JP2021075600A - Resin composition for film molding and film composed of the resin composition - Google Patents

Abstract

To provide a film that has excellent flexibility and rupture elongation and a high melting point, and has excellent adhesion to a printed layer and an adhesive without pretreatment such as corona treatment.SOLUTION: A resin composition for film molding contains acrylic resin (A), styrenic elastomer (B) and polyolefin resin (C). When the total content of the (A), (B) and (C) is 100 mass%, the acrylic resin (A) content is 15 mass% or more and the styrenic elastomer (B) content is 10-55 mass%.

Description

In the present invention, a resin composition for film molding, a film made of the resin composition, an adhesive film having an adhesive layer laminated on the film, a decorative film having a printing layer laminated on the film, and an adhesive layer on the printing layer side of the decorative film. The present invention relates to a laminated cosmetic adhesive film.

As a decorative material used for interior / exterior materials and fittings of buildings, or for surface makeup of furniture, it is well known that a decorative film with printing or coloring is attached on a base material such as wood plywood or steel plate. As a base material for the decorative film, a paper or plastic film is generally used. Further, the plastic film is generally used as the base film of the adhesive tape typified by the tape for the semiconductor manufacturing process.

The plastic film used for such applications is suitable for suppressing problems such as film breakage during handling and transportation of the film in the process of laminating the printing layer and the step of laminating the adhesive layer. It is required to have flexible flexibility and elongation.
Further, particularly when used for a semiconductor manufacturing process, the semiconductor manufacturing process includes an expanding step of stretching the adhesive tape and widening the spacing between the chips arranged on the tape, so that the film is flexible enough to stretch. It is important that it has the property and does not break.

As the material of this plastic base film, there are many cases where a vinyl chloride resin having excellent designability, adhesiveness, adhesion to an adhesive, and flexibility is used, but incineration gas treatment is required. In recent years, polyolefin-based resins have been widely used.

However, when a polyolefin resin is used, it is difficult to master it because surface treatment such as corona treatment or pretreatment such as provision of a primer layer is required when laminating the printing layer or the adhesive layer. There is a problem that the number of processes increases.

Acrylic resin can be mentioned as one of the resins that does not have a problem of incineration gas and does not require pretreatment, and films and sheets made of the resin composition have been proposed. (Patent Documents 1 to 3)
Further, a method of adding a styrene-based elastomer for the purpose of imparting flexibility to a film made of an acrylic resin and imparting a good appearance has been proposed (Patent Documents 4 to 5).

However, Patent Documents 1 to 3 relate to a film made of only an acrylic resin, and the flexibility of the obtained film and the elongation at break are not compatible with each other. In Patent Documents 4 to 5, it is attempted to achieve both flexibility and appearance by using an acrylic resin and a styrene elastomer in combination, and although it has flexibility, sufficient elongation at break cannot be obtained. .. Further, since the films described in these patent documents do not have a component having a high melting point, there is room for improvement not only in terms of flexibility and elongation at break, but also in terms of heat resistance.

Japanese Unexamined Patent Publication No. 08-48014 Japanese Unexamined Patent Publication No. 09-31287 JP-A-2007-56226 Japanese Unexamined Patent Publication No. 2004-323769 JP-A-2018-162334

In view of such conventional problems, the present invention has excellent flexibility, elongation at break, high melting point, and a film having good adhesion to a printing layer or an adhesive without pretreatment such as corona treatment. It is an object of the present invention to provide a resin composition for film molding capable of obtaining the above.
Further, the present invention can be used as a base film for an adhesive film or a decorative film, and these adhesive films and the like are suitably used for tapes for semiconductor manufacturing processes, interior and exterior applications for buildings, and further for decoration of automobiles. It is also an object of the present invention to provide a film obtained from the above-mentioned resin composition for film molding, which can be used.

As a result of diligent studies to solve the above problems, the present inventors have found a resin composition containing a predetermined blending amount of an acrylic resin, a polyolefin resin, and a styrene elastomer, and have completed the present invention. It was.
That is, the gist of the present invention is as follows.

[1] When the acrylic resin (A), the styrene elastomer (B) and the polyolefin resin (C) are contained, and the total amount of the above (A), (B) and (C) is 100% by mass. A resin composition for film molding, wherein the content of the acrylic resin (A) is 15% by mass or more, and the content of the styrene elastomer (B) is 10 to 55% by mass.
[2] The description in [1], wherein the content of the acrylic resin (A) is 15 to 65% by mass, and the content of the polyolefin resin (C) is 10 to 55% by mass. Resin composition for film molding.
[3] The resin composition for film molding according to [1], wherein the polyolefin-based resin (C) has a melting point between 100 and 240 ° C.
[4] A film obtained by molding the resin composition for film molding according to [1] to [3], wherein the tensile elongation at break is 50% or more.
[5] The film according to [4], which has a tensile elastic modulus of 50 to 1000 MPa.
[6] An adhesive film obtained by laminating an adhesive layer on at least one side of the film according to [4] or [5].
[7] A decorative film obtained by laminating a printing layer on at least one side of the film according to any one of [4] to [6].
[8] A cosmetic adhesive film obtained by further laminating an adhesive layer on the print layer side of the decorative film according to [7].

The resin composition for film molding of the present invention has excellent flexibility, elongation at break, and high melting point, and has good adhesion to a printing layer and an adhesive without pretreatment such as corona treatment. Film can be obtained. Further, since the film obtained from the resin composition for film molding has excellent adhesion to an adhesive or a printing layer, the film can be suitably used as a base film for an adhesive film or a decorative film, and also. , These adhesive films and decorative films can be suitably used for semiconductor manufacturing process tapes, building interior / exterior applications, and automobile decoration applications.

The present invention will be described in detail below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof. In addition, when the expression "-" is used in this specification, it shall be used as an expression including numerical values or physical property values before and after the expression.

The resin composition for film molding of the present invention contains an acrylic resin (A), a styrene elastomer (B) and a polyolefin resin (C), and the total amount of the above (A), (B) and (C). Is a resin composition for film molding in which the content of the acrylic resin (A) is 15% by mass or more and the content of the styrene elastomer (B) is 10 to 55% by mass when the content is 100% by mass.

