JP2018193468A - Film composed of resin composition - Google Patents

Abstract

An object of the present invention is to provide a film having excellent transparency and flexibility and excellent tear resistance.
A peak top molecular weight (Mp) obtained by polymerizing a macromonomer (A) and another comonomer (B) copolymerizable with the macromonomer (A) is 70,000 to 900,000. A resin composition containing a certain macromonomer copolymer (Y) and a film obtained therefrom.
[Selection figure] None

Description

  The present invention relates to a film made of a resin composition.

  An acrylic resin represented by polymethyl methacrylate (PMMA) is excellent in transparency and weather resistance. Therefore, in various applications, it is also used as an article exposed to the outdoor environment or a protective material for such an article. However, since it has both hard and brittle properties, it is also true that the range of application has been limited, and modification by various methods has been attempted.

  As a technique for modifying a polymer, a block polymer in which two or more polymer segments are chemically bonded is known. Even polymer segments that do not mix with each other are linked by chemical bonds, so the phase separation structure is refined (called microphase separation) and can be modified without impairing the properties of each polymer segment. .

  For example, Patent Document 1 discloses a (meth) acrylic block copolymer using a macromonomer, which is obtained by suspension polymerization having a smaller environmental load than solution polymerization, and a method for producing the same. Is disclosed. Patent Document 2 discloses a (meth) acrylic block copolymer which is a film molding material having excellent fluidity and a film which is transparent and hardly whitened even when stretched.

  Indeed, films obtained from the polymers and molding materials disclosed in these patents are excellent in transparency. Moreover, it is excellent in that the flexibility can be easily controlled by adjusting the comonomer without impairing the transparency. However, there is room for improvement in practical use, for example, in the process of laminating a film to a curved surface, it is easily torn when tension is applied.

International Publication No. 2014/098141 JP2015-157903A

  The objective of this invention is providing the film which is excellent in transparency and a softness | flexibility, and is excellent in tearing resistance.

  As a result of intensive studies, the present inventor obtained by copolymerizing a polymer having a polymerizable double bond at the terminal (macromonomer) and another polymerizable monomer (comonomer) copolymerizable with the macromonomer. A film obtained by molding the resin composition when the peak top molecular weight (Mp) of the copolymer is 70,000 or more and 900,000 or less. The present inventors have found that it is excellent in transparency and flexibility and has excellent tear resistance, and has completed the present invention.

That is, the present invention has the following features.
[1] A macromonomer copolymer obtained by polymerizing a macromonomer (A) represented by the following general formula (1) and another comonomer (B) copolymerizable with the macromonomer (A) ( A resin composition containing Y), wherein the macromonomer copolymer (Y) has a peak top molecular weight (Mp) of 70,000 or more and 900,000 or less.
(Wherein R and R ^{1 to} R ⁿ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. X _{1 to} X _n are each independently a hydrogen atom or (M is a methyl group. Z is a terminal group. N is a natural number of 2 to 10,000.)
[2] The resin composition according to [1], containing the macromonomer copolymer (Y) at a content of 50% by mass or more.
[3] A film obtained by molding the resin composition of [1] or [2].
[4] The film according to [3], wherein at least one surface is subjected to an easy adhesion treatment.

  According to the present invention, a film having excellent transparency and flexibility and excellent tear resistance can be provided.

The film of the present invention has a peak top molecular weight (A) obtained by polymerizing a macromonomer (A) represented by the following general formula (1) and a comonomer (B) copolymerizable with the macromonomer (A). It is obtained by molding a resin composition containing a macromonomer copolymer (Y) having a Mp) of 70,000 to 900,000 into a film.
(In formula (1), R and R ^{1 to} R ⁿ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. X _{1 to} X _n are each independently A hydrogen atom or a methyl group, Z is a terminal group, and n is a natural number of 2 to 10,000.)
Hereinafter, each component which comprises the film which concerns on this invention is demonstrated. In the present invention, “(meth) acrylate” is “acrylate” or “methacrylate”, “(meth) acrylic acid” is “acrylic acid” or “methacrylic acid”, and “(meth) acrylamide” is “acrylamide”. Or “(meth) acryloyl” means “acryloyl” or “methacryloyl”, respectively.
<Macromonomer (A)>
The macromonomer (A) represented by the general formula (1) is obtained by adding a radically polymerizable group having an unsaturated double bond to one end of a poly (meth) acrylate segment. Here, the macromonomer is a polymer having a polymerizable functional group, and is also called a macromer.

In the general formula (1), R and R ^{1 to} R ⁿ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. The alkyl group, cycloalkyl group, aryl group or heterocyclic group can have a substituent.

  As an alkyl group, a C1-C20 branched or linear alkyl group is mentioned, for example. Specific examples include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.

  As a cycloalkyl group, a C3-C20 cycloalkyl group is mentioned, for example. Specific examples include a cyclopropyl group, a cyclobutyl group, and an adamantyl group.

  As an aryl group, a C6-C18 aryl group is mentioned, for example. Specific examples include a phenyl group and a naphthyl group.

  As a heterocyclic group, a C5-C18 heterocyclic group is mentioned, for example. Specific examples include a γ-lactone group and an ε-caprolactone group.

As the substituent for R or R ^{1 to} R ⁿ , each independently represents an alkyl group, an aryl group, a carboxyl group, an alkoxycarbonyl group (—COOR ′), a carbamoyl group (—CONR′R ″), a cyano group, A group selected from the group consisting of a hydroxyl group, an amino group, an amide group (—NR′R ″), a halogen, an allyl group, an epoxy group, an alkoxy group (—OR ′), and a group exhibiting hydrophilicity or ionicity. Or an atom is mentioned. R ′ and R ″ are each independently the same group as R except for a heterocyclic group.

  Examples of the alkoxycarbonyl group as a substituent include a methoxycarbonyl group.

  Examples of the carbamoyl group as a substituent include an N-methylcarbamoyl group and an N, N-dimethylcarbamoyl group.

  Examples of the amide group as a substituent include a dimethylamide group.

  Examples of the halogen as the substituent include fluorine, chlorine, bromine and iodine.

  As an alkoxy group as a substituent, a C1-C12 alkoxy group is mentioned, for example. Specific examples include a methoxy group.

