JP2021187921A - Film and multilayered film - Google Patents

Abstract

To provide a film and a multilayered film which are excellent in mechanical characteristics such as a tensile elongation at break and a tear elongation.SOLUTION: A film is provided, containing a polybutylene succinate-based resin (A) and an acrylic rubber-containing polymer (B). A multilayered film is provided, having at least one layer of the film.SELECTED DRAWING: None

Description

The present invention relates to films and multilayer films.

General-purpose plastics made from petroleum are widely used due to their excellent properties and relatively low cost. However, general-purpose plastics have low decomposability in the natural environment and generate a large amount of heat during incineration. Therefore, in recent years, the effective utilization of depleting resources has been emphasized, and the utilization of renewable resources has become an important issue. The most noticeable solution is the use of bioplastics produced from renewable resources. Bioplastics are plastics that can be decomposed by microorganisms existing in soil and water. In addition, since bioplastics are manufactured from renewable resources, they can not only save depleting resources such as petroleum at the time of manufacture and take measures against global warming, but also have excellent recyclability.

Representative examples of bioplastics include aliphatic polyester resins such as polylactic acid, polybutylene succinate, and polybutylene succinate adipate.

Among them, polybutylene succinate-based resins having an aliphatic dicanlubon acid unit and an aliphatic diol unit such as polybutylene succinate and polybutylene succinate adipate have excellent features such as high crystallization rate and good moldability. Has.

For example, Patent Document 1 proposes a biodegradable sticker film in which a biodegradable resin such as polybutylene succinate contains an acrylic polymer lubricant.

Japanese Unexamined Patent Publication No. 2006-96847

However, it cannot be said that the biodegradable sticker film described in Patent Document 1 has sufficient tensile properties such as tensile elongation at break and tear properties such as tear strength. Therefore, a film made of a polybutylene succinate resin such as polybutylene succinate or polybutylene succinate adipate cannot sufficiently satisfy both tensile properties and tearing properties, and a film having both of these properties cannot be obtained. It was desired.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a film and a multilayer film having excellent mechanical properties such as tensile elongation at break and elongation at tear.

As a result of diligent studies in view of the above circumstances, the present inventors have found that the above problems can be solved by using a film containing a polybutylene succinate-based resin and an acrylic rubber-containing polymer. The invention has been completed. That is, the gist of the present invention is as follows.

[1] A film containing a polybutylene succinate resin (A) and an acrylic rubber-containing polymer (B).
[2] The mass ratio (A) / (B) of the polybutylene succinate resin (A) to the acrylic rubber-containing polymer (B) is 25/75 to 95/5, according to [1]. Film.
[3] The acrylic rubber-containing polymer (B) has an alkyl acrylate monomer (B-1a) having an alkyl group having 1 to 8 carbon atoms and an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms. An acrylic rubber polymer (B1) whose main constituent unit is a monomer component (B-1) containing at least one of the monomers (B-1b), and an alkyl having 1 to 4 carbon atoms. The film according to [1] or [2], which comprises a polymer (B2) having a monomer component (B-2) containing an alkyl methacrylate having a group as a main constituent unit.
[4] The weight of the acrylic rubber containing the acrylic rubber-containing polymer (B): 20 to 60% by mass of the acrylic rubber polymer (B1) and 80 to 40% by mass of the polymer (B2). The film according to [3], which is a coalescence and contains 10 to 100% by mass of the monomer component (B-2) in the polymer (B2).
[5] The monomer component (B-1) is 40 to 99.9% by mass of the alkyl acrylate monomer (B-1a) and 0 to 59 of the alkyl methacrylate monomer (B-1b). 9.9% by mass, another monomer (B-) having one double bond copolymerizable with the alkyl acrylate monomer (B-1a) and the alkyl methacrylate monomer (B-1b). 1c) 0 to 30% by mass, and two or more double bonds copolymerizable with the alkyl acrylate monomer (B-1a) and the alkyl methacrylate monomer (B-1b) in one molecule. The alkyl monomer (B-1a) acrylate and the methacrylic acid in 100% by mass of the monomer component (B-1) containing 0.1 to 10% by mass of the monomer (B-1d) having. The film according to [3] or [4], wherein the total amount of the alkyl monomers (B-1b) is 50 to 99.9% by mass.
[6] The film according to any one of [1] to [5], wherein the tear elongation in the TD direction at 25 ° C. measured according to JIS K7128-3 is 25% or more.
[7] The film according to any one of [1] to [6], which has a thickness of 10 to 500 μm.
[8] The film according to any one of [1] to [7], which is an extruded product.
[9] The film according to any one of [1] to [8], wherein the total light transmittance measured according to JIS K7361-1 is 88% or more.
[10] The film according to any one of [1] to [9], wherein the tensile elongation at break in the MD direction at 25 ° C. measured according to JIS K7127 is 150% or more.
[11] A multilayer film having at least one layer of the film according to any one of [1] to [10].

According to the present invention, it is possible to provide a film and a multilayer film having excellent mechanical properties such as tensile elongation at break and elongation at tear.

Hereinafter, embodiments of the film and the multilayer film according to the present invention will be described.

[the film]
The film of the present embodiment contains a polybutylene succinate resin (A) and an acrylic rubber-containing polymer (B).

Hereinafter, various compounding materials that can be used in this embodiment will be described. However, the use of materials not described in this specification is not excluded.

<Polybutylene succinate resin (A)>
The polybutylene succinate-based resin as the component A is a resin having at least a constituent unit derived from succinic acid and a constituent unit derived from 1,4-butanediol as main constituent units. The polybutylene succinate-based resin may contain other structural units other than these structural units. Specific examples of the polybutylene succinate-based resin include polybutylene succinate and polybutylene succinate adipate. Of these, polybutylene succinate is preferably used. Further, the polybutylene succinate-based resin is preferably biodegradable, and more preferably partially or wholly produced using a raw material obtained from a biomass resource.

The raw material of succinic acid may be petroleum-derived or plant-derived. Since _{it can contribute to the reduction of CO 2} emissions, it is particularly preferable that it is derived from a plant. For example, succinic acid or an acid anhydride thereof converted from a plant material, and an ester with a lower alcohol are preferable.

In the present embodiment, the polybutylene succinate-based resin suitable as a biodegradable resin may contain a structural unit other than the above as long as the effect of the present invention is not significantly impaired. Examples of other constituent units include a diol component (a constituent unit formed from a diol or a derivative thereof), a dicarboxylic acid component (a constituent unit formed from a dicarboxylic acid or a derivative thereof), an aliphatic oxycarboxylic acid component, and the like. Can be mentioned.

Specific examples of the diol component include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, and 1,4-. Cyclohexanedimethanol and the like can be mentioned.

Specific examples of the dicarboxylic acid component include adipic acid, oxalic acid, malonic acid, glutaric acid, azelaic acid, sevasic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, undecanedioic acid, and dodecanedi. Usually, the number of carbon atoms is 2 such as acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eikosandioic acid, maleic acid, fumaric acid, 1,6-cyclohexanedicarboxylic acid, dimer acid and the like. Examples thereof include chain-like or alicyclic dicarboxylic acids of 48 or less. Further, esters of these dicarboxylic acids with lower alcohols such as dimethyl ester and diethyl ester, and acid anhydrides can also be mentioned.

