JP2013189549A - Film and lamination sheet using this - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lamination sheet endowed with both of suppression of spontaneous delamination during processing and easy-delamination after molding.SOLUTION: A film has an olefin-based resin as a principal component, and a molar ratio of oxygen atoms and carbon atoms (oxygen atoms/carbon atoms) of at lease one surface, when measured by an X-ray photoelectron spectroscopy, is 0.03 or more and 0.15 or less.

Description

  The present invention relates to a film containing an olefin resin as a main component, and has a molar ratio of oxygen atoms to carbon atoms (oxygen atoms / carbon atoms) of at least one side measured by X-ray photoelectron spectroscopy of 0.03. When the thickness is 0.15 or less, for example, when used as a sheet for molding such as a transfer foil, the film does not spontaneously peel off from the resin laminated on the film during the process and can be easily peeled off after molding.

  In recent years, with the growing awareness of the environment, there has been an increasing demand for solvent-free painting and plating alternatives for building materials, automobile parts, mobile phones, electrical appliances, etc., and the introduction of decoration methods using films has progressed. As a method for decorating a substrate, a method is known in which a decoration layer is laminated on a thermoplastic resin film and transferred to the substrate simultaneously with molding. Moreover, the proposal of the film containing polyolefin resin is also made | formed with respect to such a decorating method (for example, refer patent document 1, 2).

  On the other hand, the proposal which improves adhesiveness with printing ink and a coating film by giving various surface treatments to a film is also made (for example, refer patent documents 3-5).

JP 2000-355082 A JP 2004-188708 A JP 2008-101110 A JP 2006-290108 A JP 2011-190378 A

  The film described in Patent Document 1 assumes adhesion with an acrylic resin or adhesive with an olefin resin in a molten state via an adhesive, and is used by peeling the film after molding like a transfer foil. It was not designed to be used.

  Patent Document 2 describes a film in which a release layer is formed and peeled off from a topcoat layer after molding in addition to being bonded to a polyester resin via an adhesive. However, depending on the material of the topcoat layer, there is a problem that the film and the topcoat layer are spontaneously peeled during the molding process, and the surface appearance after molding is lowered.

  The films described in Patent Documents 3 to 5 are subjected to corona treatment or UV treatment on the olefin film to improve the adhesion with the printing ink and the coating film, but the surface treatment is strong, so the adhesion is improved. There is a problem that the film is strong or the film is easily deformed, and the design is not sufficiently considered for the use in which the film is peeled off after use as in the case of a transfer foil.

  Accordingly, an object of the present invention is to eliminate the above-described problems. That is, it is to provide a film that, when used as a molding sheet such as a transfer foil, does not spontaneously peel off from the resin laminated on the film during the process and can be easily peeled off after molding.

The present invention for solving the above problems has the following configuration.
(1) A film mainly composed of an olefin resin,
A film characterized by having a molar ratio of oxygen atom to carbon atom (oxygen atom / carbon atom) of at least one surface of 0.03 or more and 0.15 or less as measured by X-ray photoelectron spectroscopy.
(2) The film according to (1), wherein the film contains a cyclic olefin-based resin as a main component.
(3) The film has an a1 layer and an a2 layer,
The cyclic olefin layer (a1 layer) having a cyclic olefin resin as a main component has a cyclic olefin layer (a2 layer) having a cyclic olefin resin as a main component on at least one side of the cyclic olefin resin as a main component according to (1) or (2). the film.
(4) The a1 layer is mainly composed of a cyclic olefin copolymer resin (hereinafter referred to as COC),
The said a2 layer is a film as described in (3) which has a cyclic olefin resin (henceforth COP) as a main component.
(5) The film according to (3) or (4), wherein the a2 layer, the a1 layer, and the a2 layer are directly laminated in this order.
(6) Any of (3) to (5), wherein the a1 layer includes 1 to 40% by mass of a polyethylene resin and / or a polypropylene resin with respect to 100% by mass of the entire a1 layer. Film.
(7) The glass transition temperature of the film is 80 ° C. or higher,
The elongation at break at a glass transition temperature of −20 ° C. of the film is 200% or less,
The film in any one of (1)-(6) whose breaking elongation in glass transition temperature +20 degreeC of a film is 500% or more.
(8) When the film according to any one of (1) to (7) is used as the thermoplastic resin base material (A) layer, the resin (B ) Layer
The peel strength between the thermoplastic resin substrate (A) layer and the resin (B) layer at 25 ° C. is 0.005 N / 10 mm or more and 2 N / 10 mm or less,
The laminated sheet whose peeling strength of the said thermoplastic resin base material (A) layer and resin (B) layer in 100 degreeC is 0.005 N / 10mm or more and 2 N / 10mm or less.
(9) The laminated sheet according to (8), which satisfies the following formula (I).
0.5 ≦ {(M ₁ −M ₀ ) −M ₂ } / (M ₁ −M ₀ ) × 100 ≦ 10 (I)
However, M ₀ : Mass of the thermoplastic resin substrate (A) layer M ₁ : Mass of the laminated sheet M ₂ : After peeling the thermoplastic resin substrate (A) layer from the laminated sheet and storing at 140 ° C. for 30 minutes (10) The laminated sheet according to (8) or (9), wherein the resin (B) layer contains a curable resin as a main component.
(11) 100% elongation stress at the glass transition temperature of the thermoplastic resin substrate (A) layer + 20 ° C. of the sheet containing the resin (B) layer obtained by peeling the thermoplastic resin substrate (A) layer from the laminated sheet The laminated sheet according to any one of (8) to (10), wherein (F100 value) is 3 MPa or less.
(12) The resin (B) layer, the decoration (C) layer, and the adhesion (D) layer are provided in this order on at least one side of the plastic resin base material (A) layer, in any one of (8) to (11) The laminated sheet as described.
(13) The laminated sheet according to any one of (8) to (12), which is used for molding.

  In the present invention, the molar ratio of oxygen atom to carbon atom (oxygen atom / carbon atom) measured by X-ray photoelectron spectroscopy is 0.03 or more and 0.0. By setting it to 15 or less, for example, when used as a molding sheet such as a transfer foil, it is possible to achieve both natural peeling suppression with the resin laminated on the film and easy peeling after molding from the building material, It can be suitably used for decorating molded parts such as automobile parts, mobile phones, electrical products, and gaming machine parts.

  The film of the present invention containing an olefin resin as a main component has a molar ratio of oxygen atom to carbon atom (oxygen atom / carbon atom) of at least one surface of 0.03 or more and 0 as measured by X-ray photoelectron spectroscopy. .15 or less. Here, the molar ratio of oxygen atom to carbon atom (oxygen atom / carbon atom) in the present invention means that at least one surface of a film placed in an ultra-high vacuum is irradiated with soft X-rays, and photoelectrons emitted from the surface are Detected with an analyzer (photoelectron escape angle: 45 °), and obtained data were obtained by performing spectrum smoothing (9-point smoothing), horizontal axis correction (C1s main peak adjusted to 284.6 eV), Refers to the molar ratio of oxygen atoms to carbon atoms.

  When the molar ratio of oxygen atom to carbon atom (oxygen atom / carbon atom) is less than 0.03, when the film is used as a molding sheet such as a transfer foil, the natural ratio of the resin laminated to the film during the process Peeling may occur and the surface appearance after molding may be deteriorated. Moreover, when the molar ratio of oxygen atom to carbon atom (oxygen atom / carbon atom) exceeds 0.15, when the film is used as a molding sheet such as a transfer foil, peeling after molding becomes heavy, It may be difficult to peel off, or the appearance of the molded body may be deteriorated due to peeling marks generated when peeling is performed by applying a strong force.

  In the present invention, when the molar ratio of oxygen atoms to carbon atoms (oxygen atoms / carbon atoms) on at least one side of the film is within a specific range, for example, when used as a molding sheet such as a transfer foil, It has been found that the natural peeling of the resin laminated on the film during the process can be suppressed without impairing easy peelability. In addition, at least one side of the film of the present invention containing an olefin-based resin as a main component from the viewpoint of better coexistence of easy peeling after molding and suppression of natural peeling between the resin laminated on the film in the process. The molar ratio of oxygen atom to carbon atom (oxygen atom / carbon atom) is preferably 0.04 or more and 0.14 or less, and more preferably 0.05 or more and 0.13 or less.

  The method of setting the molar ratio of oxygen atom to carbon atom (oxygen atom / carbon atom) on at least one side of the film containing olefin resin as a main component (oxygen atom / carbon atom) to 0.03 or more and 0.15 or less is not particularly limited. Examples thereof include a method of modifying one side of a film mainly containing a resin, a method of containing a resin having a polar group in at least the surface layer of a film mainly containing an olefin resin, and oxygen atoms on one side of the film. From the point that the molar ratio of oxygen and carbon atoms (oxygen atom / carbon atom) can be precisely controlled, and there is no change in the mechanical and thermal properties of the film due to the inclusion of a resin having a polar group. A method of performing the modification treatment is preferable.

  In the present invention, the method for the modification treatment performed on one side of the film is not particularly limited. For example, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, laser treatment, flame treatment, high frequency treatment, glow discharge treatment, ozone oxidation treatment Corona discharge treatment and ultraviolet irradiation treatment are preferably used from the viewpoint of less thermal deformation of the film during the reforming treatment, and the molar ratio of oxygen atoms to carbon atoms (oxygen atoms) on one side of the film is particularly highly accurate. / Carbon atom) can be controlled to 0.03 or more and 0.15 or less, and therefore, ultraviolet irradiation treatment is preferably used. The ultraviolet irradiation treatment and the corona discharge treatment may be performed in air, nitrogen, carbon dioxide, and a mixture thereof.

When ultraviolet irradiation treatment is used as a method for modifying one side of the film, various light sources such as a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, and an excimer lamp can be used. Of these, excimer lamps and low-pressure mercury lamps are preferred from the viewpoint of less thermal deformation of the film. The preferable integrated light quantity for controlling the molar ratio of oxygen atoms to carbon atoms (oxygen atoms / carbon atoms) on at least one side of the film to 0.03 or more and 0.15 or less is when a metal halide lamp or a high-pressure mercury lamp is used. Preferably has an integrated light quantity of 300 to 390 nm of 1,000 mJ / cm ² or more. On the other hand, when the integrated light quantity is increased, heat generation increases, and therefore, in consideration of damage to the film, it is preferably 20,000 mJ / cm ² or less. In the case of using a low-pressure mercury lamp, the integrated amount of light at 230~280nm is preferably at 200 mJ / cm ² or more 1,000 mJ / cm ² or less, more not less 400 mJ / cm ² or more 800 mJ / cm ² or less preferable. In the case of excimer lamp, the integrated amount of light at 140~227nm is preferably at 10 mJ / cm ² or more 130 mJ / cm ² or less, more preferably 20 mJ / cm ² or more 65 mJ / cm ² or less, 30 mJ It is particularly preferred that it is not less than / cm ^{2 and not} more than 50 mJ / cm ² .

  When ultraviolet irradiation treatment is used as a method for modifying the film surface, the total irradiation time to the film is preferably shorter from the viewpoint of suppressing thermal deformation of the film. Specifically, it is preferably 60 seconds or shorter, more preferably 30 seconds or shorter, particularly preferably 20 seconds or shorter. The total irradiation time is preferably 2 seconds or more from the viewpoint of proceeding with the modification treatment. Here, the total irradiation time refers to the total time that has passed through the space that receives ultraviolet rays from the ultraviolet lamp, and it may be either continuous irradiation or repeated irradiation and non-irradiation alternately. When the thermal deformation of the film is large, it is preferable to repeat irradiation and non-irradiation alternately and cool the film during non-irradiation.