  Examples of the hydrophilic or ionic group as the substituent include alkali salts of carboxyl groups or alkali salts of sulfoxyl groups, poly (alkylene oxide) groups such as polyethylene oxide groups and polypropylene oxide groups, and quaternary ammonium bases. Of the cationic substituent.

R and R ^{1 to} R ⁿ are preferably at least one selected from an alkyl group and a cycloalkyl group, and more preferably an alkyl group.

  As the alkyl group, a methyl group, an ethyl group, an n-propyl group or an i-propyl group is preferable, and a methyl group is more preferable from the viewpoint of availability.

In the general formula (1), X _{1 to} X _n are each a hydrogen atom or a methyl group, and a methyl group is preferable. Furthermore, from the viewpoint of easy synthesis of the macromonomer (A), it is preferable that half or more of X _{1 to} X _n are methyl groups.

  In the general formula (1), Z is a terminal group of the macromonomer (A). Examples of the terminal group of the macromonomer (A) include a group derived from a hydrogen atom and a radical polymerization initiator, similarly to the terminal group of a polymer obtained by known radical polymerization.

  The number average molecular weight (Mn) of the macromonomer (A) is determined from the viewpoint of controlling the mechanical properties of the molding obtained from the molding material containing the macromonomer copolymer (Y) containing the macromonomer (A) and controlling the microphase separation structure. From 1,000 to 100,000 is preferable. The lower limit value of Mn of the macromonomer (A) is more preferably 3,000 or more, further preferably 5,000 or more, and particularly preferably 7,000 or more. Further, the upper limit value of Mn of the macromonomer (A) is preferably 70,000 or less, and more preferably 50,000 or less. If Mn is not less than the above lower limit, the weight ratio of the segment derived from the macromonomer (A) in the macromonomer copolymer (Y) can be increased, the microphase separation structure can be easily controlled, and the macromonomer The mechanical properties of the copolymer (Y) are improved. If Mn is not more than the above upper limit value, the weight ratio of the segment derived from the comonomer (B) in the macromonomer copolymer (Y) can be increased, the microphase separation structure control becomes easy, and the macromonomer copolymer weight is increased. The viscosity of the mixture at the time of synthesizing the combined body (Y) falls within an easy-to-handle range.

For the number average molecular weight (Mn) of the macromonomer (A), gel permeation chromatography (GPC) (also called size exclusion chromatography (SEC)) is used, and polymethyl methacrylate (PMMA) with a known molecular weight is used as a standard polymer. Means the value calculated from the calibration curve created
[Raw material monomer of macromonomer (A)]
Examples of the raw material monomer for obtaining the macromonomer (A) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl (meth). Acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl ( (Meth) acrylates such as (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate; 2 Hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate; (meth) acrylic acid, 2- (meth) Acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxy Ethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, maleic acid Carboxy group-containing vinyl monomers such as monomethyl inoate and monomethyl itaconate; acid anhydride group-containing vinyl monomers such as maleic anhydride and itaconic anhydride; glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, Epoxy group-containing vinyl monomers such as 3,4-epoxybutyl (meth) acrylate; amino group-containing (meth) acrylate vinyl monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate Body: (meth) acrylamide, Nt-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, maleic acid amide Ami such as maleimide Vinyl monomers containing a group; vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, (meth) acrylonitrile, vinyl chloride, vinyl acetate, vinyl propionate; divinylbenzene, ethylene glycol di (meta ) Acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di ( And polyfunctional vinyl monomers such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, and N, N′-methylenebis (meth) acrylamide; One or more of these can be appropriately selected and used.

  Among these, methacrylate is preferable from the viewpoint of easy availability of the monomer.

  As the methacrylate, methyl methacrylate, n-butyl methacrylate, dodecyl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate and 4-hydroxybutyl methacrylate are preferable, and methyl methacrylate, n-butyl methacrylate and 2- Ethylhexyl methacrylate is more preferred.

  Moreover, as a raw material monomer for obtaining a macromonomer (A), it contains said methacrylate and acrylate from the heat resistant point of the macromonomer copolymer (Y) which is a product, and the molded object containing this. A monomer composition is preferred.

  Examples of the acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, and t-butyl acrylate. Among these, methyl acrylate is preferable in terms of availability.

The content of the methacrylate in the monomer composition for obtaining the macromonomer (A) is 80% by mass from the viewpoint of the heat resistance of the product, the macromonomer copolymer (Y) and the molded product containing the same. The content is preferably 100% by mass or less. The content of methacrylate is more preferably 82% by mass or more and 99% by mass or less, and still more preferably 84% by mass or more and 98% by mass or less. As content of the acrylate in the monomer composition for obtaining a macromonomer (A), 0 to 20 mass% is preferable, 1 to 18 mass% is more preferable, and 2 to 16 mass% is more preferable. % Or less is more preferable.
[Method for producing macromonomer (A)]
The macromonomer (A) can be produced by a known method. As a method for producing the macromonomer (A), for example, a method using a cobalt chain transfer agent (US Pat. No. 4,680,352), an α-substituted unsaturated compound such as α-bromomethylstyrene is used as the chain transfer agent. A method (International Publication No. 88/04304), a method of chemically bonding a polymerizable group (Japanese Patent Laid-Open No. 60-133007, US Pat. No. 5,147,952) and a method by thermal decomposition (Japanese Patent Laid-Open No. 11-240854) ) And the like.

  Among these, as a method for producing the macromonomer (A), a method using a cobalt chain transfer agent is preferable in that a catalyst having a small number of production steps and a high chain transfer constant is used.

  Examples of the cobalt chain transfer agent used in the present invention include conventionally known cobalt transfer agents such as, for example, Japanese Patent No. 3585730, Japanese Patent Publication No. 6-23209, Japanese Patent Publication No. 7-35411, US Patent No. No. 45269945, U.S. Pat. No. 4,694,054, U.S. Pat. No. 4,837,326, U.S. Pat. No. 4,886,861, U.S. Pat. No. 5,324,879, International Publication No. 95/17435, and Japanese Patent Publication No. 9-510499. What is described can be used.

