JP2020117676A - Acrylic resin composition for calender molding and film formed of the resin composition - Google Patents

Abstract

To provide an acrylic resin composition that is excellent in film peelability from a rolling roll in calender molding.SOLUTION: There are provided: an acrylic resin composition for calender molding which contains an acrylic resin, a plasticizer and a polyolefin wax having melt viscosity at 140°C of 20,000 mPa s or less; a film obtained by subjecting the composition to calender molding; a decorative sheet which is obtained by coloring the film or has a printing layer on at least one surface thereof; and a decorative material including the decorative sheet, a use in a building interior or exterior of the decorative material and a use in a molding.

Description

The present invention is an acrylic resin composition for calender molding, a calender molded film made of the resin composition, a decorative sheet obtained by coloring the film, or a decorative sheet having a printed layer on at least one surface of the film, and the cosmetic. The present invention relates to a decorative material provided with a sheet, use of the decorative material for interior and exterior construction of buildings, and use for a molded body.

As a decorative material used for interior and exterior materials of buildings and fittings, or for surface makeup of furniture, it is well known that a decorative sheet that is printed or colored is laminated on a base material such as wood plywood or steel plate. As a base material for the decorative sheet, paper or a plastic film is generally used.

As a material for this plastic substrate film, there are many cases in which vinyl chloride resin, which is excellent in design and adhesiveness, is used, but in recent years, polyolefin resin has been used because it requires exhaust gas treatment during incineration. Is widely used.

However, when a polyolefin-based resin is used, the number of steps is increased in the production because a surface treatment such as corona treatment or a pretreatment such as provision of a primer layer is required when laminating the printing layer on the film. However, there were problems such as high cost and poor yield.

On the other hand, acrylic resin is known as one of the resins which does not have the problem of exhaust gas at the time of incineration and does not require pretreatment, and films and sheets made of the resin composition have been proposed (Patent Documents 1 to 3). See).

However, although Patent Documents 1 and 2 describe an acrylic resin composition suitable for calender molding, there is room for improvement regarding peeling of a film from a rolling roll during calender molding.

Further, in Patent Document 3, an acrylic sheet is described as an example of a thermoplastic resin sheet formed by a calendering method, but there is no description of a problem relating to peeling of a film from a rolling roll during calendering, and There is no description of a resin composition suitable for calendar molding.

JP, 09-31287, A JP, 2007-56226, A Japanese Patent Laid-Open No. 08-48014

The present invention, in view of such conventional problems, it is possible to keep good peeling of the film from the rolling roll during calendar molding, also, the obtained film is excellent in printability and strength, and colored, Another object of the present invention is to provide an acrylic resin composition for calendar molding, which can be suitably used for a decorative sheet having a printed layer laminated thereon, an interior/exterior application using the decorative sheet, and a cosmetic application of a molded article. ..

As a result of intensive investigations to solve the above problems, the present inventors have found that by incorporating an acrylic resin, a plasticizer, and a specific lubricant, excellent peelability from the rolling roll of the film and printing of the obtained film They have found that an acrylic resin composition having both suitability and strength can be provided, and completed the present invention.

That is, the gist of the present invention is as follows.
[1] An acrylic resin, a plasticizer, and a polyolefin wax having a melt viscosity at 140° C. of 20000 mPa·s or less are contained, and the content of the polyolefin wax is 0.5 to 100 parts by mass of the acrylic resin. An acrylic resin composition for calender molding, which is 5 parts by mass.
[2] A calender molding film comprising the acrylic resin composition according to [1].
[3] The calendered film according to [2], which has a tensile strength at break of 12 MPa or more.
[4] A decorative sheet obtained by coloring the calendered film according to [2] or [3], or having a printed layer on at least one surface of the film.
[5] A decorative material including the decorative sheet according to [4].
[6] The decorative material according to [5] used for interior and exterior construction.
[7] A molded product using the decorative material according to [5].

INDUSTRIAL APPLICABILITY The acrylic resin composition of the present invention has excellent film releasability from a rolling roll when a film is formed by a calendar, and a film having both printability and strength can be obtained. Further, as long as it is a decorative sheet obtained by coloring the film or having a printed layer on at least one surface, and a decorative material obtained by laminating an adherend on the sheet, a decorative material having excellent processability and appearance characteristics. Can be provided.
Further, by using the decorative sheet and the decorative material of the present invention, it is possible to apply makeup to articles and molded articles used for interior and exterior construction.

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

The acrylic resin composition of the present invention contains an acrylic resin, a plasticizer, and a polyolefin wax having a melt viscosity at 140° C. of 20000 mPa·s or less.

