JP2022035851A - Film for sealant - Google Patents

Abstract

To provide a film and/or a packaging bag which is easily taken out from a packaging bag even when a content is viscous, and exhibits sufficient heat sealability.SOLUTION: A film includes a seal layer composed of a resin composition containing the following (a), (b), (c) and (d), and satisfies the following (1), (2) and (3). (a) a polypropylene-based resin, (b) a polyethylene-based resin, (c) a silylated polyethylene resin, and (d) a fatty amide. (1) Contents (a), (b) and (c) are 30-90 wt.%, 0-40 wt.% and 3-30 wt.% with respect to the whole resin composition, respectively. (2) Arithmetic average roughness Ra of the surface of the seal layer is 0.03 μm or more and 0.3 μm or less. (3) The silylated polyolefin is represented by the following formula: CH3-(CH2)n-2-CH2-Si(CH3)2O-(-Si(CH3)2-O-)d-Si(CH3)2-CH2-(CH2)n-2-CH3, in the formula, d is an integer of 1 or larger.SELECTED DRAWING: None

Description

The present invention relates to a film for a sealant and a laminate using the same. More specifically, the present invention relates to a sealant film having excellent liquid repellency, heat sealability, slipperiness and blocking resistance, and a laminated packaging bag using the same.

Packaging bags made of plastic film are lightweight, airtight, transparent, high-strength, and easy to handle. Therefore, foods and chemicals consisting of solid, liquid, powder, paste, sticky substances, and mixtures thereof. It is widely used for packaging such as.

However, when taking out foods and chemicals from the packaging bag, everyone knows empirically that it is difficult to take out the contents showing mucous properties such as liquid, paste, and sticky substances because they easily adhere to the inner surface of the packaging bag. By the way. In addition, if the packaging bag with the remaining contents is discarded, there may be a problem in terms of hygiene.

In order to solve these problems, a film in which a surfactant is coated on the surface and a film in which the surfactant is kneaded have been proposed (see, for example, Patent Documents 1, 2 and the like), but the contents are used. It cannot be said that it is easy to take out, and there are problems such as a decrease in heat seal strength.

Further, a film containing a silicone resin or silicone oil and having improved liquid repellency has been proposed (see, for example, Patent Documents 3 and 4 and the like), but the liquid repellency is also insufficient.

Further, a film having improved liquid repellency made of a silylated polyolefin has also been proposed (see, for example, Patent Documents 5, 6, 7 and the like).
However, Patent Documents 5 to 7 are inferior in productivity and handleability as a film or a laminated body because of poor slipperiness and blocking resistance.

Japanese Unexamined Patent Publication No. 2000-355362 Japanese Unexamined Patent Publication No. 2001-48229 Japanese Unexamined Patent Publication No. 08-337267 Japanese Patent No. 3539723 Japanese Patent No. 5990131 Japanese Unexamined Patent Publication No. 2014-177541 JP-A-2015-024548

The present invention has been made in consideration of the above technical background, and provides a film and / or a packaging bag that can be easily taken out from the packaging bag even if the content is sticky and exhibits sufficient heat-sealing properties. The purpose is to do.

As a result of diligent studies in view of such circumstances, the present inventors have used a resin composition containing a polypropylene-based resin and a silylated polyolefin, and set the temperature dependence of the heat seal strength in the layer composed of this resin composition within a specific range. By doing so, it was found that the above-mentioned problems could be solved, and the present invention was reached.
That is, the present invention
A film containing a seal layer composed of a resin composition containing the following (a), (b), (c), and (d), and a sealant film satisfying the following (1), (2), and (3). Is.
(A) Polypropylene-based resin (b) Polyethylene-based resin (c) Cyrilized polyolefin resin (d) Fatty acid amides (1), (a), (b), and (c) are contained in the entire resin composition. On the other hand, it is 30 to 90% by weight, 0 to 40% by weight, and 3 to 30% by weight.
(2) The arithmetic average roughness Ra of the surface of the seal layer is 0.03 μm or more and 0.3 μm or less.
(3) The silylated polyolefin is represented by the following formula.
CH _3- (CH ₂ ) _n-2- CH ₂ - _Si (CH ₃ ) ₂ O- (-Si (CH ₃ ) ₂ -O-) _d - _Si (CH ₃ ) ₂ -CH _2- (CH) ₂ ) _n-2- CH ₃
(In the formula, d is an integer of 1 or more.)

In this case, it is preferable that the resin composition contains particles made of an oxide or a synthetic resin.

Further, in these cases, it is preferable to satisfy the following (4) and (5). (4) The abundance ratio (S _i / C) of the silicon atom _Si and the carbon atom C contained in the seal layer is It is 0.001 or more and 0.02 or less.
(5) The abundance ratio (S _i / C) of the silicon atom S _i and the carbon atom C on the surface of the seal layer is 0.05 or more and 0.2 or less.

Furthermore, in these cases, it is preferable to satisfy the following (6).
(6) The abundance ratio of the silicon atom S _i and the carbon atom C on the surface of the seal layer (S _i / C) with respect to the abundance ratio (S _i / C) of the silicon atom S _i and the carbon atom C contained in the seal layer. ) Is 2 or more.

Furthermore, in these cases, it is preferable that the blocking value on the surface of the seal layer is 200 mN / 70 mm or less.

Furthermore, a laminate composed of the sealant film and the base film is suitable.

INDUSTRIAL APPLICABILITY The present invention provides a packaging bag that is easy to take out even if it is a paste-like or mucous content, and has a good heat-sealing property, an excellent slipperiness and a blocking resistance, and a sealant film. The laminate can be provided.

Values of the average _Si concentration and the surface _Si concentration of the films according to Comparative Example 2, Examples 1 to 3, 13 and 16. Schematic diagram of the procedure of the liquid repellency evaluation method EDX mapping measurement photograph of film surface TEM observation photograph of film cross section Photograph around the nozzle of the die of the resin extruder

(Seal layer)
In the present invention, the resin composition constituting the seal layer needs to contain (a) polypropylene-based resin, (b) polyethylene-based resin, (c) silylated polyolefin resin, and (d) fatty acid amide.

(Polypropylene resin)
The polypropylene-based resin used in the present invention is a homopolymer of a propylene monomer, a random copolymer of a propylene monomer and an α-olefin, or a block copolymer, or a mixture thereof, and is an α-olefin. Examples thereof include ethylene, butene-1, penten-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, octene-1, and decene-1.

The polypropylene-based resin used is preferably homopolypropylene or a polypropylene-based random copolymer, and polypropylene-α-olefin random, which is a random copolymer of 85% by weight or more of propylene and 15% by weight or less of α-olefin. More preferably, it is a copolymer.
As the α-olefin monomer for obtaining such a polypropylene random copolymer, ethylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and the like can be used, but they are produced. From the viewpoint of sex, it is particularly preferable to use ethylene and butene-1. Further, the α-olefin used for the copolymerization may be at least one kind, and if necessary, two or more kinds may be mixed and used.

The melting point peak temperature of the polypropylene-based resin set is preferably 130 ° C. or higher.
The melting point is measured by the method described in Examples described later. When the melting point peak temperature of the polypropylene resin is 130 ° C or higher, the shape of the package is less likely to collapse, the film can be transported more smoothly in high-speed packaging, and the obtained bag-making product is wrinkled more. Hateful. In addition, retort processing and semi-retort processing can also be performed.

The lower limit of the density of the polypropylene-based resin is preferably 880 kg / cm ³ , and more preferably 885 kg / cm ³ . When it is 880 kg / cm ³ or more, it is preferable because both heat resistance and heat sealability can be achieved. The upper limit of the density of the polypropylene-based resin added to the seal layer is preferably 920 kg / cm ³ , and more preferably 900 kg / cm ³ . When it is 920 kg / cm ³ or less, it is preferable because both heat resistance and heat sealability can be achieved.

The lower limit of the melt flow rate (MFR) of the polypropylene resin is preferably 2.0 g / 10 minutes, more preferably 2.5 g / 10 minutes, and further preferably 2.7 g / 10 minutes. When it is 2.0 g / 10 minutes or more, polypropylene and polyethylene resin do not separate into layers and are easily finely dispersed, and the peel strength of the seal layers after heat sealing does not decrease too much.
The upper limit of the melt flow rate of the polypropylene-based resin is preferably 10.0 g / 10 minutes, more preferably 8.0 g / 10 minutes, and further preferably 7.0 g / 10 minutes. When it is 10.0 g / 10 minutes or less, polypropylene and polyethylene resin do not dissolve in each other and tend to be finely dispersed, and the peel strength of the seal layers after heat sealing does not decrease too much.

(Polyethylene resin)
The polyethylene-based resin used in the present invention is a copolymer of an ethylene monomer and an α-olefin.
Examples of the α-olefin include propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1, decene-1, 3-methylbutene-1, 4-methylpentene-1, octene-1, and the like. Be done.
The copolymer of an ethylene monomer and an α-olefin referred to here is generally referred to as a high-pressure method low-density polyethylene, a linear low-density polyethylene, or a polyethylene-based elastomer. Elastomer means an olefin-based thermoplastic copolymer that exhibits rubber-like elasticity near room temperature.
The melting points of the high-pressure method low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and polyethylene-based elastomer are preferably in the range of 50 to 140 ° C., respectively.

In the present invention, the density range of the raw material polyethylene resin used for compounding is preferably 850 to 970 kg / m ³ , more preferably 860 to 965 kg / m ³ , and even more preferably 856 to 960 kg / m ³ . A polyethylene resin having a density of 850 kg / m ³ or more does not excessively reduce the peel strength of the seal layers after heat sealing. Similarly, in the polyethylene resin having a density of 970 kg / m ³ or less, the peel strength of the seal layers after heat sealing does not decrease too much. Moreover, polymerization is easy.

The lower limit of the melt flow rate (MFR) of the polyethylene resin is preferably 0.6 g / 10 minutes, more preferably 1.0 g / 10 minutes, and further preferably 1.5 g / 10 minutes. When it is 0.6 g / 10 minutes or more, fine dispersibility of polypropylene and polyethylene resin can be easily obtained, and the peel strength of the seal layers after heat sealing does not decrease too much.
The upper limit of the melt flow rate of the polyethylene resin is preferably 5.0 g / 10 minutes, more preferably 4.0 g / 10 minutes, still more preferably 3.5 g / 10 minutes, and particularly preferably 3. It is 0 g / 10 minutes or less. When it is 5.0 g / 10 minutes or less, fine dispersibility between polypropylene and polyethylene resin is likely to be obtained, and the peel strength of the seal layers after heat sealing is likely to be lowered.

