JP2010189617A - Film for printing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film for printing which is a rubber-modified styrene-based resin film excellent in solvent resistance and directly printable and which is excellent in heat resistance, printability, mechanical strength, resistance to moisture absorption, film-forming ability and flexibility, and further, hardly adheres to a roller during film formation, and has superior appearance. <P>SOLUTION: The film for printing is created by forming a thermoplastic resin composition (I), which is obtained by blending 7-18 pts.mass of an inorganic filler (C) with 100 pts.mass in total, consisting of 25 to 75 mass% of a rubber-modified styrene-based resin (A) and 25 to 75 mass% of a polyamide-based resin (B). The component (A) comprises either a graft copolymer obtained by polymerizing a vinyl monomer in the presence of a rubber polymer or a mixture of the graft copolymer and a (co)polymer of the vinyl monomer. The vinyl monomer contains, in addition to an aromatic vinyl compound and a vinyl cyanide compound, a vinyl monomer with a functional group, in an amount equal to 0.1 to 1.2 mass% of the component (A), and the limiting viscosity (methyl ethyl ketone, 30°C) of the acetone-soluble part of the component (A) is 0.15 to 1.5 dL/g. From 5 to 30 pts.mass of the rubber polymer are included per 100 pts.mass of the composition (I). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a printing film.
In general, the term “film” refers to a thickness of 0.254 mm (1/100 inch) or less, but the term “film” in the present invention includes a thicker “sheet”.

  Conventionally, when a printing layer is laminated on the surface of an ABS resin film, a transfer film made of a PET film having a printing layer applied to the surface in advance is heat-laminated, and then the PET film is peeled to remove the printing layer. (See Patent Document 1). The reason is that the ABS resin has low solvent resistance and cannot be directly printed on the ABS resin film. However, since the printing method using the transfer film requires a step of peeling the transfer film after transferring the printing layer, the manufacturing process is complicated, the transfer film becomes waste, and the cost increases. There is a risk that foreign matter may be mixed into the laminate in the manufacturing process.

  On the other hand, it is also conceivable to corona-treat the surface of the ABS resin film, form an anchor coat layer on the corona-treated surface, and apply a print layer to the anchor coat layer (see Patent Documents 2 and 3). However, in this printing method, a process for forming an anchor coat layer is added, so that the manufacturing process becomes complicated. Therefore, a method of printing directly on the ABS resin film has been desired.

  In addition, if a transparent resin layer such as an acrylic resin is laminated on the printed layer after applying a printed layer to the resin film, the resin film has sufficient heat resistance, sufficient mechanical strength and dimensional stability. However, the conventional ABS resin film cannot be said to have sufficient properties.

  Moreover, in the above-mentioned resin film, a problem has been found that the film may be lifted without being peeled off from a roll (for example, a cast roll: a cooling drum) during film formation, resulting in poor appearance of the film. It was. In particular, this problem is remarkable when the film forming temperature (roll temperature) is increased in order to obtain a film having excellent heat resistance.

JP 2005-178276 A JP 2007-210309 A JP 2007-211119 A

  The present invention is a directly printable rubber-modified styrenic resin film excellent in solvent resistance, excellent in heat resistance, printability, mechanical strength, moisture absorption resistance, film-forming property, flexibility, An object of the present invention is to provide a printing film that hardly adheres to a roll during film formation and has an excellent film appearance.

  As a result of diligent research to solve the above problems, the present inventors have formulated a predetermined amount of polyamide-based resin into a specific rubber-modified styrene-based resin, so that solvent resistance, heat resistance, printability, machine It has been found that a printing film that is excellent in mechanical strength, moisture absorption resistance, film-forming property, flexibility, etc. and can be printed directly is obtained. It was also found that by blending a predetermined amount of the inorganic filler, the film was prevented from sticking to the roll during film formation, and a printing film excellent in film formation appearance was obtained.

That is, according to the present invention, the following invention is provided.
[I] 7 to 18 parts by mass of inorganic filler (C) is added to 100 parts by mass in total of 25 to 75% by mass of rubber-modified styrene resin (A) and 25 to 75% by mass of polyamide resin (B). A printing film formed by molding the thermoplastic resin composition (I),
The component (A) is a graft copolymer (A1) obtained by polymerizing the vinyl monomer (b1) in the presence of the rubbery polymer (a), or the graft copolymer (A1). And a mixture of (co) polymer (A2) of vinyl monomer (b2),
The vinyl monomer (b1) and the vinyl monomer (b2) both contain an aromatic vinyl compound and a vinyl cyanide compound as essential monomer components,
At least one of the vinyl monomer (b1) and the vinyl monomer (b2) further includes a hydroxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, a substituted or unsubstituted amino group-containing compound. Containing at least one functional group-containing vinyl monomer selected from the group consisting of a saturated compound, a carboxyl group-containing unsaturated compound, an acid anhydride group-containing unsaturated compound and an oxazoline group-containing unsaturated compound,
The content of the functional group-containing vinyl monomer in the component (A) is 0.1 to 1.2% by mass, with the total amount of the component (A) being 100% by mass,
The intrinsic viscosity (methyl ethyl ketone, 30 ° C.) of the component (A) soluble in acetone is 0.15 to 1.5 dl / g,
The thermoplastic resin composition (I) contains 5 to 30 parts by mass of a rubbery polymer (a) with respect to 100 parts by mass in total of the component (A) and the component (B). .

  According to another aspect of the present invention, there is provided a decorative film in which a printing layer is laminated on at least one surface of the printing film. In the decorative film, a transparent resin layer may be laminated on the print layer.

  According to still another aspect of the present invention, there is provided a method for producing a decorative film in which a printing layer is directly laminated on at least one surface of the printing film without performing an anchor coat treatment.

  According to the present invention, solvent resistance, heat resistance, printability, mechanical strength, moisture absorption resistance, film-forming property, flexibility can be obtained by blending a specific amount of polyamide resin with a specific rubber-modified styrene resin. A printing film having excellent properties can be obtained, and the printing film can be directly printed without being subjected to anchor coating. Further, by blending a predetermined amount of the inorganic filler, the film is prevented from sticking to the roll during film formation, and a printing film having an excellent film appearance can be obtained.