<Resin composition for film molding>
The resin composition for film molding of the present invention (hereinafter, also referred to as "resin composition of the present invention") is a resin composition used for molding and obtaining a film, and is an acrylic resin (A) or a styrene-based resin. When the elastomer (B) and the polyolefin resin (C) are contained and the total amount of the (A), (B) and (C) is 100% by mass, the content of the acrylic resin (A) is 15% by mass. % Or more, and the content of the styrene-based elastomer (B) is 10 to 55% by mass.

By blending a predetermined amount of the acrylic resin (A), it is possible to impart good adhesion to the printing layer or the adhesive layer to the obtained film.
By blending a predetermined amount of the styrene-based elastomer (B), it is possible to uniformly disperse the acrylic resin in the obtained film and impart flexibility.
By blending a predetermined amount of the polyolefin resin (C), it becomes possible to impart flexibility and heat resistance to the obtained film.

The resin composition may be a single layer or a multi-layer film having a layer composed of the resin composition on at least one of the front and back surfaces.
Further, in this resin composition, depending on the performance required for the obtained film, an antioxidant, an antioxidant, a neutralizing agent, a lubricant, an antiblocking agent, a plasticizer, a heat stabilizer, and a light stabilizer are added. Agents, dyes and pigments, crystal nucleating agents, ultraviolet absorbers, fillers, inorganic fillers that impart rigidity, elastomers other than the styrene-based elastomer (B) used in the present invention for imparting flexibility, and the like are used in the present invention. It may be used as long as the effect is not impaired.

As the ultraviolet absorber, known ones can be used, and examples thereof include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a triazine-based ultraviolet absorber. Above all, it is preferable to use a benzotriazole-based ultraviolet absorber in order to reduce the coloring of the product.
Further, the molecular weight of the ultraviolet absorber is more preferably in the range of 380 to 1000, preferably in the range of 400 to 800. By setting the molecular weight in the above range, it is possible to suppress the bleed-out of the ultraviolet absorber.

As the light stabilizer, known ones can be used, and examples thereof include hindered amine-based light stabilizers.

Known antistatic agents can be used, but polymer-type antistatic agents may be used in order to impart long-term antistatic properties to the film and suppress defects caused by bleeding out to the surface. preferable.

As the polymer type antistatic agent, known ones can be used. For example, a block copolymer of a hydrophobic block and a hydrophilic block can be used, and the hydrophobic block and the hydrophilic block can be used. Block copolymers are formed by ester bonds, ether bonds, amide bonds, imide bonds, urethane bonds, urea bonds, and the like. Examples of such an antioxidant include an ether-polyolefin block copolymer, a polyether ester amide which is a block copolymer of a polyether and a hydrophobic ester amide, and a block common weight of a polyether and a hydrophobic amide. Examples thereof include a polyether amide which is a coalescence, a polyether amide imide which is a block copolymer of a polyether and a hydrophobic amide imide, and a polyethylene glycol (meth) acrylate copolymer.

Further, in order to further improve the antistatic property, an alkali metal or alkaline earth metal salt, a quaternary ammonium salt, a surfactant, an ionic liquid or the like may be blended.

<Acrylic resin (A)>
An acrylic resin (A) is added to the resin composition of the present invention in order to improve the adhesion between the film obtained by molding the resin composition and the printing layer or the adhesive layer laminated on the film. To.

The acrylic resin (A) is preferably an acrylic polymer (α-1) described below, a rubber-containing acrylic polymer (α-2), or an acrylic resin obtained by using these in combination.

Examples of the acrylic polymer (α-1) include methacrylic acid alkyl ester 50 to 100% by mass, acrylic acid alkyl ester 0 to 50% by mass, and other monofunctional monomers having a double bond copolymerizable with these 0. A polymer obtained by polymerizing a monomer component containing ~ 49% by mass is preferable.
Examples of the alkyl methacrylate ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate and the like.
Examples of the acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate and the like.

Other monofunctional monomers include (meth) acrylic acid lower alkoxy, (meth) cyanoethyl acrylate, (meth) acrylic acid amide, (meth) acrylic acid and other (meth) acrylic acid ester monomers; styrene. , Aromatic vinyl monomers such as alkyl-substituted styrene; and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile.
Examples of the polymerization method of the acrylic polymer (α-1) include a suspension polymerization method, an emulsion polymerization method and a massive polymerization method.
These can be used alone or in combination of two or more.

The rubber-containing acrylic polymer (α-2) is methacrylic acid in the presence of the rubber polymer (g) obtained by polymerizing a monomer component containing an acrylic acid alkyl ester and a polyfunctional monomer as essential components. It is a rubber-containing polymer obtained by polymerizing a monomer component containing an alkyl ester as an essential component.
Examples of the monomer other than the acrylic acid alkyl ester and the polyfunctional monomer in the monomer component constituting the rubber polymer (g) include methacrylic acid alkyl ester, or these (acrylic acid alkyl ester, poly). Examples thereof include other monofunctional monomers having a double bond copolymerizable with the functional monomer).

As a method for producing the rubber-containing acrylic polymer (α-2), it is preferable to carry out by the same method as the emulsion polymerization method and the sequential multi-stage emulsion polymerization method.
The acrylic polymer (α-1) and the rubber-containing acrylic polymer (α-2) may be used alone or in combination.

Examples of commercially available products of the acrylic resin (A) composed of the acrylic polymer (α-1) include "Acrypet MD001", "Acrypet VH001" (all manufactured by Mitsubishi Chemical Corporation), and " Examples thereof include "parapet GF" and "parapet G" (both manufactured by Kuraray Corporation).

Examples of commercially available products of the acrylic resin (A) composed of the acrylic polymer (α-1) and the rubber-containing acrylic polymer (α-2) are, for example, “Acrypet IRS204” and “Acrypet IRD50”. (Both are manufactured by Mitsubishi Chemical Corporation), "Parapet SA-NW201" (manufactured by Kuraray Co., Ltd.) and the like.

In the resin composition of the present invention, the acrylic resin (A) is 15 to 15 to 100% by mass based on a total of 100% by mass of the styrene elastomer (B), the polyolefin resin (C) and the acrylic resin (A) described later. 65% by mass is added.

