JP2011189554A - Method for continuous manufacture of resin laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for the continuous manufacture of a resin laminate which can efficiently and continuously manufacture the resin laminate which is high in adhesion of a functional layer, suppressed in layer peeling, superior in appearance and has good optical characteristics, especially a resin laminate which has a hard coat layer as the functional layer and is excellent in scratch resistance in a short time. <P>SOLUTION: A light transmitting resin sheet with the functional layer formed is used in at least one of a lower part support sheet and an upper part support sheet moving in the same direction and at the same speed. The light transmitting resin sheet is arranged to make the functional layer side inside. While a photopolymerizable monomer mixture is supplied on the lower part support sheet, the upper part support sheet is laminated on the photopolymerizable mixture. After the photopolymerizable monomer mixture is polymerized/cured by being irradiated with active rays through the light transmitting resin sheet and integrated with the functional layer, the lower part support sheet and the upper part support sheet are peeled off to form the resin laminate. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is a continuous resin laminate for continuously producing a resin laminate in which a monomer is polymerized between the lower support sheet and the upper support sheet moving in the same direction at the same speed and the surface thereof is coated with a functional layer. It relates to a manufacturing method.

  In small displays typified by mobile phones, portable game machines, car navigation systems, portable AV devices, etc., the surface of these displays has various functions such as scratch resistance, antireflection, antistatic, and antifouling. It is required to have. For example, in order to impart scratch resistance to a display, a resin laminate in which the surface of a transparent resin substrate is coated with a hard coat layer having scratch resistance as a protective material is commercially available. As a method for continuously producing a resin laminate having such a hard coat layer, a polymer film having crosslinkability is formed on the molding surface of the mold, and then a base resin material is introduced into the mold. A method for obtaining a base material having a hard coat layer by performing polymerization has been proposed (Patent Document 1). However, the base resin manufacturing method according to Patent Document 1 polymerizes the monomer supplied between the opposing faces of a pair of endless belts traveling in the same direction at the same speed by thermal polymerization. Tends to be large.

  By the way, a continuous production method of a transparent resin substrate is proposed in which a photopolymerizable monomer composition is supplied between a lower endless steel belt and an upper transparent support sheet, and the photopolymerizable monomer is polymerized by irradiating active rays. (Patent Document 2). However, when the method for producing a substrate having a hard coat layer described in Patent Document 1 is applied to this method, the transparent support sheet is a resin film and has low rigidity, so that it can resist polymerization shrinkage of the hard coat layer. In some cases, the resin film curls, and the manufactured resin laminate is affected by the influence, resulting in poor appearance.

  For such a warp of the resin film, a method for suppressing the warp of the film by reducing the thickness of the hard coat layer to be formed has been proposed (Patent Document 3) supplied between the support sheets. When the monomer mixture is polymerized and integrated with the hard coat layer, the monomer may pass through the hard coat layer and the effect of the hard coat layer may not be obtained.

Japanese Patent Publication No.49-36829 JP 2002-11742 A JP 2006-182819 A

  An object of the present invention is to provide a resin laminate having high adhesion of a functional layer, suppression of peeling of the layer, excellent appearance, and excellent optical properties, in particular, a hard coat layer as a functional layer and scratch resistance. It is providing the continuous manufacturing method of the resin laminated body which can manufacture continuously and efficiently the resin laminated body which is excellent in a short time.

  The present invention uses a translucent resin sheet in which a functional layer is formed on at least one of a lower support sheet and an upper support sheet that move at the same speed in the same direction, and the translucent resin sheet is placed on the inner side of the translucent resin sheet. The upper support sheet is laminated on the photopolymerizable monomer mixture while supplying the photopolymerizable monomer mixture on the lower support sheet, and the active ray is passed through the translucent resin sheet. It is related with the continuous manufacturing method of the resin laminated body which peels a lower support sheet and an upper support sheet, and forms a resin laminated body after polymerizing and curing a photopolymerizable monomer mixture and integrating with a functional layer.