  The present invention will be described in detail below. In the present specification, “(co) polymerization” means homopolymerization and copolymerization, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” Means acrylate and / or methacrylate.

First, the printing film of the present invention will be described.
The printing film of the present invention comprises a rubber-modified styrene resin (A) of 25 to 75% by mass and a polyamide resin (B) of 25 to 75% by mass in a total of 100 parts by mass, and an inorganic filler (C) 7 to It is obtained by molding a thermoplastic resin composition (I) containing 18 parts by mass.
Hereinafter, each component will be described in detail.

1. Component (A) (rubber-modified styrenic resin):
Component (A) used in the present invention is a graft copolymer (A1) obtained by polymerizing a vinyl monomer (b1) in the presence of a rubbery polymer (a), or the graft copolymer A rubber-modified styrenic resin composed of a mixture of the union (A1) and the (co) polymer (A2) of the vinyl monomer (b2). The (co) polymer (A2) is obtained by polymerizing the vinyl monomer (b2) in the absence of the rubbery polymer (a).

1-1. Rubber polymer (a):
The rubber polymer (a) is not particularly limited, and examples thereof include conjugated diene rubber polymers and non-conjugated diene rubber polymers. Examples of the conjugated diene rubbery polymer include polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, and hydrogenated products thereof. Non-conjugated diene rubbery polymers include, for example, ethylene / propylene copolymers, ethylene / propylene / nonconjugated diene copolymers, ethylene / 1-butene copolymers, ethylene / 1-butene / nonconjugated diene copolymers. Polymers, ethylene / 1-octene copolymers, ethylene / 1-octene / non-conjugated diene copolymers and other ethylene / α-olefin copolymer rubbers; acrylic rubbers; silicone rubbers; silicone / acrylic IPNs Rubber etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.
Of these rubber polymers (a), a conjugated diene rubber polymer is preferred in the present invention.

The gel content of the rubber polymer (a) is usually 20 to 99% by mass, preferably 30 to 98% by mass, and more preferably 40 to 98% by mass. When the gel content is in the above range, the balance between physical properties of film processability and impact resistance is excellent.
In addition, the said gel content rate can be calculated | required with the following method. First, 1 gram of the rubber polymer (a) is put into 20 ml of acetone (acetonitrile in the case of acrylic rubber), and stirred at 1,000 rpm for 2 hours under a temperature condition of 25 ° C. Thereafter, the mixture is centrifuged for 1 hour with a centrifuge (rotation speed: 22,000 rpm), the insoluble matter obtained by separating the insoluble matter and the soluble matter is weighed (the mass is defined as W1 gram), and the following formula is used. Calculated by
[Equation 1]
Gel content (mass%) = [W1 (g) / 1 (g)] × 100
The gel content is determined by appropriately selecting the type and amount of the monomer, the type and amount of the molecular weight regulator, the polymerization time, the polymerization temperature, the polymerization conversion rate, etc. during the production of the rubbery polymer (a). Adjusted.

1-2. Vinyl monomer (b1):
As the vinyl monomer (b1), an aromatic vinyl compound and a vinyl cyanide compound are used as essential components, and optionally, a hydroxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, a substituted or unsubstituted amino group. At least one functional group-containing vinyl monomer selected from the group consisting of a group-containing unsaturated compound, a carboxyl group-containing unsaturated compound, an acid anhydride group-containing unsaturated compound, and an oxazoline group-containing unsaturated compound is used. The By using these functional group-containing vinyl monomers, the compatibility between the component (A) and the component (B) of the present invention can be improved.
However, in the present invention, at least one of the vinyl monomer (b1) and the vinyl monomer (b2) needs to contain the functional group-containing vinyl monomer. When the monomer (b2) does not contain the functional group-containing vinyl monomer, the vinyl monomer (b1) needs to contain the functional group-containing vinyl monomer. In the present specification, the vinyl monomer (b1) not containing the functional group-containing vinyl monomer is referred to as vinyl monomer (b1-1) and the functional group-containing vinyl monomer. The vinyl monomer (b1) to be contained may be referred to as a vinyl monomer (b1-2).

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, Examples thereof include monobromostyrene, dibromostyrene, tribromostyrene, and fluorostyrene. Of these, styrene and α-methylstyrene are preferred. Moreover, these compounds can be used individually by 1 type or in combination of 2 or more types.

  Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, α-chloro (meth) acrylonitrile and the like. Of these, acrylonitrile is preferred. Moreover, these compounds can be used individually by 1 type or in combination of 2 or more types.

  Examples of the hydroxyl group-containing unsaturated compound include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy-2- Examples include methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and hydroxystyrene. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of substituted or unsubstituted amino group-containing unsaturated compounds include aminoethyl acrylate, aminoethyl methacrylate, aminopropyl methacrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, and N-vinyl. Examples include diethylamine, N-acetylvinylamine, acrylic amine, methacrylamine, N-methylacrylamine, acrylamide, N-methylacrylamide, and p-aminostyrene. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the acid anhydride group-containing unsaturated compound include unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline. These can be used individually by 1 type or in combination of 2 or more types.

  Further, the vinyl monomer (b1) may contain other copolymerizable monomers such as a (meth) acrylic acid ester and a maleimide compound in addition to the above.

  (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate and the like. These can be used individually by 1 type or in combination of 2 or more types. Of these, methyl methacrylate is preferred. When (meth) acrylic acid ester is used, the transparency of component (A) can be improved.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. These can be used individually by 1 type or in combination of 2 or more types. In order to introduce a maleimide monomer unit into the copolymer resin, maleic anhydride may be (co) polymerized and post-imidized. When the maleimide compound is used, the heat resistance of the component (A) can be improved.