By blending and melting the polypropylene-based resin and the polyethylene-based resin, it is possible to create a finely dispersed state. The strength at the time of peeling can be reduced.

After heat-sealing between the seal layers or the seal layer and the peripheral portion of the opening of the other container member, the strength at the time of peeling tends to decrease in the order of the ethylene-based copolymer (polyethylene-based elastomer), LLDPE, and LDPE. The reason for this is that the ethylene-based copolymer has incompatibility with the polypropylene-based resin only in the ethylene portion, but LLDPE has a side chain and thus has fine dispersibility, and LDPE has a long-chain side chain. It can be inferred that this is due to the strong microdispersity.

Specifically, an ethylene-butene copolymer elastomer (Toughmer A1085S manufactured by Mitsui Chemicals, Inc.) having a density of 885 kg / m ³ , MFR (230 ° C., 2.16 kg) 2.2 g / 10 min, a density of 869 kg / m ³ , MFR ( An example is a 1.8 g / 10 min ethylene-propylene copolymer elastomer (Toughmer P0480 manufactured by Mitsui Chemicals, Inc.) at 230 ° C., 2.16 kg).

(Cyrilized polyolefin resin)
The silylated polyolefin resin used in the present invention is selected from the group consisting of a silicon-containing compound having two or more _SiH groups in the molecule and ethylene, propylene, 1-butene, 1-pentene and 1-hexene. It is a polymer of at least one kind of olefin and is obtained by reaction with a vinyl group-containing compound containing a vinyl group at the terminal.

Examples of silicon-containing compounds having two or more SiH groups include methylhydrogenpolysiloxane represented by the formula (1), and some or all of the methyl groups in the formula (1) are ethyl groups and _propyls . Examples thereof include compounds substituted with a group, a phenyl group, a trifluoropropyl group and the like.
Equation (1)
(CH ₃ ) ₃ S _i O- (-S _i H (CH ₃ ) -O-) _a -S _i (CH ₃ ) ₃
(In the formula (1), a is an integer of 2 or more, and the upper limit is preferably 1000, more preferably 300, and more preferably 50.)

As another example of the silicon-containing compound having two or more _Si H groups, for example, a dimethylsiloxane / methylhydrogensiloxane copolymer represented by the formula (2), a part of the methyl group in the formula (2). Alternatively, a compound in which all of them are substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group or the like can be mentioned.
Equation (2)
(CH ₃ ) ₃ S _i O- (-S _i (CH ₃ ) ₂ -O-) _b- (-S _i H (CH ₃ ) -O-) _c -S _i (CH ₃ ) ₃
(In the formula (2), b is an integer of 1 or more, c is an integer of 2 or more, and the upper limit of the total of b and c is preferably 1000, more preferably 300, and more preferably 50. In addition, in equation (2), the order in which the -S _i (CH ₃ ) ₂ -O- unit and the -S _i H (CH ₃ ) -O- unit are arranged is not particularly limited and is block-like. It may be chaotic or statistically random.

As yet another example of the silicon-containing compound having two or more S _iH groups, for example, a methylhydrogenpolysiloxane represented by the formula (3), a part or all of the methyl group in the formula (3) is ethyl. Examples thereof include compounds substituted with a group, a propyl group, a phenyl group, a trifluoropropyl group and the like.
Equation (3)
HS _i (CH ₃ ) ₂ O- (-S _{i (CH 3) 2-O-) d-S i ( CH 3 ) 2 H}
(In the formula (3), d is an integer of 1 or more, and the upper limit is preferably 1000, more preferably 300, and more preferably 50.)

More specifically, such a compound includes, but is not limited to, a compound whose structure corresponding to its number average molecular weight corresponds to the structure shown below.
HS _i (CH ₃ ) ₂ O- (-S _{i (CH 3) 2-O-) 5-S i ( CH 3 ) 2 H}
HS _i (CH ₃ ) ₂ O- (-S _{i (CH 3) 2-O-) 8-S i ( CH 3 ) 2 H}
HS _i (CH ₃ ) ₂ O- (-S _{i (CH 3) 2-O-) 18-S i ( CH 3 ) 2 H}
HS _i (CH ₃ ) ₂ O- (-S _{i (CH 3) 2-O-) 80-S i ( CH 3 ) 2 H}
HS _i (CH ₃ ) ₂ O- (-S _{i (CH 3) 2-O-) 230-S i ( CH 3 ) 2 H}

(Vinyl group-containing compound)
The vinyl group-containing compound used in the present invention is obtained by copolymerizing or polymerizing at least one olefin selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene and 1-hexene. ..

The vinyl group-containing compound is an ethylene / α-olefin copolymer having an ethylene-derived structural unit in the range of 81 to 100 mol% and an α-olefin-derived structural unit having 3 to 20 carbon atoms in the range of 0 to 19 mol%. Is desirable. More preferably, it is an ethylene / α-olefin copolymer having an ethylene-derived structural unit in the range of 90 to 100 mol% and an α-olefin-derived structural unit having 3 to 20 carbon atoms in the range of 0 to 10 mol%. desirable. In particular, it is preferable that the constituent unit derived from ethylene is 100 mol%.

Further, the vinyl group-containing compound has a molecular weight distribution (ratio of weight average molecular weight to number average molecular weight, Mw / Mn) measured by gel permeation chromatography (GPC) in the range of 1.1 to 3.0. preferable.

The vinyl group-containing compound preferably has a number average molecular weight (Mn) in the range of 100 or more and 500,000 or less, more preferably 500 or more and 300,000 or less, and further preferably 1,500 or more and 100,000 or less. ..

Further, the vinyl group-containing compound preferably has a melting point of 70 ° C. or higher and 130 ° C. or lower.
The number average molecular weight of the vinyl group-containing compound in the present invention determined by the GPC method is 100 or more and 500,000 or less, and more preferably 500 or more and 300,000 or less.
More preferably, it is 1,500 or more and 100,000 or less.

Further, the vinyl group of the vinyl group-containing compound is preferably present at the end of the main chain, and more preferably the vinyl group is present only at the end of the main chain.

When the vinyl group-containing compound contains ^a vinyl group only at the end of the main chain, the terminal unsaturated rate calculated by 1H-NMR is 80 mol% or more and 99.5 mol% or less, more preferably 90 mol. % Or more and 99 mol% or less.

(Manufacturing method of silylated polyolefin resin)
The silylated polyolefin resin used in the present invention was obtained by reacting the above-mentioned vinyl group-containing compound with a silicon-containing compound in the presence of a transition metal catalyst according to the method described in JP-A-2014-223752. A silylated polyolefin resin or a derivative thereof, or a mixture thereof.

Specific examples of the silylated polyolefin resin include those having a structure represented by the formulas (4) to (6), and combinations of silicon-containing compounds and vinyl group-containing compounds are examples thereof. It is not limited to anything.

Equation (4)
(CH ₃ ) ₃ S _i O- (-S _i [CH _2- (CH ₂ ) _n-2- CH ₃ ] (CH ₃ ) -O-) _a -Si (CH ₃ ) ₃
(In the formula (4), a is an integer of 2 or more, and the upper limit is preferably 1000, more preferably 300, and more preferably 50.)

Equation (5)
(CH ₃ ) ₃ S _i O- (-S _i (CH ₃ ) ₂ -O-) _b- (-S _i [CH _2- (CH ₂ ) _n-2- CH ₃ ] (CH ₃ ) -O- ) _C -S _i (CH ₃ ) ₃
(In the formula (5), b is an integer of 1 or more, c is an integer of 2 or more, and the upper limit of the total of b and c is preferably 1000, more preferably 300, and more preferably 50. .)

Equation (6)
CH _3- (CH ₂ ) _n-2- CH ₂ - _{Si (CH 3) 2 O- (-S i ( CH 3 ) 2} -O-) _d -S _i (CH ₃ ) ₂ -CH _2- ( CH ₂ ) _n-2- CH ₃
(In the formula (6), d is an integer of 1 or more, and the upper limit is preferably 1000, more preferably 300, more preferably 50, and particularly preferably 25.)

The silylated polyolefin resin used in the present invention further preferably contains 80% by weight or more of a block copolymer having polyethylene at both ends of polydimethylsiloxane as represented by the formula (6), and contains 90% by weight or more. It is particularly preferable to do so. Further, in the formula (6), d is preferably an integer of 3 or more, and more preferably 10 or more.
In the formulas (4) to (6), n is preferably an integer of 100 or more, and more preferably 150 or more.

The silylated polyolefin resin used in the present invention preferably satisfies the following i) and ii) in order to obtain the characteristics of the film of the present invention and in producing the film of the present invention, and the following i) to iii) are preferable. ) Is more preferably satisfied, and i) to iv) below are more preferable.
i) The density is in the range of 900-1000 kg / m ³ .
ii) The melting point is in the range of 100 to 140 ° C.
iii) The number average molecular weight is in the range of 1,000 to 20,000.
iv) The copolymerization rate of silicone is in the range of 1 to 50% by weight.
The method for identifying the chemical formula and molecular weight of the silylated polyolefin resin is as described in Examples.

(Organic lubricant)
The resin composition constituting the seal layer preferably contains an organic lubricant, and the organic lubricant is preferably a fatty acid amide. Due to the synergistic effect of making the arithmetic average roughness Ra of the surface of the seal layer 0.03 μm or more and 0.3 μm or less by containing the organic lubricant, the blocking resistance and slipperiness of the seal layer are improved. Easy to improve.
Examples of the fatty acid amide include oleic acid amide, erucic acid amide, behenic acid amide, ethylene bisoleic acid amide, hexamethylene bisoleic acid amide and the like. These may be used alone, but it is preferable to use two or more of them in combination because the slipperiness and the blocking prevention effect can be maintained even in a harsh environment.
On the other hand, fatty acid esters are widely known as emulsifiers and are also known to have the effect of imparting hydrophilicity to the film surface as an anti-fog agent. Not preferable. In addition, many fatty acid esters have a low melting point, and there is concern about stickiness and poor appearance due to bleed-out. Considering these points, fatty acid amides are preferable.