<Acrylic resin>
The acrylic resin used in the present invention is an acrylic polymer (α) containing a methacrylic acid alkyl ester unit as a main component, a rubber-containing polymer (β), or an acrylic resin containing a combination thereof.
As the acrylic polymer (α), in view of the heat resistance of the matte resin layer, 50 to 100% by mass of an alkyl methacrylic acid ester, 0 to 50% by mass of an alkyl acrylate, and a double bond copolymerizable therewith. A polymer obtained by polymerizing a monomer component containing 0 to 49% by mass of the other monofunctional monomer having is preferable.

Examples of the alkyl methacrylate may include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, and the like, and impart heat resistance to the resulting acrylic polymer. From the viewpoint of, it is preferable to use methyl methacrylate. These can be used alone or in combination of two or more.

In addition, examples of the alkyl acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate and n-butyl acrylate, i-butyl acrylate, and the like. From the viewpoint of ease of adjustment, it is preferable to use n-butyl acrylate. These can be used alone or in combination of two or more.

Other monofunctional monomers include (meth)acrylic acid lower alkoxy, (meth)acrylic acid cyanoethyl, (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. These can be used alone or in combination of two or more.

Examples of the polymerization method of the acrylic polymer (α) include known polymerization methods such as a suspension polymerization method, an emulsion polymerization method, and a bulk polymerization method. From the viewpoint of easy handling of the resulting acrylic polymer, it is preferable to use the suspension polymerization method or the bulk polymerization method.

The rubber-containing polymer (β) is obtained by polymerizing a methacrylic acid alkyl ester in the presence of a 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 contained as an essential component.

Examples of the alkyl acrylate as a monomer component constituting the rubber polymer (g) include the same ones used for the production of the acrylic polymer (α). Examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylic acid, 1,4-butylene glycol di(meth)acrylic acid, and di(meth)acrylic acid. Propylene glycol (meth)acrylate and other alkylene glycol di(meth)acrylates; polyvinylbenzene such as divinylbenzene and trivinylbenzene; cyanurate monomers such as triallyl cyanurate and triallyl isocyanurate; allyl methacrylate and the like [Alpha],[beta]-unsaturated carboxylic acid; and allyl, methallyl or crotyl ester of dicarboxylic acid. These may be used alone or in combination of two or more.
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, for example, methacrylic acid alkyl ester or these (acrylic acid alkyl ester, (Functional monomer) and other monofunctional monomers having a double bond copolymerizable therewith. Examples of such other monofunctional monomers include the same ones used for the production of the acrylic polymer (α).

The rubber-containing polymer (β) is preferably produced by the same method as the emulsion polymerization method and the sequential multi-stage emulsion polymerization method.

As the acrylic resin used in the present invention, the acrylic polymer (α) and the rubber-containing polymer (β) may be used alone or in combination. From the viewpoint of flexibility and calender moldability of the obtained film, it is preferable to use the rubber-containing polymer (β) alone. Moreover, as the rubber-containing polymer (β), one kind may be used, or two or more kinds may be used in combination.

The acrylic resin used in the present invention preferably has a tensile elastic modulus of 100 MPa or more and 2000 MPa or less when a film made of only the acrylic resin is evaluated. When the tensile modulus is 100 MPa or more, it is possible to impart sufficient flexibility to the obtained film, and when it is 2000 MPa or less, calender molding can be performed without impairing the flexibility. It is preferably 150 MPa or more and 1900 MPa or less, more preferably 200 MPa or more and 1800 MPa or less.
The tensile modulus is a value obtained according to JIS K7127.

The glass transition temperature of the acrylic resin used in the present invention is preferably 70° C. or higher and 110° C. or lower when the film made of the acrylic resin alone is evaluated. If it is 70°C or higher, it becomes possible to suppress sticking to the mold during processing into a three-dimensional shape described later, and if it is 110°C or lower, it is sufficient to follow a mold having a three-dimensional shape. Can be given to. It is preferably 75° C. or higher and 105° C. or lower, and more preferably 80° C. or higher and 100° C. or lower.
The glass transition temperature is 3. in JIS K7121. This is the temperature measured as the "extrapolated glass transition start temperature" by raising the temperature in accordance with the method described in (2) at a temperature raising rate of 10°C/min. In the present invention, the glass transition temperature can be measured by DSC (Inspection Scanning Calorimeter).

<Plasticizer>
The acrylic resin composition used in the present invention contains a plasticizer as an essential component. By containing a plasticizer, the accuracy of the thickness of the film at the time of calendar molding can be improved, and by using it together with a polyolefin wax described later, the releasability from the rolling roll can be improved.

