JP2017065270A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in interlaminar strength between a layer including a 4-methyl-1-pentene-based polymer and other synthetic resin layer.SOLUTION: The laminate is provided that has a substrate layer (A) containing a 4-methyl-1-pentene-based polymer (X) and a synthetic resin layer (B), the 4-methyl-1-pentene-based polymer (X) satisfying the following condition: (a) 4-methyl-1-pentene-based polymer (X) has 60 to 100 mol% of a constitutional unit (i) derived from 4-methyl-1-pentene and 0 to 40 mol% of constitutional unit (ii) derived from ethylene and α-olefin having carbon atoms of 3 to 20, where total of (i) and (ii) is 100 mol%; (b) an MFR measured at 260°C and 5 kgf is in the range of 0.3 to 400 g/10 min. ; (c) a melting point is in the range of 100 to 260°C and; (d) a density is in the range of 820 to 850 kg/m. The laminate has a peeling rate (%)={(peeled number)/(total number)}×100 in a cross-cut test of 5% or less.SELECTED DRAWING: None

Description

  The present invention relates to a laminate having a base material layer and a synthetic resin layer containing a 4-methyl-1-pentene polymer and satisfying specific properties.

  The 4-methyl-1-pentene polymer has a low polarity and excellent releasability. Therefore, it has been pointed out that when the molded body made of 4-methyl-1-pentene polymer is coated, the adhesive strength of the paint becomes insufficient.

 A method of performing various surface treatments on a polyolefin resin such as polypropylene for the purpose of improving the adhesive strength of a paint is disclosed (see Patent Document 1), but a 4-methyl-1-pentene polymer is disclosed. It has not been.

JP2013-244652A

  The present invention has been made in view of the background art as described above, and provides a laminate having excellent interlayer strength between a layer containing a 4-methyl-1-pentene polymer and another synthetic resin layer. This is the issue.

The present inventors have conducted intensive studies and found a laminate that can solve the above-described problems. Moreover, in order to obtain the said laminated body, it discovered that it was effective to use the base material layer which performed the intro process or the atmospheric pressure plasma process, and came to complete this invention.
That is, the present invention relates to the following [1] to [6].
[1] A substrate layer (A) containing a 4-methyl-1-pentene polymer (X) and a synthetic resin layer (B), and the 4-methyl-1-pentene polymer ( A laminate in which X) satisfies the following requirements (a) to (d) and satisfies the following requirement (I).
(A) The structural unit derived from 4-methyl-1-pentene (i) selected from 60 to 100 mol% and ethylene other than 4-methyl-1-pentene and an α-olefin having 3 to 20 carbon atoms. It has 0 to 40 mol% of structural units (ii) derived from at least one (provided that the total of the structural units (i) and the structural units (ii) is 100 mol%).
(B) The melt flow rate (MFR) measured at 260 ° C. and 5 kgf in accordance with ASTM D1238 is in the range of 0.3 to 400 g / 10 min.
(C) Melting | fusing point (Tm) measured with a differential scanning calorimeter (DSC) exists in the range of 100-260 degreeC.
(D) The density measured by the density gradient tube method in accordance with JIS K7112 is in the range of 820 to 850 kg / m ³ .
(I) In a cross cut test measured in accordance with JIS K5400-8, the peel rate determined according to the following formula (1) is 5% or less.
Peeling rate (%) = {(number of peeled sheets) / (total number of sheets)} × 100 (1)
[2] The laminate according to [1], wherein the melting point (Tm) is in the range of 215 to 250 ° C. in the requirement (c).
[3] A method for manufacturing a laminate according to [1] or [2], including a step of obtaining the substrate layer (A) through an itro process.
[4] A method for producing a laminate according to [1] or [2], comprising a step of obtaining the substrate layer (A) through atmospheric pressure plasma treatment.
[5] Base material layer (A) containing 4-methyl-1-pentene polymer (X) having a surface area ratio (S-ratio) measured by AFM in the range of 1.01 to 2.0. The method for producing a laminate according to any one of [1] to [4], wherein the synthetic resin layer (B) is laminated.
[6] The method for producing a laminate according to any one of [3] to [5], wherein the base material layer (A) is selected from an injection-molded product or an extrusion-molded product.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which is excellent in the interlayer intensity | strength of the layer containing a 4-methyl-1- pentene type polymer and another synthetic resin layer can be provided.

  Hereinafter, the present invention will be specifically described.

[Laminate]
The laminate of the present invention has a base material layer (A) containing a 4-methyl-1-pentene polymer (X) and a synthetic resin layer (B).
Although there is no restriction | limiting in particular in the thickness of each layer, It is preferable in the deformation | transformation prevention of a base material layer that the thickness of a base material layer (A) is 50 micrometers or more. The thickness of the synthetic resin layer (B) is preferably 2 μm or more from the viewpoint of imparting the surface characteristics of the synthetic resin layer (B) to the base material layer (A), and is preferably 20 μm or less. It is preferable in that sufficient interlayer strength with A) can be easily obtained.
Moreover, the ratio of the thickness of the base material layer (A) and the synthetic resin layer (B) (the thickness of the base material layer (A) / the thickness of the synthetic resin layer (B)) is usually 10 to 1000.

The laminated body of the present invention only needs to contain at least one base layer (A) and a synthetic resin layer (B). Depending on the purpose, one base layer (A) is a composite of two layers. The structure may be sandwiched between the resin layers (B). A layer other than the synthetic resin layer (B) may be laminated on the surface of the synthetic resin layer (B) of the laminate.
The laminate of the present invention satisfies the requirement (I). That is, in the cross cut test measured in accordance with JIS K5400-8, the peel rate obtained according to the following formula (1) is 5% or less, preferably 2% or less. The peeling rate can be controlled by the surface treatment conditions of the base material layer (A). Note that “peeled” refers to a state of complete peeling.
Peeling rate (%) = {(number of peeled sheets) / (total number of sheets)} × 100 (1)
[Base material layer (A)]
The base material layer (A) contains a 4-methyl-1-pentene polymer (X). Other components may be included as long as the effects of the present invention are not impaired, but the other components are usually 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less. Specifically, it is exemplified in the section of “Other resin”. The 4-methyl-1-pentene polymer may be used alone or as a mixture of a plurality of 4-methyl-1-pentene polymers.

[4-Methyl-1-pentene polymer (X)]
The requirements (a) to (d) satisfied by the 4-methyl-1-pentene polymer (X) will be described in detail.
(A) The structural unit derived from 4-methyl-1-pentene (i) selected from 60 to 100 mol% and ethylene other than 4-methyl-1-pentene and an α-olefin having 3 to 20 carbon atoms. The structural unit (ii) is derived from at least one kind and has 0 to 40 mol% (provided that the total of the structural unit (i) and the structural unit (ii) is 100 mol%).
The structural unit (i) derived from 4-methyl-1-pentene is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, still more preferably 95 to 100 mol%, other than 4-methyl-1-pentene. The structural unit (ii) derived from at least one selected from ethylene and an α-olefin having 3 to 20 carbon atoms is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, still more preferably 0. ˜5 mol% (provided that the total of the structural unit (i) and the structural unit (ii) is 100 mol%).