(Resin composition)
The contents of (a) polypropylene-based resin, (b) polyethylene-based resin, and (c) silylated polyolefin resin in the resin composition constituting the seal layer of the present invention are 30 to 30 or more, respectively, with respect to the entire resin composition. It needs to be 90% by weight, 0 to 40% by weight, and 3 to 30% by weight.
When LDPE and LLDPE are included as the polyethylene resin, the contents of (a) polypropylene-based resin, (b) polyethylene-based resin, and (c) silylated polyolefin resin in the resin composition constituting the seal layer are each resin composition. It is preferably 30 to 70% by weight, 10 to 40% by weight, and 3 to 30% by weight based on the whole product.
(A) The content of the polypropylene-based resin in the resin composition is more preferably 35% by weight or more, further preferably 40% by weight or more, and particularly preferably 55% by weight or more. (A) When the polypropylene-based resin contains 30% by weight or more, the feeling of waist is maintained.
The content of the polypropylene-based resin in the resin composition is more preferably 65% by weight or less, still more preferably 60% by weight or less. (A) When the polypropylene-based resin contains 70% by weight or less, easy peeling property is recognized.
(B) The content of the polyethylene-based resin in the resin composition is more preferably 12% by weight or more, further preferably 15% by weight or more, and particularly preferably 20% by weight or more. When the polyethylene-based resin is contained in an amount of 10% by weight or more, the peel strength of the sealing layers after heat sealing tends to be lowered.
The content of the polyethylene-based resin (b) in the resin composition is more preferably 35% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less. (B) When the content of the polyethylene resin is about 40% by weight, the heat resistance does not easily decrease.
(C) The content of the silylated polyolefin resin in the resin composition is more preferably 5% by weight or more, further preferably 7% by weight or more, and particularly preferably 12% by weight or more. When the silylated polyolefin resin is contained in an amount of 3% by weight or more, sufficient liquid repellency is obtained, and particularly excellent in edible oil.
The content of the (c) silylated polyolefin resin in the resin composition is more preferably 28% by weight or less, further preferably 25% by weight or less, still more preferably 20% by weight or less, still more preferably 15% by weight. It is as follows. (C) When the content of the silylated polyolefin resin is about 30% by weight, the liquid-repellent effect is rarely further improved. (C) The smaller the content of the silylated polyolefin resin, the smaller the segregation on the surface of the seal layer.

When the polyethylene resin contains an elastomer, the contents of (a) polypropylene-based resin, (b) polyethylene-based resin, and (c) silylated polyolefin resin in the resin composition constituting the seal layer are each contained in the entire resin composition. On the other hand, it is preferably 30 to 90% by weight, 0 to 40% by weight, and 3 to 30% by weight.
(A) The content of the polypropylene-based resin in the resin composition is more preferably 35% by weight or more, further preferably 40% by weight or more, and particularly preferably 55% by weight or more. (A) When the polypropylene-based resin contains 30% by weight or more, the feeling of waist is maintained.
The content of the polypropylene-based resin in the resin composition is more preferably 80% by weight or less, still more preferably 75% by weight or less. (A) When the polypropylene-based resin contains 70% by weight or less, the easy peel property is maintained.
(B) The content of the polyethylene-based resin in the resin composition is more preferably 12% by weight or more, further preferably 15% by weight or more, and particularly preferably 20% by weight or more. When the polyethylene-based resin is contained in an amount of 10% by weight or more, the peel strength of the sealing layers after heat sealing tends to be lowered.
The content of the polyethylene-based resin (b) in the resin composition is more preferably 35% by weight or less, still more preferably 30% by weight or less, still more preferably 20% by weight or less. (B) When the content of the polyethylene resin is about 40% by weight, the heat resistance does not easily decrease.
(C) The content of the silylated polyolefin resin in the resin composition is more preferably 5% by weight or more, further preferably 7% by weight or more, and particularly preferably 12% by weight or more. When the silylated polyolefin resin is contained in an amount of 3% by weight or more, sufficient liquid repellency is obtained, and particularly excellent in edible oil.
The content of the (c) silylated polyolefin resin in the resin composition is more preferably 25% by weight or less, still more preferably 20% by weight or less, still more preferably 15% by weight or less. (C) When the content of the silylated polyolefin resin is about 30% by weight, the liquid-repellent effect is rarely further improved. (C) The smaller the content of the silylated polyolefin resin, the smaller the segregation on the surface of the seal layer.
The contents of a) polypropylene-based resin, (b) polyethylene-based resin, and (c) silylated polyolefin are determined by the method described in Examples.

(Organic lubricant)
The resin composition constituting the seal layer preferably contains an organic lubricant, and the organic lubricant is preferably a fatty acid amide. Due to the synergistic effect of making the arithmetic average roughness Ra of the surface of the seal layer 0.03 μm or more and 0.3 μm or less by containing the organic lubricant, the blocking resistance and slipperiness of the seal layer are improved. Easy to improve.
Examples of the fatty acid amide include oleic acid amide, erucic acid amide, behenic acid amide, ethylene bisoleic acid amide, hexamethylene bisoleic acid amide and the like. These may be used alone, but it is preferable to use two or more of them in combination because the slipperiness and the blocking prevention effect can be maintained even in a harsh environment.
On the other hand, fatty acid esters are widely known as emulsifiers and are also known to have the effect of imparting hydrophilicity to the film surface as an anti-fog agent. Not preferable. In addition, many fatty acid esters have a low melting point, and there is concern about stickiness and poor appearance due to bleed-out. Considering these points, fatty acid amides are preferable.
It is preferable to add an organic lubricant having a melting point of 25 ° C. or higher.
The content of (d) fatty acid amide and fatty acid ester in the resin composition is preferably 0.01 to 0.5% by weight, more preferably 0.05 to 0.4% by weight, and 0.1. It is particularly preferable to contain ~ 0.3% by weight. If the fatty acid amide is 0.5% by weight or less, the seal strength does not easily decrease.

(particle)
The resin composition constituting the seal layer preferably contains particles, and the particles are preferably particles made of an inorganic oxide or a synthetic resin. By containing the particles, the arithmetic average roughness Ra of the surface of the seal layer can be easily set to 0.03 μm or more and 0.3 μm or less. As a result, the coefficient of dynamic friction between the surfaces of the seal layer of the film or the surface of the seal layer and the surface opposite to the seal layer, and the blocking strength of slipperiness between the surfaces of the seal layer of the film are likely to be significantly reduced.
The reason is that (b) the silylated polyolefin resin is unevenly distributed on the surface of the seal layer, and by imparting specific irregularities to the film surface having a reduced crystallinity and hardness, the influence of the reduction is reduced and the dynamic friction coefficient is reduced. It is considered that the effect of reducing the blocking strength is large.
The weight average particle diameter of the particles made of an inorganic oxide or a synthetic resin is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 5 μm or more. The weight average particle size is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less.
The weight average particle size is measured by the method described in Examples.
Examples of the particles made of synthetic resin include crosslinked acrylic particles, polymethacrylic acid particles, silicone resin particles, and polyethylene particles.
Examples of the particles made of an inorganic oxide include particles made of silicon oxide, particles made of calcium carbonate, zeolite, and particles made of diatomaceous earth. Among the silicon oxides, silica particles and synthetic silica particles are preferably used, but diatomaceous earth may be used in combination.
The content of the particles made of an inorganic oxide or a synthetic resin in the resin composition is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, still more preferably 0.4% by weight or more. Further, 3.0% by weight or less is preferable, 2.5% by weight or less is more preferable, and 2.0% by weight or less is further preferable. When the content of the particles made of an inorganic oxide or a synthetic resin is 3.0% by weight or less, the protrusions on the surface do not become too large and the liquid repellency does not easily decrease.

(others)
Additives such as antioxidants, heat-resistant stabilizers, weather-resistant stabilizers, crystal nucleating agents, and ethylene-vinyl acetate copolymers as necessary in the resin composition, as long as the performance as the sealant film of the present invention is not impaired. It may contain a coalescence, an ethylene / acrylic acid ester copolymer, or the like.

(Film formation method)
Examples of the method for producing a film for a sealant of the present invention include a step of melt-kneading a polypropylene-based resin composition containing a polyethylene-based resin, and a step of melt-extruding the melt-kneaded resin composition into a molten resin composition sheet. It is preferable to adopt a step of cooling and solidifying the molten resin composition sheet.
The sealant film of the present invention may be a single layer, but laminating is more preferable. In the case of lamination, a thermoplastic resin composition, preferably polyolefin-based, is contained in a layer containing a polyethylene-based resin and a silylated polyolefin and having an arithmetic average roughness of at least one surface layer of 0.03 μm or more and 0.3 μm or less. Another layer made of the resin composition can be provided.
The thickness of the film in the case of a single layer is preferably 3 μm or more, more preferably 10 μm or more, further preferably 15 μm or more, and particularly preferably 20 μm or more. Further, 200 μm or less is preferable, 150 μm or less is more preferable, and 100 μm or less is particularly preferable. If it is less than 3 μm, the effect of the silica particles is reduced, and the effect of slip resistance and locking property is difficult to be obtained.
This will be described in detail below. The longitudinal direction means the direction in which the unstretched sheet is run, and the width direction means the direction perpendicular to it.

(Raw material mixing process)
When mixing silylated polyolefin resin and polyethylene resin, or particles such as silica particles and polypropylene resin, any method may be used as long as these are uniformly mixed, and when using a masterbatch, a ribbon blender, Examples thereof include a method of mixing using a polypropylene mixer, a tumbler mixer and the like.

(Melting and kneading process)
First, as a film raw material, the film is dried or dried with hot air so that the moisture content of polypropylene-based resin or the like is less than 1000 ppm. Next, each raw material is weighed, mixed, supplied to an extruder, and melt-kneaded.
The lower limit of the melt-mixing temperature of the polyethylene-based resin composition is preferably 200 ° C, more preferably 210 ° C, and even more preferably 220 ° C. If it is less than the above, the discharge may become unstable. The upper limit of the resin melting temperature is preferably 260 ° C. If it exceeds the above, the decomposition of the resin proceeds, and the amount of foreign substances such as crosslinked organic substances, so-called gels, produced as a result of recombination increases.
When the above-mentioned antioxidant is contained in the polyethylene-based resin composition, melt extrusion at a higher temperature is possible, but the temperature is preferably 270 ° C. or lower.