The aliphatic oxycarboxylic acid component is not particularly limited as long as it is a structural unit formed by an aliphatic oxycarboxylic acid having one hydroxyl group and a carboxylic acid group in the molecule and a derivative thereof, and a cyclic one is also a chain. You can also use the shape.

Examples of the aliphatic oxycarboxylic acid component include α, ω-hydroxycarboxylic acid, α-hydroxycarboxylic acid and the like. Further, it may be a derivative such as an ester or lactone of these aliphatic oxycarboxylic acids, lactide, or an oxycarboxylic acid polymer.
Specific examples of lactones include lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and enant lactone; 4-methylcaprolactone, 2,2,4-trimethylcaprolactone, 3,3. , 5-Methyled lactones such as trimethylcaprolactone and the like.

Specific examples of the aliphatic oxycarboxylic acid include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 2-hydroxy 3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2 -Hydroxyisocaproic acid, 4-hydroxycyclohexanecarboxylic acid, 4-hydroxymethylcyclohexanecarboxylic acid and the like can be mentioned. Further, derivatives such as these lower alkyl esters and intramolecular esters can also be mentioned. These aliphatic oxycarboxylic acid components may be used alone or in combination of two or more.

The amount of the aliphatic oxycarboxylic acid component used in the polybutylene succinate resin is arbitrary as long as the effect of the present invention is not significantly impaired. The amount of the aliphatic oxycarboxylic acid component used in the polybutylene succinate resin is preferably 0 parts by mass or more, more preferably 1.0 part by mass or more, based on 100 parts by mass of the polybutylene succinate resin. More than 0 parts by mass is more preferable. The amount of the aliphatic oxycarboxylic acid component used in the polybutylene succinate resin is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and 20 parts by mass with respect to 100 parts by mass of the polybutylene succinate resin. Less than a portion is more preferable.

The polybutylene succinate resin is selected from the group consisting of trifunctional or higher aliphatic polyhydric alcohols, aliphatic polyvalent carboxylic acids and aliphatic polyvalent oxycarboxylic acids as polyfunctional components having trifunctionality or higher. It is also preferred to have at least one unit. As a result, the melt tension of the polybutylene succinate-based resin is improved, and the processability into a laminated body can be improved. The polyfunctional component may be used alone or in combination of two or more.

The trifunctional aliphatic oxycarboxylic acid units forming the polyfunctional component unit are (i) a type having two carboxyl groups and one hydroxyl group in the same molecule, and (ii) one carboxyl group and a hydroxyl group. It is divided into a type having two in the same molecule, but any type can be used. Specific examples of the type (i) include structural units formed from malic acid and the like. Specific examples of the type (ii) include a structural unit formed of glyceric acid or the like.

Similarly, the tetrafunctional aliphatic oxycarboxylic acid unit forming the polyfunctional component unit includes (i) a type in which 3 carboxyl groups and 1 hydroxyl group are shared in the same molecule, and (ii) a carboxyl group 2. It is divided into a type that shares two hydroxyl groups and two hydroxyl groups in the same molecule, and a type that shares three (iii) hydroxyl groups and one carboxyl group in the same molecule, but either type can be used. be. Specific examples of the tetrafunctional aliphatic oxycarboxylic acid unit include units formed from citric acid and tartaric acid.

In the present embodiment, as a method for producing a polybutylene succinate-based resin, a known method for producing polyester can be adopted. Further, the polycondensation reaction at this time can be set to appropriate conditions that have been conventionally adopted, and is not particularly limited.
When producing the polybutylene succinate-based resin, the amount of each component used is set so that the polybutylene succinate-based resin having the desired composition can be obtained. Usually, it is a substantially equimolar quantity. However, at this time, the amount of succinic acid used is preferably 1 to 20 mol% in excess of 1,4-butanediol because there is distillation during the esterification reaction.

In the present embodiment, the melting point of the polybutylene succinate resin is not particularly limited, but is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher from the viewpoint of heat resistance. The melting point of the polybutylene succinate resin is preferably 180 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 140 ° C. or lower, from the viewpoint of moldability.

In the present embodiment, the crystallization temperature of the polybutylene succinate resin is not particularly limited, but the lower limit is preferably 70 ° C. or higher from the viewpoint of heat resistance. The upper limit of the crystallization temperature of the polybutylene succinate resin is preferably 100 ° C. or lower from the viewpoint of moldability.

In the present embodiment, the number average molecular weight (Mn) of the polybutylene succinate-based resin is arbitrary as long as the effect of the present invention is not significantly impaired, but is preferably 10,000 or more, and more preferably 30,000 or more. The number average molecular weight (Mn) of the polybutylene succinate resin is preferably 300,000 or less, more preferably 200,000 or less. When the number average molecular weight (Mn) is 100,000 or more, the strength and elongation of the film are improved. On the other hand, when the number average molecular weight (Mn) is 300,000 or less, the melt viscosity can be lowered, which is preferable from the viewpoint of moldability. The number average molecular weight (Mn) can generally be measured by GPC (gel permeation chromatography) or a viscosity method.

In the present embodiment, the melt flow rate (MFR; JIS K7210, 190 ° C., 2.16 kg load) of the polybutylene succinate resin is not particularly limited, but is 0.1 g / 10 minutes from the viewpoint of flexibility. The above is preferable, 1 g / 10 minutes or more is more preferable, 3 g / 10 minutes or more is further preferable, and 4 g / 10 minutes or more is particularly preferable. From the viewpoint of moldability, the melt flow rate (MFR; MFR; JIS K7210, 190 ° C., 2.16 kg load) of the polybutylene succinate resin is preferably 35 g / 10 minutes or less, and 30 g / 10 minutes or less. More preferred.

As the polybutylene succinate resin, a commercially available product may be used. Typical examples include "BioPBS (registered trademark) FZ91 [PB / PB]" and "BioPBS (registered trademark) FZ71 [PM / PB]" manufactured by PTTMCC Biochem.

<Polymer containing acrylic rubber (B)>
The acrylic rubber-containing polymer which is the B component will be described.
The acrylic rubber-containing polymer is a polymer composed of a core layer and at least one or more shell layers covering the core layer. The number of layers of the shell is not particularly limited, and may be a single layer or two or more layers. In addition, in this specification, "(meth) acrylic" means "acrylic or methacryl". Further, the acrylic monomer component constituting the acrylic rubber-containing polymer (B) may be derived from a fossil resource or a biomass resource, and can be appropriately selected.

In the present embodiment, the acrylic rubber-containing polymer (B) is an alkyl acrylate monomer (B-1a) having an alkyl group having 1 to 8 carbon atoms and a methacrylic acid having an alkyl group having 1 to 4 carbon atoms. An acrylic rubber polymer (B1) containing a monomer component (B-1) containing at least one selected from an alkyl monomer (B-1b) as a main constituent unit, and an acrylic rubber polymer (B1) having 1 to 4 carbon atoms. It is a rubber-containing polymer containing a polymer (B2) having a monomer component (B-2) containing an alkyl methacrylate having an alkyl group as a main constituent unit. The acrylic rubber-containing polymer (B) is a polymer (B2) containing 20 to 60% by mass of the acrylic rubber polymer (B1) and 10 to 100% by mass of the monomer component (B-2). : Contains 80-40% by mass.
Before polymerizing the monomer component (B-2), the monomer component (B-3) described later is polymerized in the presence of the acrylic rubber polymer (B1) in advance, and then simply. The acrylic rubber-containing polymer (B) may be produced by polymerizing the weight component (B-2).