  In the present invention, the thickness of the lower support sheet and the upper support sheet moving in the same direction at the same speed is applied with a thickness of 10 kgf / m to 10 kgf / m. Using a translucent resin sheet having a 25 μm hard coat layer formed, the translucent resin sheet is arranged so that the functional layer side is on the inside, and the photopolymerizable monomer mixture is supplied onto the lower support sheet The upper support sheet is laminated on the photopolymerizable monomer mixture, and the photopolymerizable monomer mixture is polymerized by irradiating active rays through the translucent resin sheet to be integrated with the hard coat layer. The present invention relates to a method for continuously producing a resin laminate, characterized by forming a resin laminate.

  The method for producing a resin laminate of the present invention is a resin laminate that has high adhesion of the functional layer and suppresses delamination, is excellent in appearance, and has excellent optical properties, in particular, has a hard coat layer as a functional layer. A resin laminate having excellent scratch resistance can be produced efficiently and continuously in a short time.

It is a schematic block diagram which shows an example of the manufacturing apparatus of the resin laminated body which applied the manufacturing method of the resin laminated body of this invention.

  In the continuous production method of the resin laminate of the present invention, at least one of the lower support sheet and the upper support sheet moving at the same speed in the same direction is formed of a translucent resin sheet, and the upper support sheet and the lower support sheet ( (Also referred to as upper and lower support sheets)), the photopolymerizable monomer mixture is continuously polymerized by irradiating active rays through the translucent resin sheet to continuously produce a resin laminate. In that case, the resin laminated body which has a functional layer can be obtained by using the translucent resin sheet in which the functional layer was formed. Examples of the functional layer include a hard coat layer, an antireflection layer, an antistatic layer, and an antifouling layer. When the functional layer is a hard coat layer, it is possible to use a light-transmitting resin sheet formed with a hard coat layer by applying a tension of 20 kgf / m or more and 100 kgf / m or less per unit width. As a result, it is possible to suppress warping of the translucent resin sheet having the hard coat layer, and the hard coat layer is firmly fixed to the polymer of the photopolymerizable monomer mixture and the resin laminate has an excellent appearance. The body can be manufactured continuously.

  The upper and lower support sheets used in the present invention are unwound from one end even if they are endless belts suspended on a pair of pulleys as long as the sheet surfaces are arranged facing each other and move in the same direction at the same speed. It may be a sheet wound around the other end. If a translucent resin sheet having a functional layer formed on at least one of the upper and lower support sheets is used, the translucent resin sheet on which the functional layer is formed may be used on the other side. It may be a non-molded translucent resin sheet, or may be a sheet made of other resin or a metal such as iron or stainless steel. A metal sheet is preferable because of its high rigidity against shrinkage during polymerization of the photopolymerizable monomer mixture. Moreover, since these surfaces are transcribe | transferred to the surface of the resin laminated body obtained, it is preferable that the surface is smooth. Such a translucent resin sheet preferably has a high actinic ray transmittance for polymerizing a photopolymerizable monomer mixture, which will be described later, and has releasability from the functional layer formed in the resin laminate. In the case where the translucent resin sheet does not have releasability with respect to the functional layer formed on the resin laminate, a release layer can be provided on the surface of the translucent resin sheet. It is preferable not to provide a release layer because wettability changes and good printing may not be obtained. Specific examples of the material of the translucent resin sheet include resins such as polyethylene terephthalate, polypropylene, polycarbonate, polystyrene, polyamide, polyamideimide, polyethylene, and polyvinyl chloride, and cellulose such as cellulose acetate. Of these, polyethylene terephthalate is preferable from the viewpoint of sheet surface smoothness, high thickness system, and price. Moreover, when the translucent resin sheet is fed out from a rolled state (roll shape) and supplied, it is preferable not to include an anti-blocking agent for suppressing blocking that causes sticking between sheets. When the translucent resin sheet contains an anti-blocking agent and has fine irregularities on the surface, the irregularities are transferred to the functional layer, and the appearance of the resulting resin laminate is impaired, and the translucent resin sheet functions. It may be in close contact with the layer and cause a peeling failure from the molded resin laminate.

  The thickness of the translucent resin sheet is preferably 10 μm or more, more preferably 50 μm or more, and preferably 500 μm or less, preferably 200 μm or less from the viewpoint of cost, since the generation of wrinkles and cracks is suppressed and surface smoothness is obtained. Is more preferable.