As the cobalt chain transfer agent, for example, a compound represented by the following general formula (2) can be used.
(In Formula (2), R < ₁ > -R < ₄ > is respectively independently selected from an alkyl group, a cycloalkyl group, and an aryl group, and X is respectively independently a fluorine atom, a chlorine atom, a bromine atom, hydroxyl. Group, alkoxy group, aryloxy group, alkyl group and aryl group)
More specifically, as the cobalt chain transfer agent, bis (borondifluorodimethyldioxyiminocyclohexane) cobalt (II), bis (borondifluorodimethylglyoxymate) cobalt (II), bis (borondifluorodiphenylglyoxymate) ) Cobalt (II), cobalt (II) complex of bicinalimino hydroxyimino compound, cobalt (II) complex of tetraazatetraalkylcyclotetradecatetraene, N, N′-bis (salicylidene) ethylenediaminocobalt (II) Complexes, cobalt (II) complexes of dialkyldiazadioxodialkyldodecadiene, cobalt (II) porphyrin complexes, and the like can be used, and one or more of these can be appropriately selected and used. Among them, bis (borondifluorodiphenylglyoxymate) cobalt (II), which is stably present in an aqueous medium and has a high chain transfer effect (in the formula (2), R _{1 to} R ₄ are phenyl groups, and X is a fluorine atom. Are preferred).

  Examples of the method for producing the macromonomer (A) using a cobalt chain transfer agent include a bulk polymerization method, a solution polymerization method, and an aqueous dispersion polymerization method. The aqueous dispersion polymerization method includes a suspension polymerization method and an emulsion polymerization method.

  Among these, an aqueous dispersion polymerization method and a solution polymerization method can be preferably used. According to the aqueous dispersion polymerization method, the recovery step of the macromonomer (A) can be simplified. In the aqueous dispersion polymerization method, water, a mixture of water and a water-soluble solvent (for example, ethanol), or the like can be used as the solvent. Moreover, according to the solution polymerization method, without recovering the obtained macromonomer (A), the comonomer (B), a thermal polymerization initiator, etc. are added as they are, and the polymerization reaction of the macromonomer copolymer (Y) is performed. Can start. In the solution polymerization method, for example, hydrocarbons such as toluene; ethers such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane and chloroform; ketones such as acetone; alcohols such as methanol; nitriles such as acetonitrile; A vinyl ester; a carbonate such as ethylene carbonate; and a solvent such as supercritical carbon dioxide, and one or more selected from these solvents can be used.

  The cobalt chain transfer agent is 0.0005 parts by mass or more and 0.02 parts by mass or less, preferably 0.001 parts by mass or more and 0.015 parts by mass with respect to 100 parts by mass of the raw material monomer for obtaining the macromonomer (A). It can be used in the following amounts, more preferably 0.001 parts by mass or more and 0.01 or less. When the amount of cobalt chain transfer agent used is small (for example, when the amount is less than the lower limit), the molecular weight of the resulting macromonomer (A) may not be sufficiently reduced. When the amount is large (for example, when the amount exceeds the upper limit), the resulting macromonomer (A) may be colored.

  A radical polymerization initiator can be used for the polymerization. Examples of the radical polymerization initiator that can be used in the present invention include organic peroxides and azo compounds, which can be appropriately selected depending on the solvent and raw materials used in the polymerization reaction. Specific examples of the organic peroxide include, for example, 2,4-dichlorobenzoyl peroxide, t-butyl peroxypivalate, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, cyclohexanone peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, Examples include dicumyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, and di-t-butyl peroxide. Specific examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (2,4-dimethyl). -4-methoxyvaleronitrile) and the like.

  These radical polymerization initiators can be used alone or in combination of two or more.

  The radical polymerization initiator is within the range of 0.0001 parts by mass to 10 parts by mass, preferably 0.001 parts by mass to 1 part by mass with respect to 100 parts by mass of the raw material monomer for obtaining the macromonomer (A). Can be used.

  The polymerization can be carried out in the presence of a dispersant. Examples of the dispersant usable in the present invention include poly (meth) acrylic acid alkali metal salts, copolymers of (meth) acrylic acid alkali metal salts and (meth) acrylic acid esters, and (meth) acrylic acid. Sulfoalkyl alkali metal salt and (meth) acrylic acid ester copolymer, polystyrene sulfonic acid alkali metal salt, styrene sulfonic acid alkali metal salt and (meth) acrylic acid ester copolymer, or these monomers A copolymer composed of a combination of the following: polyvinyl alcohol having a saponification degree of 70 to 100%, methyl cellulose, starch and hydroxyapatite, which can be appropriately selected according to the solvent and raw materials used in the polymerization reaction. These dispersants can be used alone or in combination of two or more. The dispersant can be used in the reaction solution in an amount of 0.005 parts by mass or more and 0.05 parts by mass or less.

  In addition, an inorganic electrolyte can be used in combination for the purpose of improving the dispersion stability during polymerization. Although it does not specifically limit as an inorganic electrolyte, For example, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium sulfate, manganese sulfate etc. are mentioned. One or more of these can be appropriately selected and used.

  There is no restriction | limiting in particular about superposition | polymerization temperature, For example, it can select suitably from the range of -100-250 degreeC, Preferably it can be set as the range of 0-200 degreeC.

  After the polymerization reaction, the obtained macromonomer (A) can be purified and recovered by any means for separating and purifying the polymer, such as filtration, dialysis, and precipitation, and if necessary, further subjected to a drying step. You may attach. The macromonomer (A) can be used in the production of a macromonomer copolymer (Y) described later in an arbitrary form (for example, a solid form such as powder, granules, pellets, etc.).

The macromonomer (A) may be used alone or in combination of two or more having different structures and compositions.
<Comonomer (B)>
The comonomer (B) is a monomer that can be polymerized with the macromonomer (A), and is not particularly limited as long as it can polymerize with the macromonomer (A), and various monomers can be used as necessary. Specifically, the same monomers as those listed above as the “raw material monomer for obtaining the macromonomer (A)” can be mentioned. Since the comonomer (B) has good copolymerizability with the macromonomer (A), (meth) acrylate is preferable, and methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) are particularly preferable. Acrylate, n-butyl (meth) acrylate, dodecyl methacrylate, stearyl methacrylate, 2-ethylhexyl (meth) acrylate, glycidyl methacrylate, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferred.

