Publication No. 2012-0090927, which is prepared using the metallocene catalyst of Formula 1, and has a melt index (190 ° C., 2.16 kgf load) of 1.2 g / 10 minutes and a density of It is a metallocene-based polyolefin plastomer of 0.885 g / cm ³ and melting temperature (Tm) of 73 ° C, and is sold under the name LC180 brand by LG Chem.

* EVA 1: ethylene-vinyl acetate copolymer with melt index (190 ℃, 2.16 kgf load) of 1.0 g / 10 min, vinyl acetate monomer content of 6 wt% and melting temperature (Tm) of 101 ℃, EF320 from LG Chem. It is sold under the brand name.

* EVA 2: Ethylene-vinyl acetate copolymer with melt index (190 ℃, 2.16 kgf load) of 1.0 g / 10 min, vinyl acetate monomer content of 9% by weight and melting temperature (Tm) of 94 ℃. It is sold under the brand name.

* EVA3 : An ethylene-vinyl acetate copolymer with a melt index (190 ℃, 2.16 kgf load) of 1.1 g / 10 minutes, a vinyl acetate monomer content of 12% by weight, and a melting temperature (Tm) of 90 ℃. Sell by name.

* LDPE : Low density polyethylene with a melt index (190 ℃, 2.16 kgf load) of 3.0 g / 10 min, density 0.920 g / cm ³ and melting temperature (Tm) of 105 ℃, sold by LG Chem under the BF500 brand name. .

Classification (wt%)	POP1	POP2	EVA1	EVA2	EVA3	LDPE
Example 1	80		20
Example 2	60		40
Example 3	80			20
Example 4	60			40
Example 5	80				20
Example 6	60				40
Comparative Example 1						100
Comparative Example 2			80			20
Comparative Example 3				80		20
Comparative Example 1	100
Comparative Example 2		100

 [Test Example 1]

Using the prepared specimens to measure the following physical properties and summarized the results as Table 2 below.

<Test item>

* Impact impact strength (Dart Impact Strength): in accordance with ASTM D-1709 to obtain the value after 20 or more measurements per film sample.

* Tensile Tensile Strength (Tensile Strength at Breat) and breaking elongation (Elongation at Breat): after cutting the breaking tensile strength and the elongation at break is a film having a predetermined thickness by the die cutter (Cutter) a specimen form the basis of the ASTM D-882 Measured. At this time, the tensile speed was 500mm / min, and measured 10 times per specimen to take the average value.

- Elmendorf (Elmendorf) tear strength (MD / TD): was measured according to ASTM D-1922. MD is the machine direction in which the film is coming out, TD is the cross direction.

* Haze: Haze was measured by ASTM D1003 method.

* Bubble Stability : When the bubble is shaken, the thickness variation of the film may occur, so when the film is formed by inflation molding of the bubble shake, the bubble is visually checked to ensure the stability of the bubble.

a) It is stable and shows no shaking ○,

b) the stability is slightly poor, showing shaking, △,

c) The thing which is difficult to produce films, such as a thing which does not have stability, a bubble does not rise, or a shake is severe, and wrinkles were made into X was made into X.

The closer to ○, the more preferable the moldability.

Film properties	Fall impact strength (g)	Tensile Strength (kg / cm 2 )		% Elongation		Elmendorf Tearing Strength (g / μm)		Cloudiness (%)	Bubble stability
		MD *	TD *	MD *	TD *	MD *	TD *
Example 1	1,113	398	381	550	650	4.7	8.5	7.9	○
Example 2	680	371	386	522	675	3.6	7.9	9.4	○
Example 3	1,210	401	452	521	663	5.8	7.3	7.4	○
Example 4	765	366	358	540	647	3.2	7.1	8.5	○
Example 5	1,289	403	433	533	657	5.5	7.1	7.0	○
Example 6	824	363	347	525	641	3.1	6.9	7.5	○
Comparative Example 1	165	233	193	356	563	2.2	2.6	19	○
Comparative Example 2	336	259	226	338	591	1.4	2.1	9.5	○
Comparative Example 3	390	191	225	350	584	2.0	2.4	7.3	○
Comparative Example 1	> 1700	427	428	533	650	4.5	6.5	10.2	△
Comparative Example 2	> 1700	560	660	610	650	5.1	7.1	7.2	△

* MD: Flow direction of specimen, TD: Reverse direction of specimen flow.