  When forming a functional layer on a translucent resin sheet, it is preferable to form it in a state in which a tension is appropriately applied to the translucent resin sheet.

  The method of forming the hard coat layer on the translucent resin sheet is not particularly limited as long as it is a method in which a tension of 20 kgf / m or more and 100 kgf / m or less per unit width is applied to the translucent resin sheet. Examples of the method include coating such as dipping, coating, and spray coating, and a method of laminating a hard coat layer previously formed in a film shape.

  The material of the hard coat layer formed on the translucent resin sheet is highly fixable to the polymer of the photopolymerizable monomer mixture, and a scratch-resistant coating is applied to the polymer surface of the photopolymerizable monomer mixture. Even if the hard coat layer can be directly formed without providing the release layer on the translucent resin sheet, the produced resin laminate can be formed. Since it can peel easily from a translucent resin sheet, it is preferable. The material of the hard coat layer is a resin obtained by polymerizing an acrylic monomer that can be radically polymerized by irradiation with active rays such as electron beam, radiation, or ultraviolet rays, and alkoxysilane, alkylalkoxysilane, etc. A silicone resin obtained by condensation polymerization of a silane compound can be used. Among these, it is preferable from the viewpoint of production efficiency to use a resin obtained from an ultraviolet curable monomer that is polymerized and cured by ultraviolet irradiation. As a method for forming a hard coat layer by polymerizing an ultraviolet curable monomer, a monomer having at least two (meth) acryloyloxy groups in the molecule as the acrylic monomer, and ultraviolet rays are used. It is preferable to use a hard coat layer forming coating solution containing a polymerization initiator that decomposes to generate radicals. It is possible to efficiently form a hard coat layer by irradiating the coating film obtained by applying such a hard coat layer forming coating liquid onto a translucent resin sheet, by irradiating with ultraviolet rays to cause a polymerization reaction. . By using the translucent resin sheet on which the hard coat layer is formed, the polymer obtained by polymerization of the photopolymerizable monomer mixture and the hard coat layer can be integrated. The hard coat layer is preferably formed by an in-line process in order to obtain a laminate having an excellent appearance. Here, the “in-line process” refers to a process incorporated in a production line for a resin laminate.

  As the monomer having at least two (meth) acryloyloxy groups in the molecule contained in the hard coat layer forming coating solution, 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or Examples include esterified products obtained from the derivatives thereof, esterified products obtained from polyhydric alcohols and polyvalent carboxylic acids or anhydrides thereof, and (meth) acrylic acid or derivatives thereof. Specific examples of the esterified product obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or a derivative thereof include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol. Di (meth) acrylate of polyethylene glycol such as di (meth) acrylate; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) Di (meth) acrylates of alkyl diols such as acrylates; trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate Pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Poly (meth) acrylates of tri- or higher functional polyols such as tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate; Etc.

  As the esterified product obtained from the above polyhydric alcohol and polyhydric carboxylic acid or anhydride and (meth) acrylic acid or derivative thereof, polyhydric alcohol and polyhydric carboxylic acid or anhydride and (meth) acrylic acid are preferable. Examples of combinations include malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, malonic acid / glycerin / (meth) acrylic acid, malonic acid / pentaerythritol / ( (Meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (meth) acrylic acid, succinic acid / glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / (meta ) Acrylic acid, adipic acid / trimethylolethane / (meth) acrylic acid Adipic acid / trimethylolpropane / (meth) acrylic acid, adipic acid / glycerin / (meth) acrylic acid, adipic acid / pentaerythritol / (meth) acrylic acid, glutaric acid / trimethylolethane / (meth) acrylic acid, glutar Acid / trimethylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (meth) acrylic acid, glutaric acid / pentaerythritol / (meth) acrylic acid, sebacic acid / trimethylolethane / (meth) acrylic acid, sebacic acid / Trimethylolpropane / (meth) acrylic acid, sebacic acid / glycerin / (meth) acrylic acid, sebacic acid / pentaerythritol / (meth) acrylic acid, fumaric acid / trimethylolethane / (meth) acrylic acid, fumaric acid / Trimethylolpropane / (meta) Crylic acid, fumaric acid / glycerin / (meth) acrylic acid, fumaric acid / pentaerythritol / (meth) acrylic acid, itaconic acid / trimethylolethane / (meth) acrylic acid, itaconic acid / trimethylolpropane / (meth) acrylic Acid, itaconic acid / glycerin / (meth) acrylic acid, itaconic acid / pentaerythritol / (meth) acrylic acid, maleic anhydride / trimethylolethane / (meth) acrylic acid, maleic anhydride / trimethylolpropane / (meth) Examples include acrylic acid, maleic anhydride / glycerin / (meth) acrylic acid, maleic anhydride / pentaerythritol / (meth) acrylic acid, and the like.