A comonomer (B) can be used individually by 1 type or in combination of 2 or more types.
<Macromonomer copolymer (Y)>
The macromonomer copolymer (Y) is a polymer obtained by polymerizing the macromonomer (A) and the comonomer (B).

  The macromonomer copolymer (Y) is composed of a block copolymer having the macromonomer (A) and the comonomer (B) as monomer units, and a graft copolymer of the comonomer (B) having the macromonomer (A) in the side chain. Includes at least one selected.

  Further, the macromonomer copolymer (Y) includes a polymer having only the macromonomer (A) as a monomer unit, a polymer having only the comonomer (B) as a monomer unit, and an unreacted macromonomer (A). At least one selected from unreacted comonomers (B) may be contained.

  The content of the unreacted macromonomer (A) in the macromonomer copolymer (Y) is preferably small in terms of the microphase separation control ability and the thermal decomposition resistance of the macromonomer copolymer (Y). The content of the unreacted macromonomer (A) in the macromonomer copolymer (Y) is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.

  The mass average molecular weight (Mw) of the macromonomer copolymer (Y) is preferably higher in order to maintain the mechanical properties when formed into a molded body, but if the Mw is too high, the fluidity is lowered and the moldability is reduced. Incurs a decline.

  The Mw of the macromonomer copolymer (Y) is preferably from 40,000 to 1,000,000, more preferably from 50,000 to 750,000, and even more preferably from 60,000 to 500,000 from the viewpoint of achieving both mechanical properties and moldability. preferable. In addition, the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the macromonomer copolymer (Y) are obtained by using gel permeation chromatography (GPC) and using polymethyl methacrylate (PMMA) having a known molecular weight as a standard polymer. It means the value calculated from the calibration curve created by using.

  The peak top molecular weight (Mp) of the macromonomer copolymer (Y) is preferably 70,000 to 900,000. The peak top molecular weight of the macromonomer copolymer (Y) is obtained by using gel permeation chromatography (GPC), and the molecular weight located at the peak top of the obtained differential molecular weight distribution is polymethyl methacrylate (PMMA) whose molecular weight is known. Means a value calculated from a calibration curve prepared using as a standard polymer.

  Mp of the macromonomer copolymer (Y) is the molecular weight of the polymer component most contained in the macromonomer copolymer (Y). When Mp is 70,000 or more, the mechanical properties of the macromonomer copolymer (Y), particularly the tear strength, are excellent. The higher the Mp is, the better the mechanical properties of the macromonomer copolymer (Y) are. However, if it is too high, the appearance of the molded product may be poor (for example, a decrease in transparency), and the Mp is preferably 900,000 or less. . From the viewpoint of compatibility between mechanical properties and good appearance, the Mp of the macromonomer copolymer (Y) is more preferably 80,000 to 900,000, and more preferably 80,000 to 600,000 (for example, 80,000 to 500,000). Or 80,000 to 400,000, and more preferably 80,000 to 300,000.

The molecular weight distribution (PDI) (mass average molecular weight (Mw) / number average molecular weight (Mn)) of the macromonomer copolymer (Y) is preferably from 2.5 to 16.0. If PDI is 2.5 or more, since it contains a low molecular weight substance, it is easy to ensure fluidity suitable for molding. Moreover, if it is 16.0 or less, it is hard to cause the appearance defect of a molded object. PDI is more preferably 3.0 or more and 12.0 or less, and further preferably 3.2 or more and 8.0 or less. However, even if the macromonomer copolymer (Y) has a molecular weight distribution exceeding the upper limit, a molded body having a good appearance can be obtained by subjecting the surface of the molded body to processing such as hot pressing.
[Method for producing macromonomer copolymer (Y)]
The method for producing the macromonomer copolymer (Y) includes a step of polymerizing the macromonomer (A) and the comonomer (B).

  The method for polymerizing the macromonomer (A) and the comonomer (B) is not particularly limited, and various methods such as solution polymerization, aqueous dispersion polymerization (for example, suspension polymerization, emulsion polymerization, etc.), bulk polymerization, and the like are used. Can do.

  Aqueous dispersion polymerization such as suspension polymerization or emulsion polymerization is advantageous in that it is easy to control the polymerization exotherm, and among these, suspension polymerization is preferred because of its simple recovery operation and high productivity. Solution polymerization is advantageous in that the reaction can be performed in a state in which the uniformity of the reaction solution is maintained until the latter stage of the polymerization. Moreover, solution polymerization and emulsion polymerization are advantageous in that they can be carried out continuously from the synthesis of the macromonomer (A) to the synthesis of the macromonomer copolymer (Y).

  Each amount of the macromonomer (A) and the comonomer (B) used for the polymerization reaction is not particularly limited, but when the total amount of both is 100 parts by mass, the macromonomer (A) is 20 parts by mass or more and 60 parts by mass or less, For example, the amount can be selected from the range of 25 parts by mass or more and 55 parts by mass or less, preferably 30 parts by mass or more and 50 parts by mass or less. By including the macromonomer (A) in this amount, the microphase-separated structure of the macromonomer copolymer (Y) can be easily controlled and good mechanical properties can be obtained, and the viscosity of the mixture in the polymerization reaction system can be reduced. It can be easy to handle.

  Although not particularly limited, in the production of the macromonomer copolymer (Y) of the present invention, the macromonomer (A) and the comonomer (B) are all put in the same reaction vessel and then polymerized. It is preferred that the reaction is initiated. Moreover, when dripping of a macromonomer (A) and a comonomer (B) is required, it is preferable to dripping what mixed both uniformly by the same composition ratio as the inside of reaction container beforehand. By these operations, the composition ratio of the macromonomer (A) and the comonomer (B) in the reaction vessel can always be kept constant, whereby only the macromonomer (A) remains or only the comonomer (B) remains. Phenomenon can be suppressed.