  The vinyl monomer (b1) is selected depending on the purpose, application, etc., and the type and amount used. The total amount of the aromatic vinyl compound and the vinyl cyanide compound is the vinyl monomer (b1). ) It is usually 50 to 100% by mass, preferably 70 to 100% by mass, and more preferably 80 to 100% by mass with respect to 100% by mass of the total amount. Content of the said functional group containing vinylic monomer is 0-50 mass% normally with respect to 100 mass% of vinyl monomers (b1) whole quantity, Preferably it is 0-30 mass%, More preferably, it is 0-20. % By mass. The use ratio of the aromatic vinyl compound and the vinyl cyanide compound (aromatic vinyl compound / vinyl cyanide compound) is usually 40 to 95% by mass to 5 to 60% by mass when the total of these is 100% by mass. Preferably, it is 50-90 mass% / 10-50 mass%, More preferably, it is 55-85 mass% / 15-45 mass%.

1-3. Vinyl monomer (b2):
As the vinyl monomer (b2), an aromatic vinyl compound and a vinyl cyanide compound are used as essential components, and optionally, a hydroxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, a substituted or unsubstituted amino group. At least one functional group-containing vinyl monomer selected from the group consisting of a group-containing unsaturated compound, a carboxyl group-containing unsaturated compound, an acid anhydride group-containing unsaturated compound, and an oxazoline group-containing unsaturated compound is used. The
However, in the present invention, at least one of the vinyl monomer (b1) and the vinyl monomer (b2) needs to contain the functional group-containing vinyl monomer. When the monomer (b1) does not contain the functional group-containing vinyl monomer, the vinyl monomer (b2) needs to contain the functional group-containing vinyl monomer. In this specification, the vinyl monomer (b2) not containing the functional group-containing vinyl monomer, the vinyl monomer (b2-1), and the functional group-containing vinyl monomer The vinyl monomer (b2) to be contained may be referred to as a vinyl monomer (b2-2).

  Examples of the aromatic vinyl compound, vinyl cyanide compound, functional group-containing vinyl monomer, and other copolymerizable monomers used as the vinyl monomer (b2) include the above vinyl monomers. Any of those described above for body (b1) can be used.

  The type and amount of the vinyl monomer (b2) is selected according to the purpose, application, etc. The total amount of the aromatic vinyl compound and the vinyl cyanide compound is the vinyl monomer (b2). ) It is usually 50 to 100% by mass, preferably 70 to 100% by mass, and more preferably 80 to 100% by mass with respect to 100% by mass of the total amount. The content of the functional group-containing vinyl monomer is usually 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 20% with respect to 100% by mass of the total amount of the vinyl monomer (b2). % By mass. The use ratio of the aromatic vinyl compound and the vinyl cyanide compound (aromatic vinyl compound / vinyl cyanide compound) is usually 40 to 95% by mass to 5 to 60% by mass when the total of these is 100% by mass. Preferably, it is 50-90 mass% / 10-50 mass%, More preferably, it is 55-85 mass% / 15-45 mass%.

1-4. Production method of rubber-modified styrenic resin (A):
Component (A) used in the present invention is a graft copolymer (A1) or a mixture of the graft copolymer (A1) and a (co) polymer (A2) of a vinyl monomer (b2). Consists essentially of

The graft copolymer (A1) may be the following component (A1-1) and / or the following component (A1-2).
Component (A1-1): Vinyl monomer (b1-1) containing an aromatic vinyl compound and a vinyl cyanide compound as essential components in the presence of the rubbery polymer (a) (however, a functional group-containing vinyl) Graft copolymer obtained by polymerizing a non-containing monomer.
Component (A1-2): aromatic vinyl compound and vinyl cyanide compound, hydroxyl group-containing unsaturated compound, epoxy group-containing unsaturated compound, substituted or unsubstituted amino in the presence of rubbery polymer (a) An essential component is at least one functional group-containing vinyl monomer selected from the group consisting of a group-containing unsaturated compound, a carboxyl group-containing unsaturated compound, an acid anhydride group-containing unsaturated compound, and an oxazoline group-containing unsaturated compound Graft copolymer obtained by polymerizing the vinyl monomer (b1-2) contained as

The (co) polymer (A2) may be the following component (A2-1) and / or the following component (A2-2).
Component (A2-1): Vinyl monomer (b2-1) containing an aromatic vinyl compound and a vinyl cyanide compound as essential components in the absence of the rubbery polymer (a) (however, containing a functional group) (Co) polymer obtained by polymerizing a vinyl-based monomer.
Component (A2-2): In the absence of the rubbery polymer (a), an aromatic vinyl compound and a vinyl cyanide compound, a hydroxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, a substituted or unsubstituted compound Essentially at least one functional group-containing vinyl monomer selected from the group consisting of amino group-containing unsaturated compounds, carboxyl group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, and oxazoline group-containing unsaturated compounds A (co) polymer obtained by polymerizing the vinyl monomer (b2-2) contained as a component.

  In the component (A) of the present invention, at least one of the vinyl monomer (b1) and the vinyl monomer (b2) needs to contain a functional group-containing vinyl monomer. Therefore, the component (A) needs to contain at least one of the component (A1-2) and the component (A2-2) as an essential component.

  Thus, when the component (A1) is the component (A1-2) or a mixture of the component (A1-1) and the component (A1-2), the component (A) is the component (A2). ) May not be contained, and when the component (A2) is contained, the component (A2) may be the component (A2-1) and / or the component (A2-2).

  Moreover, when the said component (A1) is the said component (A1-1), a component (A) contains the said component (A2), the said component (A2) is the said component (A2-2), or It is necessary to be a mixture of the component (A2-1) and the component (A2-2).

  The graft copolymer (A1) usually includes a graft copolymer in which a (co) polymer of the vinyl monomer (b1) is grafted to the rubber polymer (a), and a rubber polymer. The (co) polymer of the vinyl monomer (b1) not grafted to (a) is included. However, the graft copolymer (A1) may contain a rubbery polymer (a) in which the (co) polymer of the vinyl monomer (b1) is not grafted.