The type of plasticizer is not particularly limited and known ones can be used. For example, di-n-butyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, dioctyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl isophthalate. , Phthalic acid plasticizers such as diundecyl phthalate, bis-2-ethylhexyl adipate, di-2-decyl adipate, diisononyl adipate, dibutyl sebacate, fatty acid ester plasticizers such as di-2-ethylhexyl sebacate, Phosphate ester plasticizers such as tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyl diphenyl phosphate, tricresyl phosphate, trimellitic acid such as tri-2-ethylhexyl trimellitate and trioctyl trimellitate Ester plasticizers, adipic acid polyester plasticizers, polyester plasticizers such as phthalic acid polyester plasticizers, and terephthalic acid plasticizers such as bis(2-ethylhexyl) terephthalate can be used and are not available. From the viewpoint of ease and handling of the plasticizer, phthalic acid plasticizers, adipic acid plasticizers, and polyester plasticizers are preferably used.

The addition amount of the plasticizer is not particularly limited, and the plasticizer can be added arbitrarily within a range that does not significantly reduce the handleability and strength of the obtained film.

<Polyolefin wax (lubricant)>
The acrylic resin composition used in the present invention contains, as an essential component, a polyolefin wax having a melt viscosity at 140° C. of 20000 mPa·s or less as a lubricant in order to improve the peelability of the film from the rolling roll. Be done.

By using a polyolefin wax having a melt viscosity at 140° C. of 20000 mPa·s or less and the above-mentioned plasticizer in combination, the peelability from the rolling roll can be improved and the acrylic resin composition is processed into a film. It is possible to suppress the coloring at the time of performing. When the melt viscosity of the above-mentioned lubricant at 140° C. is 20000 mPa·s or less, the wax is sufficiently melted during calendering, and the tendency that part of the acrylic resin composition sticks to the rolling roll and the workability is deteriorated To be

The melt viscosity is preferably 15,000 mPa·s or less, more preferably 10,000 mPa·s or less, from the viewpoint of the peelability of the film from the rolling roll.
The type of polyolefin wax is not particularly limited as long as it has a melt viscosity of 20000 mPa·s or less, and known waxes can be used.
The value of the melt viscosity of the wax at 140° C. is measured by using a B-type viscometer, the measurement sample is heated from room temperature, and the viscosity measured at 140° C., which is the melting temperature of the sample or higher. It is a value.

Examples of the polyolefin wax include polyethylene wax, polypropylene wax, olefin copolymer wax (for example, ethylene copolymer wax) and the like, and partial oxides thereof or a mixture thereof may be used. ..

For the olefin copolymer, for example, two or more kinds of olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-decene, 4-methyl-1-butene, and 4-methyl-1-pentene are used. And a copolymerizable monomer such as unsaturated carboxylic acid and its acid anhydride [(meth)acrylic acid, maleic anhydride, etc.], (meth)acrylic acid ester [ Examples thereof include copolymers with a polymerizable monomer such as (meth)acrylic acid alkyl ester such as methyl (meth)acrylate and ethyl (meth)acrylate. In addition, these copolymers include random copolymers, block copolymers or graft copolymers.

The structure of the polyolefin wax may be a linear structure or a branched structure. These may be used alone or in combination of two or more.

The addition amount of the olefin wax is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the acrylic resin. By adding 0.5 parts by mass or more, it is possible to improve the peeling from the rolling roll, and by adding 5 parts by mass or less, it is possible to maintain good printability of the ink on the obtained film. Becomes It is more preferably 0.6 to 4.5 parts by mass, and even more preferably 0.7 to 4 parts by mass.

<Other additives>
In the acrylic resin composition of the present invention, if necessary, a known resin additive that is usually blended with a synthetic resin for molding, for example, an ultraviolet absorber or a light stabilizer, within a range that does not impair the effects of the present invention. , Various additives such as a weathering aid, a heat stabilizer, a flame retardant, an antistatic agent, an antibacterial and antifungal agent, a processing aid and a coloring agent can be added alone or in combination of two kinds. The above can be used in combination.

<Method for producing resin composition and film>
The acrylic resin composition of the present invention is a mixture of the above components in a heat-melted state using a known kneader such as a Banbury mixer, a single-screw extruder, a roll, a kneader, etc. It can be obtained by kneading. The acrylic resin composition thus obtained can be obtained in the form of pellets, particles, flakes, powder or the like.

Next, the obtained acrylic resin composition can be formed into a film by a calendar molding method, an inflation molding method, a T-die molding method, or the like. From the viewpoint of productivity, it is preferable to use the calender molding method.