  In the polymerization, a chain transfer agent may be used to adjust the molecular weight of the polymer. As such a chain transfer agent, mercaptans (for example, 1-octanethiol and the like), hydrogen, α-methylstyrene dimer, terpenoids and the like can be used. The chain transfer agent is used in an amount of 0.0001 parts by mass to 10 parts by mass, preferably 0.001 parts by mass to 1 part by mass with respect to 100 parts by mass of the total amount of the macromonomer (A) and the comonomer (B). be able to.

  The polymerization can be carried out in the presence of a radical polymerization initiator. Examples of the radical polymerization initiator that can be used in the production of the macromonomer copolymer (Y) include the above radical polymerization initiators.

  The radical polymerization initiator is in the range of 0.0001 parts by mass to 10 parts by mass, preferably 0.001 parts by mass to 1 part by mass with respect to 100 parts by mass of the total amount of the macromonomer (A) and the comonomer (B). Can be used within.

  The polymerization can be carried out in the presence of a dispersant. Examples of the dispersant that can be used in the present invention include the above-mentioned dispersants, which can be appropriately selected depending on the solvent and raw materials used in the polymerization reaction. A dispersing agent can be used individually or in combination of 2 or more types. The dispersant can be used in the reaction solution in an amount of 0.005 parts by mass or more and 0.05 parts by mass or less.

  In addition, an inorganic electrolyte can be used in combination for the purpose of improving the dispersion stability during polymerization. Examples of the inorganic electrolyte that can be used include the above-mentioned inorganic electrolytes, and one or more can be appropriately selected and used.

  There is no restriction | limiting in particular about superposition | polymerization temperature, For example, it can select suitably from the range of -100-250 degreeC, Preferably it is the range of 0-200 degreeC.

After the polymerization reaction, the obtained macromonomer copolymer (Y) can be purified and recovered by any means for separating and purifying the polymer such as filtration, dialysis, and precipitation, and if necessary, You may attach | subject to a drying process. Macromonomer copolymer (Y) can be made into arbitrary forms (for example, solid forms, such as a powder, a granule, and a pellet).
<Resin composition>
The resin composition of the present invention is a composition containing a macromonomer copolymer (Y). The said resin composition can be used as a raw material for manufacturing molded objects, such as a film.

  The resin composition of the present invention may contain the macromonomer copolymer (Y) in an amount of preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. By including the macromonomer copolymer (Y) in this amount, good transparency and mechanical properties can be obtained when the resin composition is formed into a film.

  In addition to the macromonomer copolymer (Y), the resin composition of the present invention may further include another polymer. Examples of such polymers include acrylic resins such as polymethyl methacrylate, fluororesins such as polyvinylidene fluoride, saturated polyesters such as polyolefin, polyamide, unsaturated polyester, polyethylene terephthalate, and polybutylene terephthalate, and polycarbonate. Among these, acrylic resins such as polymethylmethacrylate excellent in weather resistance, fluororesins such as polyvinylidene fluoride, and acrylic resins such as polymethylmethacrylate capable of producing a molded article having good transparency are particularly preferable. As a monomer which comprises an acrylic resin, the same thing as the raw material monomer which comprises the said "comonomer (B)" is mentioned. The resin composition of the present invention can contain such another polymer alone or in combination of plural types together with the macromonomer copolymer (Y).

  The resin composition of the present invention can contain additives as necessary. The amount of the additive can be appropriately selected within a range that does not impair the optical performance and mechanical properties of the film obtained by molding the resin composition of the present invention, and the smaller the amount, the better the content of the additive. 0-20 mass parts is preferable with respect to mass parts, 0-10 mass parts is more preferable, and 0-5 mass parts is still more preferable.

  Examples of additives include ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, anti-blocking agents such as synthetic silica and silicon resin powder, plasticizers, antibacterial agents, antifungal agents, bluing agents, and charging agents. An inhibitor.

  Examples of the ultraviolet absorber include benzoate compounds, benzophenone compounds, benzotriazole compounds, triazine compounds, salicylate compounds, acrylonitrile compounds, metal complex compounds, hindered amine compounds; Examples include inorganic particles such as ultrafine titanium oxide having a particle diameter of about 0.06 μm and ultrafine particle zinc oxide having a particle diameter of about 0.01 to 0.04 μm. These may be used alone or in combination of two or more.

Examples of the light stabilizer include hindered amine-based or phenol-based light stabilizers such as N-H type, N-CH ₃ type, N-acyl type, and N-OR type.

  Examples of the heat stabilizer include a phenol-based, amine-based, sulfur-based or phosphoric acid-based antioxidant.

  As the ultraviolet absorber or antioxidant, for example, a polymer type in which an ultraviolet absorber or an antioxidant is chemically bonded to a main chain or a side chain constituting the polymer can be used.

The resin composition of the present invention comprises a macromonomer copolymer (Y) and a predetermined amount of optional components as required, and any mixing means or kneading means (for example, roll, Banbury mixer, single screw extruder, twin screw extrusion). It can be prepared using a normal kneader such as a machine. The resin composition of this invention can be made into arbitrary forms, for example, can be made into solid forms, such as a powder, a granule, a pellet.
<Film>
The film of the present invention is obtained by molding the resin composition into a film.

The film of the present invention is excellent in transparency and flexibility and excellent in tear resistance.
(transparency)
The total light transmittance of the film of the present invention was measured in accordance with Japanese Industrial Standard (JIS K 7361-1) “Plastics—Test method for total light transmittance of transparent material—Part 1: Single beam method”. In some cases, 80% to 100% is preferable, 85% to 100% is more preferable, and 90% to 100% is more preferable.

  If the total light transmittance is 80% or more, sufficient transparency can be obtained even if it is a thick film.

  The haze value of the film of the present invention is preferably 0% or more and 10% or less, preferably 0% or more, when measured according to Japanese Industrial Standard (JIS K 7136) “Plastic—How to Obtain Haze of Transparent Material”. 5% or less is more preferable, and 0% or more and 3% or less is still more preferable. When the haze value is 10% or less, a transparent feeling with little cloudiness can be obtained.

  In general, the thinner the film, the higher the transparency. Therefore, the thickness of the film of the present invention is preferably 20 to 400 μm, more preferably 25 to 350 μm, and still more preferably 30 to 300 μm.