When the amount of the acrylic resin (A) added is 15% by mass or more, the adhesion between the obtained film and the printing layer or the adhesive layer laminated on the film is sufficiently exhibited. Further, preferably, by setting the content to 65% by mass or less, it is possible to maintain sufficient flexibility while ensuring adhesion. The amount of the acrylic resin (A) added is more preferably 17 to 60% by mass, and most preferably 20 to 55% by mass.

The melt flow rate (230 ° C., 3.8 kg) of the acrylic resin (A) is preferably 0.1 to 20 g / 10 minutes. When the melt flow rate is within the range of 0.1 to 20 g / 10 min, it is easy to uniformly disperse the acrylic resin (A) in the styrene elastomer (B) and the polyolefin resin (C) described later. Become. The melt flow rate of the acrylic resin (A) is more preferably 0.15 to 18 g / 10 minutes, still more preferably 0.2 to 16 g / 10 minutes.

<Styrene-based elastomer (B)>
A styrene-based elastomer (B) is added to the resin composition of the present invention in order to uniformly disperse the acrylic resin (A) described above in the film to be obtained and to impart flexibility to the film.
The styrene-based elastomer (B) is preferably a block copolymer represented by the following formula (I) or (II).
X- (YX) n ... (I)
(XY) n ... (II)

X in the general formulas (I) and (II) is an aromatic vinyl polymer block typified by styrene, and in the formula (I), the degree of polymerization may be the same or different at both ends of the molecular chain. May be good. In addition, Y is a butadiene polymer block, an isoprene polymer block, a butadiene / isoprene copolymer block, a hydrogenated butadiene polymer block, a hydrogenated isoprene polymer block, and a hydrogenated butadiene / isoprene co-weight. It is at least one selected from a coalesced block, a partially hydrogenated butadiene polymer block, a partially hydrogenated isoprene polymer block and a partially hydrogenated butadiene / isoprene copolymer block. Further, n is an integer of 1 or more.

Specific examples include styrene-ethylene / butylene-styrene copolymer, styrene-ethylene / propylene-styrene copolymer, styrene-ethylene / ethylene / propylene-styrene copolymer, and styrene-butadiene-butene-styrene copolymer. , Styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-hydrogenated butadiene diblock copolymer, styrene-hydrogenated isoprene block copolymer, styrene-butadiene diblock copolymer, Examples thereof include a styrene-isopregen block copolymer.
Among them, styrene-ethylene / butylene-styrene copolymer, styrene-ethylene / propylene-styrene copolymer, styrene-ethylene / ethylene / propylene-styrene copolymer, and styrene-butadiene-butene-styrene copolymer are the most preferable. Is.

The content of the X component in the block copolymer is preferably 5 to 50% by mass. If it is 5% by mass or more, it is possible to impart flexibility and elasticity to the obtained film, and if it is 50% by mass or less, it is possible to sufficiently maintain the elongation at break without impairing the flexibility. Become. The content of the X component is more preferably in the range of 6 to 40% by mass, still more preferably in the range of 7 to 30% by mass.

In the resin composition of the present invention, the styrene elastomer (B) is based on a total of 100% by mass of the acrylic resin (A), the styrene elastomer (B) and the polyolefin resin (C) described later. Is added in an amount of 10 to 55% by mass.
When the amount of the styrene-based elastomer (B) added is 10% by mass or more, it is possible to impart flexibility while uniformly dispersing the acrylic resin in the obtained film, and the amount is 55% by mass or less. As a result, it is possible to maintain good film-forming property while maintaining appropriate flexibility. The amount of the styrene-based elastomer (B) added is more preferably 15 to 50% by mass, still more preferably 20 to 45% by mass.

The melt flow rate (230 ° C., 2.16 kg) of the styrene-based thermoplastic elastomer is preferably 0.1 to 20 g / 10 minutes, more preferably 0.15 to 15 g / 10 minutes, and 0. It is particularly preferably 2 to 10 g / 10 minutes. When the melt flow rate of the styrene-based thermoplastic elastomer is in the range of 0.1 to 20 g / 10 min, it is possible to develop sufficient toughness in the obtained film.

Commercially available styrene-based elastomers include, for example, Toughprene A, Solprene T, Asaplen T-411, Toughtech H1221, Toughtech P1500, Toughtech M1943, Toughtech H1041, Toughtech P2000 (all manufactured by Asahi Kasei Chemicals Co., Ltd.), Elastomer AR- 850C, Elastomer AR-720, Elastomer AR-FL-75N, Elastomer AR-1050 (all manufactured by Aron Kasei Co., Ltd.), Clayton D1111, Clayton DX406, Clayton D4141, Clayton D1152, Clayton FG1901, Clayton G1640, Clayton G1726 ( Kraton Polymer Japan Co., Ltd., TR2000, TR1086, SIS5002, Dynaron 6100P, Dynaron 4600P, Dynaron 8601P, Dynaron 8630P, Dynaron 1321P, Dynaron 2324P, Dynaron 9901P (manufactured by JSR Co., Ltd.), Quintac 3520 , Quintac 3433N (above, manufactured by Nippon Zeon), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.), Septon 1001, Septon 2104, Septon HG252, Septon 8004, Septon V9461, Hybler 7311, (above, Clare Co., Ltd.) , Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Elastomer, Actimer (manufactured by Riken Technos Co., Ltd.), etc.

<Polyolefin resin (C)>
A polyolefin resin (C) is added to the resin composition of the present invention. By adding the polyolefin resin (C) described below, it becomes possible to impart flexibility and heat resistance to the obtained film.
Specific examples of the polyolefin-based resin (C) include polyethylene-based resins, polypropylene-based resins, olefin-based elastomers, cyclic olefin-based resins, and mixtures thereof.

Examples of the polyethylene-based resin include a homopolymer of ethylene and a copolymer of ethylene containing ethylene as a main component and a copolymer of other monomers copolymerizable, such as low-density polyethylene (LDPE) and high-pressure low-density polyethylene. , Linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), ethylene-α-olefin copolymer (metallocene-based polyethylene) obtained by polymerization using a metallocene-based catalyst, and a mixture of two or more of these. Etc. can be exemplified. Further, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-methyl (meth) acrylic acid ester copolymer, ethylene-ethyl (meth) acrylic acid copolymer, ethylene-vinyl alcohol. Copolymers, ethylene-based ionomer resins and the like are also classified as polyethylene-based resins.