<Acrylic resin film>
The acrylic resin film of the present invention is a film obtained by molding the above-mentioned acrylic resin composition. One preferable embodiment of the acrylic resin film of the present invention is a calender molding film made of the acrylic resin composition of the present invention.
The thickness of the acrylic resin film is not particularly limited, but is preferably 30 to 400 μm. By setting the content within the above range, the handleability of the film and the subsequent processability can be favorably maintained.

The strength of the acrylic resin film was measured in accordance with JIS K 7161 using a test piece (JIS K 6732) taken from the film, in a tensile tester under an atmosphere of 23° C. and 50% RH, at a pulling speed of 300 mm/min. The tensile strength at break when measured is preferably 12 MPa or more. When the tensile breaking strength of the obtained acrylic resin film is 12 MPa or more, the resulting acrylic resin film has sufficient strength, can prevent the film from breaking during molding, and is excellent in handleability. The pressure is more preferably 13 MPa or more, further preferably 14 MPa or more.

<Cosmetic sheet>
The acrylic resin film of the present invention can be made into a decorative sheet by kneading and coloring a colorant such as a pigment or a dye, or by laminating a printing layer on at least one surface of the film. In this case, a calendered film obtained by calendering the acrylic resin composition of the present invention can be preferably used as the acrylic resin film.

The pigment used for coloring the film is not particularly limited and may be appropriately selected and used from inorganic pigments and organic pigments depending on the use and color.
The dye used for coloring the film is not particularly limited, and can be appropriately selected from water-soluble dyes, disperse dyes, and oil-soluble dyes according to the use and color.

The printing layer laminated on one side of the film can be formed by a known method. Examples thereof include known printing methods such as offset printing, gravure rotary printing, screen printing, known coating methods such as roll coating and spray coating, and flexographic printing. Alternatively, a vapor deposition method can be used.

Examples of the print pattern include wood grain, stone grain, cloth grain, grain pattern, geometric pattern, characters, solid pattern, metallic pattern and the like.

The thickness of the printing layer can be appropriately determined as necessary.
Further, in order to improve the designability and the handleability of the film, it is possible to provide the acrylic resin film or the printing layer with unevenness such as embossing to obtain a decorative sheet.

<Cosmetic material>
A decorative material can be obtained by attaching the acrylic resin film or the decorative sheet of the present invention to an adherend.
By attaching the decorative sheet of the present invention to an adherend, it becomes possible to impart good weather resistance to the adherend.
Further, by using the acrylic resin film of the present invention or the film of the present invention as a decorative material which is used as a support for an adherend of a decorative sheet, a molded product with makeup is obtained by a molding method described below. It becomes possible.

Examples of adherends used for interior and exterior construction include wooden plate materials, metal plate materials, and resin plate materials.
The support for the adherend here is, for example, provided on the side of the surface which is in direct contact with the resin injected by the injection molding described later and is integrated with the resin, It imparts rigidity to the resin and maintains its shape, adhesion to the resin to be injected, and the property of being easily softened by heat during molding and preforming provided in the preceding step. It can also be used as a support for a decorative material used in a three-dimensional overlay laminate molding method described later.
Further, as the adherend when used as a support, a film-shaped material can be mentioned, and the film-shaped material may be transparent or colored, and a printing layer may be provided on one side or both sides. It may be laminated.

Known materials can be used as the film-shaped material, and there is no particular limitation. For example, in addition to the acrylic resin film of the same kind as the acrylic resin film of the present invention, a polycarbonate resin film as a different resin film, polyethylene Examples thereof include a terephthalate resin film.

Further, a surface protective layer may be provided for the purpose of surface protection of the film material. The surface protective layer is not particularly limited, and examples thereof include a method of laminating with a hard coat layer by a known coating method.

When the acrylic resin film or the decorative sheet of the present invention is used as a support, it is excellent in handleability (handling property) and processability into a three-dimensional shape.

When the support is composed of the acrylic resin film and the decorative sheet of the present invention, the support may be formed of a single-layer sheet or a multi-layer sheet in which two or more different resin sheets are laminated. May be. Examples of different types of resin sheets include acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-styrene-acrylic acid ester resin, polyolefin resin such as polypropylene and polyethylene, polycarbonate resin, vinyl chloride resin, polyethylene terephthalate resin ( Examples of the resin sheet include a PET resin).

It is also possible to perform surface treatment on one side or both sides of the support in order to impart adhesion to the film-shaped material, the printing layer laminated on the surface thereof, or the resin layer of a different type. The surface treatment is not particularly limited as long as it is a known method, and examples thereof include surface treatment methods such as corona treatment, plasma treatment, flame treatment, and application of a primer layer by coating.