(Filtration)
In the melt-kneading step, high-precision filtration can be performed to remove foreign substances contained in the melted polyethylene-based resin composition. The filter medium used for high-precision filtration of molten resin is not particularly limited, but in the case of a stainless sintered filter medium, Al, Si, Ti, Sb derived from additives such as catalysts in addition to foreign substances such as so-called gels. , Cu, and Ge as main components are excellent in removing aggregates and suitable. Further, the filtration accuracy is preferably 200 μm or less.

(Filter boost)
It is preferable that the amount of pressure applied to the polyethylene-based resin composition during melt-kneading is small.

(Melting extrusion process)
Next, the molten polypropylene-based resin composition sheet is melt-extruded from, for example, a T-shaped die, cast on a cooling roll, and cooled and solidified to obtain an unstretched sheet. As a specific method for this, it is preferable to cast it on a cooling roll.
Since the silylated polyolefin used in the present invention is a copolymer with polyethylene, bleed-out is not observed even after undergoing melt-kneading and extrusion steps, and foreign matter and eye tar are deposited when a silicone resin is added. Is extremely unlikely to occur.
Examples thereof include a method in which a melt-kneaded polypropylene-based resin composition sheet is melt-extruded into a film by a T-die method or an inflation method, but the T-die method is particularly preferable in that the melting temperature of the resin can be raised. ..

(Lip stain (bleed out))
When melt-extruding the silylated polyolefin, the silica particles, and the polypropylene-based resin from the T-type die, it is preferable that the lip opening of the T-type die is less contaminated. The method for measuring lip stains was the method described in Examples.

(Cooling solidification process)
For example, it is preferable to cast a molten sheet of a polyethylene-based resin composition melt-extruded from a T-shaped die onto a cooling roll for cooling. The lower limit of the cooling roll temperature is preferably 10 ° C. If it is less than the above, not only the effect of suppressing crystallization may be saturated, but also problems such as dew condensation may occur, which is not preferable. The upper limit of the cooling roll temperature is preferably 70 ° C. or lower. If it exceeds the above, crystallization progresses and transparency deteriorates, which is not preferable. When the temperature of the cooling roll is within the above range, it is preferable to lower the humidity of the environment near the cooling roll to prevent dew condensation.
In casting, the temperature of the surface of the cooling roll rises because the high temperature resin comes into contact with the surface. Normally, the cooling roll is cooled by flowing cooling water through a pipe inside, but cooling is performed by ensuring a sufficient amount of cooling water, devising the arrangement of the pipes, and performing maintenance to prevent sludge from adhering to the pipes. It is necessary to reduce the temperature difference in the width direction of the roll surface. At this time, the thickness of the unstretched sheet is preferably in the range of 3 to 200 μm.

(Multi-layer configuration)
The sealant film of the present invention preferably has a multilayer structure. In the case of a multilayer, it contains a polyolefin resin and a silylated polyolefin, and has a layer having an arithmetic average roughness of 0.03 μm or more and 0.3 μm or less on at least one side of the surface layer, and also has a thermoplastic resin composition. One layer or two or more layers can be provided with another layer made of a material, preferably a polyolefin-based resin composition.
By forming the multilayer and containing the silylated polyolefin resin only in the surface layer, the amount of the silylated polyolefin resin used can be reduced, and the precipitation thereof can be further reduced. In addition, other properties of the film can be improved or new functions can be added.
As a specific method for forming multiple layers in this way, a general multi-layer device (multi-layer feed block, static mixer, multi-layer multi-manifold, etc.) can be used.
For example, a method of stacking thermoplastic resins fed from different flow paths using two or more extruders in multiple layers using a feed block, a static mixer, a multi-manifold die, or the like can be used. It is also possible to introduce the above-mentioned multilayer device into the melt line from the extruder to the T-type die by using only one extruder.

In the case of two layers, at least one layer contains a polyolefin resin and a silylated polyolefin resin, and a layer having an arithmetic average roughness of 0.03 μm or more and 0.3 μm or less as a surface layer is a sealing layer (layer A). ), And another layer made of a thermoplastic resin composition, preferably a polyolefin-based resin composition, is preferably a laminated layer (C layer).

In the case of a three-layer structure, at least one layer contains a polyolefin resin and a silylated polyolefin resin, and a layer having an arithmetic average roughness of the surface layer of the surface layer of 0.03 μm or more and 0.3 μm or less is sealed. The layer (A layer) is used, and the other layers made of the thermoplastic resin composition, preferably the polyolefin resin composition, are used as the intermediate layer (B layer) and the laminated layer (C layer), respectively, and are included in this order. Is good. The outermost layers are A layer and C layer, respectively.

The polyolefin-based resin used for the intermediate layer (B layer) and the laminate layer (C layer) is preferably a polyethylene-based resin or a polypropylene-based resin.

(Polyethylene resin)
The polyethylene-based resin used in the intermediate layer (B layer) and the laminated layer (C layer) includes a homopolymer of an ethylene monomer, a copolymer of an ethylene monomer and an α-olefin, and an ethylene monomer. It is either a copolymer with other monomers or a mixture thereof.
Examples of the α-olefin include propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1, decene-1, 3-methylbutene-1, 4-methylpentene-1, octene-1, and the like. Be done.
Examples of other monomers include monomers such as vinyl acetate, (meth) acrylic acid, and (meth) acrylic acid ester.
The polyethylene-based resin can be either crystalline, low-crystalline or non-crystalline random or block copolymer, or a mixture thereof.
Polymers of ethylene monomers and α-olefins are also commonly referred to as high pressure low density polyethylene, linear low density polyethylene, medium density polyethylene and high density polyethylene.
When these polyethylene resins are used, they have excellent heat seal strength, hot tack property, contaminant seal property, and impact resistance, but it is better to contain a small amount or no copolymer of ethylene monomer and other monomers. good.
At this time, the polyethylene-based resins used for the intermediate layer (B layer) and the laminated layer (C layer) may be the same or different.

In this case, it is preferable that the average density of the polyethylene-based resin in each layer of the film is the sealant layer (A layer) ≤ intermediate layer (B layer) ≤ laminated layer (C layer). Since the blended organic lubricant is difficult to move to a dense layer, it is effective for maintaining the slipperiness of the sealant layer after laminating.
At this time, the lower limit of the density of the intermediate layer (B layer) is preferably 880 kg / m ³ , more preferably 890 kg / m ³ , and further preferably 900 kg / m ³ .
If it is less than the above, the waist is weak and it may be difficult to process.
The upper limit of the density of the intermediate layer (B layer) is preferably 940 kg / m ³ , more preferably 930 kg / m ³ , and further preferably 920 kg / m ³ .

(Polypropylene resin)
The polypropylene-based resin used in the intermediate layer (B layer) and the laminated layer (C layer) is a homopolymer of a propylene monomer, a random copolymer of a propylene monomer and an α-olefin, or a block copolymer weight. Combined, a mixture of these, as α-olefins, ethylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, octene-1, decene-1, and the like are used. Can be mentioned.

The above-mentioned organic lubricant may be used for the intermediate layer (B layer) of the film of the present invention, and the lower limit of the organic lubricant is preferably 200 ppm, more preferably 400 ppm. If it is less than the above, the slipperiness may deteriorate.
The upper limit of the erucic acid amide concentration in the intermediate layer is preferably 2000 ppm, more preferably 1500 ppm. If it exceeds the above, it may slip too much and cause winding misalignment.

The recovered resin may be blended in an intermediate layer (B layer) of the film of the present invention in an amount of 10 to 30% by mass.
In the present invention, it is preferable to perform an active ray treatment such as a corona treatment on the laminated layer (C layer) surface of the polyethylene-based sealant film exemplified above. The correspondence improves the laminating strength.

(Film characteristics)
The characteristics of the sealant film of the present invention will be described in detail.

(Abundance ratio of silicon atom Si and carbon atom C in the seal layer (Si / C) (average Si concentration))
The abundance ratio (Si / C) of silicon atom Si and carbon atom C in the seal layer of the sealant film of the present invention is preferably 0.001 or more. When it is 0.001 or more, the liquid repellency to the contents showing mucous properties such as cooking oil, pork cutlet sauce, and soy sauce is improved. It is more preferably 0.005 or more, further preferably 0.007 or more, and preferably 0.01 or more.
The abundance ratio (Si / C) of silicon atom Si and carbon atom C in the seal layer of the sealant film of the present invention is preferably 0.02 or less. When it is 0.02 or less, the peel strength does not easily decrease. It is more preferably 0.018 or less, and further preferably 0.016 or less.
The measuring method is the method described in Examples.

(Abundance ratio of silicon atom S _i and carbon atom C on the surface of the seal layer (S _i / C) (surface S _i concentration))
The abundance ratio ( _Si / C) of silicon atom Si and carbon atom C on the surface of the seal layer of the sealant film of the present invention is preferably 0.05 or more. When it is 0.05 or more, the liquid repellency for the contents showing mucilage such as cooking oil, pork cutlet sauce, and soy sauce is improved, and in particular, the effect of improving the liquid repellency for edible oil is very large. It is more preferably 0.07 or more, further preferably 0.1 or more, preferably 0.13 or more, and particularly preferably 0.15 or more.
The abundance ratio (S _i / C) of the silicon atom S _i and the carbon atom C on the surface of the seal layer of the sealant film of the present invention is preferably 0.3 or less. If it is 0.3 or less, the heat seal strength tends to decrease. It is more preferably 0.2 or less.
The measuring method is the method described in Examples.