Examples of the polypropylene-based resin include a propylene homopolymer, a propylene copolymer, a reactor-type polypropylene-based thermoplastic elastomer, and a mixture of two or more thereof.

Examples of the propylene copolymer include a random copolymer (random polypropylene) and a block copolymer (block polypropylene) of propylene and ethylene or other α-olefins, a block copolymer containing a rubber component, or a graft copolymer. And so on. As the other α-olefin copolymerizable with propylene, those having 4 to 12 carbon atoms are preferable, and for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4 -Methyl-1-pentene, 1-decene and the like are mentioned, and one kind or a mixture of two or more kinds thereof is used.

Olefin-based elastomers include ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-methyl-1-pentene, 3-. Copolymerization of α-olefins having 2 to 20 carbon atoms such as methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and the like. Examples thereof include a copolymer in which a monomer such as styrene, non-conjugated diene, or vinyl acetate is further copolymerized with the α-olefin or copolymer.

Specifically, for example, ethylene-propylene copolymer elastomer, ethylene-1-butene copolymer elastomer, ethylene-propylene-1-butene copolymer elastomer, ethylene-1-hexene copolymer elastomer, ethylene-1 -Octen copolymer elastomer, ethylene-styrene copolymer elastomer, ethylene-norbornene copolymer elastomer, propylene-1-butene copolymer elastomer, ethylene-propylene-non-conjugated diene copolymer elastomer, ethylene-1-butene -Non-conjugated diene copolymer elastomer, atypical elastic copolymer containing olefin as a main component such as ethylene-propylene-1-butene-non-conjugated diene copolymer elastomer, derivatives thereof, acid-modified derivatives and the like. be able to.

Commercially available olefin-based elastomers include "Welnex RFX4V" (manufactured by Japan Polypropylene Corporation, metallocene polymerized olefin-based elastomer), Mirastomer (manufactured by Mitsui Chemicals, Inc.), Thermolan (manufactured by Mitsubishi Chemical Corporation), and Newcon (Japan). Examples include Polypropylene Corporation) and EXCELINK (JSR Corporation).
Examples of the cyclic olefin-based resin include norbornene-based polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. Among these, norbornene-based polymers are preferable. Examples of the norbornene-based polymer include a ring-opening polymer of a norbornene-based monomer, a norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer and an α-olefin such as ethylene. Moreover, these hydrogenated additives can also be used.

As a commercially available product of the cyclic olefin resin, examples of the ring-opening polymer of the norbornene-based monomer include "ZEONOR" manufactured by Nippon Zeon Co., Ltd., and examples of the norbornene-based copolymer include Mitsui Kagaku. Examples include "Apel" manufactured by Polyplastics Co., Ltd. and "TOPAS" manufactured by Polyplastics Co., Ltd.

As the polyolefin-based resin (C), a polyethylene-based resin, a polypropylene-based resin, and a polyolefin-based elastomer are preferable from the viewpoint of ease of processing, handling, and availability.
Further, from the viewpoint of heat resistance of the obtained film, the melting point of the polyolefin resin (C) used is preferably in the range of 100 to 240 ° C. When the melting point is 100 ° C. or higher, it is possible to impart appropriate heat resistance to the film, and it is possible to suppress deformation of the film even in the subsequent steps of laminating the printing layer and laminating the adhesive layer. Become. When the melting point is 240 ° C. or lower, the acrylic resin (A) and the styrene elastomer (B) can be molded into a film while suppressing deterioration due to heat during molding. It is more preferably in the range of 110 to 220 ° C, still more preferably in the range of 120 to 200 ° C.

In the resin composition of the present invention, the polyolefin resin (C) is 5 to 5 based on a total of 100% by mass of the acrylic resin (A), the styrene elastomer (B) and the polyolefin resin (C) described above. It is preferable to add 65% by mass.
When the amount of the polyolefin resin (C) added is 5% by mass or more, it is possible to impart sufficient heat resistance to the obtained film. Further, by setting the content to 65% by mass or less, the acrylic resin (A) and the styrene elastomer (B) described above can be dispersed in the film while maintaining heat resistance. The amount of the polyolefin resin (C) added is more preferably 15 to 50% by mass, still more preferably 20 to 45% by mass.

The melt flow rate of the polyolefin resin (C) is appropriately selected depending on the molding method and application to which it is applied, but the value measured under a temperature condition of 190 ° C. or 230 ° C. under a load of 2.16 kg is 0.1 to 50 g. It is preferably / 10 minutes. If it is 0.5 g / 10 minutes or more, the moldability of the film becomes good, and if it is 50 g / 10 minutes or less, the thickness accuracy of the film can be kept good. The melt flow rate of the polyolefin resin (C) is more preferably 0.5 to 40 g / 10 minutes, still more preferably 1.0 to 30 g / 10 minutes.

Regarding the strength of the polyolefin resin (C), it is preferable that the tensile elastic modulus of the film produced by the polyolefin resin alone is in the range of 100 to 2000 MPa. When the tensile elastic modulus is in the range of 100 to 2000 MPa, it is possible to impart appropriate flexibility to the film obtained from the resin composition of the present invention. The tensile elastic modulus is more preferably in the range of 150 to 1900 MPa, still more preferably in the range of 200 to 1800 MPa.

<Single-layer and multi-layer films>
By molding the resin composition for film molding of the present invention, a film-shaped molded product can be obtained. Further, the film may be a single layer, or may be a multi-layer film having a layer made of the resin composition on at least one of the front and back surfaces.

A single-layer film made of the resin composition or a film having a layer made of the same on one of the front and back surfaces contains a predetermined acrylic resin (A) and is laminated on either or both of the front and back surfaces of the film. The film has excellent adhesion to the printing layer or the adhesive layer.

As a film molding method, a known method can be used, but it is preferable to use a melt extrusion molding method. Among the melt extrusion molding methods, the T die molding method in which a molten resin is extruded from an extruder having a T die and cooled and solidified to obtain a film is more preferable.