In the present invention, the thickness of the film refers to an average value of measured values measured arbitrarily at three points in a direction (TD direction) perpendicular to the flow direction during film formation.
(Mechanical properties)
The film of the present invention is easy to handle because it is difficult to tear even when tension is applied at room temperature, and exhibits flexibility and high elongation at break under heating. Heating refers to giving a temperature above room temperature by heating the film, and the temperature varies depending on the construction technique. In this specification, unless otherwise specified, “room temperature” or “under room temperature” refers to 23 ° C., and “warming” or “under warming” refers to 40 ° C.

  The elastic modulus at room temperature of the film of the present invention is 200 mm at 23 ° C. in accordance with Japanese Industrial Standard (JIS K 7127) “Plastics—Test Method for Tensile Properties—Part 3: Test Conditions for Films and Sheets”. When measured at a rate of / min, 100 MPa or more and 1200 MPa or less is preferable.

  If the elastic modulus is 100 MPa or more, it can be handled as a film. Moreover, if it is 1200 Mpa or less, it can follow a curved surface also at room temperature.

  The elastic modulus of the film of the present invention at room temperature is more preferably 150 MPa or more and 1000 MPa or less, and further preferably 200 MPa or more and 800 MPa or less.

  The elastic modulus of the film of the present invention under heating is preferably 1 MPa or more and 700 MPa or less when measured at a rate of 200 mm / min at 40 ° C. according to JIS K 7127.

  If the elastic modulus is 1 MPa or more, it can be finely adjusted (reworked) after being followed. Moreover, if it is 700 Mpa or less, it can also follow an uneven surface easily.

  The elastic modulus of the film of the present invention under heating is more preferably 10 MPa or more and 600 MPa or less, and further preferably 20 MPa or more and 500 MPa or less.

  The elongation at break of the film of the present invention is preferably 100% or more when measured at a rate of 200 mm / min at 40 ° C. according to JIS K 7127.

  If the elongation at break is 100% or more, even if the film is deformed by applying heat, the film does not break easily and is easy to construct.

  The higher the elongation at break, the better. However, the film becomes thinner as it stretches, and it is easy to break by the fine protrusions on the surface to be bonded, so 300% or less is preferable.

  The elongation at break of the film of the present invention under heating is more preferably from 120% to 300%, still more preferably from 140% to 300%.

  The tear strength of the film of the present invention at room temperature is in accordance with the Japanese Industrial Standard (JIS K 7128-3) “Plastic-Tear Strength Test Method for Films and Sheets—Part 3: Right Angle Tear Method”. When measured at a rate of 200 mm / min at 23 ° C., it is preferably 80 N / mm or more and 200 N / mm or less. If the tear strength is 80 N / mm or more, it is difficult to be torn even when a force is applied during curved surface tracking, and it is easy to handle. If the tear strength is 200 N / mm or less, the workability such as punching is excellent.

The tear strength of the film of the present invention is more preferably 85 N / mm or more from the viewpoint of durability and workability, more preferably 90 N / mm or more, and 85 N / mm or more and 200 N / mm or less. Is particularly preferable, and 90 N / mm or more and 200 N / mm or less is most preferable.
(Film surface treatment)
The film of the present invention may be used as it is, or on one or both sides, weather resistance, surface hardness, scratch resistance, chemical resistance, printing properties, easy adhesion, water repellency, antistatic, antireflection, antiglare In order to impart or improve various functions such as matting, surface processing may be performed.

Specific examples of the surface treatment include, but are not limited to, various coating treatments (for example, printing, coating, wet plating treatment, dry plating treatment, laminating treatment), easy adhesion treatment, and the like. “Easy adhesion treatment” is treatment performed to improve the adhesion between the film of the present invention and other sheets or films, paints, adhesives, etc., for example, corona treatment, plasma treatment, sputtering. Etching treatment, sulfonation treatment, grafting treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, adhesive (for example, (meth) acrylate, polyester, polyurethane, polyethyleneimine, silane coupling agent, perfluorooctane sulfonic acid, etc.) This refers to processing such as the installation of an adhesive layer. The film of the present invention is preferably an easily adhesive film that has been subjected to an easily adhesive treatment. Among these, an easy-adhesive film provided with an adhesive layer is more preferable because it is easy for humans to stick together by hand, and the interface film between the film of the present invention and the adhesive layer is less likely to occur, so a polymer having (meth) acrylate as a monomer unit. An easy-adhesion film provided with an adhesive layer containing is more preferred.
<Film production method>
The film of this invention can be manufactured by shape | molding the said resin composition in a film or a sheet form by arbitrary means. Examples of the molding method include injection molding, compression molding, hollow molding, extrusion molding, rotational molding, casting, and solvent casting. For example, the film of the present invention can be produced by a step of melting the resin composition, forming a film shape, and then cooling and solidifying. As such a method, the melt extrusion method is preferable from the viewpoint of productivity. Examples of the melt extrusion method include a T-die method and an inflation method. Of these, the T-die method is preferable from the viewpoint of economy.

The melt extrusion temperature is preferably about 170 ° C. or higher and 240 ° C. or lower. Moreover, as an extruder, a single screw extruder, a twin screw extruder, etc. can be utilized, for example.
<Application of film>
Applications of the film of the present invention include, for example, overlay film, laminate film, media printing film, etc .; weather strip, bumper, bumper guard, side mud guard, body panel, spoiler, front grill, strut mount, wheel cap, center Automotive exterior applications such as pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts; instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switches Automotive interior applications such as bases, center clusters, and dashboards; front panels, buttons, emblems for AV equipment and furniture products, Applications such as face decoration materials; applications such as mobile phone housings, display windows, buttons, etc .; furniture exterior materials; walls, ceilings, floors and other building interior materials; siding outer walls, fences, roofs, gates Architectural exterior materials such as windbreak boards; surface decorative materials for furniture such as window frames, doors, handrails, sills and duck; various displays; Fresnel lenses, polarizing films, polarizer protective films, retardation films, light Optical applications such as diffusion films, viewing angle widening films, reflection films, antireflection films, antiglare films, brightness enhancement films, prism sheets, microlens arrays, touch panel conductive films, light guide films, and electronic paper films; windows Interior / exterior use of various vehicles other than automobiles such as glass, trains, airplanes, ships, etc .; various packaging containers and packaging materials such as bottles, cosmetic containers, accessory cases, etc. Films for miscellaneous goods such as gifts and accessories; solar cell surface protective film, solar cell sealing film, solar cell back surface protective film, solar cell base film, agricultural vinyl house, highway sound insulation Examples of the protective film for plates and the outermost surface protective film for traffic signs include, but are not limited to.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

In the examples, “parts” and “%” indicate “parts by mass” and “% by mass”.
[Evaluation method]
Each evaluation in an Example and a comparative example was implemented with the following method.
(Evaluation method of resin composition)
(1) Molecular weight and molecular weight distribution Mass average molecular weight (Mw), number average molecular weight (Mn), and peak top molecular weight (Mp) were measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, trade name: HLC- 8220) and measured under the following conditions.