≪Acrylic rubber polymer (B1) ≫
The monomer component (B-1) constituting the acrylic rubber polymer (B1) includes the following monomers (B-1a), monomer (B-1b), and monomer (B-1c). And contains a monomer (B-1d).
(B-1a) Alkyl acrylate monomer having an alkyl group having 1 to 8 carbon atoms (B-1b) Alkyl methacrylate monomer having an alkyl group having 1 to 4 carbon atoms (B-1c) Alkyl acrylate Another monomer (B-1d) alkyl acrylate monomer (B) having one copolymerizable double bond with the monomer (B-1a) and the alkyl methacrylate monomer (B-1b) A monomer having two or more double bonds copolymerizable with -1a) and an alkyl methacrylate monomer (B-1b) in one molecule.

The alkyl acrylate monomer (B-1a) having an alkyl group having 1 to 8 carbon atoms may have a linear alkyl group or a branched chain. Specific examples of the alkyl acrylate monomer (B-1a) include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate and the like. .. These may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, those having a low glass transition temperature (hereinafter referred to as "Tg") are preferable, and n-butyl acrylate is preferable. If the Tg is low, the resulting film will have favorable mechanical properties and can be easily molded.

The alkyl methacrylate monomer (B-1b) having an alkyl group having 1 to 4 carbon atoms may have a linear alkyl group or a branched chain. Specific examples of the alkyl methacrylate monomer (B-1b) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type.

The monomer (B-1c) is another monomer having one double bond copolymerizable with the alkyl acrylate monomer (B-1a) and the alkyl methacrylate monomer (B-1b). Is. Specific examples of the monomer (B-1c) include (meth) acrylic monomers such as lower alkoxyacrylic acid, cyanoethyl acrylate, acrylamide, and (meth) acrylic acid; aromatics such as styrene and alkyl-substituted styrene. Vinyl monomer; Examples thereof include vinyl cyanide monomer such as acrylonitrile and methacrylonitrile. These may be used individually by 1 type, or may be used in combination of 2 or more type.

The monomer (B-1d) has two or more double bonds copolymerizable with the alkyl acrylate monomer (B-1a) and the alkyl methacrylate monomer (B-1b) in one molecule. It is a monomer. Specific examples of the monomer (B-1d) include ethylene glycol di (meth) acrylic acid, 1,3-butylene glycol di (meth) acrylic acid, 1,4-butylene glycol di (meth) acrylic acid, and di (meth) acrylic acid. Di (meth) alkylene glycol acrylate such as propylene glycol (meth) acrylate; polyvinylbenzene such as divinylbenzene and trivinylbenzene; and cyanurate monomers such as triallyl cyanurate and triallyl isocyanurate, allyl methacrylate. Such as α, β-unsaturated carboxylic acid or allyl, methallyl or crotyl ester of dicarboxylic acid can be mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more type.

The monomer component (B-1) is 40 to 99.9% by mass of the alkyl acrylate monomer (B-1a), 0 to 59.9% by mass of the alkyl methacrylate monomer (B-1b), and simply. It contains 0 to 30% by mass of a weight (B-1c) and 0.1 to 10% by mass of a monomer (B-1d). Further, the total of the alkyl acrylate monomer (B-1a) and the alkyl methacrylate monomer (B-1b) in 100% by mass of the monomer component (B-1) is 50 to 99.9% by mass. Is preferable, and 60 to 99.9% by mass is more preferable.

The Tg of the acrylic rubber polymer (B1) is preferably less than 25 ° C., more preferably 10 ° C. or lower, still more preferably 0 ° C. or lower, from the viewpoint of the flexibility of the acrylic rubber-containing polymer (B). The Tg of the acrylic rubber polymer (B1) is preferably −100 ° C. or higher, more preferably −80 ° C. or higher. In this embodiment, Tg refers to a value calculated from the FOX formula using the values described in the Polymer Handbook [Polymer HandBook (J. Brandrup, Interscience, 1989)].

Monomer component (B-1) + Monomer component (B-2) + Monomer component (B-3) (Monomer component (B-1) + Monomer component (B-2) + The content of the monomer component (B-1) in the monomer component (B-3) = 100% by mass) is preferably 5 to 80% by mass from the viewpoint of flexibility, transparency and processability. 20-70% by mass is more preferable.

When polymerizing the acrylic rubber polymer (B1), the monomer component (B-1) may be collectively put into the polymerization container and polymerized, or it may be added in two or more stages and polymerized. Is also good. From the viewpoint of the mechanical properties of the film, it is preferable to carry out the polymerization in two or more stages. When the polymerization is divided into two or more stages, the composition ratio of each monomer in the monomer component (B-1) at each polymerization stage may be the same or different. By polymerizing in two or more stages, it becomes easy to control the particle size of the finally obtained acrylic rubber polymer (B1).

≪Polymer (B2) ≫
As described above, the acrylic rubber-containing polymer (B) is a polymer (B2) obtained by polymerizing the following monomer component (B-2) in the presence of the acrylic rubber polymer (B1). ) Is contained.

The monomer component (B-2) constituting the polymer (B2) includes the following monomers (B-2a), monomer (B-2b) and monomer (B-2c).
(B-2a) Alkyl acrylate monomer having an alkyl group having 1 to 8 carbon atoms (B-2b) Alkyl methacrylate monomer having an alkyl group having 1 to 4 carbon atoms (B-2c) Alkyl acrylate having an alkyl group having 1 to 4 carbon atoms Another monomer having one double bond copolymerizable with the monomer (B-2a) and the alkyl methacrylate monomer (B-2b)

The monomer (B-2a), the monomer (B-2b) and the monomer (B-2c) are the monomer (B-1a), the monomer (B-1b) and the simpler, respectively. The same monomer as the metric (B-1c) can be used.
The monomer used as the monomer (B-2a) and the monomer used as the monomer (B-1a) may be the same compound or different compounds. May be good. Such a relationship is used as a compound used as a monomer (B-2b) and a monomer (B-1b), and as a monomer (B-2c) and a monomer (B-1c). The same applies to the compounds to be used.

The monomer component (B-2) can include a chain transfer agent. The amount of the chain transfer agent used is not particularly limited, but is preferably 0 to 5 parts by mass with respect to 100 parts by mass of the monomer component (B-2).
The chain transfer agent can be appropriately selected from those used for ordinary radical polymerization. Specific examples of the chain transfer agent include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenols, carbon tetrachloride and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type.

The content of the monomer (B-2a) in the monomer component (B-2) is preferably 0 to 20% by mass.
The content of the monomer (B-2b) in the monomer component (B-2) is preferably 51 to 100% by mass.
The content of the monomer (B-2c) in the monomer component (B-2) is preferably 0 to 49% by mass.

The Tg of the polymer (B2) is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of the flexibility of the acrylic rubber-containing polymer (B). The Tg of the polymer (B2) is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, from the viewpoint of moldability of the acrylic rubber-containing polymer (B).