  That is, examples of the 4-methyl-1-pentene polymer (X) include a homopolymer of 4-methyl-1-pentene or a copolymer of 4-methyl-1-pentene and another monomer. As a monomer for deriving structural unit (ii) derived from at least one selected from ethylene and an α-olefin having 3 to 20 carbon atoms other than 4-methyl-1-pentene, ethylene and 4-methyl-1- Examples include α-olefins having 3 to 20 carbon atoms excluding pentene. Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-octene, Examples include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene. Of these, α-olefins having 6 to 20 carbon atoms excluding 4-methyl-1-pentene are preferable, and α-olefins having 8 to 20 carbon atoms are more preferable. These α-olefins can be used singly or in combination of two or more.

(B) The melt flow rate (MFR) measured at 260 ° C. and 5 kgf in accordance with ASTM D1238 is in the range of 0.3 to 400 g / 10 min. Preferably it is 1-300 g / 10min, More preferably, it is 3-200 g / 10min. When the MFR is in the above range, it is preferable in terms of fluidity during molding.
(C) Melting | fusing point (Tm) measured with a differential scanning calorimeter (DSC) exists in the range of 100-260 degreeC. Preferably it exists in the range of 130-255 degreeC, More preferably, it is 215-250 degreeC. More preferably, it is 215-245 degreeC, Most preferably, it is 220-240 degreeC, More preferably, it is 224-240 degreeC. The melting point is measured by, for example, the method described in Examples using a differential scanning calorimeter (DSC).
(D) The density measured by the density gradient tube method in accordance with JIS K7112 is in the range of 820 to 850 kg / m ³ . Preferably 825~845kg / ^{m 3,} more preferably in the range of 828~840kg / ^{m 3.}

[Method for producing 4-methyl-1-pentene polymer]
The 4-methyl-1-pentene polymer used in the present invention polymerizes a monomer containing 4-methyl-1-pentene in the presence of a known olefin polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Can be manufactured.

  Polymerization of the monomer constituting the 4-methyl-1-pentene polymer can be carried out by a liquid phase polymerization method such as solution polymerization, suspension polymerization, bulk polymerization method, gas phase polymerization method, and other known polymerization methods. . When the polymerization is carried out by a liquid phase polymerization method, an inert hydrocarbon can be used as a solvent, or a liquid olefin that is subjected to the reaction under the reaction conditions can be used. Furthermore, in the present invention, the polymerization can be carried out by any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

  Examples of the transition metal catalyst component constituting the polymerization catalyst used in the method for producing a 4-methyl-1-pentene polymer include a solid titanium catalyst composed of magnesium, titanium, halogen and an electron donor, a metallocene catalyst, and the like. It is done. Among these, a solid titanium catalyst is preferable, and a magnesium compound suspended in an inert hydrocarbon solvent described in Japanese Patent Application Laid-Open No. 2003-105022 and an electron donor are particularly preferable. Examples thereof include a titanium catalyst composed of titanium, magnesium, halogen, and a compound having a plurality of ether bonds obtained by contacting a compound having two or more ether bonds with a plurality of atoms in between and a titanium compound in a liquid state.

Examples of the inert hydrocarbon solvent include hexane, decane and dodecane.
As electron donors, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane and 2-isopentyl-2-isopropyl-1,3-compounds having two or more ether bonds with a plurality of atoms in between. Examples include dimethoxypropane.

  Examples of magnesium compounds include anhydrous magnesium chloride and methoxy magnesium chloride.

  In the present invention, for example, in the case of a liquid phase polymerization method, the solid titanium catalyst is usually 0.0001 to 0.5 mmol, preferably 0.0005 to 0.1 in terms of titanium atoms per liter of the total liquid volume. It is preferably used in an amount of millimolar.

  In the solid titanium catalyst, the ratio of halogen and titanium (halogen / titanium) is usually 2 to 100, preferably 4 to 90, in atomic ratio, and the ratio of the compound containing two or more ether bonds and titanium. (Compound containing two or more ether bonds / titanium) is usually in a molar ratio of 0.01 to 100, preferably 0.2 to 10, and the ratio of magnesium and titanium (magnesium / titanium) is in atomic ratio. Usually 2 to 100, preferably 4 to 50.

The cocatalyst component (organometallic compound catalyst component) to be used together with the above-mentioned solid titanium catalyst, an organoaluminum compound may be mentioned, for example, an organoaluminum compound represented by R ^a _n AlX _3-n and the like.

During ^{_{R a n AlX 3-n,}} n is 1-3. R ^a is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, and an aryl group, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group. A pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group, and when n is 2 or 3, they may be the same or different. X is halogen or hydrogen, and when n is 2 or 3, they may be the same or different.

Examples of the organoaluminum compounds represented by R ^a _n AlX _3-n, for example, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trialkyl aluminum, such as trioctyl aluminum and tri-2-ethylhexyl aluminum; isoprenylaluminum Alkenyl aluminum such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride Yo Alkyl aluminum sesquihalides such as ethylaluminum sesquibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride . Of these, trialkylaluminums such as triethylaluminum and triisobutylaluminum are preferred.

  For example, when the transition metal catalyst component is a solid titanium catalyst, the amount of the cocatalyst component (organometallic compound catalyst component) is usually 0.1 to 1000000 g, preferably 100 to 1000000 g, per 1 g of the solid titanium catalyst. The amount of such a polymer may be such that it is usually 0.1 to 1000 mol, preferably about 0.5 to 500 mol, more preferably 1 to 200, per mol of titanium atom in the solid titanium catalyst. The amount in moles.

  The transition metal catalyst component is preferably suspended in an inert organic solvent (preferably a saturated aliphatic hydrocarbon) and supplied to the polymerization reactor.

  The transition metal catalyst component is preferably used as a solid catalyst component prepolymerized with an α-olefin such as 3-methyl-1-pentene or 4-methyl-1-pentene. The prepolymerization is carried out by polymerizing the above α-olefin in an amount of usually 0.1 to 1000 g, preferably 0.3 to 500 g, more preferably 1 to 200 g per 1 g of the transition metal catalyst component. The prepolymerization can be performed at a catalyst concentration higher than the catalyst concentration in the reaction system in the polymerization of 4-methyl-1-pentene.

  In the present invention, liquid phase polymerization methods such as solution polymerization and suspension polymerization (slurry polymerization) are preferably used in producing a 4-methyl-1-pentene polymer, and more preferably suspension polymerization (slurry polymerization). ) Method is used.

  If hydrogen is used during the main polymerization, the molecular weight of the polymer obtained can be adjusted, and a polymer having a high melt flow rate can be obtained.

  Furthermore, by selecting the type of electron donor contained in the solid titanium catalyst used in the main polymerization, it becomes possible to adjust the stereoregularity of the obtained polymer, thereby adjusting the melting point of the polymer. It becomes possible.

  In the present invention, the polymerization temperature and polymerization pressure of olefin vary depending on the polymerization method and the type of monomer to be polymerized, but the polymerization temperature is usually 10 to 200 ° C., preferably 30 to 150 ° C., and the polymerization pressure is usually normal pressure. It is set to ˜5 MPa-G, preferably 0.05 to 4 MPa-G.