  When corona discharge treatment is used as a method for modifying one side of the film, the molar ratio of oxygen atoms to carbon atoms (oxygen atoms / carbon atoms) of the film mainly composed of an olefin resin is the strength during corona discharge treatment (E Control is possible by changing the (value). Here, E value = W / (D × V), where W is the processing strength (W), D is the processing width (m), and V is the film speed (m / min).

When corona discharge treatment is used as a method for modifying the film surface, if the E value is increased too much, peeling after molding becomes heavy when the film is used as a molding sheet such as a transfer foil, and the film is peeled off. In some cases, the appearance of the molded body may be deteriorated due to peeling marks generated when peeling by applying a strong force. On the other hand, if the E value is too small, when the film is used as a molding sheet such as a transfer foil, natural peeling may occur from the resin laminated on the film during the process, and the surface appearance after molding may deteriorate. Therefore, E value in the case of using a corona discharge treatment is preferably 1～40W · min / ^{m 2,} more preferably 2～30W · min / ^{m 2,} particularly preferably 3～15W · min / ^{m 2.}

  In the film mainly composed of the olefin resin of the present invention, the olefin resin is mainly used as a method for adjusting the molar ratio of oxygen atom to carbon atom (oxygen atom / carbon atom) to 0.03 or more and 0.15 or less. When using a method in which a resin having a polar group is contained in at least the surface layer of the film as a component, the polar group is a functional group containing an atom having a large electronegativity such as an oxygen atom or a nitrogen atom. And functional groups such as groups, acid anhydride groups, epoxy groups, amide groups, ester groups and hydroxyl groups, and substituents containing these functional groups.

  The resin having a polar group is preferably a modified olefin resin from the viewpoint of compatibility with the main component olefin resin constituting the film of the present invention. Here, the modified olefin resin refers to an olefin resin having one or more polar groups at least one of one end, both ends, and the inside of the olefin resin.

  Examples of such modified olefin resins include ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylic acid copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer. Olefin-based copolymer resins containing polar groups such as acid copolymers, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-α Olefin copolymer, polypropylene, ethylene-propylene copolymer, methylpentene polymer, other random copolymers composed of α-olefin monomers, olefin resins such as block copolymers, or cyclic olefin resins, acrylic acid, Methacrylic acid, maleic anhydride, An olefin resin modified with a malic acid or other unsaturated carboxylic acid, or a side chain having a carbonyl group, a carboxyl group or an ester group, or modified by oxidative decomposition of the resin can be used.

  Examples of the α-olefin monomer include ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and the like, and are randomly composed of such α-olefin monomers. As the copolymer, for example, a propylene copolymer is a polymer obtained by random copolymerization of propylene and one or more α-olefin monomers excluding propylene from the α-olefin monomer. Polypropylene obtained by copolymerizing one or more α-olefin monomers excluding propylene in a range of 2 to 15% by mass by a method.

  Examples of such modified olefinic resins, such as modified olefinic resins modified with unsaturated carboxylic acids, include “Yumex” manufactured by Sanyo Chemical Co., Ltd., “Admer” manufactured by Mitsui Chemicals, Inc., Mitsubishi Chemical Corporation ) “Modic” manufactured by Toyo Kasei Co., Ltd. “Toyo Tac”, DuPont “Fusabond” and the like. Examples of the modified olefin resin modified by oxidative decomposition of the resin include “Biscol” and “Sun Wax” manufactured by Sanyo Kasei Co., Ltd. Examples of the modified olefin resin obtained by modifying the cyclic olefin resin include “Arton” manufactured by JSR Corporation.

  The film mainly composed of an olefin resin according to the present invention is a film having a molar ratio of oxygen atom to carbon atom (oxygen atom / carbon atom) of 0.03 or more and 0.15 or less, and suppresses natural peeling during the process. From the viewpoint of achieving both easy peelability after the process, the surface free energy is preferably 26 mN / m or more and 50 mN / m or less.

  The surface free energy of the surface of the film of the present invention in which the molar ratio of oxygen atom to carbon atom (oxygen atom / carbon atom) is 0.03 or more and 0.15 or less is particularly required to be easily peelable. Is preferably 26 or more and 38 mN / m or less, and is particularly preferably 38 or more and 42 N / m or less for use in which natural peeling suppression after the process is required during the process.

  The film of the present invention must contain an olefin resin as a main component. Here, the main component means that 50 mass% or more and 100 mass% or less of the olefin resin is contained when the total of all the components of the film is 100 mass%. The film of the present invention contains an olefin resin as a main component, and as the olefin resin, an olefin resin other than a cyclic olefin resin and a cyclic olefin resin described later can be used.

  The film of the present invention preferably contains a cyclic olefin resin as a main component as an olefin resin from the viewpoint of improving heat resistance during coating drying in addition to solvent resistance and easy peelability. Here, the main component of the cyclic olefin resin means that the cyclic olefin resin is contained in an amount of 50% by mass to 100% by mass when the total of all the components of the film is 100% by mass. The cyclic olefin-based resin refers to a resin having an alicyclic structure in the main chain of a polymer obtained by polymerization from a cyclic olefin as a monomer.

  Further, the cyclic olefin resin in the present invention is a resin obtained by polymerizing a cyclic olefin monomer and the like, and the total of the components derived from the cyclic olefin monomer is 50% in 100% by mass of the polymer of the cyclic olefin resin. The polymer of the aspect which is the mass% or more and 100 mass% or less is meant.

Cyclic olefin monomers include monocyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclopentadiene, 1,3-cyclohexadiene, bicyclo [2,2,1] hept-2-ene, 5-methyl-bicyclo [ 2,2,1] hept-2-ene, 5,5-dimethyl-bicyclo [2,2,1] hept-2-ene, 5-ethyl-bicyclo [2,2,1] hept-2-ene, 5-butyl-bicyclo [2,2,1] hept-2-ene, 5-ethylidene-bicyclo [2,2,1] hept-2-ene, 5-hexyl-bicyclo [2,2,1] hept- 2-ene, 5-octyl-bicyclo [2,2,1] hept-2-ene, 5-octadecyl-bicyclo [2,2,1] hept-2-ene, 5-methylidene-bicyclo [2,2,1] hept-2-ene, 5-vinyl-bicyclo [2,2,1] hept-2-ene, 5-propenyl-bicyclo [2,2,1] hept-2-ene Cyclic olefin, tricyclo [4,3,0,1 ^2.5 ] deca-3,7-diene, tricyclo [4,3,0,1 ^2.5 ] dec-3-ene, tricyclo [4,3, 0,1 ^2.5 ] undeca-3,7-diene or tricyclo [4,3,0,1 ^2.5 ] undeca-3,8-diene or partial hydrogenates thereof (or addition of cyclopentadiene and cyclohexene) as an object) tricyclo [4,3,0,1 ^2.5] undec-3-ene; 5- cyclopentyl - bicyclo [2,2,1] hept-2-ene, 5-cyclohexyl - bicyclo [2,2 , 1] hept-2-ene, 5-cycl Hexenyl bicyclo [2,2,1] hept-2-ene, 5-phenyl - Three such bicyclo [2,2,1] hept-2-ene cyclic olefins, tetracyclo [4,4,0,1 ^2.5 , 1 ^7.10 ] dodec-3-ene, 8-methyltetracyclo [4,4,0,1 ^2.5 , 1 ^7.10 ] dodec-3-ene, 8-ethyltetracyclo [4,4, 0,1 ^2.5 , 1 ^7.10 ] dodec-3-ene, 8-methylidenetetracyclo [4,4,0,1 ^2.5 , 1 ^7.10 ] dodec-3-ene, 8-ethylidene Tetracyclo [4,4,0,1 ^2.5 , 1 ^7.10 ] dodec-3-ene, 8-vinyltetracyclo [4,4,0,1 ^2.5 , 1 ^7.10 ] dodec-3 - ene, 8-propenyl - tetracyclo ^{[4,4,0,1 2.5, 1 7.10]} Tetracyclic olefin such dec-3-ene, 8-cyclopentyl-- tetracyclo ^{[4,4,0,1 2.5, 1 7.10]} dodeca-3-ene, 8-cyclohexyl - tetracyclo [4,4,0 , ^{1 2.5, 1 7.10]} dodeca-3-ene, 8-cyclohexenyl - tetracyclo ^{[4,4,0,1 2.5, 1 7.10]} dodeca-3-ene, 8-phenyl - cyclopentyl - tetracyclo ^{[4,4,0,1 2.5, 1 7.10]} dodeca-3-ene, tetracyclo ^{[7,4,1 3.6,} 0 ^{1.9, 0 2.7]} tetradeca -4 , 9,11,13- tetraene, tetracyclo ^{[8,4,1 4.7,} 0 1.10 ^{0 3.8]} pentadeca -5,10,12,14- tetraene, pentacyclo [6,6,1 ^{3 .6} , 0 ^2.7 , 0 ^9.14 ] -4-hexadecene, pentacyclo ^{[6,5,1,1 3.6,} 0 ^{2.7, 0 9.13]} -4-pentadecene, pentacyclo ^[7,4,0,0 2.7, ^{1 3. 6, 1 10.13]} -4-pentadecene, heptacyclo ^{[8,7,0,1 2.9,} 1 ^{4.7, 1 11.17, 0 3.8, 0 12.16]} -5-eicosene, Heptacyclo [8,7,0,1 ^2.9 , 0 ^3.8 , 1 ^4.7 , 0 ^12.17 , 1 ^13.16 ] ^-14 polycyclic olefins such as tetramers such as ^{eicosene and} cyclopentadiene Etc. These cyclic olefin monomers can be used alone or in combination of two or more.

  Among the above mentioned cyclic olefin monomers, bicyclo [2,2,1] hept-2-ene (hereinafter referred to as norbornene), tricyclo [4,3,0,12. 5] Tricyclic olefins having 10 carbon atoms (hereinafter referred to as tricyclodecene), tetracyclo [4,4,0,12.5,17.10] dodec-3-ene, such as deca-3-ene Of these, a tetracyclic olefin having 12 carbon atoms (hereinafter referred to as tetracyclododecene), cyclopentadiene, or 1,3-cyclohexadiene is preferably used.

  The cyclic olefin resin polymerized only the cyclic olefin monomer as long as the total of the components derived from the cyclic olefin monomer was 50% by mass or more and 100% by mass or less in 100% by mass of the polymer of the cyclic olefin resin. Any resin of resin and resin obtained by copolymerizing the cyclic olefin monomer and the chain olefin monomer may be used.

  Examples of a method for producing a resin obtained by polymerizing only a cyclic olefin monomer include known methods such as addition polymerization or ring-opening polymerization of a cyclic olefin monomer. For example, norbornene, tricyclodecene, tetracyclodecene, and derivatives thereof Ring-opening metathesis polymerization followed by hydrogenation, norbornene and its derivatives by addition polymerization, cyclopentadiene, cyclohexadiene after 1,2-, 1,4-addition polymerization and hydrogenation It is done. Among these, from the viewpoint of productivity, surface property, and moldability, a resin obtained by hydrogenating norbornene, tricyclodecene, tetracyclodecene, and derivatives thereof after ring-opening metathesis polymerization is most preferable.