Column: TSK GUARD COLUMN SUPER HZ-L (4.6 × 35 mm) and two TSK-GEL SUPER HZM-N (6.0 × 150 mm) connected in series Eluent: THF
Measurement temperature: 40 ° C
Flow rate: 0.6 mL / min Mw, Mn and Mp are calibration curves prepared using four types of polymethylmethacrylates having peak top molecular weights of 1590, 10290, 55600 and 141500 manufactured by Polymer Laboratories as standard polymers. Asked using.
(Film evaluation method)
(2) Transmittance and haze Haze and total light transmittance were measured using a haze meter NDH2000 (Nippon Denshoku) in accordance with JIS K 7136 and JIS K 7361-1. An average value was obtained by measuring three points per sample.
(3) Tensile test A 15 mm × 150 mm strip-shaped test piece was cut out from the film along the MD direction. A tensile test was performed in accordance with JIS K 7127 using a Tensilon universal testing machine RTC-1250A (Orientec) with a distance between chucks of 100 mm. Tensile tests were performed at room temperature of 23 ° C. and 40 ° C. at a speed of 200 mm / min, and the elongation at break, elastic modulus, and yield stress at each test temperature were determined from the stress strain curves at that time.
(4) Tear Test Using a right-angle type test piece punched from the film, a tear test was performed with Tensilon Universal Tester RTC-1250A (Orientec) in accordance with JIS K 7128-3. A test for tearing in the TD direction was performed at a room temperature of 23 ° C. and a tensile speed of 200 mm / min, and the tear strength, maximum point elongation, and elongation at break were determined.
<Production Example 1>
[Dispersant]
In a 1200 L reaction vessel equipped with a stirrer, a condenser and a thermometer, 61.6 parts of a 17% aqueous potassium hydroxide solution, 19.1 parts of methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, the same shall apply hereinafter) and deionized 19.3 parts of water was charged. Subsequently, the liquid in the reaction apparatus was stirred at room temperature, and after confirming an exothermic peak, it was further stirred for 4 hours. Thereafter, the reaction solution in the reaction apparatus was cooled to room temperature to obtain an aqueous potassium methacrylate solution.

  Next, in a reaction vessel having a capacity of 1050 L equipped with a stirrer, a condenser tube and a thermometer, 900 parts of deionized water, sodium 2- (methacryloyloxy) ethanesulfonate (trade name: acrylate ester, manufactured by Mitsubishi Chemical Corporation) 60 parts of SEM-Na), 10 parts of the aqueous potassium methacrylate solution and 12 parts of methyl methacrylate were added and stirred, and the temperature was raised to 50 ° C. while replacing the inside of the polymerization apparatus with nitrogen. In addition, 0.08 part of 2,2′-azobis (2-methylpropionamidine) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-50) is added as a polymerization initiator, The temperature was raised to 60 ° C.

After raising the temperature, methyl methacrylate was continuously added dropwise at a rate of 0.24 parts / minute for 75 minutes using a dropping pump. The reaction solution was held at 60 ° C. for 6 hours and then cooled to room temperature to obtain a dispersant having a solid content of 10% as a transparent aqueous solution.
<Production Example 2>
[Macromonomer]
(Synthesis of cobalt chain transfer agent)
In a synthesizer equipped with a stirrer, 2.00 g (8.03 mmol) of cobalt (II) acetate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd., Wako Special Grade) and diphenylglyoxime (Tokyo) were added in a nitrogen atmosphere. Kasei Chemical Co., Ltd., EP grade) 3.86 g (16.1 mmol) and 100 ml of diethyl ether previously deoxygenated by nitrogen bubbling were added and stirred at room temperature for 2 hours.

Next, 20 ml of boron trifluoride diethyl ether complex (manufactured by Tokyo Chemical Industry Co., Ltd., EP grade) was added, and the mixture was further stirred for 6 hours. The obtained product was filtered, and the solid was washed with diethyl ether and vacuum-dried at 20 ° C. for 12 hours to obtain 5.02 g (7.93 mmol, yield 99%) of a brown complex cobalt complex.
(Synthesis of macromonomer)
In a polymerization apparatus equipped with a stirrer, a cooling tube and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate (Na ₂ SO ₄ ) and the dispersant produced in Production Example 1 (solid content 10%) 0 .26 parts was added and stirred to obtain a uniform aqueous solution. Next, 95 parts of methyl methacrylate (MMA), 5 parts of methyl acrylate (MA) (manufactured by Mitsubishi Chemical Co., Ltd.), 0.0016 part of a cobalt chain transfer agent produced by the above method and 1,1,3 as a polymerization initiator , 3-tetramethylbutylperoxy 2-ethylhexanoate (manufactured by NOF Corporation, trade name: Perocta (registered trademark) O) 0.1 part was added to obtain an aqueous dispersion. Next, the inside of the polymerization apparatus was sufficiently purged with nitrogen, and the aqueous dispersion was heated to 80 ° C., held for 4 hours, then heated to 92 ° C. and held for 2 hours. Thereafter, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension of macromonomer. This aqueous suspension was filtered through a filter cloth, and the filtrate was washed with deionized water and dried at 40 ° C. for 16 hours to obtain a macromonomer.

  When analyzed by GPC, Mw of the macromonomer was 27000, Mn was 14000, and molecular weight distribution (PDI) was 1.9.

  The results are shown in Table 1.