  The content of the functional group-containing vinyl monomer in the component (A) is 0.1 to 1.2% by mass, preferably 0.1 to 1.2% by mass, with the total amount of the component (A) being 100% by mass. 1.1 mass%, More preferably, it is 0.2-1.0 mass%, Most preferably, it is 0.2-0.9 mass%. Thereby, sufficient mechanical strength and dimensional stability are imparted to the printing film of the present invention. The functional group-containing vinyl monomer may be derived from any of the components (A1) and (A2) as long as the content is satisfied.

  The manufacturing method of the said graft copolymer (A1) is not specifically limited, For example, a well-known polymerization method, for example, emulsion polymerization, solution polymerization, block polymerization, suspension polymerization, etc. are mentioned. Of these, emulsion polymerization is preferred. The use ratio of the rubber polymer (a) and the vinyl monomer (b1) (rubber polymer (a) / vinyl monomer (b1)) was 100% by mass. In this case, it is usually 5 to 80% by mass / 20 to 95% by mass, preferably 5 to 70% by mass / 30 to 95% by mass, and more preferably 10 to 65% by mass / 35 to 90% by mass.

  When the graft copolymer (A1) is produced by emulsion polymerization, a polymerization initiator, an emulsifier, a chain transfer agent (molecular weight regulator), an electrolyte, water, and the like are used. In addition, although an emulsifier and a chain transfer agent may not be used depending on the situation, they are usually used.

As polymerization initiators, cumene hydroperoxide, diisopropylbenzene hydroperoxide, benzoyl peroxide, lauroyl peroxide, potassium persulfate, azobisisobutyronitrile, tert-butylperoxylaurate, tert-butylperoxymono And carbonate. These can be used individually by 1 type or in combination of 2 or more types.
The polymerization initiator can be added to the reaction system all at once or continuously. Moreover, the usage-amount of the said polymerization initiator is 0.1-5 mass parts normally, when the whole quantity of the said vinylic monomer is 100 mass parts, Preferably it is 0.5-2 mass parts.

Emulsifiers include alkyl sulfonates such as alkane sulfonate, alkylbenzene sulfonate, and alkyl naphthalene sulfonate; Rosinates such as alkali metal salts (sodium salt or potassium salt) of rosin acid (usually mainly abietic acid) such as sulfates of higher alcohols, higher aliphatic carboxylates, phosphates, etc. Anionic surfactants; nonionic surfactants and the like.
The usage-amount of the said emulsifier is 0.1-5 mass parts normally, when the whole quantity of the said vinylic monomer (b1) is 100 mass parts, Preferably it is 0.1-3 mass parts.

  Examples of chain transfer agents include mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, tetraethylthiuram sulfide, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, terpinolene, etc. Is mentioned. These can be used individually by 1 type or in combination of 2 or more types. Moreover, the usage-amount of the said chain transfer agent is 0.01-5 mass parts normally, when the whole quantity of the said vinylic monomer (b1) is 100 mass parts, Preferably it is 0.05-3 mass parts. is there.

  The polymerization temperature for producing the graft copolymer (A1) by emulsion polymerization is usually 30 to 95 ° C, preferably 40 to 90 ° C. In order to recover the graft copolymer (A1) from the latex obtained by emulsion polymerization, usually an inorganic salt such as calcium chloride, magnesium sulfate or magnesium chloride; an acid such as sulfuric acid, hydrochloric acid, acetic acid, citric acid or malic acid It is performed by adding a coagulant such as. Thereafter, the solidified graft copolymer (A1) is obtained as a powder by washing with water and drying.

  Moreover, the said graft copolymer (A1) can be manufactured by solution polymerization, block polymerization, suspension polymerization, etc., for example. In the case of solution polymerization, usually a rubber polymer and a vinyl monomer are mixed with an aromatic hydrocarbon such as toluene or ethylbenzene; ketones such as methyl ethyl ketone; an inert polymerization solvent such as acetonitrile, dimethylformamide, or N-methylpyrrolidone. And may be polymerized in the presence of a polymerization initiator, or may be thermally polymerized in the absence of a polymerization initiator.

  The (co) polymer (A2) can be produced in the same manner as the above-described method for producing the graft copolymer (A1) except that the rubbery polymer (a) is not used. It can be obtained by polymerization, solution polymerization, emulsion polymerization, suspension polymerization or the like.

1-5. Physical properties of rubber-modified styrene resin:
The graft ratio of the graft copolymer (A1) is usually 20 to 170%, preferably 20 to 150%, more preferably 30 to 150%. When the graft ratio is less than 20%, a flow mark may be generated on the surface when formed into a film, and the mechanical strength may not be sufficient. On the other hand, when the graft ratio exceeds 170%, the viscosity of the graft copolymer (A1) increases, and it may be difficult to reduce the thickness.
The graft ratio of the graft copolymer (A1) is determined based on the type and amount of chain transfer agent used in the production, the type and amount of polymerization initiator, the method of adding the monomer component and the addition time during polymerization. It can adjust by selecting etc. suitably.

In addition, the said graft ratio can be calculated | required by a following formula.
[Equation 2]
Graft ratio (mass%) = {(S−T) / T} × 100
In the above formula, 1 g of graft copolymer was charged into 20 ml of acetone (acetonitrile when the rubbery polymer is an acrylic rubber), and shaken with a shaker for 2 hours under a temperature condition of 25 ° C. The mass (g) of insoluble matter obtained by centrifuging for 60 minutes with a centrifuge (rotation speed: 23,000 rpm) under a temperature condition of 5 ° C. and separating the insoluble matter and the soluble matter. , T is the mass (g) of the rubbery polymer contained in 1 gram of the graft copolymer. The mass of the rubbery polymer can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

The intrinsic viscosity [η] (measured at 30 ° C. using methyl ethyl ketone as a solvent) of the graft copolymer (A1) soluble in acetone (acetonitrile when the rubbery polymer is an acrylic rubber) is usually 0. .15 to 1.5 dl / g, preferably 0.2 to 1.2 dl / g, more preferably 0.2 to 0.8 dl / g. When the intrinsic viscosity [η] is less than 0.15, heat resistance and mechanical strength may not be sufficient. If the intrinsic viscosity [η] exceeds 1.5, the film forming property may not be sufficient.
The intrinsic viscosity [η] of the (co) polymer (A2) (measured at 30 ° C. using methyl ethyl ketone as a solvent) is usually 0.15 to 1.5 dl / g, preferably 0.2 to 1. .2 dl / g, more preferably 0.2 to 0.9 dl / g. When the intrinsic viscosity [η] is less than 0.15, heat resistance and mechanical strength may not be sufficient. If the intrinsic viscosity [η] exceeds 1.5, the film forming property may not be sufficient.