Further, when obtaining a multi-layer film, it is preferable to use a coextrusion T-die molding method using a plurality of extruders. As a coextrusion T-die molding method, a method of forming a plurality of resin layers into a film by using a multi-manifold die and then contacting the resin layers in the T-die to obtain a film, and a molten state called a feed block. A method of obtaining a multi-layer film after merging and adhering a plurality of resins using a device for merging the resins of the above can be mentioned.

If necessary, the single-layer and multi-layer films of the present invention may be surface-treated on one or both surfaces by methods such as plasma treatment, corona treatment, ozone treatment, and flame treatment.

The thickness of the single-layer and multi-layer films of the present invention is not particularly limited, but is preferably 30 to 400 μm. Within the above range, the handleability of the film and the subsequent processability can be maintained satisfactorily.

As the strength of the film, a test piece (JIS K 6732) collected from the film was used according to JIS K 7161, and the film was measured at a tensile speed of 50 mm / min with a tensile tester in an atmosphere of 23 ° C. and 50% RH. The tensile elastic modulus is preferably in the range of 50 to 1000 MPa.
If the tensile elastic modulus of the obtained film is in the range of 50 to 1000 MPa, the film is flexible and has excellent handleability. It is more preferably in the range of 60 to 900 MPa, and even more preferably in the range of 70 to 800 MPa.
As the elongation of the film, a test piece (JIS K 6732) collected from the film was used according to JIS K 7161, and measured at a tensile speed of 300 mm / min with a tensile tester at 23 ° C. and an atmosphere of 50% RH. It is preferable that the tensile elongation at break is 50% or more.

When the tensile elongation at break is 50% or more, it is necessary to suppress a defect due to film breakage when the film is taken up during melt extrusion molding, and a similar defect in the subsequent step of laminating a printing layer or an adhesive layer. It is preferable because it can be used. It is more preferably 75% or more, still more preferably 100% or more.
Further, when a multi-layer film having a layer made of the resin composition of the present invention on at least one of the front and back surfaces, a layer other than that layer in the laminated film (hereinafter, also referred to as "other layer"). ) Is also preferably a layer made of a resin composition made of an acrylic resin (A), a styrene-based elastomer (B), and a polyolefin-based resin (C). In this case, the content of the acrylic resin (A), the styrene elastomer (B), and the olefin resin (C) may be the same or different between the layer and the other layers.

It is preferable that the other layer is composed of the acrylic resin (A), the styrene elastomer (B), and the olefin resin (C), because it is possible to maintain good adhesion between the layers.
When the other layers are two or more layers, the ratio of the resins in those layers may be the same or different. The ratio can be appropriately determined according to the physical characteristics of the obtained film.
When the other layers are not used on either the front or the back, the acrylic resin (A), the styrene elastomer (B), and the polyolefin resin (C) defined as the film-forming resin composition according to the present invention. It is also possible to make it out of the range of the content of).

<Adhesive film>
The film of the present invention can be made into an adhesive film by laminating an adhesive layer on at least one surface.
The pressure-sensitive adhesive used as the pressure-sensitive adhesive layer is not particularly limited, and for example, various pressure-sensitive adhesives such as natural rubber-based resin, acrylic-based resin, styrene-based resin, silicone-based resin, and polyvinyl ether-based resin are used. Further, a functional layer such as an adhesive layer or a thermosetting resin layer may be further provided on the pressure-sensitive adhesive layer.
In the pressure-sensitive adhesive film of the present invention, one or both sides of the film before laminating the pressure-sensitive adhesive layer may be subjected to the above-mentioned surface treatment. Further, a primer layer may be provided between the base film (the film of the present invention) and the adhesive layer, if necessary.

<Cosmetic film>
The film of the present invention can be made into a decorative film by laminating a printing layer on at least one side thereof.
The print layer constituting the decorative film can be formed by a known method. Examples thereof include a known printing method such as an offset printing method, a gravure rotary printing method and a screen printing method, a known coating method such as a roll coating method and a spray coating method, and a flexographic printing method. Moreover, the vapor deposition method can also be used.
Examples of the printed pattern include a pattern consisting of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, solid surface, metallic, and the like.
The thickness of the print layer can be appropriately determined as needed.

<Adhesive film for makeup>
The decorative film of the present invention can be made into a cosmetic adhesive film by further laminating an adhesive layer on the printing layer side, if necessary. In this case, the adhesive layer may be provided on the print layer, or another layer (for example, an antistatic layer, a primer layer, etc.) may be provided on the print layer, and the adhesive layer may be provided on the other layer. It may be provided.
By attaching the cosmetic adhesive film to the adherend, it is possible to give the adherend a beautiful appearance, such as a molded body or laminate for interior / exterior construction, a molded body for automobile decoration, and the like. A laminate can be obtained.

The resin composition of the present invention is a resin composition for film molding which has excellent flexibility, elongation at break, and high melting point, and can obtain a film having good adhesion to a printing layer or an adhesive. .. Further, since the film obtained from the resin composition of the present invention has excellent adhesion to adhesives and printing layers, adhesive films and decorative films, tapes for semiconductor manufacturing processes using them, applications for interior and exterior buildings, and further. It can also be suitably used for automobile decoration applications.

Hereinafter, examples and comparative examples of the present invention will be shown and specifically described, but the present invention is not limited to these examples. The materials used in the following examples and comparative examples, the method for measuring the evaluated characteristics, and the like are as follows.