The thickness when used as a support is not particularly limited, but it is preferably in the range of 100 to 500 μm from the viewpoint of imparting rigidity to the decorative material and processability into a three-dimensional shape. The thickness is more preferably 125 to 500 μm, still more preferably 150 to 500 μm.

<Method of molding decorative material>
The method for molding the decorative material of the present invention is not particularly limited, and a known molding method can be used. Examples of the molding method include an insert molding method, an in-mold molding method, and a three-dimensional overlay laminate molding method.

With the insert molding method, the decorative material is preliminarily molded into a three-dimensional shape by vacuum molding, etc., unnecessary sheet parts are removed by trimming, then transferred to the injection molding die, and the resin as the base material is injection molded. It is a method of obtaining a molded product by integrating the above.

The in-mold molding method is a method in which a decorative material is placed in an injection molding die, vacuum molding is performed, and then a resin serving as a base material is injection-molded in the same die to integrate them to obtain a molded body. Is.

The three-dimensional overlay laminate molding method means the following method.
First, two sealed spaces partitioned by a decorative material are formed, a molded body is arranged on one space side, and both spaces or only the space where the molded body is arranged are decompressed.
Then, the decorative material is softened by heating, and the molded body is pressed against the surface of the decorative material from one space side to the other space side, and only the other space where the molded body is not placed is returned to normal pressure. , Apply the decorative material to the molded body using the differential pressure.
In the three-dimensional overlay laminate molding method, the heated decorative material is uniformly and uniformly applied to the surface of the molded body, so that the molded material can be satisfactorily formed even if the surface of the molded body is a curved surface. Can be pasted on.
An example of an apparatus for performing three-dimensional overlay lamination molding is "TOM (trade name)" manufactured by Fuse Vacuum Co., Ltd.

<Molded body>
The molded product of the present invention is a molded product obtained by using the above-mentioned decorative material and molding method.
Moreover, since the acrylic resin film of the present invention is excellent in processability into a three-dimensional shape as described above, it is possible to apply makeup to an article having a more complicated three-dimensional shape by using the film. Become.
The article having a three-dimensional shape to be used is not particularly limited, and examples thereof include plastic parts, metal parts, and other articles.
The molding method of the molded body is not particularly limited, and the molding method described above can be used.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The materials used in the following examples and comparative examples, the methods for measuring the evaluated properties, and the like are as follows.

[Materials used]
<Acrylic resin>
Acrylic resin (β-1): manufactured by Mitsubishi Chemical Corporation, rubber-containing polymer (tensile modulus: 560 MPa, glass transition temperature: 87°C)
Acrylic resin (β-2): manufactured by Mitsubishi Chemical Corporation, rubber-containing polymer (tensile elastic modulus: 1300 MPa, glass transition temperature: 94°C)

<Plasticizer>
[Phthalate plasticizer]
Diundecyl phthalate: manufactured by J-Plus Co., Ltd., product name "DUP"
Bis(2-ethylhexyl) terephthalate
: Product name “NEO-T” manufactured by Aikei Yuka Co., Ltd.
[Adipic acid plasticizer]
Diisononyl adipate
: Product made by J-Plus Co., Ltd., "DINA"
[Polyester plasticizer]
Adipic acid polyester
: Product name "D620" manufactured by J-Plus Co., Ltd.

<Lubricant>
[Polyethylene wax]
Polyethylene wax-1: Mitsui Chemicals, Inc., product name "High Wax 220MP", oxidized polyethylene wax, melt viscosity at 140°C 80 mPa·s
Polyethylene wax-2: manufactured by Clariant Chemicals Co., Ltd., product name “LICOWAX PED191”, oxidized polyethylene wax, melt viscosity at 140° C. 1800 mPa·s
Polyethylene wax-3: manufactured by Clariant Chemicals Co., Ltd., product name “LICOWAX PE190”, polyethylene wax, melt viscosity at 140° C. 25000 mPa·s

[Other than polyethylene wax]
Zinc stearate: Nitto Kasei Co., Ltd. product name "Zn-St"
Silicone-based surface conditioner: manufactured by BYK Japan KK, product name "BYK307"
Ethylenebislauric acid amide: Nippon Kasei Co., Ltd. product name "Sripax L"

<Processing aid>
Acrylic processing aid: Mitsubishi Chemical Co., Ltd. product name "Metablene P-530A"

<Colorant>
Titanium oxide: Product name "NBD-1169 White", manufactured by Hibo Bigs Co., Ltd.