The intrinsic viscosity [η] was measured by the following method. First, the soluble part of the graft copolymer (A1) or the (co) polymer (A2) was dissolved in methyl ethyl ketone to prepare five different concentrations. The intrinsic viscosity [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.
The intrinsic viscosity can be adjusted by appropriately selecting the type and amount of chain transfer agent used during production, the type and amount of polymerization initiator, the polymerization temperature, and the like.

  The content of the rubber-like polymer (a) in the rubber-modified styrene resin according to the present invention is preferably 5 to 80% by mass, more preferably 5 to 70% by mass, based on 100% by mass of the entire rubber-modified styrene resin. %, More preferably 10 to 65% by mass.

2. Component (B) (polyamide resin):
Examples of the component (B) used in the present invention include a polyamide obtained by polycondensation of a lactam having three or more members, a polymerizable ω-amino acid, or a dibasic acid and a diamine. Specifically, polymers such as ε-caprolactam, aminocaproic acid, enanthractam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidone, hexamethylenediamine, nonamethylene Obtained by polycondensation with diamines such as diamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine, and dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecanedioic acid, and glutaric acid. Polymers or copolymers thereof, for example nylon 4, 6, 7, 8, 11, 12, 6.6, 6.9, 6.10, 6.11, 6.12, 6T, 6/6. 6, 6/12, 6 / 6T, 6T / 6I, MXD6 and the like. These compounds may be used alone or in combination of two or more.

  The terminal of the polyamide resin used in the present invention may be sealed with a carboxylic acid or an amine, and a polyamide resin sealed with a carboxylic acid or amine having 6 to 22 carbon atoms is particularly desirable. Examples of the carboxylic acid used for sealing include aliphatic monocarboxylic acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples of the amine used for sealing include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine. The amount of carboxylic acid or amine used for sealing is preferably about 30 μeq / g.

  In addition, the polyamide resin used in the present invention needs to have a polymerization degree within a certain range, that is, a relative viscosity. The relative viscosity of the polyamide-based resin is usually 2.0 to 4.0 as a value measured at a concentration of 1% in 98% sulfuric acid and a temperature of 25 ° C. according to JIS-K6810. If the relative viscosity is lower than 2.0, the mechanical strength may decrease. On the other hand, if the relative viscosity is higher than 4.0, the film forming property may be deteriorated. Particularly preferred polyamides in the present invention include nylon 6, copolymer nylon 6/66, and nylon 66 from the viewpoint of heat resistance, mechanical strength, and film-forming property.

3. Component (C) (inorganic filler):
As the inorganic filler as the component (C) used in the present invention, a known inorganic filler can be used, and the shape is not particularly limited, and any of fibrous, plate-like, needle-like, spherical, powder, etc. It may be a shape. The types of inorganic fillers are glass fiber, carbon fiber, talc, mica, glass flake, wollastonite, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, glass beads, balloon, calcium carbonate, silica, Examples include kaolin, clay, carbon black, titanium oxide, barium sulfate, zinc oxide, and magnesium hydroxide, and these can be used alone or as a mixture of two or more. The inorganic filler is preferably glass fiber, mica, talc, or wollastonite because it is excellent in the balance of strength and surface appearance of the printing film and is easily available.

As the inorganic filler (C) in the present invention, talc is preferably used. Talc is a kind of clay mineral of hydrous magnesium silicate, and its composition is (MgO) x (SiO ₂ ) y · zH ₂ O (x, y, z are positive values), typically [(MgO) ₃ (SiO ₂ ) ₄ H ₂ O]. A part of Mg in talc may be substituted with a divalent metal ion such as Ca ²⁺ . The particle size of talc is not particularly limited, but is usually 0.5 to 50 μm, preferably 1.0 to 25 μm, and more preferably 1.5 μm to 20 μm as an average particle size by a laser scattering method. When the average particle diameter of talc is less than 0.5 μm, the dispersibility of talc is insufficient and the film appearance may be insufficient. On the other hand, if the average particle size of talc exceeds 50 μm, the film appearance may be insufficient.

3. Thermoplastic resin composition (I):
The thermoplastic resin composition (I) of the present invention is obtained by mixing and melting and kneading the component (A), the component (B) and the component (C) at a predetermined blending ratio.

  The component (A) is useful for imparting moisture absorption resistance to the printing film of the present invention, and the blending amount is 25 to 75, with the total of the components (A) and (B) being 100% by mass. It is mass%, Preferably it is 30-70 mass%, More preferably, it is 30-65 mass%. When the amount is less than 25% by mass, the moisture absorption resistance is inferior, and when it exceeds 75% by mass, the solvent resistance and heat resistance are inferior.

  The component (B) is useful for imparting solvent resistance and heat resistance to the printing film of the present invention. The amount of the component (A) and (B) is 100% by mass as the sum of the components (A) and (B). It is 25-75 mass%, Preferably it is 30-70 mass%, More preferably, it is 35-70 mass%. When the blending amount is less than 25% by mass, the solvent resistance and heat resistance are inferior, and when it exceeds 75% by mass, the hygroscopic resistance is inferior.