Monomer component (B-1) + Monomer component (B-2) + Monomer component (B-3) (Monomer component (B-1) + Monomer component (B-2) + The content of the monomer component (B-2) in the monomer component (B-3) = 100% by mass) is preferably 20 to 95% by mass from the viewpoint of flexibility, transparency and processability. More preferably, it is 30 to 80% by mass.

When the polymer (B2) is polymerized, the monomer component (B-2) can be added all at once into the polymerization vessel for polymerization, or it can be added in two or more stages and polymerized. When the polymerization is divided into two or more stages, the composition ratio of each monomer in the monomer component (B-2) at each polymerization stage may be the same or different. By polymerizing in two or more stages, it becomes easy to control the particle size of the finally obtained polymer (B2).

≪Polymer (B3) ≫
The acrylic rubber-containing polymer (B) is obtained by polymerizing the following monomer component (B-3) in the presence of the acrylic rubber polymer (B1) before polymerizing the polymer (B2). It is preferable to contain the obtained polymer (B3).

The monomer component (B-3) constituting the polymer (B3) is the following monomer (B-3a), monomer (B-3b), monomer (B-3c) and a single amount. Includes body (B-3d).
(B-3a) Alkyl acrylate monomer having an alkyl group having 1 to 8 carbon atoms (B-3b) Alkyl methacrylate monomer having an alkyl group having 1 to 4 carbon atoms (B-3c) Alkyl acrylate Another monomer (B-3d) alkyl acrylate monomer (B) having one copolymerizable double bond with the monomer (B-3a) and the alkyl methacrylate monomer (B-3b) A monomer having two or more double bonds copolymerizable with -3a) and an alkyl methacrylate monomer (B-3b) in one molecule.

The monomer (B-3a), the monomer (B-3b), the monomer (B-3c) and the monomer (B-3d) are the monomer (B-1a) and the simpler, respectively. Monomers similar to the mer (B-1b), monomer (B-1c) and monomer (B-1d) can be used.
The monomer used as the monomer (B-3a) and the monomer used as the monomer (B-1a) may be the same compound or different compounds. May be good. Such a relationship is used as a compound used as a monomer (B-3b) and a monomer (B-1b), as a monomer (B-3c) and a monomer (B-1c). The same applies to the compound and the compound used as the monomer (B-3d) and the monomer (B-1d).

The content of the monomer (B-3a) in the monomer component (B-3) is preferably 9.9 to 90% by mass.
The content of the monomer (B-3b) in the monomer component (B-3) is preferably 9.9 to 90% by mass.
The content of the monomer (B-3c) in the monomer component (B-3) is preferably 0 to 20% by mass.
The content of the monomer (B-3d) in the monomer component (B-3) is preferably 0.01 to 10% by mass.

The Tg of the polymer (B3) obtained by polymerizing the monomer component (B-3) is preferably higher than the Tg of the acrylic rubber polymer (B1) from the viewpoint of film flexibility.
The type or ratio of the monomer in the monomer component (B-3) is preferably different from the type or ratio of the monomer in the monomer component (B-1). The flexibility of the film is improved by the difference between the type or ratio of the monomer in the monomer component (B-1) and the type or ratio of the monomer in the monomer component (B-3). Is easy.

The Tg of the polymer (B3) is preferably 0 to 100 ° C. From the viewpoint of the flexibility of the acrylic rubber-containing polymer (B), the Tg of the polymer (B3) is preferably 0 ° C. or higher. The Tg of the polymer (B3) is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 70 ° C. or lower, from the viewpoint of moldability of the acrylic rubber-containing polymer (B).

Monomer component (B-1) + Monomer component (B-2) + Monomer component (B-3) (Monomer component (B-1) + Monomer component (B-2) + The content of the monomer component (B-3) in the monomer component (B-3) = 100% by mass) is preferably 5 to 35% by mass from the viewpoint of flexibility, transparency and processability. 7 to 20% by mass is more preferable.

When the polymer (B3) is polymerized, the monomer component (B-3) can be added all at once into the polymerization vessel to polymerize, or it can be added in two or more stages and polymerized. When the polymerization is divided into two or more stages, the composition ratio of each monomer in the monomer component (B-3) at each polymerization stage may be the same or different. By polymerizing in two or more stages, it becomes easy to control the particle size of the finally obtained acrylic rubber-containing polymer (B).

The Tg of the acrylic rubber-containing polymer (B) obtained by polymerizing each of the above-mentioned monomer components is preferably 60 ° C. or higher from the viewpoint of the mechanical properties of the film. The Tg of the acrylic rubber-containing polymer (B) is more preferably 70 ° C. or higher, further preferably 80 ° C. or higher. The Tg of the acrylic rubber-containing polymer (B) is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, from the viewpoint of film moldability.

The gel content of the acrylic rubber-containing polymer (B) is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of the mechanical properties of the film. Further, the gel content of the acrylic rubber-containing polymer (B) is more advantageous as the gel content is larger from the viewpoint of the mechanical properties of the film, but the presence of a certain amount or more of the free polymer is desired. , 80% by mass or less is preferable.

The mass average molecular weight of the acrylic rubber-containing polymer (B) is preferably 20,000 or more, more preferably 30,000 or more, from the viewpoint of the mechanical properties of the film. The mass average molecular weight of the acrylic rubber-containing polymer (B) is preferably 200,000 or less, more preferably 70,000 or less, from the viewpoint of film moldability.

The mass average particle size of the acrylic rubber-containing polymer (B) is preferably 0.03 μm or more from the viewpoint of the mechanical properties of the film. The mass average particle size is preferably 0.3 μm or less, more preferably 0.15 μm or less, still more preferably 0.13 μm or less, from the viewpoint of film transparency. Further, the mass average particle size is more preferably 0.07 μm or more, further preferably 0.09 μm or more, from the viewpoint of the mechanical properties of the film.

The film of the present embodiment preferably has a mass ratio (A) / (B) of 25/75 to 95/5 of the polybutylene succinate resin (A) and the acrylic rubber-containing polymer (B). The mass ratio (A) / (B) is more preferably 60/40 or more, and further preferably 65/35 or more. The mass ratio (A) / (B) is more preferably 90/10 or less, and even more preferably 85/15. When the mass ratio (A) / (B) is 25/75 to 95/5, the flexibility of the film is excellent, so that the occurrence of breakage and cracking is suppressed during laminating on various resin molded bodies having a three-dimensional shape. can do.

<Manufacturing method of acrylic rubber-containing polymer (B)>
Examples of the method for producing the acrylic rubber-containing polymer (B) include a sequential multi-stage emulsion polymerization method and a monomer component (B-3), if necessary, in the presence of the acrylic rubber polymer (B1). There is an emulsified suspension polymerization method in which the monomers are sequentially subjected to multi-stage emulsion polymerization and then converted into a suspension polymerization system at the time of polymerization of the monomer component (B-2).
As a method for producing the acrylic rubber-containing polymer (B) by the sequential multi-stage emulsification polymerization method, for example, a monomer component (B-1) for obtaining the acrylic rubber polymer (B1), water and surface activity. The emulsion prepared by mixing the agents is supplied to the reactor for polymerization, and then the monomer component (B-3) and the monomer component (B-2) are sequentially supplied to the reactor for polymerization. The method can be mentioned.
The film obtained by using the acrylic rubber-containing polymer (B) obtained by the above method is preferable in that the number of fish eyes in the film is small.
Examples of the surfactant used for producing the acrylic rubber-containing polymer (B) by the sequential multi-stage emulsification polymerization method include anionic, cationic and nonionic surfactants. These may be used individually by 1 type, or may be used in combination of 2 or more type.