[Other resins]
You may add another resin to a base material layer (A) in the range which does not impair the characteristic of 4-methyl- 1-pentene type polymer. The addition amount is generally 30% by mass or less, preferably 20% by mass or less. Examples of other resins include olefin polymers, polyesters, polyamides, modified olefin polymers, and the like.

  As said olefin polymer, what is obtained by superposing | polymerizing 1 or more types of olefins chosen from ethylene and a C3-C20 linear or branched alpha olefin is mentioned. Specific examples of the linear or branched α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, and 3-methyl-1. -Pentene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like. As these α-olefins, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.

  In addition to the α-olefin described above, the olefin polymer is a cyclic olefin, a functionalized vinyl compound, a polar group (for example, a carbonyl group, a hydroxyl group, an ether bonding group, etc.) A monomer having a carbon-carbon double bond in the molecule (hereinafter also referred to as a polar group-containing monomer), a conjugated diene, a non-conjugated polyene, or the like may be included as a comonomer.

  Cyclic olefins include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5. , 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like.

  Examples of functionalized vinyl compounds include aromatic vinyl compounds and alicyclic vinyl compounds. Examples of the aromatic vinyl compound include mono- or poly-styrene such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene. Functional group-containing styrene derivatives such as alkyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene; and 3-phenylpropylene, 4 -Phenylpropylene, α-methylstyrene and the like are mentioned, and examples of the alicyclic vinyl compound include vinylcyclohexane and vinylcycloheptane.

  The functionalized vinyl compound may be a homopolymer of the functionalized vinyl compound or a copolymer with a copolymer component. Specific examples of copolymer components include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid and methacrylic acid, unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, sodium methacrylate, acrylic Unsaturated carboxylic acid salts such as sodium acetate, unsaturated carboxylic acid esters such as vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, methyl methacrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, etc. Examples include, but are not limited to, saturated carboxylic acid amides. These copolymerization components may use only 1 type and may use 2 or more types together.

  Examples of the polyester include aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, hexamethylene glycol, alicyclic glycols such as cyclohexanedimethanol, and aromatic dihydroxy compounds such as bisphenol. And aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, undecadicarboxylic acid, hexahydroterephthalic acid, etc. A crystalline thermoplastic resin formed from the alicyclic dicarboxylic acid or two or more dicarboxylic acids selected from these alicyclic dicarboxylic acids. The polyester may be modified with a small amount of trihydroxy or higher polyhydroxy compound such as triol or tricarboxylic acid, polycarboxylic acid or the like as long as it exhibits thermoplasticity. Specific examples of this polyester include polylactic acid, polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate / terephthalate copolymer, and the like.

  Examples of the polyamide include hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine, 1,3- or 1,4-bis (aminomethyl). ) Diamines such as cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine, alicyclic diamine or aromatic diamine, and adipic acid, suberic acid, sebacic acid, cyclohexane Polyamides obtained by polycondensation with dicarboxylic acids such as aliphatic dicarboxylic acids such as dicarboxylic acid, terephthalic acid and isophthalic acid, alicyclic dicarboxylic acids and aromatic dicarboxylic acids, ε-aminocaproic acid, 11-aminoundecanoic acid, etc. Obtained by condensation of aminocarboxylic acid Polyamides, .epsilon.-caprolactam, .omega. polyamides obtained from lactams laurolactam such or copolymerized polyamide composed of these ingredients, more like a mixture of these polyamides. Specific examples of the polyamide include nylon 6, nylon 66, nylon 6110, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon 6/11, and aromatic nylon.

[Other additives]
Other additives for resin can be arbitrarily added to the laminate of the present invention within a range that does not impair the effects of the present invention, depending on the application. Examples of such additives for resins include pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, antistatic agents, and weathering stability. Agent, heat stabilizer, anti-slip agent, anti-blocking agent, foaming agent, crystallization aid, anti-fogging agent, (transparent) nucleating agent, anti-aging agent, hydrochloric acid absorbent, impact modifier, crosslinking agent, co-crosslinking agent , Crosslinking aids, adhesives, softeners, processing aids, and the like. These additives can be used singly or in appropriate combination of two or more.

  Examples of the pigment include inorganic contents (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake type, thioindigo type, phthalocyanine type, anthraquinone type). Examples of the dye include azo series, anthraquinone series, and triphenylmethane series. The addition amount of these pigments and dyes is not particularly limited, but is generally 5% by mass or less, preferably 0.1 to 3% by mass in total with respect to the total mass of the 4-methyl-1-pentene polymer. It is.

  Fillers include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicate (calcium silicate, talc, clay, etc.), metal oxide ( Iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate, etc.) and various metals (magnesium, silicon, aluminum, titanium, copper, etc.) powder, mica, glass flakes and the like. These fillers may be used alone or in combination of two or more.

  Examples of the lubricant include wax (such as carnauba wax), higher fatty acid (such as stearic acid), higher alcohol (such as stearyl alcohol), and higher fatty acid amide (such as stearic acid amide).

  Examples of plasticizers include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methylacetylricinoleate), aliphatic dialcolic acid esters (such as adipic acid-propylene glycol polyester), and aliphatic tricarboxylic acids. Examples include esters (such as triethyl citrate), phosphoric acid triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.

  Examples of mold release agents include lower (C1-4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters (such as hardened castor oil) of fatty acids (C4-30), glycol esters of fatty acids, liquid paraffin, etc. Is mentioned.

Antioxidants include phenolic (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenolic (2,2′-methylenebis (4-methyl-6-t-butylphenol), etc.) Phosphorus-based (tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonate etc.), amine-based (N, N-diisopropyl-p-phenylenediamine etc.) antioxidants Can be mentioned.

  Examples of flame retardants include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.). Can be mentioned.

  Examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylic acid, and acrylate.

  Antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, organic iodine, and the like.

  Surfactants can include nonionic, anionic, cationic or amphoteric surfactants. Nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, fatty acid esters of polyethylene oxide and glycerin. Polyanhydric alcohol type nonionic surfactants such as fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, etc. For example, sulfate salts such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, paraffin sulfonates, Include a phosphoric acid ester salts such as grade alcohol phosphate ester salt, the cationic surfactants, such as quaternary ammonium salts such as alkyl trimethyl ammonium salts. Examples of amphoteric surfactants include amino acid-type double-sided surfactants such as higher alkylaminopropionates, betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyl hydroxyethylbetaine.

  Examples of the antistatic agent include the above surfactants, fatty acid esters, and polymer antistatic agents. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymer antistatic agents include polyether ester amides.

  The addition amount of various additives such as the above fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, antistatic agents, and the like impairs the purpose of the present invention. Although it does not specifically limit according to a use within the range which is not, It is preferable that it is 0.01-30 mass%, respectively with respect to the said 4-methyl-1- pentene type polymer.

[Synthetic resin layer (B)]
The synthetic resin layer (B) is a layer made of a synthetic resin different from the 4-methyl-1-pentene polymer (X) contained in the base material layer (A).
The synthetic resin forming the synthetic resin layer (B) is at least one resin selected from ionizing radiation curable resins, thermoplastic resins, and thermosetting resins. These may be used alone or in combination of two or more. Definitions and production methods for thermoplastic resins or thermosetting resins are well known, and are described, for example, in publications such as “Practical Plastics Dictionary” (edited by the Practical Plastics Dictionary Editorial Board, published by Sangyo Kaisha)
1-1. Ionizing radiation curable resin As the ionizing radiation curable resin, a resin that crosslinks and cures with ionizing radiation such as ultraviolet rays, visible rays, and electron beams can be used. In that case, it is preferable to use a radical photopolymerization initiator together as needed.