(Ratio of surface Si concentration and average Si concentration)
The abundance ratio of silicon atom S _i and carbon atom C on the surface of the seal layer to the abundance ratio (S _i / C) of silicon atom S _i and carbon atom C contained in the seal layer of the sealant film of the present invention ( The ratio of S _i / C) is preferably 2 or more, more preferably 3 or more, further preferably 5 or more, further preferably 6 or more, and more preferably 8 or more. It is particularly preferable, and most preferably 10 or more.
The measuring method is the method described in Examples.
(Arithmetic Mean Roughness Ra)
It is preferable that the arithmetic average roughness Ra of the surface of the seal layer of the sealant film of the present invention is 0.05 μm or more. When it is 0.05 μm or more, the coefficient of kinetic friction between the layers or between the layers and the film surface on the opposite side of the layer is reduced, and the coefficient of kinetic friction between the surfaces of the seal layers of the film or the surface of the seal layer and the opposite surface thereof is increased. Easy to lower. The blocking strength of slipperiness between the surfaces of the sealing layer of the film is also likely to be reduced. As a result, the handleability of the film is improved. The arithmetic average roughness of the surface of the seal layer is more preferably 0.06 or more, and further preferably 0.07 or more.
It is preferable that the arithmetic average roughness Ra of the surface of the seal layer of the sealant film of the present invention is 0.3 μm or less. When it is 0.3 μm or less, the coefficient of dynamic friction between the layers or between the layers and the film surface on the opposite side of the layers is not too small, the film is less likely to be unwound, and the handleability of the film is improved. It is more preferably 0.25 or less.
The measuring method is the method described in Examples.

(Maximum protrusion height Rz)
It is preferable that the maximum protrusion height Rz on the surface of the sealant layer of the sealant film of the present invention is 1 μm or more. When it is 1 μm or more, the contact area between the layers or between the layers and the film surface on the opposite side of the layers is reduced, the blocking prevention effect is greatly improved, and the handleability of the film is improved. The maximum protrusion height Rz on the surface of the seal layer is more preferably 1 μm or more, and further preferably 3 μm or more.
It is preferable that the maximum protrusion height Rz on the surface of the sealant layer of the sealant film of the present invention is 30 μm or less. When it is 30 μm or less, the volume of the gap between the layers or between the layer and the film surface on the opposite side of the layer is not too large, the film is less likely to be unwound, and the handleability of the film is improved. It is more preferably 25 μm or less.
The measuring method is the method described in Examples.

(Young's modulus / longitudinal direction)
The lower limit of the Young's modulus (longitudinal direction) of the sealant film of the present invention is preferably 100 MPa, more preferably 150 MPa, still more preferably 200 MPa, and particularly preferably 250 MPa. If it is 100 MPa or more, the waist is not too weak and it is easy to process.
The upper limit of the Young's modulus (longitudinal direction) of the sealant film of the present invention is preferably 600 MPa, more preferably 500 MPa, and further preferably 400 MPa.

(Young's modulus / width direction)
The lower limit of the Young's modulus (width direction) of the sealant film of the present invention is preferably 100 MPa, more preferably 150 MPa, still more preferably 200 MPa, and particularly preferably 250 MPa. If it is 100 MPa or more, the waist is not too weak and it is easy to process.
The upper limit of the Young's modulus (width direction) of the sealant film of the present invention is preferably 600 MPa, more preferably 500 MPa, and further preferably 400 MPa.

(Haze)
The upper limit of the haze of the sealant film of the present invention is preferably 15%, more preferably 10%, and even more preferably 6%. If it is 15% or less, the contents can be easily visually recognized.
The lower limit of the haze of the sealant film of the present invention is preferably 0%, but even 2% is practically satisfactory.
The measuring method is the method described in Examples.

(Liquid repellent)
The residual amount of sticky contents such as cooking oil, pork cutlet sauce, and soy sauce, which is an index for evaluating the liquid repellency of the sealant film of the present invention, is 0.08 mg / 28 cm ² for at least two of them. It is preferably 0.8 mg / 28 cm ² or less for the three types, and more preferably 0.8 mg / 28 cm 2 or less.
The measuring method is the method described in Examples.

(Presence state of silylated polyolefin resin)
The sealant film of the present invention preferably has a silylated polyolefin resin segregated on the surface. However, it is preferable that the silylated polyolefin resin is not deposited on the surface of the seal layer in a separated state.
At this time, it is preferable that the silylated polyolefin resin is finely dispersed in the seal layer of the sealant film of the present invention and exhibits a microphase-separated structure.
The presence or absence of the silylated polyolefin resin or silicone resin on the surface of the seal layer can be observed using a scanning electron microscope, and qualitative analysis of Si element and C element can also be performed by energy dispersive X-ray.
Further, the cross section of the seal layer can be observed using a transmission electron microscope.
The measurement is carried out by the method described in Examples.

(Dynamic friction coefficient)
The upper limit of the dynamic friction coefficient between the seal layers of the sealant film of the present invention is preferably 1.5, more preferably 1.0, still more preferably 0.7, and even more preferably 0.5. It is particularly preferably 0.4, and most preferably 0.3. When the coefficient of dynamic friction between the seal layers is 1.5 or less, the opening property after bag making is good and the loss during processing is likely to be reduced.
The lower limit of the coefficient of dynamic friction between the seal layers of the sealant film of the present invention is preferably 0.05, more preferably 0.08, and even more preferably 0.1. If it is 0.05 or more, heat sealing during bag making is easy to be performed, and loss during processing is likely to be reduced.
The upper limit of the dynamic friction coefficient between the seal layer of the sealant film of the present invention and the opposite surface of the film is preferably 2.0, more preferably 1.5, still more preferably 1.2, and even more preferably. It is 1.0, particularly preferably 0.7, and most preferably 0.5. When the coefficient of dynamic friction between the sealing layer and the opposite surface of the film is 2.0 or less, the film is less likely to wrinkle during winding, and the loss during processing is likely to be reduced.
The lower limit of the dynamic friction coefficient between the seal layer of the sealant film of the present invention and the opposite surface of the film is preferably 0.05, more preferably 0.08, and even more preferably 0.1. If it is 0.05 or more, the film does not slip too much during winding and is less likely to be unwound.
The measuring method is the method described in Examples.

(Standing coefficient of friction)
The upper limit of the coefficient of static friction between the seal layers of the sealant film of the present invention is preferably 1.5, more preferably 1.0, still more preferably 0.7, and even more preferably 0.5. It is particularly preferably 0.4, and most preferably 0.3. When the coefficient of dynamic friction between the seal layers is 1.5 or less, the opening property after bag making is good and the loss during processing is likely to be reduced.
The lower limit of the coefficient of static friction between the seal layers of the sealant film of the present invention is preferably 0.05, more preferably 0.08, and even more preferably 0.1. If it is 0.05 or more, heat sealing during bag making is easy to be performed, and loss during processing is likely to be reduced.
The measuring method is the method described in Examples.

(Blocking value)
The upper limit of the blocking value of the slipperiness between the surfaces of the sealant film of the present invention is preferably 100 mN / 70 mm, more preferably 90 mN / 70 mm, still more preferably 80 mN / 70 mm, and particularly preferably 80 mN / 70 mm. It is 70 mN / 70 mm, most preferably 60 mN / 20 mm. When the blocking strength of slipperiness between the surfaces of the seal layer is 100 mN / 70 mm or less, unwinding from the film roll for processing can be smoothly performed.
The lower limit of the blocking strength between the surfaces of the sealant film of the present invention is preferably 0 mN / 70 mm, but even 15 mN / 70 mm is practically satisfactory.
The measuring method is the method described in Examples.

(150 ° C easy peel strength)
The 150 ° C. easy peel strength of the sealant film of the present invention is preferably 25 mN / 15 mm or less, preferably 20 mN / 15 mm or less, and even more preferably 15 mN / 10 mm or less.
The measuring method is the method described in Examples.

(190 ℃ easy peel strength)
The 190 ° C. easy peel strength of the sealant film of the present invention is preferably 30 mN / 15 mm or less, preferably 25 mN / 15 mm or less, and even more preferably 20 mN / 15 mm or less.
The measuring method is the method described in Examples.

(200 ° C easy peel strength)
The 200 ° C. easy peel strength of the sealant film of the present invention is preferably 35 mN / 15 mm or less, preferably 30 mN / 15 mm or less, and even more preferably 25 mN / 20 mm or less.
The measuring method is the method described in Examples.

(150 ° C peel strength)
The peel strength at 150 ° C. of the sealant film of the present invention is preferably 0.5 N / 15 mm or more, preferably 0.7 N / 15 mm or more, and more preferably 0.9 N / 15 mm or more.
The measuring method is the method described in Examples.

(190 ° C peel strength)
The 190 ° C. peel strength of the sealant film of the present invention is preferably 1N / 15 mm or more, preferably 1,5 N / 15 mm or more, and further preferably 1.8 N / 15 mm or more.
The measuring method is the method described in Examples.

(200 ° C peel strength)
The peel strength at 200 ° C. of the sealant film of the present invention is preferably 1N / 15 mm or more, preferably 1,5 N / 15 mm or more, and further preferably 1.8 N / 15 mm or more.
The measuring method is the method described in Examples.

(Laminated body)
The sealant film of the present invention is further laminated with at least one other base film, and is generally used as a wrapping film or a wrapping sheet.
The base film is not particularly limited, but is not particularly limited, such as a polyolefin film such as polyethylene and polypropylene, a styrene resin film, a polyester film such as polyethylene terephthalate and polybutylene terephthalate, and nylon 6 and nylons 6 and 6. Polyamide film or stretched film thereof, laminated film of polyolefin film and polyamide film or gas barrier resin film such as ethylene-vinyl alcohol copolymer film, metal foil such as aluminum, or aluminum or silica. A vapor-deposited film, paper, or the like on which or the like is vapor-deposited is appropriately selected and used according to the purpose of use of the laminated body. This base film can be used not only by one type but also by laminating two or more types in combination.

The base film adjacent to the sealant layer preferably does not contain the silylated polyolefin. Further, the base film adjacent to the sealant layer is preferably a polyolefin film.

Examples of the method of laminating the sealant film on the base film include a method of dry laminating the base film (Y) and the sealant film, and an extrusion lamination method of extruding and laminating only the sealant layer resin on the base film. Etc. can be adopted.
Among these, dry lamination is preferable from the viewpoint of productivity.

In order to bond the sealant film of the present invention to another base film more firmly, the sealant film / adhesive layer / other base film can be configured. When an anchor coating agent such as a urethane-based or isocyanate-based adhesive is used as the adhesive layer, or a modified polyolefin such as an unsaturated carboxylic acid graft polyolefin is used as the adhesive resin, the adjacent layers can be firmly bonded. can.

The thickness of the laminate is not particularly limited, but is preferably 10 to 200 μm when the laminate is used as a film such as a lid material, and preferably 200 to 1000 μm when used as a cup or tray sheet.