  The content of the rubber-like polymer (a) in the thermoplastic resin composition (I) according to the present invention is 5 to 30 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B). Preferably it is 10-30 mass parts, More preferably, it is 10-22 mass parts. When the content of the rubbery polymer (a) is in this range, the printing film has sufficient mechanical strength and film forming property.

  The component (C) is useful for preventing the film from sticking to the roll during film formation, and giving an excellent film-forming appearance to the printing film of the present invention. ) And (B) in a total of 100 parts by mass, 7 to 18 parts by mass, preferably 7 to 15 parts by mass, and more preferably 8 to 12 parts by mass. If the blending amount is less than 7 parts by mass, the initial purpose cannot be achieved, and if it exceeds 15 parts by mass, the solvent resistance (cracking property) of the film is poor. Since the component (C) can prevent the film from sticking to the roll during film formation, the film forming temperature (roll temperature) can be increased in the present invention. As a result, a film with more excellent heat resistance (heating elongation rate) can be obtained.

  In addition, the thermoplastic resin composition (I) of the present invention includes a nucleating agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a flame retardant, an anti-aging agent, a plasticizer, an antibacterial agent, and coloring as necessary. Various additives such as an agent can be contained within a range not impairing the object of the present invention.

  In the thermoplastic resin composition (I) of the present invention, each component is mixed in a predetermined blending ratio with a tumbler mixer, a Henschel mixer, etc., and then a single screw extruder, twin screw extruder, Banbury mixer, kneader, roll, feeder. It can be manufactured by melt-kneading under suitable conditions using a mixer such as a ruder. A preferred kneader is a twin screw extruder. Furthermore, when each component is kneaded, each component may be kneaded in a lump or may be kneaded in multiple stages. In addition, after knead | mixing with a Banbury mixer, a kneader, etc., it can also pelletize with an extruder. Moreover, it is more preferable to supply the fibrous thing among fillers from the middle of an extruder with a side feeder in order to prevent the cutting | disconnection in kneading | mixing. The melt kneading temperature is usually 200 to 300 ° C, preferably 220 to 280 ° C.

  The printing film according to the present invention can be produced by various molding methods such as calendar molding, inflation molding, T-die extrusion molding, etc., using the thermoplastic resin composition (I) as a molding material. Of these, T-die extrusion is preferred.

  T-die extrusion molding is a method in which a molten resin is discharged from a T-die to form a soft film, and is then extruded onto a cast roll with an air knife and brought into surface contact and solidified by cooling. The number of cast rolls is not particularly limited. Two or more may be used. In addition, examples of the arrangement method of the cast roll include, but are not limited to, a linear type, a Z type, and an L type. Further, the way of passing the molten resin extruded from the opening of the die through the cast roll is not particularly limited.

  The degree of adhesion of the extruded sheet-like thermoplastic resin to the cast roll varies depending on the temperature of the cast roll. When the temperature of the cast roll is raised, the adhesion is improved. However, when the temperature is raised too much, the sheet-like thermoplastic resin is not peeled off from the cast roll, and there is a possibility that a problem of sticking to the cast roll may occur.

  The thickness of the printing film according to the present invention is usually 50 to 2500 μm, preferably 70 to 1400 μm, more preferably 70 to 1000 μm, and particularly preferably 70 to 500 μm.

The printing film according to the present invention comprises a thermoplastic resin composition (I) comprising the above component (A), the above component (B) and the above component (C), and a heat having a composition excluding the above component (C). A laminated structure in which the thermoplastic resin composition (II) is disposed at least on the side in contact with the cast roll, that is, (I) / (II) or (I) / (II) A stacked structure of / (I) can also be used.

A printing layer (design layer) can be provided on the surface of the printing film according to the present invention by direct printing. The printing layer can be formed by various printing methods. The ink used for printing may be either water-based ink or non-water-based ink such as solvent-based ink.
Examples of the direct printing method include known printing methods such as offset printing, gravure printing, screen printing, and ink jet printing.

Since the printing film according to the present invention is excellent in solvent resistance, a printing layer can be directly formed on the surface of the film using a solvent-based ink without forming an anchor coat layer.
As another method, as described in JP-A-2005-178276, a printed layer can be formed by a method of transferring a design from a PET film on which a design has been printed in advance to the surface of the printing film of the present invention.

A transparent resin layer can be laminated on the printing layer of the printing film of the present invention according to a known method.
The transparent resin layer is usually composed of a molded resin layer of a thermoplastic resin. The thermoplastic resin is not particularly limited as long as it is transparent. For example, acrylic resin, polycarbonate resin, polypropylene resin, polyethylene resin, polyester resin, polystyrene resin, ABS resin, polyamide resin, and four fluororesin are used. Ethylene fluoride resin, ethylene tetrafluoride-hexafluoropropylene copolymer resin, ethylene tetrafluoride-ethylene copolymer resin, ethylene tetrafluoride-perfluorovinyl ether copolymer resin, ethylene trifluoride chloride resin, vinylidene fluoride Resins can be used. Of these thermoplastic resins, an acrylic resin is preferably used from the viewpoint of adhesion to the printing layer. As the acrylic resin, those containing methyl methacrylate as a constituent monomer component are preferable.

  The transparent resin layer can be laminated by thermally laminating the thermoplastic resin previously formed into a film shape or a sheet shape so as to cover the printing layer. As another method, the thermoplastic resin may be laminated by extrusion lamination so as to cover the printing layer of the printing film on which the printing layer is formed.

  The thickness of the transparent resin layer is usually 20 μm to 2000 μm, preferably 50 μm to 1500 μm, and more preferably 50 μm to 1000 μm. If the thickness is less than 20 μm, surface roughness may occur due to the influence of the printed layer. When this thickness exceeds 2000 micrometers, a weight may increase or it may become economically disadvantageous.

  The printing film of the present invention thus obtained is a decorative film produced by printing in the fields of building materials, OA / home appliances, electric / electronics, miscellaneous goods, sanitary, automobiles, etc. It can be suitably used as a material.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited at all to the following Example, unless the summary is exceeded. In the examples, parts and% are based on mass unless otherwise specified.