Examples of the anionic surfactant include rosin soap; potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate and other carboxylates; sodium lauryl sulfate and the like. Sulfate ester salt; Sulfate such as sodium dioctyl sulfosuccinate, sodium dodecylbenzene sulfonate, sodium alkyldiphenyl ether disulfonic acid; phosphoric acid such as polyoxyethylene alkylphenyl ether sodium phosphate, polyoxyethylene alkyl ether sodium phosphate, etc. Examples include ester salts.
Specific examples of commercially available anionic surfactants include Eleminor NC-718 manufactured by Sanyo Chemical Industries, Ltd., Phosphanol LS-529 manufactured by Toho Chemical Industry Co., Ltd., Phosphanol RS-610NA, and Phospha. Knoll RS-620NA, Phosphanol RS-630NA, Phosphanol RS-640NA, Phosphanol RS-650NA, Phosphanol RS-660NA, and Latemul P-0404, Latemul P-0405, manufactured by Kao Corporation. Examples thereof include Latemul P-0406 and Latemul P-0407 (both are trade names).

As a method for preparing an emulsion by mixing a monomer component (B-1), water and a surfactant, for example, after charging the monomer component (B-1) in water, a surfactant is used. Method of adding; method of adding the monomer component (B-1) after charging the surfactant in water; and adding water after charging the surfactant in the monomer component (B-1). The method can be mentioned.
As a mixing device for preparing an emulsion by mixing the monomer component (B-1) with water and a surfactant, for example, a stirrer equipped with a stirring blade; a forced emulsifying device such as a homogenizer or a homomixer; And a membrane emulsifier.

The emulsified liquid is a W / O type in which water droplets are dispersed in the oil of the monomer component (B-1), and an O / W type in which oil droplets of the monomer component (B-1) are dispersed in water. Any of the dispersions can be used.
As the polymerization method of the acrylic rubber polymer (B1), for example, a method of polymerizing the monomer component (B-1) at once and a method of polymerizing the monomer component (B-1) into two or more are divided. A method of polymerizing in multiple stages can be mentioned. For the monomer component (B-1) to be polymerized in multiple stages, the monomer component of the same component may be polymerized in multiple stages, or the monomer components having different components may be polymerized in multiple stages. good.

Initiation of polymerization used when polymerizing the monomer component (B-1), the monomer component (B-2) and the monomer component (B-3) in the acrylic rubber-containing polymer (B). As the agent, a known agent can be used. Examples of the above-mentioned polymerization initiator include peroxides, azo-based initiators, and redox-based initiators in which a peroxide or azo-based initiator is combined with an oxidizing agent / reducing agent. These may be used individually by 1 type, or may be used in combination of 2 or more type. Of these, it is preferable to use a redox-based initiator from the viewpoint of radical generation efficiency.

Specific examples of the redox-based initiator include a sulfoxylate-based initiator in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalit and hydroperoxide are combined. Specific examples of hydroperoxide include cumene hydroperoxide and t-butyl hydroperoxide.
The amount of the polymerization initiator used can be appropriately determined according to the polymerization conditions and the like. In addition, the polymerization initiator can be added to either or both of the aqueous phase and the monomeric phase.

As a method for producing the latex of the acrylic rubber-containing polymer (B), the following method is particularly preferable from the viewpoint of polymerization stability. First, ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalit and water are charged into a reactor to prepare an aqueous solution, and the aqueous solution is heated to the polymerization temperature. On the other hand, a monomer component (B-1), a polymerization initiator such as a peroxide, water and a surfactant are mixed to prepare an emulsion. Next, this emulsion is supplied into the reactor after the temperature rise to polymerize the monomer. Next, the monomer component (B-3) is supplied into the reactor together with a polymerization initiator such as a peroxide to polymerize. Next, the monomer component (B-2) is supplied into the reactor together with a polymerization initiator such as a peroxide to polymerize.

The polymerization temperature for obtaining the latex of the acrylic rubber-containing polymer (B) varies depending on the type and amount of the polymerization initiator used, but from the viewpoint of polymerization stability, it is usually preferably 40 ° C. or higher, and 60 ° C. or higher. Is more preferable. The polymerization temperature for obtaining the latex of the acrylic rubber-containing polymer (B) is preferably 120 ° C. or lower, more preferably 95 ° C. or lower.

The latex of the acrylic rubber-containing polymer (B) obtained by the above method is preferably treated using a filtration device equipped with a filter medium, if necessary. By this filtration treatment, the scale generated during the polymerization, impurities in the raw material, and impurities mixed from the outside in the process of polymerization can be removed from the latex of the acrylic rubber-containing polymer (B).

The acrylic rubber-containing polymer (B) can be obtained as a powder by recovering (solid-liquid separation and collecting) the acrylic rubber-containing polymer (B) from the latex produced by the above method. ..
As a method for recovering the acrylic rubber-containing polymer (B) as a powder from the latex of the acrylic rubber-containing polymer (B), specifically, the latex is brought into contact with an aqueous metal salt solution to solidify or salt. After analysis and solid-liquid separation, this is washed with water about 1 to 100 times by mass of the polymer, dehydrated by filtration or the like to obtain a wet powder, and the wet powder is further dried in a dryer. A method of drying with or the like can be used. In addition, the latex may be directly dried by a spray drying method. The drying temperature and drying time of the polymer can be appropriately determined depending on the type of the polymer.

Examples of the coagulant used for coagulation of the acrylic rubber-containing polymer (B) include organic salts such as sodium acetate, calcium acetate, potassium formate and calcium formate, sodium chloride, potassium chloride, calcium chloride and magnesium chloride. Examples thereof include inorganic salts such as sodium sulfate. Of these, calcium salts such as calcium acetate and calcium chloride are preferable. In particular, calcium acetate is preferable in terms of the temperature-resistant water whitening property of the powder-molded film and in terms of lowering the water content of the recovered powder. These may be used individually by 1 type, or may be used in combination of 2 or more type.
The coagulant is usually used as an aqueous solution. The concentration of the coagulant, preferably the concentration of the aqueous solution of calcium acetate, is preferably 0.1% by mass or more, more preferably 1% by mass or more, because the acrylic rubber-containing polymer (B) can be stably coagulated and recovered. .. Further, the concentration of the coagulant, preferably the aqueous solution of calcium acetate, is such that the amount of the coagulant remaining in the recovered acrylic rubber-containing polymer (B) is small, and particularly in the resin molded product having warm water whitening resistance and coloring property. 20% by mass or less is preferable, and 15% by mass or less is more preferable, because the performance is hardly deteriorated. Further, if the concentration of calcium acetate is 20% by mass or less, it is possible to prevent calcium acetate from precipitating due to saturation even at 10 ° C. or lower.