(Package)
The sealant films of the laminated body face each other, or the sealant film layer of the laminated body and another base film face each other, and then at least one of the surroundings so as to form a desired container shape from the outer surface side. A container can be manufactured by heat-sealing the portion. Further, by heat-sealing the entire periphery, a sealed bag-shaped container can be manufactured. Combining this bag-shaped container molding process with the content filling process, that is, by heat-sealing the bottom and sides of the bag-shaped container, filling the contents, and then heat-sealing the top, the package is manufactured. can do. Therefore, this laminate can be used for an automatic packaging device for solids such as snack foods, powders, or liquid materials.

Further, the contents are filled in a container formed into a cup shape by vacuum molding or pressure molding, a container obtained by injection molding or blow molding, a container formed from a paper base material, or the like, and then the laminate of the present invention is used. A container containing the contents can also be obtained by covering it as a lid material and heat-sealing it.

Hereinafter, embodiments of the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
The detailed description of the present invention and the measured values of each item in Examples and Comparative Examples were measured by the following methods.

(Characteristics of raw materials)
The following methods are used to determine the density, melt flow rate (MFR) and melting point of the polyolefin resin and silylated polyolefin used to prepare the sealant film, and the weight average particle size and content ratio of the particles made of inorganic oxide or synthetic resin. Measured in.
For these values, if the sealant film consists of a single layer, check the boundaries of all layers, and if the sealant film consists of multiple layers, check the boundaries of the corresponding layers with an electron microscope, and then scrape off only the relevant layers to obtain only the target raw material. After filtering the solution dissolved in an insoluble solvent, the residue from which the solvent has been removed may be measured in the same manner. When scraping only the corresponding layer from the multilayer film, it can be relatively easily performed by laminating a film for a lubricant on a polyethylene terephthalate (PET) film or the like and then scraping it with a razor or the like.

(Density: kg / cm ³ )
It was measured by the density gradient tube method according to JIS-K7112.

(Melt flow rate (MFR): g / 10 minutes)
According to JIS-K7210, the temperature of the polyethylene-based resin was 190 ° C., and the temperature of the polypropylene-based resin was 230 ° C.

(Melting point: ° C)
Using a differential scanning calorimeter (DSC) manufactured by SII, the measurement was performed at a sample amount of 10 mg and a heating rate of 10 ° C./min. The melting endothermic peak temperature detected here was taken as the melting point.

(Content of particles made of inorganic oxide or synthetic resin in the film:% by weight)
The content of the particles made of an inorganic oxide or a synthetic resin in the film was calculated from the amount added to the raw material resin composition before processing.
Even after the film is formed, the silica particles should be separated and measured by using decane as a solvent, dissolving the film at a temperature at which it completely dissolves, and filtering the residue with a filter with a filtration accuracy of 2 μm. Is also possible.
(Weight average particle size of particles made of inorganic oxide or synthetic resin: μm)
Particles made of inorganic oxide or synthetic resin are, for example, cumulatively 50% by mass from the smaller particle size in the particle size distribution curve measured using the laser diffraction / scattering type particle size distribution measuring device "MT3200II" of Nikkiso Co., Ltd. Can be calculated as the particle size.

The ease with which the compound was deposited from the resin composition constituting the seal layer of the obtained sealant film was measured by the following method.
(Easiness of precipitation of compounds from the resin composition constituting the seal layer)
The resin composition used for the seal layer of Comparative Example 1 was discharged from a large number of nozzles having a diameter of 4 mm provided on the die of the extruder in the width direction at 230 ° C., and one hour after the start of ejection, the molten resin was discharged. The degree of accumulation (dirt) of the compound around the nozzle was visually observed, and it was classified into the following ○ and × using it as a reference (○).
〇: The accumulation of the compound around the nozzle cannot be confirmed.
X: The accumulation of the compound around the nozzle can be clearly confirmed.

(Characteristics of sealant film)
The characteristics of the obtained sealant film were measured by the following methods.

(Abundance ratio of silicon atom Si and carbon atom C on the surface of the seal layer)
Before measuring the surface of the sealant layer of the sealant film, the surface of the film was wiped with ethanol. Excited X-rays: monochrome ALKα rays, X-ray output: 12 kV, 6 mA, photoelectron escape angle: 90 °, using an X-ray electron spectroscopy (ESCA) measuring instrument (K-Alpha manufactured by Thermo Fisher Scientific) on the surface of the seal layer. The spot size was 400 μmφ, the path energy was 50 eV (narrow scan), and the step was 0.1 eV (narrow scan), and the surface composition ratio of the detected element was calculated.
The surface composition ratio of the obtained element is for a depth region of about several nm to 10 nm from the film surface.

(Abundance ratio of silicon atom Si and carbon atom C contained in the seal layer ( _Si / C) (average Si concentration))
1) After roughly grasping the layer composition by observing the cross section in advance, only the resin composition constituting the seal layer is scraped off with a feather blade. The scraped material was completely dissolved at 135 ° C. in a mixed solvent having an o-dichlorobenzene / deuterated benzene = 80/20 volume ratio. The sample concentration was about 25 to 30 mg / 0.7 mL. In the one-dimensional _Si -NMR measurement, about 1 wt% of acetylacetone chromium (III) was added to the measuring solution.
The following measurements were carried out on this sample to identify the chemical formula and molecular weight of the silylated polyolefin resin contained in the resin composition constituting the seal layer, and the content thereof.
2) First, refer to the Aldrich standard spectrum, standard sample, etc. using the ¹ H-NMR spectrum, ¹³ C-NMR spectrum, ¹³ C-DEPT spectrum, and ²⁹ _Si -NMR spectrum of 1-dimensional NMR. While investigating how the H, C, and Si elements are bonded, the rough structure of the compound was identified.
The measurement conditions are shown below.
Device :: Fourier Transform Nuclear Magnetic Resonance Device (AVANCE NEO 600 type, Bruker Japan Co., Ltd.)
Resonance frequency :: ^{1 1} H-NMR: 600.13 MHz, ¹³ C-NMR: 150.92 MHz, ²⁹ _Si -NMR: 119.22 MHz
Measurement temperature :: ^{1 1} H-NMR: 110 or 115 ° C, ¹³ C-NMR: 110 or 115 ° C, ¹³ C-DEPT: 110 or 115 ° C, ²⁹ Si-NMR: 110 ° C
Pulse repetition time :: ¹ H-NMR: 3.75 seconds, ¹³ C-NMR: 2.8 to 2.9 seconds, ¹³ C-DEPT: 3.5 seconds, ²⁹ _Si -NMR: 7.0 seconds Detection Pulse angle :: ^{1 1} H-NMR: 30 °, ¹³ C-NMR: 30 °, ²⁹ _Si -NMR: 90 °
¹ H decoupler method :: ¹³ C-NMR: full decoupler, ²⁹ _Si -NMR: inverse gate decoupler (FID capture time 0.7 seconds)
Number of integrations :: ¹ H-NMR: 16 times, ¹³ C-NMR: about 300 to 1200 times, ¹³ C-DEPT: about 100 to 1100 times, ²⁹ _Si -NMR: about 4000 times 3) Further, two-dimensional NMR Using COSY, TOCSY, ¹³ C-HSQC, HMBC, ²⁹ S _i -HMBC, the correlation peak between adjacent ¹ Hs, and the correlation peak between adjacent 1 Hs, and further adjacent and further adjacent ¹ Hs. Directly coupled ¹ H, ¹³ C correlation peak, 2 or 3 coupled heteronuclear species ( ¹ H, ¹³ C) correlated peak, 2 or 3 coupled heteronuclear species ( ¹ H, ²⁹ Si) The correlation peaks of the above were investigated, and the connection of the structures found by 1-dimensional NMR was identified in more detail.
4) The abundance ratio of silicon atoms per carbon atom ( _Si / C) (average Si concentration) in the resin composition constituting the seal layer of the sealant film is that of the silylated polyolefin resin contained in the resin composition. It can be derived from the molecular formula and molecular weight, and the content ratio in the resin composition constituting the seal layer.
As specific examples below, the resin composition constituting the seal layer is a polymer composed of only a structural unit derived from ethylene containing a vinyl group at the end of the main chain, a silylated polyolefin resin using dimethylsiloxane as a raw material compound, and a silylated polyolefin resin. The calculation method in the case of a mixture of polyethylene resins is given.
The dimethylsiloxane concentration in the silylated polyolefin is calculated from the molecular formula of the silylated polyolefin resin, and assuming that the resin concentration is 26% by weight, a composition obtained by adding 10 parts by weight of the silylated polyolefin to 90 parts by weight of the polypropylene resin. The average polydimethylsiloxane concentration is 2.6% by weight.
The molecular formula per unit of dimethylsiloxane is C ₂ H ₆ SI O (unit molecular weight _74.15 ), and the molecular formula of silylated polyolefin resin per unit of polyolefin is C ₂ H ₄ (unit molecular weight 28.05), polypropylene resin. The molecular formula per unit of propylene is C ₃ H ₆ (unit molecular weight 42.08).
The amount of dimethylsiloxane per 1 kg of resin composition is (1000 × 2.6 / 100) /74.15=0.35 mol, and the amount of polyolefin of silylated polyolefin resin is (1000 × (10-2.6) / 100) / 28. 05 = 2.6 mol, polypropylene resin is (1000 × 90/100) /42.08 = 21.4 mol.
Therefore, per 1 kg of the resin composition, _Si (silicon) is 0.35 mol and C (carbon) is 0.35 × 2 + 2.6 × 2 + 21.4 × 2 = 48.7 mol, which is one carbon atom in the resin composition. The silicon atom abundance ratio ( _Si / C) per unit is calculated to be 0.35 / 48.7 = 0.007.

(Arithmetic mean roughness Ra: μm)
Arithmetic mean roughness Ra of any 1 mm x 0.2 mm part of the sealant layer surface of a 3 cm x 3 cm square sealant film is based on JIS B0601-2001, and the contact type surface roughness (manufactured by Kosaka Laboratory, model) ET4000A) was used. It was measured at three places and the average value was taken as the arithmetic mean roughness Ra.