The ionizing radiation curable resin specifically includes ionizing radiation in which prepolymers (including so-called oligomers) and / or monomers having radically polymerizable unsaturated bonds or cationically polymerizable functional groups in the molecule are appropriately mixed. A curable composition is preferably used. These prepolymers or monomers are used alone or in combination.

Specifically, the prepolymer or monomer is a (meth) acryloyl group, (
It consists of a compound having a radically polymerizable unsaturated group such as a (meth) acryloyloxy group and a cationically polymerizable functional group such as an epoxy group. A polyene / thiol-based prepolymer based on a combination of polyene and polythiol is also preferably used. The (meth) acryloyl group means an acryloyl group or a methacryloyl group. Examples of prepolymers having radically polymerizable unsaturated groups include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, melamine (meth) acrylate , Triazine (meth) acrylate,
Silicone (meth) acrylates and the like can be used. The molecular weight is usually 250 to 10
A thing of about 10,000 is used.

Here, the epoxy (meth) acrylate-based prepolymer is, for example, (meth) on the oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin.
It can be obtained by reacting acrylic acid and esterifying. This epoxy (
A carboxyl-modified epoxy (meth) acrylate prepolymer obtained by partially modifying a (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate-based prepolymer can be obtained, for example, by esterifying a polyurethane prepolymer obtained by reaction of polyether polyol or polyester polyol with polyisocyanate with (meth) acrylic acid. Examples of the polyester (meth) acrylate-based prepolymer include a hydroxyl group of a polyester prepolymer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol (
It can be obtained by esterifying with (meth) acrylic acid, or by esterifying the terminal hydroxyl group of a prepolymer obtained by adding alkylene oxide to polyvalent carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate prepolymer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

Furthermore, other polymerizable prepolymers include polybutadiene (meth) acrylate-based prepolymers with high hydrophobicity having (meth) acrylate groups in the side chains of polybutadiene oligomers, and silicone (meth) acrylates having polysiloxane bonds in the main chain. Prepolymers,
In a molecule such as aminoplast resin (meth) acrylate prepolymer modified with aminoplast resin having many reactive groups in a small molecule, or novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. Include a prepolymer having a cationically polymerizable functional group.

As an example of the monomer having a radically polymerizable unsaturated group, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate is preferable. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (
(Meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate , Propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

<Radical radical polymerization initiator>
Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A-2001-139663, etc.), 2, 3 -Dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.

  Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone is included.

Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether It is.

Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4'-dimethylaminobenzophenone (Michler ketone), 3, 3 ′, 4, 4′-tetra (t-butylperoxycarbonyl) benzophenone and the like are included.

  Examples of the borate salt are described in Japanese Patent Nos. 2764769 and 2002-116539, and in Kunz, Martin “Rad Tech'98. Proceding April 19-22, 1998, Chicago”. And the organic borate compounds described. For example, the compounds described in JP-A-2002-116539, paragraph numbers [0022] to [0027] can be mentioned. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Specific examples include organoboron transition metal coordination complexes and the like, and specific examples include ion complexes with cationic dyes.

  Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the active esters include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], sulfonic acid esters, cyclic active ester compounds, and the like.

  Specifically, Examples 1 to 21 described in JP-A 2000-80068 are particularly preferable.

Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

  Specific examples of the active halogens include Wakabayashi et al. “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830, M.M. P. Hutt “Journal of Heterocyclic Chemistry” Vol. 1 (No. 3), (1970), and the like, and in particular, an oxazole compound substituted with a trihalomethyl group: s-triazine compound. More preferable examples include s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specific examples include S-triazine and oxathiazole compounds. 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di ( Ethyl acetate) amino) phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole. Specifically, p. 14 to p. 30 of JP-A No. 58-155.03, p.sub.6 to p.sub.10 of JP-A No. 55-77742, and p. No. described in p. 1-No. 8, No. pp. 443 to p444 of JP-A-60-239736. 1-No. 17, No. 4,701,399. Compounds such as 1-19 are particularly preferred.

  Examples of inorganic complexes include bis (η 5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1 H-pyrrol-1-yl) -phenyl) titanium. .

  Examples of coumarins include 3-ketocoumarin.

  These initiators may be used alone or in combination.

  “Latest UV Curing Technology”, Technical Information Association, 1991, p. 1 5 9, and “UV Curing System” written by Kiyomi Kato, 1989, General Technology Center, p. Various examples are also described in 6 5 to 1 4 8 and are useful in the present invention.

  Examples of commercially available photo radical polymerization initiators include KAYACURE (DETX-S, BP-100, BDMMK, CTX, manufactured by Nippon Kayaku Co., Ltd. BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, MCA, etc.), manufactured by Ciba Specialty Chemicals Co., Ltd. Irgacure (6 5 1, 1 8 4, 5 0 0, 8 1 9, 9 0 7, 3 6 9, 1 1 7 3, 18 7 0, 2 9 5 9, 4 2 6 5, 4 2 6 3, etc. ), Saccur, manufactured by Sartomer (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP) 1 5 0, TZ T) and the like and combinations thereof are preferred examples.

  The photoinitiator is 0 .0 to 0 parts by mass of the polyfunctional monomer. It is preferably used in the range of 1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass.

<Photosensitizer>
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

Furthermore, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.

As a commercially available photosensitizer, KAYACURE (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd.
Etc.

1-2. Thermosetting resin Examples of the thermosetting resin include polyurethane, epoxy resin, thermosetting unsaturated polyester resin, urea resin, melamine resin and phenol resin, and mixed resins thereof. Among these, (1) epoxy resin, (2) thermosetting unsaturated polyester resin, and (3) phenol resin are preferable. Preferred examples of these resins are shown below. In the following description, the thermosetting resin before thermosetting is described.

(1) Epoxy resin An epoxy resin is typically a resin obtained by reacting an aromatic diol (for example, bisphenol A) and epichlorohydrin in the presence of an alkali. In the present invention, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin having an epoxy equivalent of 170 to 5000 are preferable. Such epoxy resins are commercially available, and examples thereof include trade names such as Epomic (Mitsui Chemicals Co., Ltd.), Epicron (Dainippon Ink Chemical Co., Ltd.), Sumi Epoxy (Sumitomo Chemical Co., Ltd.), and the like.

(2) Thermosetting unsaturated polyester resin The thermosetting unsaturated polyester resin is typically a resin obtained by an esterification reaction between an aliphatic unsaturated dicarboxylic acid and an aliphatic diol. In the present invention, a resin obtained by esterifying an unsaturated dicarboxylic acid such as maleic acid or fumaric acid and a diol such as ethylene glycol or diethylene glycol is preferred. Such thermosetting unsaturated polyester resins are commercially available, and examples thereof include trade name Rigolac (Showa High Polymer Co., Ltd.), Sumicon (Sumitomo Bakelite Co., Ltd.) and the like.