  In the case of a resin obtained by copolymerizing a cyclic olefin monomer and a chain olefin monomer, preferred chain olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-1-butene. 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl- 1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc. Can be mentioned. Among these, ethylene can be particularly preferably used from the viewpoint of productivity and cost. Examples of the method for producing a resin obtained by copolymerizing a cyclic olefin monomer and a chain olefin monomer include known methods such as addition polymerization of a cyclic olefin monomer and a chain olefin monomer. For example, norbornene and its derivatives Examples include a method of addition polymerization of ethylene. Among these, from the viewpoints of productivity, surface properties, and moldability, a copolymer of norbornene and ethylene is most preferable.

  In the film of the present invention, when the cyclic olefin-based resin is a main component, the film of the present invention may be composed of only the cyclic olefin-based resin, or may contain other olefin-based resins. You may contain resin other than resin.

  Examples of the olefin resin other than the cyclic olefin resin used in the film of the present invention having a cyclic olefin resin as a main component include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, and metallocene. Polyethylene resin such as ethylene-α / olefin copolymer polymerized using catalyst, polypropylene resin such as polypropylene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, polyolefin such as methylpentene polymer Series resins can be used. Further, a polymer composed of an α-olefin monomer such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and a random copolymer composed of the α-olefin monomer. Also, a block copolymer comprising the α-olefin monomer can be used. Among these, from the viewpoint of compatibility with the cyclic olefin resin, various polyethylene resins and various polypropylene resins are preferably used as the olefin resin other than the cyclic olefin resin.

  When the film of the present invention contains a cyclic olefin-based resin as a main component, by further including a polyethylene-based resin and a polypropylene-based resin, the shear stress in the extrusion process can be reduced, and the generation of foreign matters due to cross-linking is prevented. This is preferable because it can be suppressed and toughness can be further improved. On the other hand, when the content of polyethylene resin or polypropylene resin increases, the self-holding property tends to decrease. From the viewpoint of quality, toughness, and self-holding property, the content of the polyethylene resin and / or the polypropylene resin may be 1 to 40% by mass with respect to 100% by mass in total of all components of the film of the present invention. Preferably, 1 to 30% by mass is more preferable, and 1 to 20% by mass is most preferable. Among polyethylene resins and polypropylene resins, polyethylene resins are preferably used from the viewpoint of compatibility with cyclic olefin resins, and low density polyethylene and linear low density polyethylene are particularly preferably used. Density polyethylene is most preferably used. When the film of the present invention contains a cyclic olefin resin as a main component, when the polyethylene resin and the polypropylene resin are both contained, the total amount of the polyethylene resin and the polypropylene resin is within the above-described range, that is, It is preferable to set it as 1-40 mass% with respect to the total of 100 mass% of all the components of a film, It is more preferable if it is 1-30 mass%, Most preferably, it is 1-20 mass%.

  In addition, the polyethylene-type resin in this invention means the polymer of the aspect whose sum total of an ethylene origin component is 50 to 100 mass% in 100 mass% of polymers of a polyethylene-type resin.

  Moreover, the polypropylene resin in the present invention means a polymer in an aspect in which the total of propylene-derived components is 50% by mass or more and 100% by mass or less in 100% by mass of the polymer of the polypropylene resin.

  In the present invention, when the cyclic olefin-based resin is a main component, from the viewpoint of self-holding property, the total thickness may be 100%, and the total thickness of layers having a glass transition temperature of 80 ° C. or higher may be 50% or higher. preferable. Here, “the total thickness of the layers having a glass transition temperature of 80 ° C. or higher” means the thickness of the layer when the glass transition temperature is 80 ° C. or higher, and the glass transition temperature is 80 ° C. or higher. When there are a plurality of layers, this is the total thickness of those layers. The method for controlling the glass transition temperature of each layer is not particularly limited. For example, when a copolymer of norbornene and ethylene is used as the cyclic olefin resin, the glass transition temperature can be increased by increasing the content of norbornene in the layer. The temperature can be increased. Furthermore, the glass transition temperature of the layer can also be adjusted by blending two kinds of cyclic olefin resins having different norbornene contents. In addition, for example, when a cyclic hydrogenated resin obtained by subjecting norbornene, tricyclodecene, and their derivatives to hydrogenation after ring-opening metathesis polymerization is used as the cyclic olefin resin, the cyclic olefin to be polymerized (norbornene, tricyclodecene, tetracyclohexene, The glass transition temperature can be increased by increasing the molecular weight of cyclodecene and derivatives thereof, or by increasing the number of rings to form a rigid structure. In addition, the glass transition temperature of the layer can also be increased by blending two types of norbornene, tricyclodecene, tetracyclodecene, and their derivatives, which have different glass transition temperatures, and hydrogenated resins after the ring-opening metathesis polymerization. Can be adjusted.

  More preferably, the total thickness of layers having a glass transition temperature of 85 ° C. or higher is 50% or higher when the total thickness is 100%, and the total thickness of layers having a glass transition temperature of 90 ° C. or higher is 50% or higher. Is particularly preferred. When there are a plurality of glass transition temperatures, such as when a plurality of resins are mixed in one layer, the glass transition temperature on the high temperature side is set as the glass transition temperature of the layer.

  When the film of the present invention has a cyclic olefin-based resin as a main component, the film has an a1 layer and an a2 layer, and is cyclic on at least one surface of a cyclic olefin layer (a1 layer) that has a cyclic olefin-based resin as a main component. It is preferable to have the cyclic olefin layer (a2 layer) which has an olefin resin as a main component.

  About a1 layer, having cyclic olefin resin as a main component means that the sum total of all the components of a1 layer is 100 mass%, and contains 50 mass% or more and 100 mass% or less of cyclic olefin resin. The a1 layer is more preferably an aspect containing 70% by mass or more and 100% by mass or less of a cyclic olefin-based resin, with the total of all components of the layer being 100% by mass, and further if it is an aspect containing 80% by mass or more and 100% by mass or less. An embodiment containing 90% by mass or more and 100% by mass or less is particularly preferable.

  About a2 layer, making cyclic olefin resin the main component means that the sum total of all the components of a2 layer is 100 mass%, and contains 50 to 100 mass% of cyclic olefin resin. The a2 layer is more preferably an aspect containing 70% by mass or more and 100% by mass or less of the cyclic olefin-based resin, with the total of all components of the layer being 100% by mass, and further if it is an aspect containing 80% by mass or more and 100% by mass or less An embodiment containing 90% by mass or more and 100% by mass or less is particularly preferable. When the a2 layer is a single layer, the total of all the components of the a2 layer is 100% by mass, and the cyclic olefin resin is contained in an amount of 50% by mass to 100% by mass. When there are two layers, it is determined whether each layer has a cyclic olefin resin as a main component. That is, for one of the two a2 layers, when the total of all components of the a2 layer is 100% by mass, the cyclic olefin resin is contained in an amount of 50% to 100% by mass. The layer is the main component, and the same determination is made for the other a2 layer.

  The cyclic olefin-based resin has lower toughness than the polyethylene-based resin and the polypropylene-based resin, but the toughness can be improved by including the polyethylene-based resin and the polypropylene-based resin. On the other hand, when a polyethylene resin or a polypropylene resin is contained, the surface appearance tends to be lowered. For this reason, in order to achieve both toughness and surface appearance, the film of the present invention containing an olefin resin as a main component is cyclic on at least one surface of a cyclic olefin layer (a1 layer) containing a cyclic olefin resin as a main component. It is preferable to have the cyclic olefin layer (a2 layer) which has an olefin resin as a main component, and said a1 layer is 1 to polyethylene resin and / or polypropylene resin with respect to 100 mass% of the whole (a1 layer). It is preferable to contain 40 mass%. Here, when the a1 layer includes a polyethylene resin and a polypropylene resin, the a1 layer is 1 to 40% by mass in total of the polyethylene resin and the polypropylene resin with respect to 100% by mass of the entire (a1 layer). It is preferable to include.

  In addition, from the viewpoint of toughness and self-holding property, the polyethylene resin and / or polypropylene resin in (a1 layer) is preferably 1 to 30% by mass with 100% by mass as a whole (a1 layer), 1 to 20% by mass is most preferable.

  From the viewpoint of surface appearance, the content of the polyethylene resin and / or the polypropylene resin in the cyclic olefin layer (a2 layer) mainly composed of the cyclic olefin resin is based on 100 mass% of the total (a2 layer). The content is preferably 0% by mass or more and 10% by mass or less, more preferably 0% by mass or more and 5% by mass or less, and most preferably the polyethylene resin and / or the polypropylene resin is 0% by mass.

  When the film of the present invention has an a1 layer and an a2 layer, the lamination ratio (total thickness of a2 layer / a1 layer thickness) is 0.25 from the viewpoint of toughness, self-holding property, and surface appearance. ~ 1 is preferred. The stacking ratio (total thickness of a2 layers / a1 layer thickness) is the sum of the thicknesses of a2 layers existing when there are two a2 layers / thickness of a1 layers. The total thickness of the a2 layer / the thickness of the a1 layer is the thickness of the a2 layer / the thickness of the a1 layer when the a2 layer is one layer. The lamination ratio (total thickness of a2 layers / thickness of a1 layers) is more preferably 0.4 to 0.8. The lamination ratio can be measured by observing the cross section of the film with a scanning electron microscope, a transmission electron microscope, an optical microscope or the like at a magnification of 500 to 10,000 times.

  Moreover, it is preferable that the film of this invention is the structure on which the a2 layer, the a1 layer, and the a2 layer were directly laminated | stacked in this order from a viewpoint of handleability. Here, “directly laminated” means a state where other layers such as an adhesive layer are not interposed between the a1 layer and the a2 layer.

  In the present invention, the a1 layer preferably contains a cyclic olefin copolymer resin (hereinafter referred to as COC) as a main component, and the a2 layer preferably contains a cyclic olefin resin (hereinafter referred to as COP) as a main component. With this configuration, particularly excellent moldability, surface appearance, and toughness can be achieved.

  In the present invention, COP means a resin in an embodiment in which only “a repeating unit containing a cyclic olefin in the main chain” is polymerized. The COC in the present invention is an embodiment in which at least two or more kinds of repeating units of “a repeating unit containing a cyclic olefin in the main chain” and “a repeating unit made of an olefin not containing a cyclic olefin in the main chain” are polymerized. It means a resin (a repeating unit containing a cyclic olefin may be referred to as a cyclic olefin monomer).

  Here, CO1 as the main component in the a1 layer means that the a1 layer contains 50% by mass or more and 100% by mass or less of COC, where the total of all components of the a1 layer is 100% by mass. The aspect which contains 70 mass% or more and 100 mass% or less of COC is more preferable when the sum total of all the components of a1 layer is 100 mass%, It is further more preferable if it is an aspect containing 80 mass% or more and 100 mass% or less, 90 mass% or more and 100 It is particularly preferable if it is an embodiment containing at most mass%.