<Production Example 3>
[Macromonomer copolymer (Y-1)]
An aqueous dispersion medium for suspension was prepared by mixing 145 parts of deionized water, 0.1 part of sodium sulfate and 0.26 part of the dispersant produced in Production Example 1.

  In a separable flask with a condenser, 40 parts of the macromonomer synthesized in Production Example 2 as the macromonomer (A), 36 parts of n-butyl acrylate (BA) (manufactured by Mitsubishi Chemical Corporation) as the comonomer (B) and methyl 24 parts of methacrylate and 0.1 part of 1-octanethiol were mixed and heated to 50 ° C. with stirring to obtain a raw material syrup. After cooling the raw material syrup to 40 ° C. or less, 0.3 part of AMBN (2,2′-azobis (2-methylbutyronitrile)) manufactured by Otsuka Chemical Co., Ltd. was dissolved in the raw material syrup to obtain syrup.

  Next, after adding an aqueous dispersion medium for suspension to the syrup, the stirring rotation speed was increased while the atmosphere in the separable flask was replaced with nitrogen by nitrogen bubbling to obtain a syrup dispersion.

  The syrup dispersion was heated to 75 ° C., and the external temperature of the separable flask was maintained until a polymerization exothermic peak appeared. After the polymerization exothermic peak appeared, when the syrup dispersion reached 75 ° C., the syrup dispersion was heated to 85 ° C. and held for 30 minutes to complete the polymerization to obtain a suspension.

  After the suspension is cooled to 40 ° C. or lower, the suspension is filtered through a filter cloth, the filtrate is washed with deionized water, and dried at 40 ° C. for 16 hours to obtain a macromonomer copolymer (Y-1). Got.

  The results are shown in Table 2. Mw of the macromonomer copolymer (Y-1) was 248000, Mn was 52000, and PDI was 4.8. Mp was 65300.

<Production Example 4>
[Macromonomer copolymer (Y-2)]
In Production Example 3, a macromonomer copolymer (Y-2) was obtained in the same manner except that n-butyl acrylate (BA) and methyl methacrylate (MMA) were used as comonomer (B) as shown in Table 2. .

The results are shown in Table 2. Mw of the macromonomer copolymer (Y-2) was 247000, Mn was 57100, and PDI was 4.3. Moreover, Mp was 84400.
<Production Example 5>
[Macromonomer copolymer (Y-3)]
In Production Example 3, a macromonomer copolymer (Y-3) was obtained in the same manner except that n-butyl acrylate (BA) and methyl methacrylate (MMA) were used as comonomer (B) as shown in Table 2. .

The results are shown in Table 2.
Mw of the macromonomer copolymer (Y-3) was 209000, Mn was 57900, and PDI was 3.6. Moreover, Mp was 84400.
<Example 1>
[Production of film]
The macromonomer copolymer (Y-2) produced in Production Example 4 was preliminarily dried at 50 ° C. overnight and then extruded at a maximum temperature of 220 ° C. by a φ30 mm twin-screw kneading extruder (manufactured by Werner & Pfleiderer). A molding material (resin composition) was obtained.

  The pellets obtained were pre-dried overnight at 50 ° C., and then extruded at 180 to 220 ° C. and T die temperature of 220 ° C. using a φ30 mm single screw extruder (GM Engineering) equipped with a 150 mm wide T-die. A film (Example 1) having a thickness of 50 μm was obtained by forming a film at a cooling roll temperature of 40 ° C.

  Table 3 shows the tensile test results at 23 ° C., the tensile test results at 40 ° C., the tear test results at 23 ° C., and the optical test results of the obtained film.

<Comparative example 1, Example 2>
In Example 1, except that the macromonomer copolymer (Y-1) obtained in Production Example 3 or the macromonomer copolymer (Y-3) obtained in Production Example 5 was used as the macromonomer copolymer. Similarly, the film of the comparative example 1 and Example 2 was obtained from each copolymer.

  Table 3 shows the evaluation results of the film.

  As shown in Table 3, the films described in Examples 1 and 2 are superior in tear strength to the film described in Comparative Example 1, and are not easily torn when applied at room temperature of 23 ° C., and are excellent in handleability. . Also, the elongation at break in the tensile test at 40 ° C. is significantly high. When the film is secondarily processed, it is difficult to break when heated to 40 ° C. and pulled, so that it is excellent in workability. Moreover, since the total light transmittance exceeds 90% and the haze value is as low as 1% or less, the film described in Examples 1 and 2 has excellent transparency. That is, it can be seen that the films shown in Examples 1 and 2 are transparent and have excellent handleability and workability.

  Macromonomer copolymers (Y-1) to (Y-3) are not significantly different in both number average molecular weight and weight average molecular weight (Table 2). However, since the macromonomer copolymers (Y-2) and (Y-3) have a higher peak top molecular weight than the macromonomer copolymer (Y-1), and contain many polymer chains having a relatively high molecular weight. It is thought that excellent mechanical properties were exhibited.

  It is surprising that such an effect was achieved by slightly changing the charging ratio of the comonomer (B) in the polymerization of the macromonomer copolymer.

  As exemplified above, it was revealed that a film having excellent transparency and flexibility and excellent tear resistance can be obtained by molding a macromonomer copolymer having a peak top molecular weight of a predetermined value or more.

  The film of the present invention can be suitably used for design films, agricultural films, in-vehicle films, exterior films, architectural interior films, packaging materials, and the like.

Claims (4)

A macromonomer copolymer (Y) obtained by polymerizing a macromonomer (A) represented by the following general formula (1) and another comonomer (B) copolymerizable with the macromonomer (A): A resin composition comprising: the macromonomer copolymer (Y) having a peak top molecular weight (Mp) of 70,000 or more and 900,000 or less.
(Wherein R and R ^{1 to} R ⁿ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. X _{1 to} X _n are each independently a hydrogen atom or (M is a methyl group. Z is a terminal group. N is a natural number of 2 to 10,000.)   The resin composition according to claim 1, comprising the macromonomer copolymer (Y) in a content of 50% by mass or more.   A film obtained by molding the resin composition according to claim 1.   The film according to claim 3, wherein at least one surface is subjected to easy adhesion treatment.