(3) Phenolic resin In the present invention, the phenolic resin includes both so-called novolak type and resol type, but a novolak type cured with hexamethylenetetramine and a solid resol type resin mainly composed of dimethylene ether bond are preferable. . Such a phenol resin is commercially available, and examples thereof include trade names Sumicon PM (Sumitomo Bakelite Co., Ltd.), Nikkaline (Nippon Synthetic Chemical Industry Co., Ltd.), and the like.

1-3. The following (1)-(16) is mentioned as a typical thing as a thermoplastic resin. These may be used alone or in combination of two or more.

(1) Olefin polymer (2) Polyamide (3) Polyester (4) Polyacetal (5) Polystyrene, acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylic rubber-styrene resin, acrylonitrile-ethylene rubber-styrene resin, (meth) Styrene resins such as acrylic ester-styrene resin and styrene-butadiene-styrene resin (6) Acrylic resin such as polymethyl methacrylate and polyethyl methacrylate (7) Polycarbonate (8) Polyphenylene oxide (9) Polyvinyl chloride, Poly Chlorine resins such as vinylidene chloride (10) Vinyl acetate resins such as polyvinyl acetate and ethylene-vinyl acetate resins (11) Ethylene- (meth) acrylic acid ester copolymers (12) Ethylene-acrylic Resins, ethylene-methacrylic acid resins and their ionomer resins (13) Vinyl alcohol resins such as polyvinyl alcohol and ethylene-vinyl alcohol resins (14) Cellulose resins (15) Vinyl chloride elastomers, urethane elastomers, polyester elastomers, etc. (16) Various copolymer rubbers (17) Fluororesin Next, specific examples of each thermoplastic resin will be given.

(1) Olefin polymer As the olefin polymer, olefin homopolymers such as polyethylene, polypropylene, poly-1-butene, polymethylbutene; ethylene-α-olefin random copolymer, propylene-ethylene random copolymer Examples thereof include ethylene, α-olefin / non-conjugated polyene copolymer, and the like.

  The olefin polymer can be, for example, an ethylene (co) polymer. The ethylene (co) polymer is preferably an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Specific examples of the ethylene homopolymer include ultra high molecular weight polyethylene, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, and the like.

  The olefin polymer may be a propylene homopolymer (polypropylene) or a propylene (co) polymer of propylene and ethylene or an α-olefin having 4 to 20 carbon atoms.

  Examples of the α-olefin having 3 to 20 carbon atoms or the α-olefin having 4 to 20 carbon atoms are the same as those described in the section of the 4-methyl-1-pentene polymer (X). In addition, an alpha olefin may be used individually by 1 type, and may use 2 or more types together.

  Furthermore, the olefin polymer may be an ethylene / α-olefin / non-conjugated polyene copolymer. In this case, the copolymer is preferably a copolymer of ethylene [A], an α-olefin [B] having 3 to 12 carbon atoms and a non-conjugated polyene [C], and is a polymer obtained by random copolymerization. Is more preferable. As an alpha olefin, the C3-C20 alpha olefin mentioned above is mentioned. As the nonconjugated polyene, a cyclic or chain nonconjugated polyene is used. Examples of the cyclic non-conjugated polyene include cyclopentene, cycloheptene, norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, methyltetrahydroindene, tetracyclododecene, and the like. Examples of the chain non-conjugated polyene include 1,4-hexadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4-ethylidene-1,7-undecadiene, and the like. Is mentioned. Of these, 5-ethylidene-2-norbornene, dicyclopentadiene, and 5-vinyl-2-norbornene are preferable. These cyclic or chain nonconjugated polyenes may be used alone or in combination of two or more.

  Examples of the ethylene / α-olefin / non-conjugated polyene random copolymer include ethylene / propylene / diene terpolymer (EPDM).

Further, as the olefin polymer, a propylene / α-olefin / non-conjugated polyene copolymer, a 1-butene / α-olefin / non-conjugated polyene copolymer, or the like can be used.
The olefin polymer may be unmodified, but may be modified with a polar compound containing a double bond.

  The graft modification of the olefin polymer can be performed by a known method. For example, an olefin polymer is dissolved in an organic solvent, and then a polar compound containing a double bond such as an unsaturated carboxylic acid and a radical initiator are added to the resulting solution, usually at 60 to 350 ° C., preferably 80 to The method of making it react at the temperature of 190 degreeC for 0.5 to 15 hours, Preferably it is 1 to 10 hours can be illustrated.

  As another graft modification method, a method of reacting an olefin polymer with a polar compound containing a double bond such as an unsaturated carboxylic acid without using a solvent, preferably using an extruder or the like. Is mentioned. The reaction conditions in this case are such that the reaction temperature is usually not lower than the melting point of the olefin polymer, specifically 100 to 350 ° C. The reaction time can usually be 0.5 to 10 minutes.

(2) Polyamide As polyamide, Nylon-6, Nylon-66, Nylon-10, Nylon-11, Nylon-12, Nylon-46, Nylon 66, Nylon-610, Nylon-612, etc., aliphatic polyamide, aromatic Aromatic polyamides produced from dicarboxylic acids and aliphatic diamines can be mentioned.

(3) Polyester Examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polycaprolactone, polyhydroxybutyrate, and polyester elastomers.

(4) Polyacetal Examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, and polybutyraldehyde.

(5) Styrene resin The styrene resin may be a homopolymer of styrene, and is a binary copolymer of styrene and acrylonitrile, methyl methacrylate, α-methylstyrene or the like, for example, acrylonitrile-styrene copolymer. It may be a coalescence. Further, acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylic rubber-styrene resin, acrylonitrile-ethylene rubber-styrene resin, (meth) acrylic ester-styrene resin, or various styrene-based elastomers may be used. As an acrylonitrile-butadiene-styrene (ABS) resin, it contains a structural unit derived from acrylonitrile in an amount of 20 to 35 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, What contains the structural unit derived from styrene in the quantity of 40-60 mol% is used preferably. The total of these structural units is 100 mol%.

  Moreover, as a styrene-type elastomer, the well-known styrene-type elastomer which has a polystyrene phase as a hard segment can also be used. Specifically, styrene / butadiene copolymer (SBR), styrene / isoprene / styrene copolymer (SIS), styrene / butadiene / styrene copolymer (SBS), styrene / ethylene / butadiene / styrene copolymer ( SEBS) and hydrides thereof, styrene / isobutylene / styrene triblock copolymer (SIBS), and styrene / isobutylene diblock copolymer (SIB). Preferred are styrene / isobutylene / styrene triblock copolymer (SIBS) and styrene / isobutylene diblock copolymer (SIB).

(6) Acrylic resin Examples of acrylic resin fat include polymethacrylate and polyethylmethacrylate.

(7) Polycarbonate As the polycarbonate, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4 Examples thereof include those obtained from -hydroxyphenyl) butane and the like.

(8) Polyphenylene oxide The polyphenylene oxide is preferably poly (2,6-dimethyl-1,4-phenylene oxide).