  Further, the C2 as a main component in the a2 layer means that the total of all components in the a2 layer is 100% by mass, and the COP is contained in an amount of 50% by mass to 100% by mass. More preferably, the total content of all components of the a2 layer is 100% by mass, and COP is 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less. It is particularly preferable if it is an embodiment containing at most mass%. When the a2 layer is a single layer, the total of all components of the a2 layer is 100% by mass, and the COP is contained in an amount of 50% to 100% by mass. If it exists, it is determined whether each layer has COP as a main component. That is, for one of the two a2 layers, when the total of all components of the a2 layer is 100% by mass and the COP is contained in an amount of 50% by mass to 100% by mass, the a2 layer is mainly used. The determination is made in the same manner for the other a2 layer.

  From the viewpoints of moldability and self-holding property, the film of the present invention has a glass transition temperature of 80 ° C. or higher, a glass transition temperature of the film of −20 ° C. and a breaking elongation of 200% or lower. The elongation at break at the transition temperature + 20 ° C. is preferably 500% or more. By setting the glass transition temperature to 80 ° C. or more and the elongation at break at a glass transition temperature of −20 ° C. to 200% or less, sufficient self-holding property can be secured, and handling properties are improved.

  The glass transition temperature of the film of the present invention is more preferably 85 ° C. or higher, and particularly preferably 90 ° C. or higher. Moreover, it is preferable that the glass transition temperature of the film of this invention is 160 degrees C or less. The elongation at break of the film of the present invention at a glass transition temperature of −20 ° C. is more preferably 190% or less, and most preferably 180% or less from the viewpoint of self-holding property and brittleness resistance. The elongation at break of the film of the present invention at a glass transition temperature of −20 ° C. is preferably 3% or more, more preferably 90% or more, and particularly preferably 100% or more. Moreover, the outstanding moldability can be made compatible by making the breaking elongation in glass transition temperature +20 degreeC of the film of this invention into 500% or more. The elongation at break of the film of the present invention at a glass transition temperature + 20 ° C. is more preferably 600% or more, and most preferably 700% or more from the viewpoint of moldability and dimensional stability. The elongation at break of the film of the present invention at the glass transition temperature + 20 ° C. is preferably 2,000% or less, more preferably 1,000% or less, and particularly preferably 970% or less.

  As a method for setting the glass transition temperature of the film to 80 ° C. or more, the breaking elongation at a glass transition temperature of −20 ° C. of the film to 200% or less, and the breaking elongation at a glass transition temperature of the film + 20 ° C. of 500% or more. And a method of using a cyclic olefin resin having a glass transition temperature of 80 ° C. or higher as a main component and a polyethylene resin and / or a polypropylene resin in an amount of 30% by weight or less.

  In addition, even when the film of the present invention is a laminated film or a single layer film and a plurality of resins are mixed, when the glass transition temperature of the film is measured, a plurality of glass transition temperatures are present. When observed, the glass transition temperature on the high temperature side is adopted as the glass transition temperature of the film.

  The film of the present invention is suitably used as a thermoplastic resin substrate (A) layer of a laminated sheet having a structure in which a resin (B) layer is laminated on at least one side of a thermoplastic resin substrate (A) layer. In addition, when the film of this invention is used as a thermoplastic resin base material (A) layer, the laminated sheet of the structure by which a resin (B) layer is laminated | stacked on at least one side is hereafter called the laminated sheet of this invention. . Since the configuration is not particularly limited as long as the resin (B) layer is laminated on at least one side of the thermoplastic resin substrate (A) layer, the laminate sheet of the present invention includes the thermoplastic resin substrate (A) layer and the resin. (B) Either the aspect in which the layer is directly laminated or the aspect in which the layer is laminated via another layer (such as a coating layer) may be used. For example, a configuration having a thermoplastic resin substrate (A) layer, a resin (B) layer, a decoration (C) layer, and an adhesive (D) layer in this order (the configuration is a thermoplastic resin substrate (A) layer / resin (B) layer / decoration (C) layer / adhesion (D) layer, and so on), thermoplastic resin substrate (A) layer / resin (B) layer / decoration (C) layer, thermoplastic The structure of resin base material (A) layer / resin (B) layer / adhesion (D) layer, thermoplastic resin base material (A) layer / resin (B) layer can be considered. In the laminated sheet of the present invention, when the resin (B) layer is laminated on at least one side of the thermoplastic resin base material (A) layer, the moles of oxygen atoms and carbon atoms in the thermoplastic resin base material (A) layer. It is preferable to have a resin (B) layer on the surface where the ratio (oxygen atom / carbon atom) is 0.03 or more and 0.15 or less. A coating layer for adjusting the peel strength between the thermoplastic resin substrate (A) layer and the resin (B) layer by adjusting the molar ratio of oxygen atoms to carbon atoms (oxygen atoms / carbon atoms) within such a range. Even if it does not provide, it is possible to achieve both the natural peeling suppression during the process and the easy peeling after the process.

  The film of the present invention is a thermoplastic resin substrate of a laminated sheet having a resin (B) layer, a decoration (C) layer, and an adhesive (D) layer in this order on at least one side of the thermoplastic resin substrate (A) layer. It can be suitably used as (A).

  The laminated sheet of the present invention preferably has a resin (B) layer on at least one side of the thermoplastic resin substrate (A) layer from the viewpoint of the appearance and durability of the molded article after molding decoration. Although it does not specifically limit as resin which a resin (B) layer contains, In order to provide durability, such as a weather resistance, a scratch resistance, an impact resistance, and water resistance, it is preferable that a curable resin is made into a main component. Here, the curable resin refers to a resin that is cured by three-dimensional crosslinking by applying heat or an electron beam. In the resin (B) layer, the phrase “having a curable resin as a main component” means that 50% by mass or more and 100% by mass or less of a curable resin is contained in 100% by mass of all components of the resin (B) layer. .

  When the resin (B) layer contains a curable resin as a main component, it is preferable that the resin (B) is cured after molding from the viewpoint of appearance and durability. This is not preferable because the properties are reduced. For this reason, before molding, it is preferable to be in a semi-cured state to such an extent that moldability can be maintained and handling properties do not deteriorate.

  As the thermosetting resin preferably used as the curable resin, for example, one or more selected from polycarbonate resin, acrylic resin, polyester resin, phenoxy resin, epoxy resin, polyolefin resin, and the like You may use what mixed these.

  Moreover, as an electron beam curable resin suitable as a curable resin, for example, 1 selected from urethane acrylate resins, polyester acrylate resins, unsaturated polyester resins, silicone acrylate resins, epoxy acrylate resins, and the like More than a seed. Moreover, when using an electron beam curable resin, you may use what mixed the photoinitiator etc. as needed.

  These thermosetting resins and electron beam curable resins may be mixed with curing agents, curing accelerators, binders, surface conditioners, pigments, plasticizers, ultraviolet absorbers, light stabilizers, etc. as necessary. May be.

  The thermosetting resin or electron beam curable resin may be a copolymer or a mixture of different resins.

  In the present invention, the thickness of the resin (B) layer is preferably 2 μm or more and 100 μm or less, more preferably 5 μm or more and 80 μm or less, from the viewpoint of appearance and durability, and 10 μm or more and 70 μm or less. Most preferred.

The resin (B) layer of the present invention is provided on one side of the thermoplastic resin base material (A) layer (that is, on one side of the thermoplastic resin base material (A) layer or separate from the thermoplastic resin base material (A) layer). (On one side of another layer in a laminate composed of the above layer) can be obtained by coating the raw material composition used to form the resin (B) layer. The method for coating the raw material composition used to form the resin (B) layer of the present invention is not particularly limited. For example, coating is performed using a gravure coater, bar coater, comma coater, die coater, knife coater, or the like. can do.

The laminated sheet of the present invention preferably has a decoration (C) layer from the viewpoint of design. In particular, it is preferable to have a resin (B) layer, a decoration (C) layer, and an adhesion (D) layer in this order on at least one side of the thermoplastic resin substrate (A) layer.

  In the present invention, the decoration (C) layer is a layer different from the thermoplastic resin base material (A) layer and the resin (B) layer, and is colored, uneven, patterned, wood grain, metal tone, pearl tone. For example, it is composed of a binder resin and a colorant. In the case of a metallic tone, it is composed of a metal thin film layer.

When the decoration (C) layer includes a binder resin and a colorant, a thermoplastic resin and / or a curable resin can be used as the binder resin. As a thermoplastic resin suitable as the binder resin, a resin obtained by mixing a solvent with a resin such as polyethylene resin, polypropylene resin, polycarbonate resin, acrylic resin, or polystyrene resin can be used. In addition, the curable resin suitable as the binder resin is preferably cured after molding from the viewpoint of appearance and durability. On the other hand, if it is cured before molding, the mold followability is lowered. This is not preferable. For this reason, before molding, it is preferable to be in a semi-cured state to such an extent that moldability can be maintained and handling properties do not deteriorate. In addition, it is preferable that binder resin has a curable resin as a main component. Here, the binder resin having a curable resin as a main component means that 50% by mass or more and 100% by mass or less of the curable resin is contained in 100% by mass of all components of the binder resin. As the curable resin, the resins listed in the resin (B) layer are preferably used. The binder resin may be a copolymer or a mixture of different resins. In the present invention, since it is easy to handle and inexpensive, a thermosetting resin is preferably used. In particular, from the viewpoint of moldability, a mixture containing a urethane resin and an acrylic resin can be used as a binder resin. preferable.

  The decorative (C) layer is preferably cured after molding from the viewpoint of durability after molding and surface glossiness. On the other hand, if it is cured before molding, molding followability is reduced. Therefore, it is not preferable. For this reason, before molding, it is preferable to be in a semi-cured state to such an extent that moldability can be maintained and handling properties do not deteriorate.

  In addition, as a colorant, from the viewpoint of dispersibility, appearance, and concealment, in particular, black pigments such as carbon black and black iron oxide, white pigments such as titanium oxide, barium sulfate, zinc white, and zinc sulfate, metal powder pigments, metal It is preferable to contain a metallic pigment such as a foil pigment or a metal-deposited foil pigment in an amount of 5% by mass to 30% by mass with respect to 100% by mass of all the components of the decoration (C) layer.

  In addition, when the decoration (C) layer is a metal thin film layer, a method for producing the metal film is not particularly limited, but a vacuum deposition method, an EB deposition method, a sputtering method, an ion plating method, or the like can be used. As the metal to be used, it is preferable to deposit a metal compound having a melting point of 150 to 400 ° C. from the viewpoint of molding followability and appearance. Although it does not specifically limit as a metal compound whose melting | fusing point is 150-400 degreeC, Indium (157 degreeC) and tin (232 degreeC) can use preferably.

The thickness of the decoration (C) layer of the present invention should be 0.5 μm or more and 50 μm or less from the viewpoint of base concealing property and thickness unevenness when the decoration (C) layer includes a binder resin and a colorant. Is preferably 1 μm or more and 40 μm or less. Further, when the decoration (C) layer is a metal thin film layer, the thickness of the decoration (C) layer is preferably 0.05 μm or more and 1.5 μm or less from the viewpoint of moldability and appearance after molding, and preferably 0.1 μm. More preferably, it is 1 μm or less.