(1) Evaluation method:
The measuring methods of various evaluation items in the following examples and comparative examples are shown below.

(1-1) Mass melt flow rate (MFR):
According to ISO1133, the measurement was performed under the conditions of a measurement temperature of 240 ° C. and a load of 98N. The unit of the measured value is g / 10 minutes.

(1-2) Heat resistance: Heat elongation rate:
The film before color-printing printing was cut into 1 inch width × 300 mm length, and a test sample suspended with a load of 500 g was left in a thermostatic bath maintained at 130 ° C. for 10 seconds, and measured 100 mm long (L0 ) Was measured and determined as L1 / L0 × 100 (%).

(1-3) Mechanical strength: film impact:
Using a pendulum film impact tester (film impact tester: manufactured by Yasuda Seiki Seisakusho), the film impact (before coating) of a 100 mm × 100 mm film was measured. The evaluation was performed under the conditions of an impact sphere radius: 6.35 mm and an additional weight: 1390 g. In addition, color printing was performed on one surface of the film using a curable solvent-based ink, and then the film was allowed to stand in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours to apply a printing layer. . Then, the film impact (after coating) from the coated surface was measured by the same method as described above. And the film impact retention rate was calculated | required according to the following formula.

(1-4) Solvent resistance (cracking property):
A test piece of 100 mm (MD) × 100 mm (TD) was cut out from the same coated film as described above, bent along the axis of symmetry in the MD direction, and then bent along the axis of symmetry in the TD direction. The bent specimen was reciprocated twice on each crease at a speed of 5 mm / sec using a manual crimping roll (2000 g) according to JIS-Z0237. Thereafter, the folds were expanded and returned to the original state, and the state of the test piece was visually observed. Evaluation was performed at n = 5 times. The judgment criteria are shown below.
◯: No creases are broken in all n = 5 times.
Δ: Some creases were broken.
X: The crease is broken in all of n = 5 times.

(1-5) Printability (print surface adhesion):
One surface of the film was color-printed using a curable solvent-based ink, and then left in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours to form a printing layer. Then, an adhesive tape having a width of 18 mm and a length of about 75 mm was affixed to the surface of the printed layer, and it was adhered with finger pressure and then peeled off at once. Whether the printed layer remained or not was visually observed and judged according to the following criteria. The adhesive tape was attached and peeled according to JIS-K5600-5-6.
○: Adhesion is good and there is no practical problem.
X: Print layer peeled off.

(1-6) Film forming property:
Evaluation was performed according to the following criteria when the film was formed.
○: A film can be stably formed, and a beautiful film with a uniform surface can be obtained.
Δ: The end of the film sometimes meanders or breaks.
X: A film cannot be stably formed, and a beautiful film with a nonuniform surface cannot be obtained.

(1-7) Film sticking followability (flexibility):
The film before color-printing printing cut into 300 mm width (MD) x 215 mm length (TD) was wound around the outer peripheral surface of a cylindrical product having a diameter of 9 cm and a height of 40 cm, and evaluated according to the following criteria. In addition, the MD direction was made to follow the circumferential direction of a cylindrical thing.
○: The entire film can be wound around a cylindrical object.
X: The whole film cannot be wound around a cylindrical object.

(1-8) Hygroscopicity (dimensional change rate):
The film before color-printing printing is cut into 15 mm width (MD) × 100 mm length (TD) and left in a constant temperature and humidity chamber (40 ° C. × 90%) for 24 hours, and the dimensional change rate of the film in the TD direction is shown below. Obtained according to the formula.

(1-9) Roll adhesiveness during film formation:
The sheet on the cast roll was visually evaluated during film formation.
○: The sheet-like thermoplastic resin peels off from the cast roll and does not wind around the cast roll.
X: The sheet-like thermoplastic resin is wound around the cast roll without peeling off from the cast roll.

(1-10) Film appearance:
The appearance of the sheet after film formation was visually evaluated.
○: There is no wrinkle and the cast roll surface is transferred.
X: There are wrinkles and the cast roll surface is not transferred.

(2-1) Component (A) (rubber-modified styrenic resin):
A polymer obtained by the polymerization method described in Table 1 and having a copolymerization ratio and physical property values described in Table 1 was used.

(2-2) Component (B) (polyamide resin):
B1: Nylon 6; NOVAMID 1015J (trade name: manufactured by Mitsubishi Engineering Plastics), relative viscosity 3.0 (98% sulfuric acid method).
B2: Nylon 6; NOVAMID 1020J (trade name: manufactured by Mitsubishi Engineering Plastics), relative viscosity 3.5 (98% sulfuric acid method).

(2-3) Component (C) (inorganic filler: talc):
C1: “Microace K-1” manufactured by Nippon Talc Co., Ltd. was used. This product had an average particle size D50 (laser diffraction method) of 8 μm and an apparent density (JIS-K5101) of 0.25 g / ml.
C2: “Microace P-3” manufactured by Nippon Talc Co., Ltd. was used. This product had an average particle diameter D50 (laser diffraction method) of 5 μm and an apparent density (JIS-K5101) of 0.16 g / ml.

(2-4) Additive:
D1: Calcium stearate; Ca-St (trade name: manufactured by Nitto Kasei Kogyo)
D2: Pentaerystole tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]; IRGANOX 1010 (trade name: manufactured by Ciba Specialty Chemicals Co., Ltd.)

Examples 1-12 and Comparative Examples 1-6:
After mixing each component described in each table with a Henschel mixer at the mixing ratio described in Table 2-1 to Table 2-3, using a twin screw extruder (manufactured by Nippon Steel Works, TEX44, barrel setting temperature 250 ° C.) Kneaded and pelletized. Using the obtained pellets, a film was produced by the following method.
First, using a film forming machine equipped with a T die (die width: 1400 mm, lip interval: 0.5 mm) and an extruder with a screw diameter of 65 mm, pellets are supplied to the extruder, and from the T die, the melting temperature Resin was discharged at 270 ° C. to obtain a soft film. Thereafter, the soft film was brought into surface contact with a cast roll set to a predetermined surface temperature with an air knife, and cooled and solidified to obtain a film. The evaluation results of the obtained film are shown in Tables 2-1 to 2-3.
The thickness of the film was measured using a thickness gauge (model “ID-C1112C, manufactured by Mitutoyo Co., Ltd.), and after 1 hour from the start of film production, the film was cut out, centered in the film width direction, and directed from the center to both ends The thickness was measured at intervals of 10 mm, and the average value was taken, and the value at the measurement point in the range of 20 mm from the edge of the film was removed from the calculation of the average value.