  Other compounds having at least two (meth) acryloyloxy groups in the molecule include trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) ), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl per mole of polyisocyanate obtained by trimerization of diisocyanates such as isophorone diisocyanate and trimethylhexamethylene diisocyanate (Meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, Urethane obtained by reacting 3 mol or more of an acrylic monomer having active hydrogen such as 15,3-propanetriol-1,3-di (meth) acrylate and 3-acryloyloxy-2-hydroxypropyl (meth) acrylate ( (Meth) acrylate; poly [(meth) acryloyloxyethylene] isocyanurate such as di (meth) acrylate or tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid; epoxy poly (meth) acrylate; urethane poly (meth) ) Acrylate; Here, “(meth) acryl” means “methacryl” or “acryl” (the same applies hereinafter).

  Specific examples of the polymerization initiator contained in the hard coat layer molding coating solution include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, Benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, Carbonyl compounds such as 1-hydroxy-cyclohexyl-phenyl-ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; tetramethylthiuram monosulfide, tetramethylthiuram Sulfur compounds such as disulfides; phosphorus compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzoyldiethoxyphosphine oxide; be able to. These polymerization initiators may be used alone or in combination of two or more.

  The addition amount of the polymerization initiator that decomposes by ultraviolet rays contained in the hard coat layer molding coating solution to generate radicals is 0.1 parts by mass or more in 100 parts by mass of the hard coat layer molding coating solution. It is preferable that it is below mass parts. If the addition amount of the polymerization initiator is 0.1% by mass or more, the polymerization reaction can proceed efficiently, and if it is 10 parts by mass or less, a good color tone of the hard coat layer can be maintained.

  The coating liquid for forming a hard coat layer may be various types such as a slip improver, a leveling agent, an inorganic fine particle, a light stabilizer (ultraviolet absorber, HALS, etc.) as long as it does not hinder the functions of the above substances. It may contain components. The content of these components is preferably 10 parts by mass or less in 100 parts by mass of the hard coat layer forming coating solution from the viewpoint of maintaining transparency. In addition, anti-reflective agent, anti-glare agent, anti-static agent, anti-smudge agent, etc. are added to hard coat layer molding coating solution, anti-reflective function, anti-glare function, anti-static function, anti-stain function to hard coat layer Can also be given. Further, a layer having these functions can be provided by being stacked on the hard coat layer.

  Examples of the coating method of the coating liquid for forming the hard coat layer on the translucent resin sheet include casting, roller coating, bar coating, spray coating, air knife coating, spin coating, and flow coating. Method, curtain coating method, film cover method, dipping method.

  The tension applied to the translucent resin sheet when forming the hard coat layer is 20 kgf / m or more and 100 kgf / m or less per unit width. The direction in which tension is applied to the translucent resin sheet is the moving direction of the translucent resin sheet, and the unit width per unit with respect to the width of the translucent resin sheet perpendicular to the moving direction of the translucent resin sheet. The width of A translucent resin having a good appearance of the translucent resin sheet even if the tension in the above direction applied to the translucent resin sheet when molding the hard coat layer is specified per unit cross-sectional area of the hard coat layer Although a sheet cannot be obtained, a translucent resin sheet having a good appearance can be obtained regardless of the thickness of the translucent resin sheet by specifying per unit width. If the tension per unit width applied to the translucent resin sheet is 20 kgf / m or more, the translucent resin sheet on which the hard coat layer is formed can be prevented from being warped or wavy. It is possible to suppress the appearance failure of the resulting resin laminate and the appearance failure with time. Further, if the tension per unit width applied to the translucent resin sheet is 100 kgf / m or less, it is possible to suppress the difficulty in peeling the resin laminate from the translucent resin sheet, An increase in the size of the apparatus can be suppressed. The tension applied to the translucent resin sheet is preferably 25 kgf / m or more and 50 kgf / m or less. Here, the tension applied to the translucent resin sheet can be obtained by measuring the tension applied to the nip roll provided immediately before forming the hard coat layer and dividing the value by the film width. Moreover, the tension | tensile_strength loaded to a translucent resin sheet can also be calculated | required from the holding angle of the translucent resin sheet hung on a roll.