[Film forming properties]
The acrylic resin composition was mixed using a Henschel mixer, and then kneaded with a Banbury mixer at 160° C. for 3 minutes. The obtained kneaded product was kneaded by calender molding at 180° C. for 7 minutes using two rolling rolls to produce an acrylic resin film. The peelability of the roll from the rolling roll during molding was evaluated according to the following criteria.
◎: Peeling is easy without the film sticking to the rolling roll ◯: The film is slightly sticking to the rolling roll, but easy to peel ×: The film is markedly sticking to the rolling roll, and peeling is difficult

[Yellow of film]
The obtained acrylic resin film was visually observed and evaluated according to the following criteria.
A: No yellowing is observed.
◯: Slight yellowing is recognized.
X: Remarkable yellowing is recognized.

[Printability evaluation 1]
The inks manufactured by Dainichiseika Co., Ltd. described below were applied to an acrylic resin film using a gravure printing tester “GP-2” and a printing plate “54L6 gradation” manufactured by Kurashiki Spinning Co., Ltd. .. The coated film was aged at 40° C. for 5 days to obtain a decorative sheet having a printed layer of ink laminated thereon.
A cellophane tape was attached to the print layer of the obtained decorative sheet, and by peeling the tape, the adhesion between the print layer and the acrylic resin film was evaluated according to the following criteria.
A: No peeling is observed.
◯: Slight peeling is recognized.
X: Remarkable peeling was recognized, and the remaining area of the printed layer was half or less.

<Ink manufactured by Dainichi Seika Co., Ltd.>
100 parts by mass of "SBM-NT95 black (M)" and 3 parts by mass of "PTC-LT curing agent (K)" were mixed and stirred to prepare an ink.
"SBM-NT95 black (M)": A paint composed of a polyurethane resin and isopropyl alcohol, ethyl acetate, methyl ethyl ketone, and propylene glycol monomethyl ether acetate as a solvent "PTC-LT curing agent (K)": curing agent, ethyl acetate Hardener consisting of methyl ethyl ketone, isopropyl alcohol, propylene glycol monomethyl ether

[Printability evaluation 2]
The inks manufactured by DIC Graphics Co., Ltd. described below were applied to an acrylic resin film by using a gravure printing tester “GP-2” and a printing plate “54L6 gradation” manufactured by Kurashiki Spinning Co., Ltd. .. The coated film was aged at 40° C. for 5 days to obtain a decorative sheet having a printed layer of ink laminated thereon.
A cellophane tape was attached to the print layer of the obtained decorative sheet, and by peeling the tape, the adhesion between the print layer and the acrylic resin film was evaluated according to the following criteria.
A: No peeling is observed.
◯: Slight peeling is recognized.
X: Remarkable peeling was recognized, and the remaining area of the printed layer was half or less.

<Ink manufactured by DIC Graphics Co., Ltd.>
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)": 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": a mixture of butyl acetate/ethyl acetate/methyl ethyl ketone

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

[Example 1]
As the acrylic resin, 70 parts by mass of the rubber-containing polymer (β-1) and 30 parts by mass of the rubber-containing polymer (β-2) were used. As a plasticizer, 12 parts by mass of phthalic acid-based diundecyl phthalate, as a lubricant, 1 part by mass of oxidized polyethylene wax "High Wax 220MP", and as a processing aid, an acrylic processing aid, "Metablene P-530A". Was added to 5 parts by mass of titanium oxide "NFD-1169 White" as a colorant to 100 parts by mass of the acrylic resin to prepare an acrylic resin composition.
The acrylic resin composition was mixed using a Henschel mixer, and then kneaded with a Banbury mixer at 160° C. for 3 minutes. The obtained kneaded product was kneaded by calender molding at 180° C. for 7 minutes by using two rolling rolls to produce a white acrylic resin film.
The thickness of the obtained film was 0.1 mm, the film did not stick to the rolling roll, and the peelability was good.
Then, the film was printed, and the adhesion was evaluated by peeling with cellophane tape. As a result, it was confirmed that there was no peeling of the print and good adhesion was exhibited.
The tensile breaking strength of the film was 17.8 MPa.

[Example 2]
Example 1 was repeated except that the plasticizer was changed to 6 parts by mass.
The thickness of the obtained film was 0.1 mm, the film did not stick to the rolling roll, and the peelability was good.
Then, the film was printed, and the adhesion was evaluated by peeling with cellophane tape. As a result, it was confirmed that there was no peeling of the print and good adhesion was exhibited.
The tensile breaking strength of the film was 20.2 MPa.

[Example 3]
The same procedure as in Example 2 was carried out except that the lubricant was changed to oxidized polyethylene wax "LICOWAX PED191".
The thickness of the obtained film was 0.1 mm, the film did not stick to the rolling roll, and the peelability was good.
Then, the film was printed, and the adhesion was evaluated by peeling with cellophane tape. As a result, it was confirmed that there was no peeling of the print and good adhesion was exhibited.
The tensile breaking strength of the film was 19.9 MPa.