The laminated sheet of the present invention preferably has an adhesive (D) layer from the viewpoint of adhesion to the adherend. The adhesion (D) layer means a layer having adhesion to an adherend. The adhesive (D) layer is preferably adjusted as appropriate according to the material of the adherend. For example, a phenol resin adhesive, a resorcinol resin adhesive, a phenol-resorcinol resin adhesive, an epoxy resin adhesive A radical-reactive adhesive comprising a thermosetting resin adhesive such as an adhesive, a urea resin adhesive, a polyurethane adhesive and a polyaromatic adhesive, or a radical polymerizable composition such as an unsaturated polyester or acrylate, Thermoplastic resin adhesive such as vinyl acetate resin, acrylic resin, acrylic urethane resin, ethylene vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, vinyl chloride, nylon and cyanoacrylate resin, polyolefin resin, chloroprene adhesive, nitrile rubber Adhesive, SBR adhesive and natural rubber Rubber adhesives such as wear agents.

  The thickness of the adhesive (D) layer in the present invention is preferably 0.1 μm or more and 50 μm or less, more preferably 1 μm or more and 40 μm or less from the viewpoint of adhesiveness and thickness unevenness, and 2 μm or more and 30 μm or less. Is most preferable.

The method for forming the colored (D) layer of the present invention is not particularly limited. For example, it can be formed by coating using a gravure coater, bar coater, comma coater, die coater, knife coater, or the like.

In the laminated sheet of the present invention, the peel strength between the thermoplastic resin substrate (A) layer and the resin (B) layer at 25 ° C. is preferably 0.005 N / 10 mm or more and 2 N / 10 mm or less. When the peeling strength at 25 ° C. is less than 0.005 N / 10 mm, the peeling strength is too low, and natural peeling may occur during processes such as sheet conveyance and winding. On the other hand, if the peel strength is greater than 2 N / 10 mm, it may be difficult to peel off after molding. The peel strength at 25 ° C. between the thermoplastic resin substrate (A) layer and the resin (B) layer is more preferably 0.01 N / 10 mm or more and 1 N / 10 mm or less, and 0.01 N / 10 mm or more and 0.5 N / Most preferably, it is 10 mm or less.

  In addition, regarding the peeling strength between the thermoplastic resin substrate (A) layer and the resin (B) layer at 25 ° C., a coating layer or the like is provided between the thermoplastic resin substrate (A) layer and the resin (B) layer. When the layer is interposed, there are a case where the thermoplastic resin substrate (A) layer and another layer peel off, and a case where the resin (B) layer and the other layer peel. Furthermore, in the case where a plurality of other layers are interposed between the thermoplastic resin base material (A) layer and the resin (B) layer, there are cases in which the separation occurs between the other layers. In the present invention, in any of the above cases, the thermoplastic resin substrate (A) layer and the resin (B) at 25 ° C. are regarded as peeling between the thermoplastic resin substrate (A) layer and the resin (B) layer. ) Determine the peel strength with the layer.

  In the laminated sheet of the present invention, the method for setting the peel strength between the thermoplastic resin substrate (A) layer and the resin (B) layer at 25 ° C. to 0.005 N / 10 mm or more and 2 N / 10 mm or less is not particularly limited. For example, the surface free energy of the surface in contact with the resin (B) layer of the thermoplastic resin substrate (A) layer is preferably 25 mN / m or more and 42 mN / m or less. Further, the oxygen atom and carbon on at least one surface of the thermoplastic resin substrate (A) layer, measured by X-ray photoelectron spectroscopy, of the surface of the thermoplastic resin substrate (A) layer in contact with the resin (B) layer The molar ratio of atoms (oxygen atom / carbon atom) is also preferably 0.03 or more and 0.15 or less.

  In the laminated sheet of the present invention, the peel strength between the thermoplastic resin substrate (A) layer and the resin (B) layer at 100 ° C. is preferably 0.005 N / 10 mm or more and 2 N / 10 mm or less. When the peeling strength at 100 ° C. is less than 0.005 N / 10 mm, the peeling strength when the laminated sheet is heated is too low, and natural peeling occurs during heating. On the other hand, when the peel strength is greater than 2 N / 10 mm, it becomes difficult to peel off after molding. The peel strength at 100 ° C. between the thermoplastic resin substrate (A) layer and the resin (B) layer is more preferably 0.01 N / 10 mm or more and 1 N / 10 mm or less, and more preferably 0.01 N / 10 mm or more and 0.5 N / Most preferably, it is 10 mm or less.

The peel strength at 100 ° C. of the present invention is interpreted similarly to the peel strength at 25 ° C. when another layer such as a coating layer is interposed between the thermoplastic resin substrate (A) layer and the resin (B) layer. That is, when another layer is interposed between the thermoplastic resin substrate (A) layer and the resin (B) layer, the case where the thermoplastic resin substrate (A) layer and the other layer peel off, Case where peeling occurs between the resin (B) layer and another layer, and when a plurality of other layers are interposed between the thermoplastic resin substrate (A) layer and the resin (B) layer, There are cases of peeling between these layers, and any case is regarded as peeling between the thermoplastic resin substrate (A) layer and the resin (B) layer, and the thermoplastic resin substrate (A) layer at 100 ° C. And peel strength between the resin (B) layer.

In the laminated sheet of the present invention, the method of setting the peel strength between the thermoplastic resin substrate (A) layer and the resin (B) layer at 100 ° C. to 0.005 N / 10 mm or more and 2 N / 10 mm or less is not particularly limited. For example, satisfying the following formula (I) is preferable because the peel strength at 100 ° C. can be set to 0.005 N / 10 mm or more and 2 N / 10 mm or less.
0.5 ≦ {(M ₁ −M ₀ ) −M ₂ } / (M ₁ −M ₀ ) × 100 ≦ 10 (I)
However, M ₀ : Mass of the thermoplastic resin substrate (A) layer M ₁ : Mass of the laminated sheet M ₂ : After peeling the thermoplastic resin substrate (A) layer from the laminated sheet and storing at 140 ° C. for 30 minutes The weight of the sheet containing the resin (B) layer of the sheet Here, the sheet containing the resin (B) layer obtained by peeling the thermoplastic resin substrate (A) layer from the laminated sheet is the resin (B) layer. Laminate of resin (B) layer / decoration (C) layer, resin (B) layer / decoration (C) layer / adhesion (D) layer, resin (B) layer / adhesion (D) layer, etc. A configuration is also mentioned.

  Formula (I) shows a formula for measuring the amount of volatile components such as residual solvent contained in the sheet including the resin (B) layer. For example, when a resin (B) layer, a decoration (C) layer, an adhesive (D) layer, or the like is applied to a thermoplastic resin base material (A) layer, the composition for forming each layer is used as a solvent. A method of dispersing and coating is preferably used, but the amount of residual solvent can be adjusted depending on the drying conditions after coating. Examples of the solvent used include water, alcohol solvents, ketone solvents, ether solvents, ester solvents, hydrocarbon solvents, and aromatic hydrocarbon solvents. These can be used alone or in combination of two or more.

  When the resin (B) layer, the decoration (C) layer, the adhesive (D) layer, etc. are formed by coating, examples of the alcohol solvent used for dissolving the composition include methanol, ethanol, isopropyl alcohol, n -Butanol, sec-butanol, isobutanol, tert-butanol and the like can be mentioned. Examples of the ketone solvent used for the same purpose include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ether solvent used for the same purpose include dibutyl ether, propylene glycol monoethyl ether acetate, and tetrahydrofuran. Examples of the ester solvent used for the same purpose include ethyl acetate and butyl acetate. Examples of the hydrocarbon solvent used for the same purpose include hexane and cyclohexane. Examples of the aromatic hydrocarbon solvent used for the same purpose include benzene, toluene, xylene and the like.

  The above-mentioned solvent preferably used has a boiling point of 140 ° C. or lower, and by storing at 140 ° C. for 30 minutes, almost 100% by mass of the residual solvent can be removed. For this reason, volatile substances, such as a residual solvent of the sheet | seat containing a resin (B) layer, can be evaluated by (I) Formula.

In the present invention, 0.5% by mass or more of the residual solvent of the sheet satisfying the formula (I), that is, the sheet containing the resin (B) layer obtained by peeling the thermoplastic resin substrate (A) layer from the laminated sheet, By setting it as 10 mass% or less, the peeling strength of the thermoplastic resin base material (A) layer and the resin (B) layer at 100 ° C. can be achieved to 0.005 N / 10 mm or more and 2 N / 10 mm or less. If {(M ₁ −M ₀ ) −M ₂ } / (M ₁ −M ₀ ) × 100 is less than 0.5, peeling between the thermoplastic resin substrate (A) layer and the resin (B) layer The strength tends to increase, and the easy peelability after molding may decrease. On the other hand, if {(M ₁ −M ₀ ) −M ₂ } / (M ₁ −M ₀ ) × 100 is greater than 10, the peel strength between the thermoplastic resin substrate (A) layer and the resin (B) layer Tends to be low, and may be smaller than 0.005 N / 10 mm. In order to achieve a peel strength between the thermoplastic resin substrate (A) layer and the resin (B) layer at 100 ° C. of 0.005 N / 10 mm or more and 2 N / 10 mm or less, more preferably the formula (I) ′ It is preferable to satisfy, and it is more preferable to satisfy the formula (I) ”.
0.5 ≦ {(M ₁ −M ₀ ) −M ₂ } / (M ₁ −M ₀ ) × 100 ≦ 8 (I) ′
1 ≦ {(M ₁ −M ₀ ) −M ₂ } / (M ₁ −M ₀ ) × 100 ≦ 5 (I) ”

The laminated sheet of the present invention is a thermoplastic resin substrate (of a sheet containing a resin (B) layer obtained by peeling a thermoplastic resin substrate (A) layer from a laminated sheet in order to suppress natural peeling during heat molding. The stress at 100% elongation (F100 value) at the glass transition temperature + 20 ° C. of the layer A) is preferably 3 MPa or less. When the 100% elongation stress (F100 value) of the sheet including the resin (B) layer is greater than 3 MPa at the glass transition temperature of the thermoplastic resin substrate (A) layer + 20 ° C., the laminated sheet is heated. The sheet part including the resin (B) layer becomes difficult to follow the molding of the thermoplastic resin base material (A) layer, and peeling occurs between the thermoplastic resin base material (A) layer and the resin (B) layer. May end up. In order to further improve the molding followability to the thermoplastic resin substrate (A) layer, the thermoplastic resin group of the sheet including the resin (B) layer obtained by peeling the thermoplastic resin substrate (A) layer from the laminated sheet The 100% elongation stress (F100 value) at the glass transition temperature + 20 ° C. of the material (A) layer is preferably 2.5 MPa or less, and most preferably 0.01 MPa or more and 2 MPa or less.

100% elongation stress (F100 value) at the glass transition temperature of the thermoplastic resin substrate (A) layer + 20 ° C. of the sheet containing the resin (B) layer from which the thermoplastic resin substrate (A) layer was peeled from the laminated sheet ) To 3 MPa or less, for example, a sheet containing a resin (B) layer from which a thermoplastic resin substrate (A) layer has been peeled is a resin (B) layer, a decoration (C) layer, an adhesion (D) In the case of a sheet composed of layers, it is preferable to select a flexible resin as the resin used for the resin (B) layer, decoration (C) layer, and adhesive (D) layer. In addition, when a curable resin is used in each layer of the resin (B) layer, the decorative (C) layer, and the adhesive (D) layer, the laminated sheet of the present invention is prepared and stored at as low a temperature as possible. In the case where the curable resin is an electron beam curable resin, it is preferably stored in an environment where no electron beam is applied.