[Material used]
<Acrylic resin (A)>
Acrylic resin (A-1):
"Acrypet MD001" manufactured by Mitsubishi Chemical Corporation (Acrylic resin made of acrylic polymer (α-1), melt flow rate at 230 ° C. 3.8 kg = 6.0 g / 10 minutes)
Acrylic resin (A-2):
"Acrypet IRS204" manufactured by Mitsubishi Chemical Corporation (mixture of acrylic polymer (α-1) and rubber-containing acrylic polymer (α-2), melt flow rate at 230 ° C. and 3.8 kg = 14.0 g / 10 minutes)

<Styrene-based elastomer (B)>
"Tough Tech H1221" manufactured by Asahi Kasei Corporation (hydrogenated styrene-ethylene / butylene-styrene block copolymer, melt flow rate at 230 ° C. 2.16 kg = 4.5 g / 10 minutes)

<Polyolefin resin (C)>
Polyolefin resin (C-1):
"FW4B" manufactured by Japan Polypropylene Corporation (random polypropylene, melt flow rate at 230 ° C. 2.16 kg = 8.0 g / 10 minutes, melting point = 136 ° C., tensile elastic modulus of a single film = 600 MPa)
Polyolefin resin (C-2)
"MA3U" manufactured by Japan Polypropylene Corporation (homopolypropylene, melt flow rate at 230 ° C. 2.16 kg = 11 g / 10 minutes, melting point = 160 ° C., tensile elastic modulus of a single film = 1000 MPa)
Polyolefin resin (C-3)
"LC500" manufactured by Japan Polyethylene Corporation (low density polyethylene, melt flow rate at 190 ° C. 2.16 kg = 4.0 g / 10 minutes, melting point = 111 ° C., tensile elastic modulus of a single film = 120 MPa)

[Melting point of polyolefin resin]
Using a differential scanning calorimetry device (DSC823e manufactured by METTLER TOLEDO), about 5 mg of each polyolefin resin is heated from 25 ° C to 230 ° C at a heating rate of 10 ° C / min, and then cooled at a cooling rate of 10 ° C / min. The melting peak temperature of the chart measured when the temperature was lowered to 25 ° C. and again raised to 230 ° C. at a heating rate of 10 ° C./min was taken as the melting point.

<Antistatic agent>
Polymer-type antistatic agent: "Perectron PVL" manufactured by Sanyo Chemical Industries, Ltd. (polypropylene-polyether block copolymer)

<Preparation of resin composition>
Acrylic resin (A), styrene elastomer (B), and polyolefin resin (C), which are the raw materials used, are adjusted so as to have a total of 100% by mass, and the raw materials shown in Table 1 are used and they are dry-blended. And mixed. It was visually confirmed that the mixture was uniformly mixed, and a resin composition for film molding was obtained.

<Method of forming a single-layer film>
Dry-blended raw materials are put into the hopper of a single-screw extruder (50φ mm, L / D = 32) manufactured by Toshiba Machine Co., Ltd., the extruder temperature is set to 200 to 210 ° C., and a 650 mm wide T-die (temperature setting 210 ° C., lip). Extruded from an opening of 0.3 mm). The extruded molten resin is cooled and solidified by a winder equipped with a cooling roll (cooling roll 700 mm width x φ350 mm, roll temperature 30 ° C.), and is wound without corona treatment, and has a thickness of about 80 μm. A layered film was obtained.

<Method of forming a multi-layer film>
For each hopper of three Toshiba Machine single-screw extruders (for outer layer: 35φ mm, L / D = 25 mm, for intermediate layer: 50φ mm, L / D = 32, for outer layer: 35φ mm, L / D = 25 mm) The dry-blended raw material is put in, the extruder temperature for each of the outer layer and the intermediate layer is set to 200 to 210 ° C., and the extruder is merged into the three-layer structure of the outer layer / intermediate layer / outer layer at the feed block portion to have a width of 650 mm. Extruded from a T-die (temperature setting 210 ° C., lip opening 0.5 mm). As for the thickness configuration, each extruder rotation speed was set so as to be 8 μm / 64 μm / 8 μm.
The extruded molten resin is cooled and solidified by a winder equipped with a cooling roll (cooling roll 700 mm width × φ350 mm, roll temperature about 30 ° C.), and is wound without corona treatment to a thickness of about 80 μm. A substantially single-layer film of 1 type and 3 layers or a multi-layer film composed of 2 types and 3 layers was obtained.

[Film film forming property]
The film-forming properties of the single-layer film and the multi-layer film were visually evaluated using the following criteria.
⊚: Film formation is possible without the film sticking to the cooling roll ○: Film can be formed although the film slightly sticks to the cooling roll ×: The film sticks significantly to the cooling roll and film formation is not possible

[Appearance of film]
The obtained film was visually observed and evaluated according to the following criteria.
◯: The raw materials are uniformly dispersed and the appearance is good. ×: The raw materials are not uniformly dispersed and remarkable irregularities occur on the film surface.

[Tension modulus]
A No. 1 dumbbell test piece was collected from the obtained film, and a tensile elastic modulus (MPa) was obtained at a tensile speed of 50 mm / min using an autograph (AGS-X manufactured by Shimadzu Corporation) at 23 ° C. and an atmosphere of 50% RH. ) Was measured.
The tensile elastic modulus was measured in the extrusion direction (MD) of the film.

[Tensile breaking strength]
A No. 1 dumbbell test piece was collected from the obtained film, and stretched at a tensile speed of 300 mm / min using a small tabletop tester (EZ-L manufactured by Shimadzu Corporation) in an atmosphere of 23 ° C. and 50% RH. The degree (%) was measured.
The tensile elongation at break was measured in the extrusion direction (MD) of the film.

[Ink adhesion]
Apply the inks described below to DIC Graphics Co., Ltd. to single-layer and multi-layer films using Kurashiki Spinning Co., Ltd., gravure printing tester "GP-2", and printing plate "54L6 gradation". went. The coated film was aged at 40 ° C. for 5 days to obtain a decorative film in which a printing layer with ink was laminated.
A cellophane tape was attached to the print layer of the obtained decorative film, and the adhesiveness between the print layer and the acrylic resin film was evaluated according to the following criteria by peeling the tape.
◯: Ink peeling is not observed ×: Ink peeling is observed

<Ink manufactured by DIC Graphics Corporation>
An ink was prepared by mixing and stirring 95 parts by mass of "VTP-NT40 yellow (A)" and 5 parts by mass of "AT-NT solvent".
"VTP-NT40 Yellow (A)": Paint consisting of a mixture of vinyl chloride / vinyl acetate copolymer and acrylic resin and methyl isobutyl ketone as a solvent "AT-NT solvent": Mixture of butyl acetate / ethyl acetate / methyl ethyl ketone

[Example 1]
By preparing a resin composition using an acrylic resin (A-1), a styrene elastomer (B), and a polyolefin resin (C-1) as shown in Table 1, and then molding the resin composition into a film. A single layer film was obtained.
This film did not stick to the cooling roll and had excellent film-forming properties, and the appearance of the obtained film was also good.
The obtained film has a tensile elastic modulus of 330 MPa and a tensile elongation at break of 670%, and it has been confirmed that it has excellent heat resistance because it has a melting point of 136 ° C. by using a polyolefin resin (C-1). Was done.
Further, in the evaluation of the adhesion of the decorative film in which the ink was laminated on this film, peeling from the ink was not observed, and it was confirmed that the film had sufficient adhesion to the ink without corona treatment.