The method of bringing the latex into contact with the coagulant is, for example, a method of continuously adding the latex to the stirring of the aqueous solution of the coagulant and continuing the stirring for a certain period of time, or a method of keeping the aqueous solution of the coagulant and the latex constant. Examples thereof include a method of continuously injecting the mixture into a container equipped with a stirrer at a ratio and bringing them into contact with each other, and continuously extracting the mixture containing the solidified acrylic resin composition and water from the container. The amount of the aqueous solution of the coagulant is preferably 10 parts by mass or more, and preferably 500 parts by mass or less with respect to 100 parts by mass of the latex of the acrylic rubber-containing polymer (B). The temperature of the solidification step is preferably 30 ° C. or higher, and more preferably 100 ° C. or lower.

When the acrylic rubber-containing polymer (B) is recovered by a solidification method by a salting out treatment using a metal salt, the residual metal content in the finally obtained acrylic rubber-containing polymer (B) is 800 ppm. It is preferable that the content is as follows, and the smaller the residual metal content is, the more preferable.
When a metal salt having a strong affinity with water such as calcium, magnesium, sodium, etc., preferably a calcium salt is used as the metal salt in the salting out treatment, the residual metal in the acrylic rubber-containing polymer (B) is used. By reducing the content as much as possible, the whitening phenomenon when the film is immersed in boiling water can be easily suppressed.

<Other resins>
The film of the present embodiment may contain other resins in addition to the above-mentioned polybutylene succinate-based resin (A) and acrylic rubber-containing polymer (B).

Examples of other resins include ultra-low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, polypropylene, ethylene-propylene rubber, vinyl acetate, polybutene and the like. Can be mentioned. Further, polyamide resins such as 4-nylon, polyamino acid resins such as polyaspartic acid, polyether resins such as polyethylene glycol and polypropylene glycol, polysaccharides such as cellulose and purulan, and biodegradable resins such as polyvinyl alcohol resin can be mentioned. .. When these other resins are used, one or more kinds of resins may be used in combination in any combination. In particular, it is preferable to use a biodegradable resin in combination in that the biodegradation rate of the film of the present embodiment is increased and the degradability after decomposition is improved.

<Compounding agent>
The film of the present embodiment can contain a general compounding agent used in the field of film as long as the effect of the present invention is not significantly impaired. Examples of this compounding agent include antioxidants, stabilizers, lubricants, processing aids, matting agents, light diffusing agents, plasticizers, impact resistant agents, foaming agents, fillers, antibacterial agents, fungicides, and release agents. Examples thereof include mold agents, antistatic agents, colorants, ultraviolet absorbers, light stabilizers, flame retardants, sealants, pigments, compatibilizers and the like.

As the antioxidant, for example, a phenol-based, sulfur-based, phosphorus-based or other antioxidant can be used.
As the stabilizer, for example, a hindered phenol-based, sulfur-based, hydrazine-based or the like heat stabilizer can be used.
As the lubricant, for example, fatty acid ester-based, fatty acid-based, metal soap-based, fatty acid amide-based, higher alcohol-based, and paraffin-based lubricants can be used.
As the plasticizer, for example, phthalate ester-based, phosphoric acid ester-based, fatty acid ester-based, aliphatic dibasic acid ester-based, oxybenzoic acid ester-based, epoxy-based, polyester-based plasticizers and the like can be used.
As the filler, for example, calcium carbonate, barium sulfate, talc, pyrophyllite, kaolin and the like can be used.
As the antistatic agent, for example, a cationic, anionic, nonionic, zwitterionic or the like antistatic agent can be used.
As the ultraviolet absorber, for example, a benzotriazole-based or triazine-based ultraviolet absorber can be used.
As the light stabilizer, for example, a hindered amine-based light stabilizer can be used.
As the flame retardant, for example, a bromine-based, phosphorus-based, chlorine-based, nitrogen-based, aluminum-based, antimony-based, magnesium-based, boron-based, zirconium-based or other flame retardant can be used.
The sequestering agent is not particularly limited as long as it is a compound capable of blocking the carboxyl end group of the polymer, and is used as a sequestering agent for the carboxyl end of the polymer such as an epoxy compound, an oxazoline compound, an oxazine compound and a carbodiimide compound. Can be used.
As the compatibilizer, for example, a high molecular weight compatibilizer, a low molecular weight organic compound, an inorganic compound, an organic-inorganic composite, or the like can be used.
These combinations may be used alone or in combination of two or more.

The content of the compounding agent is 0.05 to 10 parts by mass with respect to 100 parts by mass in total of the polybutylene succinate resin (A) and the acrylic rubber-containing polymer (B) from the viewpoint of bleed-out resistance. Is preferable, and 0.1 to 5 parts by mass is more preferable.

<Film composition>
The structure of the film of the present embodiment is particularly limited as long as it has at least one layer containing the polybutylene succinate resin (A) and the acrylic rubber-containing polymer (B). is not it. For example, when the film of the present embodiment has a laminated structure of two types and three layers, the layer arranged on the front surface / the back surface is laminated with the layer (II) and the layer arranged on the central layer is laminated with the layer (I). The characteristics of the film can be adjusted by variously adjusting the material composition of the layer (I) and the layer (II). Further, when the film of the present embodiment has a laminated structure, the lamination ratio of each layer (ratio of the thickness of each layer) is not particularly limited, and the lamination of each layer is combined with the above adjustment of the material composition of each layer. By adjusting the ratio variously, the characteristics of the film and the multilayer film can be adjusted.
In particular, in the case of the above-mentioned three layers having a preferable layer structure of (II) layer / (I) layer / (II) layer, the thickness ratio thereof is in the range of 1: 2: 1: 1 to 1: 10: 1. Is preferable.

The thickness of the film of this embodiment is preferably 10 to 500 μm. The thickness of the film of the present embodiment is more preferably 20 μm or more, further preferably 30 μm or more. The thickness of the film of the present embodiment is more preferably 200 μm or less, further preferably 100 μm or less. A thin film is easy to obtain a film having high transparency, and a thick film is easy to obtain a film having high mechanical strength.
The thickness of the multilayer film having at least one layer of the film of the present embodiment can be appropriately adjusted depending on the intended use, but is preferably 10 to 500 μm. The thickness of the multilayer film of the present embodiment is more preferably 20 μm or more, further preferably 30 μm or more. The thickness of the multilayer film of the present embodiment is more preferably 200 μm or less, further preferably 100 μm or less.

<Film manufacturing method>
The film of this embodiment can be produced by extrusion molding. That is, the film of this embodiment is an extruded product. Examples of the extrusion molding include a melt extrusion method such as a melt casting method, a T-die method, and an inflation method, and a calender method, but the T-die method is preferable from the viewpoint of economy.
The film of the present embodiment can be made into a roll-shaped article by forming a film with an extruder or the like and then winding it with a tubular object such as a paper tube with a winder. In addition, if necessary, during the film forming process, uniaxial stretching (flow direction or lateral direction (direction perpendicular to the flow direction)), biaxial stretching (sequential biaxial stretching, simultaneous biaxial stretching), etc. by a known stretching method, etc. Can be provided with a stretching step.

The extrusion temperature is preferably 160 to 250 ° C, more preferably 170 to 230 ° C. Controlling the dispersion state of the material by optimizing the extrusion temperature and the state of shearing is also effective in setting various physical and mechanical properties of the film described in detail below to desired values.