The laminated sheet of the present invention has a peel strength between the thermoplastic resin substrate (A) layer and the resin (B) layer at 25 ° C. of 0.005 N / 10 mm or more and 2 N / 10 mm or less, and the thermoplastic resin group at 100 ° C. By controlling the peel strength between the material (A) layer and the resin (B) layer to 0.005 N / 10 mm or more and 2 N / 10 mm or less, the sheet containing the resin (B) layer is transferred to the adherend simultaneously with molding. The decorative molded body can be obtained. The method for transferring the sheet containing the resin (B) layer to the adherend is not particularly limited, and examples thereof include a method for transferring the sheet to the adherend simultaneously with vacuum forming. In this method, as the adherend, for example, polypropylene resin, acrylic resin, polystyrene resin, AS (acrylonitrile / styrene copolymer) resin, ABS (acrylonitrile / butadiene / styrene copolymer) resin, polycarbonate Resins such as polyester resins, polyester resins, and the like, alloy resins thereof, and resins reinforced with carbon fibers, glass fibers, and the like. Furthermore, a metal member, a glass member, etc. are mentioned.

  Moreover, the method of transferring simultaneously with injection molding can also be used. In this case, the above-mentioned resin is preferably used as the adherend.

  In addition, since the lamination sheet of this invention is excellent in the moldability at the time of a heating, it can be used suitably for various shaping | molding uses, such as vacuum forming, pressure forming, and press molding. And it uses suitably for a vacuum forming use especially.

In the laminated sheet of the present invention, the resin (B) layer is laminated on at least one side of the thermoplastic resin substrate (A) layer, and the thermoplastic resin substrate (A) layer and the resin (B) at 25 ° C. The peel strength with respect to the layer is 0.005 N / 10 mm or more and 2 N / 10 mm or less, and the peel strength between the thermoplastic resin substrate (A) layer and the resin (B) layer at 100 ° C. is 0.005 N / 10 mm. As described above, since it is 2N / 10 mm or less, the thermoplastic resin base material (A) layer and the resin (B) layer do not spontaneously peel off during the process and can be easily peeled off after molding. It can be suitably used for decorating molded members such as equipment, electrical products, automobile parts, and gaming machine parts.

The laminated sheet of the present invention was produced and evaluated by the following method.
(1) The total thickness of the film and laminated sheet and the thickness of each layer When measuring the total thickness of the film and laminated sheet, use a dial gauge to determine the thickness of any five locations of the sample cut out from the sheet. The average value was obtained by measurement.

Moreover, when measuring the layer thickness of each layer of a film and a lamination sheet, the transmitted light was photographed on the conditions of the magnification | multiplying_factor of the sheet | seat 100 times using the Leica DMLM made from Leica Microsystems. And from the photograph | photographed photograph, arbitrary five places thickness was measured for every layer of the lamination sheet, and the average value was made into the layer thickness of each layer.
(2) Glass transition temperature of film Using a differential scanning calorimeter (Seiko Denshi Kogyo, RDC220), measurement and analysis were performed in accordance with JIS K7121-1987 and JIS K7122-1987.

  A film of 5 mg was used as a sample. The specific heat change based on the transition from the glass state to the rubber state when the sample was heated from 25 ° C. to 300 ° C. at 20 ° C./min was read. Determine the glass transition temperature at the midpoint of the point where the straight line equidistant from the extended straight line of each baseline in the direction of the vertical axis (the axis indicating the heat flow) and the curve of the stepwise change part of the glass transition intersect. It was. When a plurality of glass transition temperatures exist, the glass transition temperature on the high temperature side was adopted as the glass transition temperature of the film.

(3) Peel strength An OPP adhesive tape (Damplon Ace No. 375) manufactured by Nitto Denko Corporation was bonded to the sheet side including the resin (B) layer in the laminated sheet of the present invention, and the width was 10 mm and the length was 150 mm. A sample was cut into a rectangle. The sample was forcibly peeled between the thermoplastic resin substrate (A) layer and the resin (B) layer, and using a tensile tester (Tensilon UCT-100 manufactured by Orientec), the initial tensile chuck distance was 100 mm, A 180 ° peel test was performed at a speed of 20 mm / min. The measurement was performed until the peel length reached 130 mm (distance between chucks 230 mm), and the average value of the loads having a peel length of 25 mm to 125 mm was defined as the peel strength. In addition, the measurement was performed 5 times and the average value was adopted.

  Here, in the case where another layer is interposed between the thermoplastic resin substrate (A) layer and the resin (B) layer, the case where the thermoplastic resin substrate (A) layer and the other layer peel off , The case of peeling between the resin (B) layer and another layer, and when a plurality of other layers are interposed between the thermoplastic resin substrate (A) layer and the resin (B) layer, Although there are cases where peeling occurs between the different layers, each case was measured assuming that it was between the thermoplastic resin substrate (A) layer and the resin (B) layer.

  The peel strength at 25 ° C. was measured in a room adjusted to 25 ° C., and the breaking strength at 100 ° C. was set in a constant temperature layer previously set at 100 ° C., and pre-heated for 60 seconds and then subjected to a 180 ° peel test. Went.

(4) {(M ₁ −M ₀ ) −M ₂ } / (M ₁ −M ₀ ) × 100
The laminated sheet of the present invention was cut into a size of 100 mm × 100 mm to make a sample, and the mass of the obtained sample was measured as follows. In addition, evaluation was performed 3 times and the average value was employ | adopted.
M ₀ : Mass of the thermoplastic resin substrate (A) layer M ₁ : Mass of the laminated sheet M ₂ : Resin after peeling the thermoplastic resin substrate (A) layer from the laminated sheet and storing at 140 ° C. for 30 minutes (B) Mass of the sheet containing the layer (5) Breaking elongation In one arbitrary direction of the laminated sheet of the present invention and in a direction perpendicular thereto, a rectangular sample having a length of 100 mm and a width of 10 mm was obtained as a sample. Using a tensile tester (Orientec Tensilon UCT-100), an initial tensile chuck distance was 20 mm, a tensile speed was 200 mm / min, and a tensile test was performed in an arbitrary direction and a direction orthogonal thereto.

  The measurement is set in advance at predetermined temperatures (in the case of the present invention, the glass transition temperature of the thermoplastic resin substrate (A) layer is −20 ° C. and the glass transition temperature of the thermoplastic resin substrate (A) layer is + 20 ° C.). A sample was set in the constant temperature layer, and a tensile test was performed after preheating for 60 seconds. The elongation when the sample broke was defined as the breaking elongation. In addition, the measurement was performed 5 times in each sample and in each direction, and the average value (average value obtained from the average value in each direction) was evaluated.

(6) Stress at 100% elongation (F100 value) of the sheet containing the resin (B) layer obtained by peeling the thermoplastic resin substrate (A) layer from the laminated sheet
The sheet containing the resin (B) layer from which the thermoplastic resin base material (A) layer is peeled from the laminated sheet of the present invention has a rectangular shape with a length of 100 mm and a width of 10 mm in an arbitrary direction and a direction perpendicular to the direction. A cut sample was obtained. Using a tensile tester (Orientec Tensilon UCT-100), an initial tensile chuck distance was 20 mm, a tensile speed was 200 mm / min, and a tensile test was performed in an arbitrary direction and a direction orthogonal thereto. Measurement is performed by setting a sample in a constant temperature layer set in advance at a predetermined temperature (in the case of the present invention, glass transition temperature of the thermoplastic resin substrate (A) layer + 20 ° C.), and after 60 seconds of preheating, a tensile test Went. Read the load applied to the sheet when the sample is stretched 100% (when the distance between chucks is 40 mm) and divide by the cross-sectional area (sheet thickness x 10 mm) of the sample before the test. F100 value). In addition, the measurement was performed 5 times for each sample and each direction, and the average value was evaluated.

(7) The surface of the thermoplastic resin substrate (A) layer in an ultrahigh vacuum (oxygen atom / carbon atom) molar ratio on one side of the film is irradiated with soft X-rays under the following conditions and released from the surface. Photoelectrons were detected with an analyzer.
・ Device: Quantera SXM (PHI)
Excitation X-ray: monochromic Al Ka 1, 2 line (1486.6 eV)
・ X-ray diameter: 200mm
-Photoelectron escape angle (inclination of detector with respect to sample surface): 45 °
Further, the obtained data was processed and analyzed as follows.
-Spectrum (narrow scan) smoothing: 9-point smoothing
-Horizontal axis correction: C1s main peak was adjusted to 284.6 eV.

(8) Using a contact angle meter (CA-D type manufactured by Kyowa Interface Chemical Co., Ltd.) for water that has been conditioned for 24 hours under the conditions of surface free energy of 23 ° C. and 65% RH, The static contact angle with respect to the film surface was determined using a contact angle meter CA-D type manufactured by Kyowa Interface Chemical Co., Ltd. using four types of measurement solutions of ethylene glycol, formamide, and methylene iodide. Each component of the contact angle and the surface tension of the measurement liquid obtained for each liquid was substituted into the following equation, and simultaneous equations consisting of four equations were solved for γ ^L , γ ⁺ and γ ⁻ .

(γ ^L γ _j ^L ) ^1/2 +2 (γ ⁺ γ _j ⁻ ) ^1/2 +2 (γ _j ⁺ γ ⁻ ) ^1/2 = (1 + cos θ) [γ _j ^L +2 (γ _j ⁺ γ _j ⁻ ) ^{1 / 2} ] / 2
However, γ = γ ^L +2 (γ ⁺ γ ₋ ) ^1/2 γ _j = γ _j ^L +2 (γ _j ⁺ γ _j ⁻ ) ^1/2 where γ, γ ^L , γ ⁺ and γ ⁻ are respectively , Surface free energy of the substrate surface, long-range force term, Lewis acid parameter, Lewis base parameter, and γ _j , γ _j ^L , γ _j ⁺ , γ _j ^- are the surface of the measurement solution used, respectively It represents free energy, long-range force term, Lewis acid parameter, and Lewis base parameter.

  The surface tension of each liquid used here was the value shown in Table 1 proposed by Oss ("Fundamentals of Adhesion", L.H. Lee (Ed.), P153, Plenum ess, New York (1991)).

(9) A laminated sheet of the present invention having a winding property of 500 mm width and 200 m length (6 inches, 550 mm length core winding) is prepared, and rolled back to a 3 inch, 550 mm length core under the following conditions. Evaluation was performed.
Unwinding: upper unwinding, tension 200 N / m, winding: upper unwinding, tension 100 N / m
Speed: 5m / min
A: No peeling occurred between the thermoplastic resin substrate (A) layer / resin (B) layer.
B: Peeling was observed between the thermoplastic resin substrate (A) layer / resin (B) layer, but no air was caught in the peeled portion.
C: Separation was observed between the thermoplastic resin base material (A) layer / resin (B) layer, and some air entrainment occurred at the delamination site (air entrapment rate (the total area of the laminated sheet was 100%) The ratio of the area in which the air is caught is less than 5%).
D: Peeling was observed between the thermoplastic resin base material (A) layer / resin (B) layer, and air entrainment occurred at the delamination site (air entrapment rate (when the total area of the laminated sheet was 100%) The ratio of the area in which the air is caught is 5% or more) or completely peeled off.