[Example 2]
The procedure was the same as in Example 1 except that the acrylic resin (A-2) was used.
This film did not stick to the cooling roll and had excellent film-forming properties, and the appearance of the obtained film was also good.
The obtained film has a tensile elastic modulus of 310 MPa and a tensile elongation at break of 740%, and it has been confirmed that it has excellent heat resistance because it has a melting point of 136 ° C. by using a polyolefin resin (C-1). Was done.
In addition, no peeling from the ink was observed, and it was confirmed that the film had sufficient adhesion to the ink without corona treatment.

[Example 3]
The procedure was the same as in Example 1 except that the polyolefin resin (C-2) was used.
This film did not stick to the cooling roll and had excellent film-forming properties, and the appearance of the obtained film was also good.
The obtained film has a tensile elastic modulus of 410 MPa and a tensile elongation at break of 720%, and it has been confirmed that it has excellent heat resistance because it has a melting point of 160 ° C. by using a polyolefin resin (C-2). Was done.
In addition, no peeling from the ink was observed, and it was confirmed that the film had sufficient adhesion to the ink without corona treatment.

[Example 4]
The procedure was the same as in Example 1 except that the polyolefin resin (C-3) was used.
This film did not stick to the cooling roll and had excellent film-forming properties, and the appearance of the obtained film was also good.
The obtained film has a tensile elastic modulus of 180 MPa and a tensile elongation at break of 50%, and it has been confirmed that it has excellent heat resistance because it has a melting point of 111 ° C. by using a polyolefin resin (C-3). Was done.
In addition, no peeling from the ink was observed, and it was confirmed that the film had sufficient adhesion to the ink without corona treatment.

[Example 5]
The same procedure as in Example 1 was carried out except that the acrylic resin (A-1), the styrene elastomer (B), and the polyolefin resin (C-1) were blended as shown in Table 1.
This film did not stick to the cooling roll and had excellent film-forming properties, and the appearance of the obtained film was also good.
The obtained film has a tensile elastic modulus of 240 MPa and a tensile elongation at break of 700%, and it has been confirmed that it has excellent heat resistance because it has a melting point of 136 ° C. by using a polyolefin resin (C-1). Was done.
In addition, no peeling from the ink was observed, and it was confirmed that the film had sufficient adhesion to the ink without corona treatment.

[Example 6]
The same procedure as in Example 1 was carried out except that the acrylic resin (A-1), the styrene elastomer (B), and the polyolefin resin (C-1) were blended as shown in Table 1.
Although a slight sticking of this film to the cooling roll was observed, the film could be formed because it could be easily peeled off. The appearance of the obtained film was also good.
The obtained film has a tensile elastic modulus of 150 MPa and a tensile elongation at break of 730%, and it has been confirmed that it has excellent heat resistance because it has a melting point of 136 ° C. by using a polyolefin resin (C-1). Was done.
In addition, no peeling from the ink was observed, and it was confirmed that the film had sufficient adhesion to the ink without corona treatment.

[Example 7]
Acrylic resin (A-1), styrene elastomer (B), polyolefin resin (C-1) and antistatic agent were added, and the same as in Example 1 was carried out as shown in Table 1.
This film did not stick to the cooling roll and had excellent film-forming properties, and the appearance of the obtained film was also good.
The obtained film has a tensile elastic modulus of 630 MPa and a tensile elongation at break of 290%, and it has been confirmed that it has excellent heat resistance because it has a melting point of 136 ° C. by using a polyolefin resin (C-1). Was done.
In addition, no peeling from the ink was observed, and it was confirmed that the film had sufficient adhesion to the ink without corona treatment.

[Example 8]
The same procedure as in Example 1 was carried out except that the acrylic resin (A-1), the styrene elastomer (B), and the polyolefin resin (C-1) were blended as shown in Table 1.
Although a slight sticking of this film to the cooling roll was observed, the film could be formed because it could be easily peeled off. The appearance of the obtained film was also good.
The obtained film has a tensile elastic modulus of 160 MPa and a tensile elongation at break of 550%, and it has been confirmed that it has excellent heat resistance because it has a melting point of 136 ° C. by using a polyolefin resin (C-1). Was done.
In addition, no peeling from the ink was observed, and it was confirmed that the film had sufficient adhesion to the ink without corona treatment.

[Example 9]
The same procedure as in Example 1 was carried out except that the acrylic resin (A-1), the styrene elastomer (B), and the polyolefin resin (C-1) were blended as shown in Table 1.
This film did not stick to the cooling roll and had excellent film-forming properties, and the appearance of the obtained film was also good.
The obtained film has a tensile elastic modulus of 240 MPa and a tensile elongation at break of 310%, and it has been confirmed that it has excellent heat resistance because it has a melting point of 136 ° C. by using a polyolefin resin (C-1). Was done.
In addition, no peeling from the ink was observed, and it was confirmed that the film had sufficient adhesion to the ink without corona treatment.

[Example 10]
The same procedure as in Example 1 was carried out except that the acrylic resin (A-1), the styrene elastomer (B), and the polyolefin resin (C-1) were blended as shown in Table 1.
Although a slight sticking of this film to the cooling roll was observed, the film could be formed because it could be easily peeled off. The appearance of the obtained film was also good.
The obtained film has a tensile elastic modulus of 300 MPa and a tensile elongation at break of 60%, and it has been confirmed that it has excellent heat resistance because it has a melting point of 136 ° C. by using a polyolefin resin (C-1). Was done.
In addition, no peeling from the ink was observed, and it was confirmed that the film had sufficient adhesion to the ink without corona treatment.