  The following are clear from Tables 2-1 to 2-3.

  Examples 1 to 12, which are printing films formed by molding the thermoplastic resin composition (I) containing the components (A), (B) and (C) of the present invention, adhere to the roll during film formation. It is difficult and excellent in film-forming appearance, and further excellent in film-forming properties, heat resistance, solvent resistance, printability, and moisture absorption resistance.

  Comparative Example 1 and Comparative Example 3 in which the blending amount of talc (component (C)) is small outside the range specified in the present invention are easy to stick to the roll during film formation, and the film-forming appearance is also inferior. Comparative Example 2 and Comparative Example 4 in which the blending amount of talc is outside the range specified in the present invention are inferior in solvent resistance (cracking property). The comparative example 5 which does not mix talc tends to stick to the roll during film formation, and is inferior in film formation appearance. Comparative Example 6 in which talc is not blended and the roll temperature is 30 ° C. is inferior in heat resistance.

Example 13:
A transparent resin film was thermocompression bonded to the printing surface of the film of Example 1 under the press conditions of 150 ° C., 20 kg / cm ² and 15 minutes to laminate a transparent resin layer to prepare a decorative film. As the transparent film, an acrylic resin film having a thickness of 50 μm made of a copolymer of methyl methacrylate / butyl acrylate / styrene = 81/16/3 (mass ratio, total of three components is 100 parts by mass) is used. It was. As a result, there was no problem in film forming properties, and a cosmetic film having a beautiful appearance was obtained.

Example 14:
A decorative film was prepared in the same manner as in Example 14 except that the film of Example 5 was used. As a result, there was no problem in film forming properties, and a cosmetic film having a beautiful appearance was obtained.

Claims (9)

Thermoplastic in which 7 to 18 parts by mass of inorganic filler (C) is blended with 100 parts by mass in total of 25 to 75% by mass of rubber-modified styrene resin (A) and 25 to 75% by mass of polyamide resin (B). A printing film formed by molding the resin composition (I),
The component (A) is a graft copolymer (A1) obtained by polymerizing the vinyl monomer (b1) in the presence of the rubbery polymer (a), or the graft copolymer (A1). And a mixture of (co) polymer (A2) of vinyl monomer (b2),
The vinyl monomer (b1) and the vinyl monomer (b2) both contain an aromatic vinyl compound and a vinyl cyanide compound as essential monomer components,
At least one of the vinyl monomer (b1) and the vinyl monomer (b2) further includes a hydroxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, a substituted or unsubstituted amino group-containing compound. Containing at least one functional group-containing vinyl monomer selected from the group consisting of a saturated compound, a carboxyl group-containing unsaturated compound, an acid anhydride group-containing unsaturated compound and an oxazoline group-containing unsaturated compound,
The content of the functional group-containing vinyl monomer in the component (A) is 0.1 to 1.2% by mass, with the total amount of the component (A) being 100% by mass,
The intrinsic viscosity (methyl ethyl ketone, 30 ° C.) of the component (A) soluble in acetone is 0.15 to 1.5 dl / g,
The thermoplastic resin composition (I) contains 5 to 30 parts by mass of a rubbery polymer (a) with respect to 100 parts by mass in total of the component (A) and the component (B). .   The printing film according to claim 1, wherein the inorganic filler (C) is talc.   The thermoplastic resin composition (I) contains 10 to 22 parts by mass of a rubbery polymer (a) with respect to 100 parts by mass in total of the component (A) and the component (B). 2. The printing film according to 2.   The printing film according to claim 1, wherein the rubbery polymer (a) is a conjugated diene rubber. The film for printing according to claim 1, wherein the component (A1) is the following component (A1-1) and / or the following component (A1-2).
Component (A1-1): Graft copolymer obtained by polymerizing a vinyl monomer (b1-1) comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of the rubbery polymer (a) Coalescence.
Component (A1-2): aromatic vinyl compound and vinyl cyanide compound, hydroxyl group-containing unsaturated compound, epoxy group-containing unsaturated compound, substituted or unsubstituted amino in the presence of rubbery polymer (a) Vinyl comprising at least one functional group-containing vinyl monomer selected from the group consisting of group-containing unsaturated compounds, carboxyl group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, and oxazoline group-containing unsaturated compounds A graft copolymer obtained by polymerizing the monomer (b1-2). The film for printing according to claim 1, wherein the component (A2) is the following component (A2-1) and / or the following component (A2-2).
Component (A2-1): obtained by polymerizing a vinyl monomer (b2-1) comprising an aromatic vinyl compound and a vinyl cyanide compound in the absence of the rubbery polymer (a) (co-polymer) ) Polymer.
Component (A2-2): In the absence of the rubbery polymer (a), an aromatic vinyl compound and a vinyl cyanide compound, a hydroxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, a substituted or unsubstituted compound Consists of at least one functional group-containing vinyl monomer selected from the group consisting of amino group-containing unsaturated compounds, carboxyl group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, and oxazoline group-containing unsaturated compounds (Co) polymer obtained by polymerizing vinyl monomer (b2-2).   A decorative film comprising a printing layer laminated on at least one surface of the printing film according to claim 1.   The decorative film according to claim 7, wherein a transparent resin layer is laminated on the printed layer.   The manufacturing method of the decorative film which laminates | stacks a printing layer directly on at least 1 surface of the printing film in any one of Claims 1-6, without performing an anchor-coat process.