(10) Natural peeling test during heating The laminated sheet of the present invention was set on a sheet clamp frame at the top in a vacuum forming apparatus (manufactured by Fuse Vacuum, NGF-0406-T). Subsequently, the degree of vacuum in the upper and lower boxes was reduced to 99.0 kPa, and the behavior when heated using an infrared heater was evaluated according to the following criteria.
A: Even at a sheet temperature of 140 ° C., no peeling occurred between the thermoplastic resin substrate (A) layer / resin (B) layer.
B: Peeling occurred between the thermoplastic resin substrate (A) layer / resin (B) layer at a sheet temperature of 120 ° C. or more and less than 140 ° C.
C: Peeling occurred between the thermoplastic resin substrate (A) layer / resin (B) layer at a sheet temperature of 100 ° C. or more and less than 120 ° C.
D: Peeling occurred between the thermoplastic resin substrate (A) layer / resin (B) layer at a sheet temperature of less than 100 ° C.

(11) Three types of polypropylene-shaped bodies (length 100 mm × width 100 mm, heights 20 mm, 25 mm, and 30 mm) on an up-and-down lifting table in a moldable vacuum forming apparatus (made by Fuse Vacuum, NGF-0406-T) ) And the laminated sheet of the present invention (length 300 mm × width 200 mm) was set on the sheet clamp frame at the top of the shaped body in the apparatus. Subsequently, the vacuum degree in the upper and lower boxes is reduced to 99.0 kPa, and the surface temperature of the laminated sheet is heated using an infrared heater until the glass transition temperature of the thermoplastic resin substrate (A) layer becomes + 20 ° C. The body was raised, the shaped body and the laminated sheet were brought into close contact, and held for 3 seconds. Then, the laminated sheet was shaped by releasing only the upper box to atmospheric pressure, and a decorative molded body was obtained. In addition, about the thing whose glass transition temperature was not able to be measured, heating attainment temperature and holding temperature were 110 degreeC.

In Examples 1 to 19 and Comparative Examples 1 to 4, the decorative molded bodies obtained as described above were evaluated as follows.
A: Molding was possible at a height of 30 mm.
B: Although it was able to be molded at a height of 25 mm, the shape could not be reproduced at 30 mm.
C: Although it was able to be molded at a height of 20 mm, the shape could not be reproduced at 25 mm.
D: The shape could not be reproduced at a height of 20 mm.

(12) Easy moldability after molding The decorative molded body obtained as described in (11) is peeled off between the thermoplastic resin substrate (A) layer / resin (B) layer and evaluated according to the following criteria. went. When the resin (B) layer was a curable resin, peeling was performed after the resin (B) layer was cured. In this example, ultraviolet irradiation treatment was performed from the thermoplastic resin substrate (A) layer side to cure the resin (B) layer so that the integrated light amount was 1,000 mJ / cm ² with a high-pressure mercury lamp. It was.
A: It was able to peel without a problem.
B: Although there was some resistance, it was able to peel off.
C: It peeled off when taking out from the molding machine.
D: It did not peel off.
B or higher was accepted.

(13) Surface decoration after molding The decorative molded body obtained as in (11) was evaluated according to the following criteria.
A: The surface gloss was high and the outline of the fluorescent lamp was almost clearly reflected.
B: Wavy unevenness was partially observed on the surface, but the outline of the fluorescent lamp was almost clearly reflected as in A except for the above.
C: Wavy unevenness was observed on the surface, and the outline of the fluorescent lamp was blurred.
D: Since it did not peel off, evaluation was not possible.

(14) Integrated light quantity The illuminance meter was transported under the same conditions (conveyance speed, distance between the film and the lamp) as when the film was irradiated with ultraviolet rays, and the integrated light quantity was measured. The following illuminometers were used according to the type of lamp.
Metal halide lamp, high-pressure mercury lamp: “PD-365” manufactured by Iwasaki Electric Co., Ltd. (measurement wavelength range: 300 to 390 nm)
Low pressure mercury lamp: “PD-254” manufactured by Iwasaki Electric Co., Ltd. (measurement wavelength range: 230 to 280 nm)
Excimer lamp: “EVUV-200” manufactured by Iwasaki Electric Co., Ltd. (measurement wavelength range: 140 to 227 nm, calibration wavelength: 172 nm)
(15) Resin used for production of the film of the present invention.

(Cyclic olefin copolymer resin A)
TOPAS 8007F-04 manufactured by Polyplastics was used.

(Cyclic olefin copolymer resin B)
TOPAS 6013F-04 manufactured by Polyplastics was used.

(Cyclic olefin copolymer resin C)
TOPAS 6015S-04 manufactured by Polyplastics was used.

(Cyclic olefin resin D)
“ZEONOR 1060R” manufactured by Nippon Zeon Co., Ltd. was used.

(Cyclic olefin resin E)
“ZEONOR 1430R” manufactured by Nippon Zeon Co., Ltd. was used.

(Polyethylene resin)
Evolue SP2540 manufactured by Prime Polymer Co., Ltd. was used.

(Polypropylene resin)
“R101” manufactured by Sumitomo Chemical Co., Ltd. was used.

(Polymethylpentene resin)
A polyolefin-based resin having a polymethylpentene unit (melting point: 225 ° C., Vicat softening temperature: 153 ° C.) was used.

(Modified olefin resin)
“Yumex 1010” manufactured by Sanyo Kasei Co., Ltd. was used.

(Polyethylene terephthalate resin)
A polyethylene terephthalate resin (intrinsic viscosity 0.65) in which the terephthalic component was 100 mol% as the dicarboxylic acid component, the ethylene glycol component was 99 mol% and the diethylene glycol component was 1 mol% as the glycol component was used.

(Antioxidant)
“Irganox 1010” manufactured by Ciba Specialty Chemicals was used.

  (16) Resin used for the production of the resin (B) layer of the present invention.

KHC-T1 (manufactured by Kyoeisha Chemical, UV curable resin, solid content: 50%)
(17) A coating composition for a decorative layer was prepared by mixing the resin main component and the curing agent used in the production of the decorative (C) layer of the present invention at the following blending ratio.
Main agent: R2325 (Nihon Bee Chemical Co., solid component: 36%) 100 parts by mass Curing agent: D-178N (Mitsui Chemicals, solid component: 100%) 2 parts by mass (18) Adhesion of the present invention (D ) A resin composition for the adhesive layer was prepared by mixing the polyolefin hot-melt adhesive below the resin used in the production of the layer and a solvent in the following compounding ratio.
Polyolefin hot melt adhesive: M-28 (manufactured by Toyobo, maleic anhydride modified chlorinated polypropylene) 20 parts by mass Solvent: 80 parts by mass of toluene (Example 1)
The film has a three-layer structure. The composition of each layer is as shown in the table, and each is supplied to a single screw extruder (L / D = 28). The supply part temperature is 220 ° C. and the subsequent temperature is melted at 240 ° C., and a leaf disk filter with a filtration accuracy of 20 μm is obtained. After passing, after laminating so as to be a2 layer / a1 layer / a2 layer (see the table for the lamination thickness ratio) in the feed block installed on the top of the die, the temperature was controlled to 75 ° C. from the T die. The sheet was discharged on a metal roll. At that time, a nip was made with a rubber roll (nip pressure: 0.2 MPa) to obtain a film having a thickness of 100 μm.

The obtained film was used as a thermoplastic resin base material (A) layer, and on one side, an excimer lamp was subjected to ultraviolet irradiation treatment with an irradiation time of 10 seconds so that the integrated light amount was 25 mJ / cm ^2, and then ultraviolet irradiation was performed. On the treated surface, the resin (B) layer was coated with a slot die coater, and dried at 80 ° C. for 5 minutes. Subsequently, the decorative (C) layer and the adhesive (D) layer were further coated under the same conditions as the resin (B) layer to obtain a laminated sheet.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 2)
A laminated sheet was obtained in the same manner as in Example 1 except that drying after application of the resin (B) layer, the decorative (C) layer, and the adhesive (D) layer was performed at 80 ° C. for 8 minutes. .

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 3)
A laminated sheet was obtained in the same manner as in Example 1 except that drying after coating of the resin (B) layer, the decoration (C) layer, and the adhesion (D) layer was performed at 80 ° C. for 10 minutes. .

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

Example 4
A laminated sheet was obtained in the same manner as in Example 1 except that drying after application of the resin (B) layer, the decoration (C) layer, and the adhesion (D) layer was performed at 80 ° C. for 20 minutes. .

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 5)
A laminated sheet was obtained in the same manner as in Example 1 except that drying after coating of the resin (B) layer, the decoration (C) layer, and the adhesion (D) layer was performed at 80 ° C. for 30 minutes. .

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 6)
Except that the ultraviolet irradiation treatment on one side of the thermoplastic resin substrate (A) layer was performed with an excimer lamp so that the integrated light amount was 18 mJ / cm ² and the irradiation time was 7 seconds, the same as in Example 1, A laminated sheet was obtained.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 7)
Except that the ultraviolet irradiation treatment on one side of the thermoplastic resin substrate (A) layer was performed with an irradiation time of 30 seconds so that the accumulated light amount was 250 mJ / cm ² with a low-pressure mercury lamp, the same as in Example 1, A laminated sheet was obtained.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 8)
Lamination was performed in the same manner as in Example 1 except that the ultraviolet irradiation treatment on one side of the thermoplastic resin substrate (A) layer was performed with an excimer lamp so that the integrated light amount was 100 mJ / cm ² and the irradiation time was 40 seconds. A sheet was obtained.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

Example 9
Lamination was performed in the same manner as in Example 1 except that the ultraviolet irradiation treatment on one side of the thermoplastic resin substrate (A) layer was performed with an excimer lamp so that the integrated light amount was 120 mJ / cm ² and the irradiation time was 48 seconds. A sheet was obtained.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 10)
Except that the ultraviolet irradiation treatment on one side of the thermoplastic resin substrate (A) layer was performed with an irradiation time of 30 seconds so that the accumulated light amount was 250 mJ / cm ² with a low-pressure mercury lamp, the same as in Example 1, A laminated sheet was obtained. In the present example, the obtained laminated sheet was subjected to ultraviolet irradiation treatment with a metal halide lamp from the thermoplastic resin substrate (A) layer side with an irradiation time of 25 seconds so that the accumulated light amount was 200 mJ / cm ² . Later, evaluation was performed by the method described in (1) to (13).

(Example 11)
The film has a three-layer structure. The composition of each layer is as shown in the table, and each is supplied to a single-screw extruder (L / D = 28). The supply part temperature is 220 ° C., the subsequent temperature is melted at 230 ° C., and a leaf disk filter with a filtration accuracy of 20 μm is obtained. After passing, after laminating so as to be a2 layer / a1 layer / a2 layer (see the table for the lamination thickness ratio) in the feed block installed on the upper part of the die, the temperature was controlled to 65 ° C. from the T die. The sheet was discharged on a metal roll. At that time, a nip was made with a rubber roll (nip pressure: 0.2 MPa) to obtain a film having a thickness of 100 μm.