[Example 11]
Same as in Example 1 except that the content of the acrylic resin (A-1) was 70% by mass and the styrene elastomer (B) and the polyolefin resin (C-1) were blended as shown in Table 1. I went to.
This film did not stick to the cooling roll and had excellent film-forming properties, and the appearance of the obtained film was also good.
It was confirmed that the obtained film has a tensile elastic modulus of 1200 MPa and a tensile elongation at break of 40%, and has a melting point of 136 ° C. due to the use of the polyolefin resin (C-1), and thus has excellent heat resistance. It was.
However, since the content of the acrylic resin is high, the tensile elastic modulus is high and the tensile elongation at break is also low.

[Comparative Example 1]
The same as in Example 1 except that the content of the acrylic resin (A-1) was 10% by mass and the styrene elastomer (B) and the polyolefin resin (C-1) were blended as shown in Table 1. I went to.
This film did not stick to the cooling roll and had excellent film-forming properties, and the appearance of the obtained film was also good.
The obtained film has a tensile elastic modulus of 400 MPa and a tensile elongation at break of 810%, and it has been confirmed that it has excellent heat resistance because it has a melting point of 136 ° C. by using a polyolefin resin (C-1). Was done.
However, the content of the acrylic resin was as low as 10% by mass, and peeling of the ink from the decorative film using this film was observed. Therefore, it was confirmed that the film was inferior in adhesion to the ink.

[Comparative Example 2]
The procedure was the same as in Example 1 except that the styrene-based elastomer (B) was not added.
This film did not stick to the cooling roll and was excellent in film forming property, but the acrylic resin and the polyolefin resin were not uniformly dispersed, and the film surface had remarkable irregularities and appearance. It was confirmed that the film was inferior to.

[Comparative Example 3]
The same as in Example 1 was carried out as shown in Table 1 except that the content of the styrene-based elastomer (B) was 60% by mass.
Since this film contained a large amount of the styrene-based elastomer (B), it was soft and had a tack property on the film surface. Therefore, it was confirmed that the film was remarkably attached to the cooling roll and was inferior in film forming property. ..

[Comparative Example 4]
The same as in Example 1 was carried out as shown in Table 1 except that the polyolefin resin (C) was not added.
This film did not stick to the cooling roll and had excellent film-forming properties, and the appearance of the obtained film was also good.
The tensile elastic modulus of the obtained film was 280 MPa, and the tensile elongation at break was 60%. Further, since the polyolefin resin (C) was not used, it was confirmed that it did not have a melting point in the range of 100 to 240 ° C. and was inferior in heat resistance.

[Example 12]
The resin compositions shown in Table 2 were put into each of the three extruders to obtain a multi-layer film composed of two types and three layers.
This film did not stick to the cooling roll and had excellent film-forming properties, and the appearance of the obtained film was also good.
The obtained film has a tensile elastic modulus of 200 MPa and a tensile elongation at break of 700%, and it has been confirmed that it has excellent heat resistance because it has a melting point of 136 ° C. by using a polyolefin resin (C-1). Was done.
In addition, no peeling from the ink was observed, and it was confirmed that the film had sufficient adhesion to the ink without corona treatment.

[Example 13]
Acrylic adhesive (SK Dyne 1502C manufactured by Soken Kagaku Co., Ltd.) is applied on the separator by the comma coating method so that the thickness of the adhesive layer after drying is 25 μm, and it is used in a hot air dryer at 80 ° C. After drying for 5 minutes, an adhesive layer was formed and bonded to one surface of the single-layer film prepared in Example 1 to obtain an adhesive film composed of a single-layer film / adhesive layer / separator.
The adhesion between the single-layer film and the adhesive layer was confirmed by performing the same evaluation as the evaluation of the adhesion of the ink. As a result of the evaluation, no peeling of the adhesive layer was observed, so it was confirmed that the film had sufficient adhesion to the adhesive layer without corona treatment.

[Example 14]
A cosmetic adhesive film was obtained by further laminating an adhesive layer on the print layer side of the decorative film prepared in Example 1 in the same manner as in Example 13.
The obtained cosmetic adhesive film has good adhesion to ink, and by adhering this cosmetic adhesive film to a steel plate, a decorative material for interior and exterior construction, which has excellent adhesion between ink and film, can be obtained. Confirmed that it is possible to obtain.

As described above, according to the configuration of the present invention, a film having excellent flexibility, elongation at break, high melting point, and good adhesion to a printing layer or an adhesive without pretreatment such as corona treatment can be obtained. Obtainable. Furthermore, since the obtained film has excellent adhesion to adhesives and printing layers, it is suitably used for adhesive films, decorative films, tapes for semiconductor manufacturing processes using them, building interior / exterior applications, and automobile decoration applications. be able to.

According to the configuration of the present invention, a film having excellent flexibility, elongation at break, high melting point, and good adhesion to a printing layer or an adhesive can be obtained without pretreatment such as corona treatment. .. Furthermore, since the obtained film has excellent adhesion to adhesives and printing layers, it is suitably used for adhesive films, decorative films, tapes for semiconductor manufacturing processes using them, building interior / exterior applications, and automobile decoration applications. be able to.

Claims (8)

Acrylic resin containing acrylic resin (A), styrene elastomer (B) and polyolefin resin (C), and the total amount of (A), (B) and (C) is 100% by mass. A resin composition for film molding in which the content of (A) is 15% by mass or more and the content of the styrene-based elastomer (B) is 10 to 55% by mass. The resin composition for film molding according to claim 1, wherein the content of the acrylic resin (A) is 15 to 65% by mass, and the content of the polyolefin resin (C) is 10 to 55% by mass. The resin composition for film molding according to claim 1 or 2, wherein the polyolefin-based resin (C) has a melting point between 100 and 240 ° C. A film obtained by molding the resin composition for film molding according to any one of claims 1 to 3.
The film having a tensile elongation at break of 50% or more. The film according to claim 4, which has a tensile elastic modulus of 50 to 1000 MPa. An adhesive film obtained by laminating an adhesive layer on at least one side of the film according to claim 4 or 5. A decorative film obtained by laminating a printing layer on at least one side of the film according to any one of claims 4 to 6. A cosmetic adhesive film obtained by further laminating an adhesive layer on the print layer side of the decorative film according to claim 7.