(9) Chlorine resins such as polyvinyl chloride and polyvinylidene chloride Polyvinyl chloride may be a homopolymer of vinyl chloride, or a copolymer of vinyl chloride and vinylidene chloride, acrylate ester, acrylonitrile, propylene, etc. It may be. On the other hand, polyvinylidene chloride is usually a resin containing 85% or more of vinylidene chloride units. For example, vinylidene chloride is co-polymerized with vinyl chloride, acrylonitrile, (meth) acrylic acid ester, allyl ester, unsaturated ether, styrene, etc. Coalescence is used. A vinyl chloride elastomer may be used.

(10) Vinyl acetate resins such as polyvinyl acetate and ethylene-vinyl acetate resin Polyvinyl acetate may be a homopolymer of vinyl acetate, or a copolymer of vinyl acetate, ethylene, and vinyl chloride. May be. Of these, ethylene-vinyl acetate copolymer is preferred. Further, it may be a modified ethylene-vinyl acetate copolymer such as a saponified ethylene-vinyl acetate copolymer or a graft-modified ethylene-vinyl acetate copolymer.

(11) Ethylene- (meth) acrylic ester copolymer As ethylene- (meth) acrylic ester copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer Polymers and ethylene-ethyl methacrylate copolymers are preferred.

(12) Ethylene-acrylic acid resins, ethylene-methacrylic acid resins and their ionomer resins. Ethylene-acrylic acid copolymers and ethylene-methacrylic acid copolymers are copolymers of ethylene and various (meth) acrylic acids. It can be. These may be further metallized to form metal salts (ionomers). The metal element of the metal salt is preferably at least one selected from K, Na, Ca and Zn. It is more preferable that the metal elements are K, Na, Ca and Zn because modification is easy.

(13) Vinyl alcohol-based resins such as polyvinyl alcohol and ethylene-vinyl alcohol resin Polyvinyl alcohol, ethylene-vinyl alcohol resin and the like can be mentioned. The ethylene-vinyl alcohol resin is obtained by hydrolysis of a copolymer of ethylene and vinyl acetate.

(14) Cellulose resin A typical example of the cellulose resin is acetylcellulose. By using a plasticizer such as dibutyl phthalate in combination, it has the characteristics of a thermoplastic resin.

(15) Thermoplastic Elastomer A thermoplastic polyurethane material mentioned as a thermoplastic urethane elastomer will be described. The structure of the thermoplastic polyurethane material is composed of a soft segment made of a polymer polyol (polymeric glycol), a chain extender constituting the hard segment, and a diisocyanate. Here, as the polymer polyol used as a raw material, any of those conventionally used in the technology relating to thermoplastic polyurethane materials can be used, and is not particularly limited. For example, there are a polyester type and a polyether type, and the polyether type is preferable to the polyester type in that a thermoplastic polyurethane material having high rebound resilience and excellent low temperature characteristics can be synthesized. Examples of the polyether polyol include polytetramethylene glycol and polypropylene glycol. Polytetramethylene glycol is particularly preferable from the viewpoint of the resilience modulus and low temperature characteristics. The average molecular weight of the polymer polyol is preferably 1000 to 5000, and particularly preferably 2000 to 4000 in order to synthesize a thermoplastic polyurethane material having high resilience. As the chain extender, those used in the conventional technology relating to thermoplastic polyurethane materials can be suitably used. For example, 1,4-butylene glycol, 1,2-ethylene glycol, 1,3-butanediol, 1 , 6-hexanediol, 2,2-dimethyl-1,3-propanediol and the like, but are not limited thereto. These chain extenders preferably have an average molecular weight of 20 to 15000. As the diisocyanate, those used in the conventional technology relating to thermoplastic polyurethane materials can be suitably used. For example, aromatics such as 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate can be used. Aliphatic diisocyanates, aliphatic diisocyanates such as hexamethylene diisocyanate, and the like, but are not limited thereto.

(16) Various copolymer rubbers Examples of rubbers other than the above-mentioned elastomers include polybutadiene rubber, polyisoprene rubber, neoprene rubber, nitrile rubber, butyl rubber, halogenated butyl rubber, polyisobutylene rubber, natural rubber, and silicone rubber. These rubbers may be used alone or in combination of two or more.
(17) Fluorine resin Examples of the fluorine resin include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA) made of a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, tetrafluoroethylene and hexafluoropropylene. Copolymer (FEP), copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether and hexafluoropropylene (EPE), copolymer of tetrafluoroethylene and ethylene or propylene (ETFE), polychlorotrifluoroethylene resin (PCTFE), ethylene And chlorotrifluoroethylene copolymer (ECTFE)
), Vinylidene fluoride resin (PVDF), vinyl fluoride resin (PVF), and the like. Among these fluororesins, polyvinyl fluoride resin (PVF) excellent in strength, heat resistance, weather resistance, etc., and a copolymer of tetrafluoroethylene and ethylene or propylene (
ETFE) is particularly preferred.

Preferred resin as the synthetic resin forming the synthetic resin layer (B) The synthetic resin forming the synthetic resin layer (B) is preferably at least one resin selected from ionizing radiation curable resins among the examples exemplified above. More preferably, it is selected from ultraviolet curable acrylate resins.

Preferred Properties of Synthetic Resin Forming Synthetic Resin Layer (B) The adhesion between the base material layer (A) and the synthetic resin layer (B) in the laminate of the present invention is a fine uneven shape formed on the base material layer (A). Therefore, it is desirable that the synthetic resin layer (B) has high fluidity that can penetrate into the uneven shape.

[Manufacturing method of laminate]
As a manufacturing method of a laminated body, a base material layer (A) containing 4-methyl-1-pentene polymer (X) having a surface area ratio (S-ratio) in the range of 1.01 to 2.0. It is preferable to laminate a synthetic resin layer (B). The surface area ratio of the base material layer (A) is more preferably 1.25 to 1.9, and further preferably 1.2 to 1.8.

  Hereinafter, the manufacturing method of a laminated body is explained in full detail in order of the shaping | molding method of a base material layer (A), the surface treatment method of a base material layer (A), and the lamination | stacking method of a synthetic resin layer (B).

[Formation of substrate layer (A)]
A base material layer (A) can be shape | molded, for example by the method shown below, respectively.

(1) Extrusion molding Obtained by molding with a general extrusion molding machine. For example, molding is performed at a cylinder temperature of 250 to 300 ° C. and a cast roll temperature of 0 to 90 ° C. with a single screw extruder to form extruded films, sheets, and various extruded molded bodies.

  As long as the effect of the present invention is not hindered, other resins and multilayer films may be used, or laminated paper may be used as laminated paper, and co-extrusion molding, extrusion lamination, thermal lamination, dry lamination, etc. should be used. Can do. In addition, the film surface may be embossed or may be stretched during or after film formation. Furthermore, the film obtained by molding may be further subjected to an annealing treatment at a temperature lower than the melting point of the resin.

(2) Stretched film The stretched film may be produced by producing a raw sheet and stretching it. There is no restriction | limiting in particular in the manufacturing method of a raw fabric sheet, For example, it can shape | mold by well-known methods, such as methods, such as press molding, extrusion molding, and inflation molding, or a solution casting method.

  From the viewpoint of improving production efficiency, an extrusion molding method, an inflation molding method, a solution casting method, or the like may be used. Furthermore, from the viewpoint of production efficiency and stabilization of the stretched molded body, it is preferable to obtain a stretched molded body by stretching and orienting the raw sheet formed by the melt extrusion molding method.