Further, the film of the present embodiment has antistatic treatment, corona treatment, printing, coating, surface treatment such as vapor deposition, as well as bag making and perforation processing using various solvents and heat seals, as necessary. Can be applied.

<Film characteristics>
(1) Tensile Properties in the MD Direction The film of the present embodiment preferably has a tensile elongation at break of 150% or more in a tensile test in the MD direction. The tensile test is performed in accordance with JIS K7127 at an initial chuck distance of 100 mm, a tensile speed of 50 mm / min, and a temperature of 23 ° C. The tensile elongation at break is more preferably 200% or more, further preferably 250% or more. When the tensile elongation at break is 150% or more, it is possible to suppress the occurrence of breakage and cracking when laminating on various resin molded bodies having a three-dimensional shape. Further, from the viewpoint of the formability of the film, the tensile elongation at break is preferably 600% or less, more preferably 500% or less. Here, the "MD direction" means the extrusion direction of the film.
Further, the film of the present embodiment preferably has a tensile elastic modulus of 200 to 1500 MPa in a tensile test in the MD direction from the viewpoint of molding processability. The tensile elastic modulus is more preferably 300 MPa or more, further preferably 400 MPa or more. Further, the tensile elastic modulus is more preferably 1400 MPa or less, further preferably 1300 MPa or less.

(2) Tear characteristics in the TD direction The film of the present embodiment preferably has a tear elongation of 25% or more in the tear test in the TD direction. The tear test is performed in accordance with JIS K7128-3 (right angle tear method) at an initial chuck distance of 50 mm, a tensile speed of 200 mm / min, and a temperature of 23 ° C. The tear elongation is more preferably 30% or more, still more preferably 35% or more. When the tear elongation is 25% or more, it is possible to suppress the occurrence of breakage and cracking when laminating on various resin molded bodies having a three-dimensional shape. Further, from the viewpoint of the formability of the film, the tear elongation is preferably 150% or less, more preferably 120% or less. Here, the "TD direction" means a direction perpendicular to the extrusion direction of the film.
Further, the film of the present embodiment preferably has a tear strength of 100 N / mm or more in the tear test in the TD direction from the viewpoint of molding processability. The tear strength is more preferably 160 N / mm or more, further preferably 210 N / mm or more.

(3) Optical Properties As the light transmittance of the film of the present embodiment, for example, it is preferable that the total light transmittance of a film having a thickness of 100 μm measured in accordance with JIS K7361-1 is 88% or more. The total light transmittance is more preferably 89% or more, further preferably 90% or more. When the total light transmittance is 88% or more, the transparency of the film can be obtained.

According to the film of the present embodiment, it is possible to provide a film and a multilayer film having excellent mechanical properties such as tensile elongation at break and tensile elongation and also having excellent flexibility.

Hereinafter, the present invention will be illustrated and described with reference to examples. The following examples do not limit the content of the present invention. In addition, "part" represents "mass part". The abbreviations used in the following description are as follows.
MMA: Methyl methacrylate MA: Methyl acrylate n-BA: n-Butyl acrylate 1,3-BD: Butyl butyl methacrylate glycol AMA: Allyl methacrylate CHP: Cumene hydroperoxide t-BH: t-Butyl hydroperoxide n-OM: n-octyl mercaptan EDTA: ethylenediamine disodium tetraacetate SFS: sodium formaldehyde sulfoxylate (longalit)
RS610NA: Polyoxyethylene alkyl ether sodium phosphate (manufactured by Toho Chemical Industry Co., Ltd., trade name: Phosphanol RS610NA)

As the polybutylene succinate resin (A) used in each Example and Comparative Example, manufactured by PTTMCC Biochem, trade name: BioPBS® FZ91PB (melting point 115 ° C., MFR [190 ° C., 2.16 kg] 5 g / 10 min). )It was used.

[Preparation example]
"Manufacturing of Acrylic Rubber-Containing Polymer (B)"
After charging 8.5 parts of ion-exchanged water into a container equipped with a stirrer and a cooler, 0.3 parts of MMA, 4.5 parts of n-BA, 0.2 parts of 1,3-BD, 0.05 parts of AMA, 0.025 parts of CHP. The monomer component (B-1-1) consisting of parts was added, and the mixture was stirred and mixed.
Next, 1.3 parts of RS610NA as an emulsifier was put into the above container while stirring, and stirring was continued for 20 minutes again to prepare an emulsion containing the monomer component (B-1-2).

Next, 186.5 parts of ion-exchanged water was put into a reaction vessel with a cooler, the temperature was raised to 70 ° C., and further, 0.20 parts of SFS and 0.0001 parts of ferrous sulfate were added to 5 parts of ion-exchanged water. The mixture prepared by adding 0.0003 parts of EDTA was added all at once.
Next, the emulsion containing the monomer component (B-1-1) was added dropwise to the reaction vessel over 8 minutes while stirring under nitrogen, and then the reaction was continued for 15 minutes to continue the monomer component (B). A polymer consisting of 1-1) was obtained.

Subsequently, in the container, a monomer component (B-1-2) consisting of 1.5 parts of MMA, 22.5 parts of n-BA, 1.0 part of 1,3-BD, 0.25 parts of AMA, and 0.016 parts of CHP. Was added over 90 minutes, and then the reaction was continued for 60 minutes to obtain an acrylic rubber polymer (B1). Here, the Tg of the acrylic rubber polymer (B1) was −47 ° C.

Subsequently, the monomer component (B-3) consisting of 6.0 parts of MMA, 4.0 parts of n-BA, 0.075 parts of AMA, and 0.013 part of CHP was added dropwise to the reaction vessel over 45 minutes, and then for 60 minutes. The reaction was continued to form an intermediate polymer. Here, the Tg of the polymer (B3) composed of the monomer component (B-3) was 20 ° C.

Next, the monomer component (B-2) consisting of 55.2 parts of MMA, 4.8 parts of n-BA, 0.22 parts of n-OM, and 0.075 parts of t-BH was added dropwise to the reaction vessel over 140 minutes. , The reaction was continued for 60 minutes to obtain a latex of the acrylic rubber-containing polymer (B). Here, the Tg of the polymer (B2) composed of the monomer component (B-2) was 84 ° C.

The latex of the obtained acrylic rubber-containing polymer (B) was filtered using a vibration type filtration device equipped with a SUS mesh (average opening 62 μm) as a filter medium. Then, it was salted out in an aqueous solution containing 3 parts of calcium acetate, washed with water and recovered, and then dried to obtain a powdery acrylic rubber-containing polymer (B).

Evaluation of various characteristics of the film in each Example and Comparative Example was carried out by the following method.

(1) Tension characteristics in the MD direction The tensile elongation at break and the tensile elastic modulus of the film were measured according to JIS K7127. A film having a thickness of 100 μm was cut into a size of 150 mm in the MD direction and 15 mm in the TD direction to obtain a test piece. Using a precision universal testing machine (autograph, model: AGS-X) manufactured by Shimadzu Corporation, the initial chuck distance is 100 mm, the tensile speed is 50 mm / min, and the tensile elongation at break in the MD direction of the film at an atmospheric temperature of 23 ° C. And the tensile modulus was measured, and the average value of the measured values of 5 times was recorded.