The obtained film was used as a thermoplastic resin substrate (A) layer, and one side of the film was subjected to ultraviolet irradiation treatment with an irradiation time of 60 seconds so as to obtain an integrated light quantity of 700 mJ / cm ² with a low-pressure mercury lamp, and then irradiated with ultraviolet light. On the treated surface, the resin (B) layer was coated with a slot die coater and dried at 70 ° C. for 30 minutes. Subsequently, the decorative (C) layer and the adhesive (D) layer were further coated under the same conditions as the resin (B) layer to obtain a laminated sheet.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 12)
The film has a three-layer structure. The composition of each layer is as shown in the table, and each is supplied to a single-screw extruder (L / D = 28), the supply part temperature is 240 ° C., the subsequent temperature is melted at 255 ° C., and a leaf disk filter with a filtration accuracy of 20 μm is obtained. After passing, the layers were laminated so as to be a2 layer / a1 layer / a2 layer (see the table for the lamination thickness ratio) in the feed block installed on the top of the die, and then the temperature was controlled to 90 ° C. from the T die. The sheet was discharged on a metal roll. At that time, a nip was made with a rubber roll (nip pressure: 0.2 MPa) to obtain a film having a thickness of 100 μm.

  Using the obtained film as the thermoplastic resin substrate (A) layer, the resin (B) layer, the decoration (C) layer, and the adhesive (D) layer were further applied and dried in the same manner as in Example 11. A laminated sheet was obtained.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 13)
The film has a three-layer structure. The composition of each layer is as shown in the table, and each is supplied to a single-screw extruder (L / D = 28), the supply section temperature is 260 ° C., the temperature after that is melted at 280 ° C., and a leaf disk filter with a filtration accuracy of 20 μm is obtained. After passing, after laminating so as to be a2 layer / a1 layer / a2 layer (see the table for the lamination thickness ratio) in the feed block installed on the top of the die, the temperature was controlled to 120 ° C. from the T die. The sheet was discharged on a metal roll. At that time, a nip was made with a rubber roll (nip pressure: 0.2 MPa) to obtain a film having a thickness of 100 μm.

  Using the obtained film as the thermoplastic resin substrate (A) layer, the resin (B) layer, the decoration (C) layer, and the adhesive (D) layer were further applied and dried in the same manner as in Example 11. A laminated sheet was obtained.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 14)
The film has a three-layer structure. The composition of each layer is as shown in the table, and each is supplied to a single-screw extruder (L / D = 28). The supply part temperature is 265 ° C., the temperature after that is melted at 290 ° C., and a leaf disk filter with a filtration accuracy of 20 μm After passing, the layers were laminated so as to be a2 layer / a1 layer / a2 layer (see the table for the lamination thickness ratio) in the feed block installed on the upper part of the die, and then the temperature was controlled to 140 ° C. from the T die. The sheet was discharged on a metal roll. At that time, a nip was made with a rubber roll (nip pressure: 0.2 MPa) to obtain a film having a thickness of 100 μm.

  Using the obtained film as the thermoplastic resin substrate (A) layer, the resin (B) layer, the decoration (C) layer, and the adhesive (D) layer were further applied and dried in the same manner as in Example 11. A laminated sheet was obtained.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 15)
A laminated sheet was obtained in the same manner as in Example 13 except that the thickness of the film was 50 μm.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 16)
The film has a three-layer structure. The composition of each layer is as shown in the table, and each is supplied to a single screw extruder (L / D = 28). The supply part temperature is 220 ° C. and the subsequent temperature is melted at 240 ° C., and a leaf disk filter with a filtration accuracy of 20 μm is obtained. After passing, after laminating so as to be a2 layer / a1 layer / a2 layer (see the table for the lamination thickness ratio) in the feed block installed on the top of the die, the temperature was controlled to 75 ° C. from the T die. The sheet was discharged on a metal roll. At that time, a nip was made with a rubber roll (nip pressure: 0.2 MPa) to obtain a film having a thickness of 100 μm.

  The obtained film was used as a thermoplastic resin substrate (A) layer, and the resin (B) layer was coated on one side with a slot die coater and dried at 80 ° C. for 5 minutes. Subsequently, the decorative (C) layer and the adhesive (D) layer were further coated under the same conditions as the resin (B) layer to obtain a laminated sheet.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 17)
A laminated sheet for molding was obtained in the same manner as in Example 16 except that the composition of each layer of the film was as shown in the table.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Example 18)
The film has a single layer configuration. The composition was as shown in the table, and it was supplied to a single screw extruder (L / D = 28). The supply part temperature was 230 ° C., and the subsequent temperature was melted at 250 ° C., and passed through a leaf disk filter having a filtration accuracy of 20 μm. Thereafter, the sheet was discharged from a T die onto a metal roll whose temperature was controlled to 50 ° C. At that time, a nip was made with a rubber roll (nip pressure: 0.2 MPa) to obtain a film having a thickness of 100 μm.

The obtained film was used as a thermoplastic resin base material (A) layer, and was subjected to ultraviolet irradiation treatment with an excimer lamp on one side so that the integrated light amount was 25 mJ / cm ² for an irradiation time of 10 seconds. On the surface, the resin (B) layer was coated with a slot die coater, and dried at 80 ° C. for 10 minutes. Subsequently, the decorative (C) layer and the adhesive (D) layer were further coated under the same conditions as the resin (B) layer to obtain a laminated sheet.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13). In addition, since the glass transition temperature above 25 degreeC was not detected with this composition, it did not evaluate about the breaking elongation of a film.

(Example 19)
The film has a single layer configuration. The composition was as shown in the table, and it was supplied to a single-screw extruder (L / D = 28). The supply part temperature was 260 ° C., and the subsequent temperature was melted at 280 ° C. and passed through a leaf disk filter with a filtration accuracy of 20 μm Thereafter, the sheet was discharged from a T die onto a metal roll whose temperature was controlled to 50 ° C. At that time, a nip was made with a rubber roll (nip pressure: 0.2 MPa) to obtain a film having a thickness of 100 μm.

The obtained film was used as a thermoplastic resin base material (A) layer, and was subjected to ultraviolet irradiation treatment with an irradiation time of 48 seconds so that the integrated light amount became 120 mJ / cm ^{2 on} one side with an excimer lamp, and then ultraviolet irradiation treatment. On the surface, the resin (B) layer was coated with a slot die coater, and dried at 80 ° C. for 10 minutes. Subsequently, the decorative (C) layer and the adhesive (D) layer were further coated under the same conditions as the resin (B) layer to obtain a laminated sheet.

  About the obtained lamination sheet, it evaluated by the method as described in (1)-(13). In addition, since the glass transition temperature above 25 degreeC was not detected with this composition, it did not evaluate about the breaking elongation of a film.

(Comparative Example 1)
In the same manner as in Example 11, a thermoplastic resin substrate (A) layer was obtained.
After the ultraviolet ray irradiation treatment on one side of the thermoplastic resin substrate (A) layer was performed with an excimer lamp so that the integrated light amount was 150 mJ / cm ² and the irradiation time was 60 seconds, the resin ( The layer (B) and the decoration (C) layer were further coated with an adhesive (D) layer and dried to obtain a laminated sheet.
About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Comparative Example 2)
Lamination was performed in the same manner as in Comparative Example 1 except that the ultraviolet irradiation treatment on one side of the thermoplastic resin substrate (A) layer was performed with a metal halide lamp so that the integrated light amount was 900 mJ / cm ² and the irradiation time was 20 seconds. A sheet was obtained.
About the obtained lamination sheet, it evaluated by the method as described in (1)-(13).

(Comparative Example 3)
The film has a single film configuration. The resin to be used is dried at 150 ° C. for 5 hours in a vacuum dryer, and after sufficiently removing moisture, the composition is as shown in the table and supplied to a single screw extruder (L / D = 28). It was melted at a temperature of 265 ° C. and a subsequent temperature of 280 ° C., and the short tube temperature was 275 ° C., the die temperature was 275 ° C., and discharged from a T-die onto a metal roll whose temperature was controlled to 50 ° C. At that time, a rubber roll was used for nip (nip pressure: 0.2 MPa) to obtain a thermoplastic resin substrate (A) layer having a thickness of 100 μm.
The obtained film was used as a thermoplastic resin substrate (A) layer, and the resin (B) layer was coated on one side with a slot die coater and dried at 70 ° C. for 15 minutes. Subsequently, the decorative (C) layer and the adhesive (D) layer were further coated under the same conditions as the resin (B) layer to obtain a laminated sheet.

  About the obtained lamination sheet, although it evaluated by the method as described in (1)-(13), it did not peel at all between a thermoplastic resin base material (A) layer and resin (B) layer.

Claims (13)

A film mainly composed of an olefin resin,
A film characterized by having a molar ratio of oxygen atom to carbon atom (oxygen atom / carbon atom) of at least one surface of 0.03 or more and 0.15 or less as measured by X-ray photoelectron spectroscopy.   The film according to claim 1, wherein the film contains a cyclic olefin-based resin as a main component. The film has an a1 layer and an a2 layer,
The film of Claim 1 or 2 which has the cyclic olefin layer (a2 layer) which has a cyclic olefin resin as a main component in the at least single side | surface of the cyclic olefin layer (a1 layer) which has a cyclic olefin resin as a main component. The a1 layer is mainly composed of a cyclic olefin copolymer resin (hereinafter referred to as COC),
The said a2 layer is a film of Claim 3 which has a cyclic olefin resin (henceforth COP) as a main component.   The film according to claim 3 or 4, wherein the a2 layer, the a1 layer, and the a2 layer are directly laminated in this order.   The film according to any one of claims 3 to 5, wherein the a1 layer contains 1 to 40% by mass of a polyethylene resin and / or a polypropylene resin with respect to 100% by mass of the entire a1 layer. The glass transition temperature of the film is 80 ° C. or higher,
The elongation at break at a glass transition temperature of −20 ° C. of the film is 200% or less,
The film in any one of Claims 1-6 whose breaking elongation in glass transition temperature +20 degreeC of a film is 500% or more. When the film according to any one of claims 1 to 7 is used as a thermoplastic resin substrate (A) layer, a resin (B) layer is provided on at least one side of the thermoplastic resin substrate (A) layer. ,
The peel strength between the thermoplastic resin substrate (A) layer and the resin (B) layer at 25 ° C. is 0.005 N / 10 mm or more and 2 N / 10 mm or less,
The laminated sheet whose peeling strength of the said thermoplastic resin base material (A) layer and resin (B) layer in 100 degreeC is 0.005 N / 10mm or more and 2 N / 10mm or less. The laminated sheet according to claim 8, which satisfies the following formula (I).
0.5 ≦ {(M ₁ −M ₀ ) −M ₂ } / (M ₁ −M ₀ ) × 100 ≦ 10 (I)
However, M ₀ : Mass of the thermoplastic resin substrate (A) layer M ₁ : Mass of the laminated sheet M ₂ : After peeling the thermoplastic resin substrate (A) layer from the laminated sheet and storing at 140 ° C. for 30 minutes Of the sheet including the resin (B) layer   The laminated sheet according to claim 8 or 9, wherein the resin (B) layer contains a curable resin as a main component.   100% elongation stress (F100 value) at the glass transition temperature of the thermoplastic resin substrate (A) layer + 20 ° C. of the sheet containing the resin (B) layer from which the thermoplastic resin substrate (A) layer was peeled from the laminated sheet ) Is 3 MPa or less, the laminated sheet according to any one of claims 8 to 10.   The laminated sheet according to any one of claims 8 to 11, comprising a resin (B) layer, a decoration (C) layer, and an adhesion (D) layer in this order on at least one side of the thermoplastic resin substrate (A) layer. .   The laminated sheet according to any one of claims 8 to 12, which is used for molding.