(Maximum protrusion height Rz: μm)
The maximum mountain height Rz of any 1 mm x 0.2 mm part of the sealant layer surface of the 3 cm x 3 cm square sealant film is based on JIS B0601-2001, and the contact type surface roughness (manufactured by Kosaka Research Institute, model ET4000A). ) Was used. The measurement was performed at three points, and the average value was taken as the maximum protrusion height Rz.

(Young's modulus, tensile breaking strength, tensile breaking elongation)
The obtained sealant film was measured for Young's modulus in the longitudinal direction and the width direction of the film according to JIS K7127 at 23 ° C.
The sample was cut out from a film to a size of 15 mm × 200 mm, had a chuck width of 100 mm, and was set in a tensile tester (dual column desktop tester Instron 5965 manufactured by Instron Japan Company Limited). A tensile test was performed at a tensile speed of 200 mm / min.
From the obtained strain-stress curve, Young's modulus was obtained from the slope of the straight line portion at the initial stage of elongation.
The tensile breaking strength and the tensile breaking elongation were taken as the strength and elongation at the time when the sample broke, respectively.

(Haze)
Only the obtained sealant film was measured using a direct reading haze meter manufactured by Toyo Seiki Seisakusho Co., Ltd. in accordance with JIS-K-7105.
Haze (%) = [Td (diffusion transmittance%) / Tt (total light transmittance%)] x 100

(Liquid repellent)
The liquid repellency of the obtained sealant film was evaluated as follows.
(1) A film for sealant is cut into a size of 10 cm in the longitudinal direction and 5 cm in the width direction, and double-sided tape (Nichiban) is applied to the surface of the laminated layer at the end of one side in the longitudinal direction and the end of one side in the width direction adjacent to the end. Co., Ltd., NW-5, 5 mm width), fold it so that the sealing surface faces up at the center in the width direction, and attach the double-sided tape and the surface of the other laminated layer to form a 10 cm x 2.5 cm cylinder. I made a strip of paper.
(2) The weight of the tubular strip prepared in (1) was weighed.
(3-1) The following evaluation solutions were placed in a 100 ml descup so as to have a volume of about 70%. The tubular strip weighed in the evaluation solution was soaked for 1 second so as to be immersed at a position of 5.6 cm from the bottom. If a metal ruler or the like is inserted as a support from the opening of the tubular strip during immersion, it is easy to handle and it is possible to avoid accidentally immersing the mouth of the bag in the evaluation solution.
Evaluation liquid: Edible oil (trade name; Nisshin salad oil, manufactured by Nisshin Oillio Group Co., Ltd.), Tonkatsu sauce (product name; rich sauce, manufactured by Kagome Co., Ltd.), soy sauce (name; Koikuchi soy sauce (honjo brewing)) ), Kikkoman Foods Co., Ltd.).
(3-2) With the evaluation liquid adhering to the tubular strip, suspend the tubular strip for 10 seconds while the longitudinal direction is vertical, and then keep the width direction horizontal and the longitudinal direction becomes 45 ° with respect to the horizontal. It was hung for 50 seconds in a tilted state.
(4) The weight of the tubular strip to which the evaluation liquid adhered immediately after (3-2) was weighed, and the amount of residual liquid adhered was determined from the difference from the weight of (2). The surface area of the tubular strip from the bottom to the position of 5.6 cm is 28 cm ² .
Of the 3 types of evaluation liquid, 2 or more types are inferior when they exceed 0.08 / 8 cm ² , 2 types are good when 0.08 / 8 cm ² or less, and 3 types are 0.08 / 8 cm ² or less. The case was excellent ◎.

(Observation of dispersion state of silylated polyolefin)
The surface of the seal layer of the obtained sealant film was observed using a scanning electron microscope and irradiated with energy dispersive X-rays, and the surface was subjected to elemental qualitative analysis for mapping. The cross section was observed using a transmission electron microscope. The observation method is described in detail below.

(Energy dispersive X-ray (EDX) element qualitative analysis)
A sample of the obtained sealant film (size 1 cm x 1 cm) was cut out, placed on a sample table with carbon tape attached, and platinum-palladium was coated at about 2 nm with a magnetron sputtering device to ensure conductivity and high vacuum. Observed in mode.
The measurement was performed by irradiating X-rays with an acceleration voltage of 8 kV using a scanning electron microscope S-3400N manufactured by Hitachi and an energy dispersive X-ray detector XFlash5010 manufactured by Bruker.
A qualitative analysis of the elements was carried out from the X-ray spectrum of the entire observation field of the sample of the sealant film, and among the recognized elements, carbon C was mapped to red and silicon Si was mapped to green.

(Transmission electron microscope (TEM) observation)
Both sides of the obtained sealant film (size 1 cm × 1 cm) were vapor-deposited with osmium, treated to prevent peeling from the epoxy resin, and then embedded in the epoxy resin.
Using a cryomicrotome in which the embedded sample was set at −130 ° C., ultrathin sections were obtained by cutting perpendicular to the film surface in a frozen state.
After dyeing the cross section in ruthenium tetroxide steam for 30 minutes, carbon vapor deposition was performed, and a JEM2100 transmission electron microscope manufactured by JEOL Ltd. was used at an acceleration voltage of 200 kV to observe and photograph the cross section.

(Dynamic friction coefficient)
For each film surface of the polyethylene-based resin of the sealant film, the dynamic friction coefficient was measured according to JIS-K-7125 except for the following conditions.
Environmental conditions: Measured after humidity control for 2 hours or more in a 23 ° C. and 50% RH environment.
Measuring device: TENSILON STM-T-50BP manufactured by Toyo Baldwin
Measurement condition:
Fixed test piece size: 297 mm (longitudinal direction) x 105 mm (width direction)
Movement test piece size: 70 mm (longitudinal direction) x 50 mm (width direction)
Weight of load weight: 0.5 kg
Crosshead speed: 20mm / min
Travel distance: 100 mm or more Calculation method: Calculated from the following formula using the average test force and the mass of the load weight with a stroke between 10 mm and 50 mm.
Friction coefficient = average test force with stroke 10 mm to 40 mm / mass of load weight

(Standing coefficient of friction)
For each film surface of the polyethylene-based resin of the sealant film, the static friction coefficient was measured in accordance with JIS-P-8147 except for the following conditions.
Environmental conditions: Measured after humidity control for 2 hours or more in a 23 ° C. and 50% RH environment.
Measuring device: Friction measuring machine AN manufactured by Toyo Seiki Seisakusho Co., Ltd.
Measurement condition:
Specimen size: 200 mm (longitudinal direction) x 100 mm (width direction)
Load weight size: 100 mm (longitudinal direction) x 60 mm (width direction)
Weight of load weight: 1.0 kg
Tilt speed: 1.5 ° / sec
Measurement method: When one test piece is fixed to the inclined plate, the load weight with the other test piece is gently placed, then the inclined plate is inclined at a constant speed, and the test piece with the weight starts to slide. The tangent (tan θ) of the angle of was calculated and used as the coefficient of static friction. The test was performed three times, and the average value was calculated.

(Blocking value)
The blocking value was measured according to ASTM D1893-67, except that the surfaces of the sealant layers of the sealant film were placed on each other under the following conditions.
A sample (10 cm in the width direction, 15 cm in the longitudinal direction) in which the measurement surfaces are overlapped is placed in a heat press (manufactured by Tester Sangyo Co., Ltd., model: SA-303) in the length direction (15 cm) at the center of the sample width (10 cm). An aluminum plate (thickness 2 mm) having a size of 7 cm × 7 cm was placed at a position 1 cm inside so as to align with each other, and pressure treatment was performed at a temperature of 50 ° C., a pressure of 440 kgf / cm ² , and 15 minutes.
When the sample and bar (diameter 6 mm, material: aluminum) blocked by this pressure treatment are attached to the autograph (Shimadzu model: UA-3122) and the bar peels off the blocking part at a speed (100 m / min). The force was measured.
In this case, it is assumed that the bar and the peeling surface are horizontal. The same sample was measured 4 times and displayed as an average value.

(Easy peeling)
The easy peel strength was defined as the easy peel strength sealed at 190 ° C., the strength of which was 20 mN / 15 mm or less was excellent, 30 mN / 15 mm or less was good, and the strength of more than 30 mN / 15 mm was inferior ×.

(Easy peel strength: mN / 15mm)
A dry laminating adhesive (TM569, CAT-10L) manufactured by Toyobo Co., Ltd. was applied to the corona surface of a nylon film (biaxially stretched nylon film manufactured by Toyobo Co., Ltd .: N1100, 15 μm) so that the solid content was 3 g / m ² . After volatilizing and removing the solvent in an oven at 80 ° C., the corona surface of the sealant film and the adhesive coated surface of the nylon film were niped and laminated on a temperature control roll at 60 ° C. The laminated laminated film was aged at 40 ° C. for 2 days, and the laminated film was collected.
The sealant surface of the collected laminated film and an unstretched CPP sheet (WF577PG × 100%) 300 μm are overlapped with each other, and the seal width is 15 mm, the seal pressure is 0.2 MPa, the seal time is 1.0 second, and the seal temperatures are 150, 190 ° C, and 200 ° C. So, I did a heat seal.
A test piece was obtained by heat-sealing the laminate so that the width was 15 mm in parallel with the longitudinal direction.
These test pieces were set on an autograph (manufactured by Shimadzu Corporation, model: UA-3122), the sealed surface was peeled off at a speed of 200 mm / min, and the maximum value was measured. Three test pieces were measured at each seal temperature, and the average value was taken as the easy peel strength at each seal temperature.

(Peeling strength: mN / 15mm)
A dry laminating adhesive (TM569, CAT-10L) manufactured by Toyobo Co., Ltd. was applied to the corona surface of a nylon film (biaxially stretched nylon film manufactured by Toyobo Co., Ltd .: N1100, 15 μm) so that the solid content was 3 g / m ² . After volatilizing and removing the solvent in an oven at 80 ° C., the corona surface of the sealant film and the adhesive coated surface of the nylon film were niped and laminated on a temperature control roll at 60 ° C. The laminated laminated film was aged at 40 ° C. for 2 days, and the laminated film was collected.
Seal width 15 mm, seal pressure 0.2, 0.4, 0.6 MPa, seal time 1.0 second, seal temperature so that the sampled laminated films are aligned in the longitudinal direction and the sealant films face each other. Heat-sealed at 150, 190 ° C, and 200 ° C.
A test piece was obtained by heat-sealing the laminate so that the width was 15 mm in parallel with the longitudinal direction.
These test pieces were set on an autograph (manufactured by Shimadzu Corporation, model: UA-3122), the sealed surface was peeled off at a speed of 200 mm / min, and the maximum value was measured. Three test pieces were measured at each seal temperature, and the average value was taken as the peel strength at each seal temperature.