(2) Tear characteristics in the TD direction The tear elongation and tear strength of the film were measured according to JIS K7128-3 (right angle tear method). A 100 μm thick film is cut into an angle shape, and using a precision universal testing machine (autograph, model: AGS-X) manufactured by Shimadzu Corporation, the initial chuck distance is 50 mm, the tensile speed is 200 mm / min, and the ambient temperature. The tear elongation and tear strength of the film in the TD direction at 23 ° C. were measured, and the average value of the five measurements was recorded.

(3) Transparency The total light transmittance of the film was measured according to JIS K7361-1. Using a haze meter (model: NDH4000) manufactured by Nippon Denshoku Industries Co., Ltd. and a D65 light source, the total light transmittance of the film at an atmospheric temperature of 23 ° C. was measured.

[Example 1]
75.0 parts of polybutylene succinate resin (A), 25.0 parts of the acrylic rubber-containing polymer (B) obtained in Preparation Example 1, and 0.1 part of Irganox 1076 (trade name, manufactured by BASF). , Hindered phenolic antioxidant) was mixed to prepare a resin mixture.

This resin mixture was supplied to a degassing twin-screw kneading extruder (manufactured by Toshiba Machine Co., Ltd., trade name: TEM-35B) heated to 220 ° C. and kneaded to obtain pellets of the resin mixture. Further, the pellets were dried at 80 ° C. in a dehumidifying dryer for 24 hours a day.
The pellets of the resin mixture obtained by drying are subjected to a cylinder temperature of 200 to 220 ° C. and a T die using a 30 mmφ (diameter) non-vent screw type extruder (L / D = 25) equipped with a 200 mm wide T die. A film was formed under the conditions of a temperature of 250 ° C. and a cooling roll temperature of 40 ° C. to obtain a film having a thickness of 100 μm. Table 1 shows the composition of the materials of the obtained film. Table 2 shows the evaluation results of various characteristics of the obtained film.

[Example 2]
The film of Example 2 was obtained in the same manner as in Example 1 except that the blending amount was 50.0 parts of the polybutylene succinate resin (A) and 50.0 parts of the acrylic rubber-containing polymer (B). rice field. Table 1 shows the composition of the materials of the obtained film. Table 2 shows the evaluation results of various characteristics of the obtained film.

[Example 3]
The film of Example 3 was obtained in the same manner as in Example 1 except that the blending amount was 25.0 parts of the polybutylene succinate resin (A) and 75.0 parts of the acrylic rubber-containing polymer (B). rice field. Table 1 shows the composition of the materials of the obtained film. Table 2 shows the evaluation results of various characteristics of the obtained film.

[Comparative Example 1]
A film of Comparative Example 1 was obtained in the same manner as in Example 1 except that only the acrylic rubber-containing polymer (B) was blended. Table 1 shows the composition of the materials of the obtained film. Table 2 shows the evaluation results of various characteristics of the obtained film.

[Comparative Example 2]
A film of Comparative Example 2 was obtained in the same manner as in Example 1 except that only the polybutylene succinate resin (A) was blended. Table 1 shows the composition of the materials of the obtained film. Table 2 shows the evaluation results of various characteristics of the obtained film.

The films obtained in Examples 1 to 3 show high values in both tensile elongation at break and tear elongation. Therefore, for example, when the film is directly laminated on the surface of various resin molded products, woodworking products or metal molded products having a three-dimensional shape, or when the film is laminated on various resin sheets, various resin molded products having a three-dimensional shape are used. , When laminated on the surface of a woodwork product or a metal molded product, it has excellent workability and can suppress breakage and cracking. Further, the obtained molded product is excellent in transparency and design.
On the other hand, the film obtained in Comparative Example 1 has good transparency and tensile elastic modulus, but is inferior in flexibility due to low tensile elongation at break and tensile elongation. Further, the film obtained in Comparative Example 2 has good transparency and tensile elastic modulus, but is inferior in flexibility due to its low tensile elongation at break. Therefore, it is difficult to handle, and for example, when laminated directly or on a resin sheet and then laminated on the surface of various three-dimensional resin molded products, woodwork products, or metal molded products, breakage or cracking may occur frequently. There is sex.

Since the film of the present invention has excellent tensile properties and tear properties, it is used for laminate films, adhesive tape films, agricultural films for tunnel houses and pipe houses, electrically insulating films, heavy-duty packaging films, and solar cells. Suitable for a wide range of applications such as films, optical films, films for liquid crystal displays, design films, shrink films, automobile parts, home appliance parts, medical parts, building parts, plastic optical fibers, touch panels, film sensors, etc. can.

Claims (11)

A film containing a polybutylene succinate resin (A) and an acrylic rubber-containing polymer (B). The film according to claim 1, wherein the mass ratio (A) / (B) of the polybutylene succinate resin (A) to the acrylic rubber-containing polymer (B) is 25/75 to 95/5. The acrylic rubber-containing polymer (B) is an alkyl acrylate monomer (B-1a) having an alkyl group having 1 to 8 carbon atoms and an alkyl methacrylate monomer having an alkyl group having 1 to 4 carbon atoms. It has an acrylic rubber polymer (B1) whose main constituent unit is a monomer component (B-1) containing any one or more selected from (B-1b), and an alkyl group having 1 to 4 carbon atoms. The film according to claim 1 or 2, which comprises a polymer (B2) having a monomer component (B-2) containing alkyl methacrylate as a main constituent unit. The acrylic rubber-containing polymer (B) is an acrylic rubber polymer containing the acrylic rubber polymer (B1): 20 to 60% by mass and the polymer (B2): 80 to 40% by mass. The film according to claim 3, wherein the polymer (B2) contains 10 to 100% by mass of the monomer component (B-2). The monomer component (B-1) is 40 to 99.9% by mass of the alkyl acrylate monomer (B-1a) and 0 to 59.9% by mass of the alkyl methacrylate monomer (B-1b). %, The other monomer (B-1c) having one double bond copolymerizable with the alkyl acrylate monomer (B-1a) and the alkyl methacrylate monomer (B-1b) 0 ~ 30% by mass, and a single amount having two or more double bonds in one molecule that can be copolymerized with the alkyl acrylate monomer (B-1a) and the alkyl methacrylate monomer (B-1b). The amount of the alkyl acrylate monomer (B-1a) and the alkyl methacrylate in 100% by mass of the monomer component (B-1) containing 0.1 to 10% by mass of the body (B-1d). The film according to claim 3 or 4, wherein the total body (B-1b) is 50 to 99.9% by mass. The film according to any one of claims 1 to 5, wherein the tear elongation in the TD direction at 25 ° C. measured according to JIS K7128-3 is 25% or more. The film according to any one of claims 1 to 6, which has a thickness of 10 to 500 μm. The film according to any one of claims 1 to 7, which is an extruded product. The film according to any one of claims 1 to 8, wherein the total light transmittance measured according to JIS K7361-1 is 88% or more. The film according to any one of claims 1 to 9, wherein the tensile elongation at break in the MD direction at 25 ° C. measured according to JIS K7127 is 150% or more. A multilayer film having at least one layer of the film according to any one of claims 1 to 10.