[Example 4]
Example 1 was repeated except that the acrylic resin was changed to 100 parts by mass of the rubber-containing polymer (β-1) and the plasticizer was changed to 10 parts by mass of bis(2-ethylhexyl) terephthalate.
The thickness of the obtained film was 0.1 mm, the film did not stick to the rolling roll, and the peelability was good.
Then, the film was printed, and the adhesion was evaluated by peeling with cellophane tape. As a result, it was confirmed that there was no peeling of the print and good adhesion was exhibited.
The tensile breaking strength of the film was 15.7 MPa.

[Example 5]
The procedure of Example 4 was repeated, except that bis(2-ethylhexyl) terephthalate was changed to 5 parts by mass.
The thickness of the obtained film was 0.1 mm, and although the film was slightly attached to the rolling roll, the peelability was good.
Then, the film was printed, and the adhesion was evaluated by peeling with cellophane tape. As a result, it was confirmed that there was no peeling of the print and good adhesion was exhibited.
The tensile breaking strength of the film was 16.8 MPa.

[Example 6]
Example 4 was repeated except that bis(2-ethylhexyl) terephthalate was changed to 19 parts by mass.
The thickness of the obtained film was 0.1 mm, the film did not stick to the rolling roll, and the peelability was good.
Next, the film was printed, and the adhesion was evaluated by peeling with cellophane tape. It was confirmed that although the peeling of the print was slightly observed, the film showed good adhesion.
The tensile breaking strength of the film was 11.3 MPa.

[Example 7]
Example 6 was carried out in the same manner as in Example 6 except that 70 parts by mass of the rubber-containing polymer (β-1) and 30 parts by mass of the rubber-containing polymer (β-2) were used as the acrylic resin.
The thickness of the obtained film was 0.1 mm, the film did not stick to the rolling roll, and the peelability was good.
Next, the film was printed, and the adhesion was evaluated by peeling with cellophane tape. It was confirmed that although the peeling of the print was slightly observed, the film showed good adhesion.
The tensile breaking strength of the film was 13.5 MPa.

[Example 8]
As the plasticizer, the same procedure as in Example 7 was performed except that the amount of diisononyl adipate, which is an adipic acid plasticizer, was changed to 12 parts by mass.
The thickness of the obtained film was 0.1 mm, the film did not stick to the rolling roll, and the peelability was good.
Then, the film was printed, and the adhesion was evaluated by peeling with cellophane tape. As a result, it was confirmed that there was no peeling of the print and good adhesion was exhibited.
The tensile breaking strength of the film was 15.6 MPa.

[Example 9]
Example 8 was repeated except that the amount of diisononyl adipate was changed to 6 parts by mass.
The thickness of the obtained film was 0.1 mm, the film did not stick to the rolling roll, and the peelability was good.
Then, the film was printed, and the adhesion was evaluated by peeling with cellophane tape. As a result, it was confirmed that there was no peeling of the print and good adhesion was exhibited.
The tensile breaking strength of the film was 19.6 MPa.

[Example 10]
As the plasticizer, the same procedure as in Example 6 was carried out except that the amount of adipic acid polyester, which is a polyester plasticizer, was changed to 7 parts by mass.
The thickness of the obtained film was 0.1 mm, the film did not stick to the rolling roll, and the peelability was good.
Then, the film was printed, and the adhesion was evaluated by peeling with cellophane tape. As a result, it was confirmed that there was no peeling of the print and good adhesion was exhibited.
The tensile breaking strength of the film was 17.6 MPa.

[Comparative Example 1]
Example 6 was repeated except that no plasticizer was used.
Since no plasticizer was added, workability deteriorated, the thickness of the obtained film was 0.17 mm, and the film markedly stuck to the rolling roll, and it was difficult to peel the film.

[Comparative Example 2]
Example 6 was repeated except that bis(2-ethylhexyl) terephthalate was 5 parts by mass and no lubricant was used.
The thickness of the obtained film was 0.1 mm, and the lubricant was not added to the rolling roll, so that the film was markedly stuck and it was difficult to peel off the film.

[Comparative Example 3]
The procedure of Comparative Example 2 was repeated, except that the oxidized polyethylene wax “Hiwax 220MP” was changed to 0.4 parts by mass as a lubricant.
The thickness of the obtained film was 0.1 mm, and the amount of the lubricant added to the rolling roll was small, so that the film was significantly stuck and it was difficult to remove the film.