  In the case of performing melt extrusion molding, specifically, a raw sheet is formed by molding at a predetermined cylinder temperature and a predetermined cast roll temperature with a single screw extruder. When a raw sheet is obtained by melt extrusion molding, the transparency of the resulting sheet can be further increased by pressing and compressing between rolls of the extruder. The raw sheet manufactured in advance by melt extrusion molding may be supplied to a stretch molding apparatus, or melt extrusion molding and stretch molding may be performed continuously.

  The formed raw sheet is stretched and formed at a predetermined stretching speed with a stretching machine. Stretching may be performed by any of uniaxial stretching, biaxial stretching, sequential stretching, and the like.

  The stretching temperature is usually in the temperature range of the glass transition point (Tg) to 200 ° C of the resin, preferably Tg to 180 ° C, more preferably Tg to 150 ° C. Moreover, in order to improve stretchability, it is preferable to preheat the raw sheet before stretching. It is sufficient to perform preheating before stretching in a temperature range of Tg to 180 ° C, more preferably Tg to 150 ° C, usually for about 5 minutes.

  The stretching speed is usually 0.1 mm / sec to 500 mm / sec, more preferably 0.5 mm / sec to 100 mm / sec. The draw ratio is usually 1.5 to 6 times, preferably 2 to 5 times. In order not to increase the crystallinity and the crystal size, it may be preferable to reduce the stretching ratio and increase the stretching speed. The direction of stretching is preferably performed in the direction of extruding the original sheet. If it extends | stretches on such conditions, an extending | stretching molded object can be manufactured efficiently, without producing | generating an extending | stretching nonuniformity and extending | stretching interruption.

  By stretching the film, a film having mechanical strength can be obtained. The thickness of the stretched film can be adjusted by changing the thickness of the original fabric sheet, the stretch ratio, and the like. There is no particular upper limit to the thickness of the stretched film, and it includes what was conventionally called a “sheet” in this technical field. Moreover, when using a stretched film as an optical film, it is set as the thickness which can be used for an optical use. The thickness of the stretched film is usually 10 to 200 μm, preferably 20 to 200 μm. If it is such a range, productivity of a film will improve more, and sufficient mechanical strength will also be obtained, without producing a pinhole etc. at the time of film forming.

(3) Inflation film The film of the present invention may be produced by an inflation molding method. Specifically, an inflation film can be obtained by extruding from an inflation die in an upward direction opposite to the direction of gravity with a single cylinder extruder at a predetermined cylinder temperature.

  The take-up speed of the inflation film is usually 2 to 40 m / min, preferably 4 to 30 m / min. Although the thickness of a film is not specifically limited, Usually, 10-300 micrometers, Preferably it is 20-250 micrometers, More preferably, it is 30-60 micrometers.

(4) Injection-molded product An injection-molded product can be obtained at a molding temperature of usually 250 to 300 ° C. and a molding cycle of usually 20 to 120 seconds.

[Surface treatment of substrate layer (A)]
(1) The surface treatment method of the itro-treated substrate layer (A) includes itro treatment. Itro treatment forms a silicon oxide film on the surface of the substrate through a burner. As an intro treatment apparatus, Flame Bond (manufactured by Soft 99 Corporation) may be mentioned. In the present invention, in order to firmly bond the base material layer (A) and the synthetic resin layer (B), the distance between the burner and the base material layer (A) and the flame treatment speed by the burner are important. The distance between the burner and the base material layer (A) is usually in the range of 15 to 30 mm. The flame treatment speed is usually in the range of 100 to 1000 m / s. In addition, when the substrate layer (A) is subjected to itro treatment twice or more, a silicon oxide film is uniformly formed on the substrate, and the adhesion between the substrate layer (A) and the synthetic resin layer (B) is further improved. Become strong.
(2) Atmospheric pressure plasma treatment As a surface treatment method of the atmospheric pressure plasma treatment base material layer (A), atmospheric pressure plasma treatment is exemplified. Atmospheric pressure plasma treatment is also called atmospheric pressure plasma treatment. The distance between the plasma irradiation nozzle and the base material layer (A) is usually in the range of 0.1 to 30 mm, preferably in the range of 0.5 to 10 mm. The processing speed is usually in the range of 1 to 500 m / s. The surface temperature of the base material layer (A) is preferably in the range of 60 ° C. to 100 ° C. in terms of interlayer adhesion, but in order to suppress warp deformation of the base material layer (A), the surface temperature is 0 to 50 ° C. It is preferable to be in the range, and normal temperature is more preferable. In the atmospheric pressure plasma treatment, since a flame is not used and the treatment can be performed in a state in which the surface temperature is suppressed, there is an advantage that it can be easily applied to, for example, a relatively thin molded body that is easily deformed by heat.

[Lamination of synthetic resin layer (B)]
The method for laminating the synthetic resin layer (B) is not particularly limited. Examples of the coating method include commonly used coating methods such as brushes, rollers, roll coaters, air sprays, and airless sprays. The coating method can be appropriately selected according to the type and use of the substrate.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

  The physical properties measured in the examples were carried out according to the following methods.

<Constitutional unit contained in 4-methyl-1-pentene polymer>
The molar ratio of the structural unit derived from 4-methyl-1-pentene and the molar ratio of the structural unit derived from α-olefin having 3 to 20 carbon atoms other than ethylene or 4-methyl-1-pentene are ¹³ Measured by C-NMR. The measurement conditions are as follows.

Measuring apparatus: Nuclear magnetic resonance apparatus (ECP500 type, manufactured by JEOL Ltd.)
Observation nucleus: ¹³ C (125 MHz)
Sequence: Single pulse proton decoupling Pulse width: 4.7 μsec (45 ° pulse)
Repeat time: 5.5 seconds Accumulated number: 10,000 times or more Solvent: Orthodichlorobenzene / deuterated benzene (volume ratio: 80/20) mixed solvent Sample concentration: 55 mg / 0.6 mL
Measurement temperature: 120 ° C
Standard value of chemical shift: 27.50ppm
<Melting point (Tm)>
Using a Perkin Elmer DSC 6220, 3-7 mg of the sample is sealed in an aluminum pan, heated from room temperature to 280 ° C. at 10 ° C./min, and the sample is held at 280 ° C. for 5 minutes to completely melt. . It is then cooled to −50 ° C. at 10 ° C./min and placed at −50 ° C. for 5 minutes, after which the sample is heated again to 280 ° C. at 10 ° C./min. The peak temperature in the second heating test was adopted as the melting point (Tm).

<Cross-cut peel test>
After placing a cut line on the synthetic resin layer (B) side of the laminate in a temperature of 23 ° C. and a relative humidity of 50% so as to be 1 mm in length, 1 mm in width, and 25 squares, cellophane tape (manufactured by Nichiban, CT-24) ) And 90 ° C. peeling is performed. The result of the cross-cut peel test was calculated as the peel rate according to the following formula (1). “Peeled” refers to a state of complete peeling.
(Formula 1) Peeling rate (%) = {(number of peeled sheets) ÷ (total number of sheets)} × 100
<Surface area ratio (S-ratio)>
Using a scanning probe microscope (manufactured by Hitachi High-Tech Science Co., Ltd.) equipped with an Olympus cantilever (model number OMCL-AC200TS-R3), the treated surface of the base material layer (A) was observed in 2 μm square in DFM mode. A value obtained by dividing an area including irregularities by time by an observation area was measured as a surface area ratio (S-ratio).