As shown in Table 2, a) the polyolefin plastomer resin having a) melting temperature (Tm) of the present invention 100 ℃ or less; And b) an ethylene-vinyl acetate copolymer having a melting temperature (Tm) of 101 ° C. or lower, particularly 90 to 101 ° C .; The improved effect was confirmed in all measured physical properties such as bubble stability.

On the other hand, b) melting temperature (Tm) which is one component which comprises the composition of this invention in the film of the comparative example 1 which used the low density polyethylene which is not the resin composition of this invention alone, and the low density polyethylene of the comparative example 1, ethylene of 101 degrees C or less The films of Comparative Examples 2 and 3 in which the vinyl acetate copolymer was excessively administered showed poor effects on all measured physical properties such as impact impact strength, tensile strength, elongation, tear strength, cloudiness, and bubble stability compared to Examples 1 to 6. It was.

Additional Experimental Example 1

The same experiment as in Example 1 was repeated except that the POP content was replaced by 50% by weight and the EVA 1 content by 50% by weight.

The measured physical properties were: 589 g fall impact strength, 363 kg / cm ² (MD) / 379 kg / cm ² (TD), elongation 545% (MD) / 680% (TD), Elmendorf tear strength 3.5 g / μm (MD) /7.4 g / μm (TD), cloudiness of 9.5%, compared with Examples 1 to 5 it was confirmed that the impact strength, tensile strength and Elmendorf tear strength is lowered.

Additional Experimental Example 2

When the density of POP less than 0.87 g / cm ³ was used, the melt temperature was low and sticky, so the film was not processed well, and the melt index (190 ℃, 2.16kgf) exceeded 20 g / 10min. In addition, film processing was not good.

<Example 1>

The EPDM rubber packaged with the 50 μm thick film prepared in Example 1 was blended at 105 ° C., but the compounding process was carried out in an unpeel state without peeling off the film. It was confirmed that the dispersion was uniform in color.

<Example 2>

Except for replacing the 50 ㎛ film prepared in Example 1 to 50 ㎛ film prepared in Comparative Example 2 in the use example 2 was carried out in the same unpeel (unpeel) blending process. The resultant rubber compound was confirmed that the packaging film did not melt well and acted as an impurity to show a uniform color.

Claims (14)

1. a) polyolefin resin having a melting temperature (Tm) of 100 ° C. or less; And b) an ethylene-vinyl acetate copolymer having a melting temperature (Tm) of 101 ° C. or less.

   Resin composition for films.
2. The method of claim 1,

   The polyolefin resin of a) is characterized in that the polyolefin plastomer

   Resin composition for films.
3. The method of claim 2,

   The polyolefin plastomer is characterized in that the molecular weight distribution is 3.5 or less

   Resin composition for films.
4. The method of claim 2,

   The polyolefin plastomer is characterized in that the melt index (190 ℃, 2.16 kgf load) is 0.5 to 20 g / 10 minutes and the density is 0.87 to 0.92 g / cm ³

   Resin composition for films.
5. The method of claim 2,

   The polyolefin plastomer is characterized in that the ethylene-alpha olefin copolymer

   Resin composition for films.
6. The method of claim 5,

   The alpha olefin content in the ethylene-alpha olefin copolymer is characterized in that 2 to 20 mol%.

   Resin composition for films.
7. The method of claim 1,

   The polyolefin resin of a) is characterized in that contained within 50 to 90% by weight of the total 100% by weight of the resin composition for the film

   Resin composition for films.
8. The method of claim 1,

   The ethylene-vinyl acetate copolymer of b) is characterized in that the vinyl acetate monomer is included in the range of 6 to 12% by weight

   Resin composition for films.
9. The method of claim 1,

   The ethylene-vinyl acetate copolymer of b) is 10 to 50% by weight in a total of 100% by weight of the resin composition for film Characterized in that included within the scope

   Resin composition for films.
10. A film made of the resin composition of any one of claims 1 to 9.
11. The method of claim 10,

    The film is characterized in that the melting temperature (Tm) is 105 ℃ or less
12. The method of claim 10,

    The film is an unpeel packaging film of synthetic rubber.
13. The method of claim 12,

    The synthetic rubber has a softening point of 105 ℃ or less film.
14. The method of claim 10,

    The film has a thickness of 10 to 300 ㎛.