[Comparative Example 4]
The procedure of Comparative Example 2 was repeated, except that the polyethylene wax “LICOWAX PE190” was changed to 1.0 part by mass as the lubricant.
The thickness of the obtained film was 0.1 mm, and the viscosity of the lubricant was high, so that the film markedly adhered to the rolling roll, and it was difficult to peel off the film.

[Comparative Example 5]
Comparative Example 2 was repeated, except that zinc stearate "Zn-St" was changed to 1.0 part by mass as a lubricant.
The thickness of the obtained film was 0.1 mm, and although the film was slightly attached to the rolling roll, the peelability was good. However, the obtained film was inferior in appearance due to coloring and yellowing.

[Comparative Example 6]
The same procedure as in Comparative Example 2 was repeated except that the surface modifier "BYK307" as a lubricant was changed to 1.0 part by mass.
The thickness of the obtained film was 0.1 mm, and although the film was slightly attached to the rolling roll, the peelability was good. However, the obtained film was inferior in appearance due to coloring and yellowing.

[Comparative Example 7]
Comparative Example 2 was repeated except that the amount of ethylene bislauric acid amide "Sripax L" was changed to 1.0 part by mass as a lubricant.
The thickness of the obtained film was 0.1 mm, and although the film was slightly attached to the rolling roll, the peelability was good. However, the adhesion of the ink after applying the ink was poor, and the adhesion to the ink was poor.

The evaluation results of Examples 1 to 10 and Comparative Examples 1 to 7 described above are shown in Table 1 below.

[Example 11]
The resin composition prepared from the acrylic resin film of Example 1 was calendered in the same manner as in Example 1 to produce a white acrylic resin film having a thickness of 0.2 mm.
By using the obtained white acrylic resin film as a support and laminating a printing layer by the method described in Printability Evaluation 2, a decorative material was obtained.
This decorative material is placed in a mold having a vacuuming function so that the printing layer side is on the mold side, heated by a heater until the sheet reaches 190°C, and then vacuum-formed to a length of 150 mm. A box-shaped molded body having a width of 120 mm and a depth of 10 mm was obtained.
Then, unnecessary portions of the vacuum-formed decorative material (portions in the final laminate that do not adhere to the substrate) were trimmed using a Thomson punching die.
Next, the trimmed vacuum-molded decorative material is arranged so that the printing layer side is on the mold side, and the ABS resin melted on the base material side (manufactured by UMG ABS Co., Ltd., product name Diapet ABS "Bulksum TM25B" )) was injected, and a box-shaped molded product having a printed layer on the surface layer and having a length of 150 mm, a width of 120 mm, a thickness of 2 mm and a depth of 10 mm was obtained by insert molding.
Since the calendered film of the present invention is flexible, the obtained molded product is excellent in handleability (handling property) as a decorative material, and defects such as cracking due to trimming and peeling of the film from the ABS resin are observed. There wasn't. Further, since the decorative material of the present invention was able to sufficiently follow a mold having a three-dimensional shape, no defect in appearance due to poor follow-up of the decorative material was observed in the obtained molded body.

Thus, the acrylic resin composition obtained by the constitution of the present invention, an acrylic resin film formed by molding the acrylic resin composition, the releasability of the film from the rolling roll in calendar molding is good, Since it is also excellent in printability and strength, it can be suitably used for decorative sheets laminated with printing layers and for interior and exterior building applications.
Further, by using the calendered film of the present invention as a support, a decorative material having excellent processability can be obtained, and by molding it, a molded product using the film as a support can be provided. it can.

Acrylic resin composition obtained by the constitution of the present invention, an acrylic resin film formed by molding the acrylic resin composition, the peelability of the film from the rolling roll in calendar molding is good, printability and strength. Since it is also excellent, it can be suitably used for decorative sheets laminated with printing layers and for interior/exterior applications. Further, by using the calendered film of the present invention as a support, it is possible to obtain a decorative material having excellent processability, and further to provide a molded product using the film as a support by molding it. You can

Claims (7)

An acrylic resin, a plasticizer, and a polyolefin wax having a melt viscosity at 140° C. of 20000 mPa·s or less are contained, and the content of the polyolefin wax is 0.5 to 5 parts by mass with respect to 100 parts by mass of the acrylic resin. An acrylic resin composition for calender molding. A calender molding film comprising the acrylic resin composition according to claim 1. The calendered film according to claim 2, which has a tensile breaking strength of 12 MPa or more. A decorative sheet obtained by coloring the calendered film according to claim 2 or 3, or having a printed layer on at least one surface of the film. A decorative material comprising the decorative sheet according to claim 4. The decorative material according to claim 5, which is used for interior and exterior construction. A molded body using the decorative material according to claim 5.