The following raw materials were used in Examples and Comparative Examples.
(Polypropylene resin)
(1) WF577PG (ethylene copolymer polypropylene, manufactured by Sumitomo Chemical Co., Ltd., MFR 3.2 g / 10 min, melting point 142 ° C.)
(2) EP3721 (propylene-ethylene block copolymer, manufactured by Sumitomo Chemical Co., Ltd., MFR 2.5 g / 10 min, melting point 143 ° C.)
(Polyethylene resin)
(1) F222 (low density polyethylene, manufactured by Ube Maruzen Polyethylene Co., Ltd., density 922 kg / m ³ , MFR 2.0 g / 10 min, melting point 110 ° C)
(2) FV407 (metallocene-based linear low-density polyethylene, manufactured by Sumitomo Chemical Co., Ltd., density 930 kg / m ³ , MFR 3.2 g / 10 min, melting point 124 ° C.)
(3) A-4070S (ethylene / α-olefin copolymer, manufactured by Mitsui Chemicals, Inc., density 870 kg / m ³ , MFR 3.6 g / 10 min, melting point 55 ° C.)
(4) A-1085S (ethylene / α-olefin copolymer, manufactured by Mitsui Chemicals, Inc., density 885 kg / m ³ , MFR 1.2 g / 10 min, melting point 66 ° C.)
(5) RS1405 (Mixture of ethylene / α-olefin copolymer, manufactured by Mitsui Chemicals, Inc.)
(6) P0480 (ethylene / α-olefin copolymer, manufactured by Mitsui Chemicals, Inc., MFR 1.8 g / 10 min)

(Cyrilized polyolefin resin)
(1) Exfora PP2000 (manufactured by Mitsui Kagaku Fine Co., Ltd., containing 30% by weight of silylated polyprefin (olefin / silicone copolymer), 70% by weight of polypropylene, density 917 kg / m ³ , MFR 20 g / 10 min, Melting points 125 ° C and 160 ° C)
(2) Exfora PE3027 (manufactured by Mitsui Kagaku Fine Co., Ltd., containing 30% by weight of silylated polyprefin (olefin / silicone copolymer), 70% by weight of low density polyethylene, density 932 kg / m ³ , MFR 30 g / 10 min, melting points 114 ° C and 122 ° C)
(3) Exfora LL1513 (manufactured by Mitsui Kagaku Fine Co., Ltd., containing 30% by weight of silylated polyprefin (olefin / silicone copolymer), 70% by weight of metallocene-based linear low-density polyethylene, density 921 kg / m ³ , MFR 15 g / 10 min, melting points 102 ° C and 121 ° C)

(Particles made of inorganic oxides)
(1) / (2) / (3) = 90/6/4 (% by weight) mixed pellet (MB)
(1) WF577PG (ethylene copolymerized polypropylene)
(2) KMP-130-10 (spherical silica particles, manufactured by Shinetsu Silicone Co., Ltd., weight average particle size 10 μm)
(3) KMP-130-4 (spherical silica particles, manufactured by Shinetsu Silicone Co., Ltd., weight average particle size 10 μm)

(Organic lubricant)
(1) MS07 (containing 5% by weight of erucic acid amide, manufactured by Sumitomo Chemical Co., Ltd.)

(Examples 1 to 16)
Polypropylene resin, polyethylene resin, silylated polyolefin, spherical silica, ethylene bisoleic acid amide, and erucic acid amide were mixed and melted in a twin-screw extruder so as to have the content ratio (% by weight) shown in Table 1. It was used as a seal layer.

Further, polypropylene resin and erucic acid amide were mixed and melted in a twin-screw extruder so as to have the content ratio (% by weight) shown in Table 1 to form an intermediate layer.

Further, as shown in Table 1, the polypropylene resin was melted in a twin-screw extruder to form a laminated layer.

Using a multilayer film molding device, the resin composition of the molten sealant layer, the resin composition of the intermediate layer and the resin composition of the laminated layer are laminated, and a single multilayer molten sheet is co-extruded with a T-die into a cooling roll. It was grounded and cooled and solidified to obtain an unstretched sheet.
After corona discharge treatment was applied to the surface of the laminated layer of the obtained sheet, the film was wound into a roll at a speed of 20 m / min to obtain a sealant film having a thickness of 60 μm and a wet tension of 45 N / m on the surface of the laminated layer. The detailed conditions are as follows.
Sealant layer extruder diameter: 60 mm
Intermediate layer extruder diameter: 90 mm
Laminate layer extruder diameter: 45 mm
Mixing and melting temperature of raw materials for sealant layer, intermediate layer, and laminate layer: 250 ° C
T-die width: 1600 mm
Pick-up speed of multilayer molten sheet: 20 m / min
Cooling roll temperature: 40 ° C
Thickness of sealant layer in sealant film: thickness of 6 μm Thickness of intermediate layer in sealant film: 42 μm
Thickness of laminated layer in sealant film: 12 μm
The longitudinal direction means the direction in which the unstretched sheet is run, and the width direction means the direction perpendicular to it. The characteristics of the obtained film are shown in Table 2.

The sealant films obtained in Examples 1 to 16 were excellent in liquid repellency and heat sealability. In addition, the coefficient of friction and the blocking value were small, and it had very stable slipperiness and blocking resistance. In addition, the haze was small and the appearance was excellent.
Moreover, the resin composition used for the seal layer has less precipitation of the compound and is excellent in film forming processability. The reason for this is that the silylated polyolefin used for the seal layer has a dimethylsiloxane component and therefore has a small surface energy, so that it segregates on the surface of the seal layer.
FIG. 1 shows the values of the average Si concentration and the surface Si concentration of the films described in Comparative Example 2 and Examples 1 to 3, 13 and 16, but Comparative Example 2 and Examples 1 to 3, 13 and 16. The Si concentration of the film described in 1 is up to about 47 times higher than the calculated value on the surface, and it can be seen that the silylated polyolefin is segregated on the surface.

FIG. 3 shows analytical images of silicon mapping on the surface of the seal layer of Example 1 and Comparative Example 2. In Example 1, silicon (green) is present on the entire surface, but it is not seen in Comparative Example 2. Silica, which is a particle, is emphasized because it contains silicon as a main component.
FIG. 4 shows TEM observation images of the cross sections of the seal layers of Example 1 and Comparative Example 4. Since the silylated polyolefin of Example 2 is a copolymer of dimethylsiloxane and polyethylene, it is difficult to separate dimethylsiloxane from polyethylene, so that although it exhibits a microphase-separated structure, it is only finely dispersed. I understand. On the other hand, Comparative Example 4 contains a silicone resin, and its phase separation and precipitation can be considered.
FIG. 5 is a photograph of the vicinity of a die nozzle in which the seal layer raw materials of Example 1 and Comparative Example 4 are melt-kneaded by a twin-screw extruder. In Example 1, no deposition of the compound was observed, and it is considered that the silylated polyolefin in the seal layer does not precipitate on the surface thereof. On the other hand, in Comparative Example 4, precipitation of the silicone resin is observed, and there is a concern that foreign matter on the film and deterioration of the working environment may occur.

(Comparative Examples 1 to 4)
A sealant film was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used as raw materials for the resin composition of the seal layer, the laminate layer, and the intermediate layer.

The sealant film obtained in Comparative Example 1 was excellent in liquid repellency, but had a small coefficient of friction and a small blocking value, and was inferior in slipperiness and blocking resistance.

The sealant film obtained in Comparative Example 2 was inferior in liquid repellency, slipperiness and blocking resistance.

The sealant film obtained in Comparative Example 3 was inferior in liquid repellency, slipperiness and blocking resistance.

Although the sealant film obtained in Comparative Example 4 was excellent in liquid repellency, the compound was easily precipitated from the seal layer, and the sealant film was inferior.

The sealant film of the present invention provides a packaging bag that is easy to take out even if it is a sticky substance such as a paste or a viscous substance, and has good heat sealability, excellent slipperiness and blocking resistance. It is possible to provide a film for use and a laminate thereof, and the contribution to the industry is great.

Claims (6)

A film containing a seal layer composed of a resin composition containing the following (a), (b), (c), and (d), and a sealant film satisfying the following (1), (2), and (3). ..
The contents of (a) polypropylene-based resin (b) polyethylene-based resin (c) silylated polyolefin resin (d) fatty acid amide (1) (a), (b), and (c) are each relative to the entire resin composition. 30 to 90% by weight, 0 to 40% by weight, and 3 to 30% by weight.
(2) The arithmetic average roughness Ra of the surface of the seal layer is 0.03 μm or more and 0.3 μm or less.
(3) The silylated polyolefin is represented by the following formula.
CH _3- (CH ₂ ) _n-2- CH ₂ - _{Si (CH 3) 2 O- (-S i ( CH 3 ) 2} -O-) _d -S _i (CH ₃ ) ₂ -CH _2- ( CH ₂ ) _n-2- CH ₃
(In the formula, d is an integer of 1 or more.) The film for a sealant according to claim 1, wherein the resin composition contains particles made of an inorganic oxide or a synthetic resin. The sealant film according to claim 1 or 2, which satisfies the following (4) and (5).
(4) The abundance ratio (S _i / C) of the silicon atom S _i and the carbon atom C contained in the seal layer is 0.001 or more and 0.02 or less.
(5) The abundance ratio (S _i / C) of silicon atom Si and carbon atom C on the surface of the seal layer is 0.05 or more and 0.2 or less. The sealant film according to any one of claims 1 to 3, which satisfies the following (6).
(6) The abundance ratio of the silicon atom S _i and the carbon atom C on the surface of the seal layer (S _i / C) with respect to the abundance ratio (S _i / C) of the silicon atom S _i and the carbon atom C contained in the seal layer. ) Is 2 or more. The sealant film according to any one of claims 1 to 4, wherein the blocking value on the surface of the seal layer is 200 mN / 70 mm or less. A laminate comprising the sealant film and the base film according to any one of claims 1 to 5.

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