[material]
As 4-methyl-1-pentene polymer, Mitsui Chemicals, Inc. TPX (registered trademark), structural unit 98.3 mol% derived from 4-methyl-1-pentene, structural unit 1 derived from 1-decene 0.7 mol%, MFR (260 ° C., 5 kgf): 9 g / 10 min, melting point (Tm) 232 ° C., density 833 kg / m ³ was used.

[Example 1]
For the injection-molded piece (120 mm × 130 mm × 2 mm) of 4-methyl-1-pentene polymer (A), manufactured by Soft 99 Corporation, surface modification device (product name: Flamebond, product number: FB) -4) was used for itro treatment. The distance between the injection-molded piece and the burner was fixed at 30 mm and processed twice at a speed of 300 mm / sec. Table 1 shows the surface area ratio (S-ratio) of the obtained molded piece after the treatment.

  Subsequently, a commercially available acrylic lacquer (manufactured by Asahi Pen Co., Ltd., product name: Aspen Lacquer Spray) was applied to the test piece after the intro treatment at a thickness of 10 μm, and dried for 24 hours to produce a laminate 1. Table 1 shows a cross-cut peel test of the obtained laminate.

[Example 2]
In the test piece after the intro treatment obtained in the same manner as Example 1, 3 parts of urethane acrylate resin for coating (trade name, Olester RA4800M, manufactured by Mitsui Chemicals), 3 parts of IRGACURE 1173 (manufactured by BASF Japan), A composition composed of 103 parts of butyl acetate was coated with a wire bar # 10 (film thickness: 5 μm), dried at 60 ° C. with a hot air dryer (DN-43 manufactured by Yamato Kagaku), and then a UV conveyor (electrodeless discharge). The laminate 2 was produced by passing through a lamp H bulb F600V, output 100%, lamp height 70 mm) at a conveyor speed of 15 m / min (UVA integrated light quantity 190 mJ / cm 2). Table 1 shows a cross-cut peel test of the obtained laminate.
[Example 3]
A surface-treated sample was obtained in the same manner as in Example 1 except that the ittro treatment speed was set to 900 mm / sec. Table 1 shows the surface area ratio (S-ratio) of the obtained molded piece after the treatment.

Subsequently, a commercially available urethane paint (manufactured by Asahi Pen Co., Ltd., product name: Aspen Lacquer Spray) was applied to the test piece after the intro treatment at a thickness of 10 μm, and dried for 24 hours to produce a laminate 3. Table 1 shows a cross-cut peel test of the obtained laminate.
[Example 4]
Fluorine-based coating resin (trade name, Obligard SS0057, manufactured by AGC Co-Tech Co., Ltd.) was applied to a test piece obtained in the same manner as in Example 1 at a thickness of 10 μm and dried at room temperature. The laminated body 4 was produced. Table 1 shows a cross-cut peel test of the obtained laminate.
[Comparative Example 1]
A molded piece was produced in the same manner except that the itro process was not performed in Example 1. Table 1 shows the surface area ratio (S-ratio) of the obtained molded piece.

  Subsequently, a commercially available acrylic lacquer (manufactured by Asahi Pen Co., Ltd., product name: Aspen Lacquer Spray) was applied to the test piece after the intro treatment at a thickness of 10 μm and dried for 24 hours to prepare a laminate. Table 1 shows a cross-cut peel test of the obtained laminate.

[Example 5]
For an injection-molded piece (120 mm × 130 mm × 2 mm) of 4-methyl-1-pentene polymer (A), an atmospheric pressure plasma device (product name: ultra-high density atmospheric pressure plasma unit) manufactured by Fuji Machine Co., Ltd. , Product number: FPE20). The distance between the injection-molded piece and the burner was fixed to 10 mm and processed once at a speed of 200 mm / sec.

Subsequently, a commercially available acrylic lacquer (manufactured by Asahi Pen Co., Ltd., product name: Aspen Lacquer Spray) was applied to the test piece after the intro treatment at a thickness of 10 μm, and dried for 24 hours to produce a laminate 1. Table 2 shows a cross-cut peel test of the obtained laminate.
[Example 6]
For an injection-molded piece (120 mm × 130 mm × 2 mm) of 4-methyl-1-pentene polymer (A), an atmospheric pressure plasma device (product name: ultra-high density atmospheric pressure plasma unit) manufactured by Fuji Machine Co., Ltd. , Product number: FPE20). The distance between the injection-molded piece and the burner was fixed to 10 mm and processed once at a speed of 200 mm / sec.

  Subsequently, Nippon Seika Co., Ltd. silicone hard coat agent NSC-5104 was applied to the test piece after the intro treatment in a thickness of 5 μm and dried for 24 hours to produce a laminate 1. Table 2 shows a cross-cut peel test of the obtained laminate.

Claims (6)

It has a base material layer (A) containing a 4-methyl-1-pentene polymer (X) and a synthetic resin layer (B), and the 4-methyl-1-pentene polymer (X) is A laminate that satisfies the following requirements (a) to (d) and satisfies the following requirement (I).
(A) The structural unit derived from 4-methyl-1-pentene (i) selected from 60 to 100 mol% and ethylene other than 4-methyl-1-pentene and an α-olefin having 3 to 20 carbon atoms. It has 0 to 40 mol% of structural units (ii) derived from at least one (provided that the total of the structural units (i) and the structural units (ii) is 100 mol%).
(B) The melt flow rate (MFR) measured at 260 ° C. and 5 kgf in accordance with ASTM D1238 is in the range of 0.3 to 400 g / 10 min.
(C) Melting | fusing point (Tm) measured with a differential scanning calorimeter (DSC) exists in the range of 100-260 degreeC.
(D) The density measured by the density gradient tube method in accordance with JIS K7112 is in the range of 820 to 850 kg / m ³ .
(I) In a cross cut test measured in accordance with JIS K5400-8, the peel rate determined according to the following formula (1) is 5% or less.
Peeling rate (%) = {(number of peeled sheets) / (total number of sheets)} × 100 (1)   The laminate according to claim 1, wherein the melting point (Tm) is in the range of 215 to 250 ° C in the requirement (c).   It is a manufacturing method of the laminated body of Claim 1 or 2, Comprising: The manufacturing method of a molded object including the process of obtaining the said base material layer (A) through an itro process.   It is a manufacturing method of the laminated body of Claim 1 or 2, Comprising: The manufacturing method of a molded object including the process of obtaining the said base material layer (A) through atmospheric pressure plasma processing. In the base material layer (A) containing 4-methyl-1-pentene polymer (X), the surface area ratio (S-ratio) measured by AFM is in the range of 1.01 to 2.0. The manufacturing method of the laminated body as described in any one of Claims 1-4 which laminates | stacks a resin layer (B). The manufacturing method of the laminated body as described in any one of Claims 3-5 by which the said base material layer (A) is chosen from an injection molded body or an extrusion molded body.