  The thickness of the functional layer formed on the translucent resin sheet is required for the function, the density of the layer, the type of the photopolymerizable monomer, the material of the translucent resin sheet, and the obtained resin laminate. Can be selected from a range in which the appearance and the occurrence of warping can be suppressed. When the functional layer is a hard coat layer, the thickness is preferably 10 μm or more and 25 μm or less. When the thickness of the hard coat layer is 10 μm or more, the photopolymerizable monomer mixture penetrates into the hard coat layer and suppresses the deterioration of the scratch resistance of the resin laminate obtained by reducing the surface hardness. If it is 25 μm or less, it is possible to suppress warping of the translucent resin sheet due to polymerization shrinkage of the ultraviolet curable monomer, and even when no warp causing a problem occurs in the translucent resin sheet. It can suppress that the external appearance deterioration which fluctuates on the surface of the resin laminated body obtained arises. The thickness of the hard coat layer is more preferably 12 μm or more and 20 μm or less. As the thickness of the hard coat layer, a measurement value obtained by a measurement method described later can be adopted.

  Any material that can hold the photopolymerizable monomer mixture in the form of a sheet as described above is used for the upper and lower support sheets that do not use the light-transmitting resin sheet formed with the functional layer such as the hard coat layer. Although it may be used, specifically, a steel endless belt whose surface is mirror-finished on a lower support sheet to which a photopolymerizable monomer mixture is supplied using a translucent resin sheet as an upper support sheet Can be used.

  The moving speed of the upper and lower support sheets can be adjusted by the polymerization rate of the photopolymerizable monomer described later, and the upper and lower support sheets are arranged at a distance corresponding to the thickness of the resin laminate formed by the facing surface. Can be arranged.

  In addition to the photopolymerizable monomer component that is polymerized by irradiation with actinic radiation, the photopolymerizable monomer mixture that is supplied onto the lower support sheet starts polymerization that decomposes by irradiation with actinic radiation to generate radicals. It is preferable to contain an agent. Examples of the photopolymerizable monomer component include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, alkyl methacrylate such as benzyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2- (Meth) alkyl acrylates such as ethylhexyl acrylate, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, acid anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, N-cyclohexylmaleimide , Maleimide derivatives such as N-t-butylmaleimide, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl Hydroxyl group-containing monomers such as tacrylate, nitrogen atom-containing monomers such as (meth) acrylamide, (meth) acrylonitrile, diacetone acrylamide, and dimethylaminoethyl methacrylate, epoxy groups such as allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate Containing monomers, styrene monomers such as styrene and α-methylstyrene, polyfunctional monomers such as ethylene glycol diacrylate, allyl acrylate, ethylene glycol dimethacrylate, allyl methacrylate, divinylbenzene, trimethylolpropane triacrylate Etc. These can be used alone or in combination of two or more. From the viewpoint of optical properties, scratch resistance, and adhesion of the hard coat layer of the obtained resin laminate, it is preferable that methyl methacrylate is contained in the photopolymerizable monomer mixture in an amount of 30% by mass or more, and more preferably 35% by mass. % Or more, more preferably 60% by mass or more.

  The photopolymerizable monomer component contains the above monomers in order to shorten the curing time, reduce the polymerization shrinkage of the resulting polymer, increase the viscosity of the photopolymerizable monomer mixture and facilitate handling. A prepolymerized oligomer or polymer may be contained, and these can be dissolved in a monomer and used.

  The polymerization initiator contained in the photopolymerizable monomer mixture is one that generates radicals that initiate the polymerization reaction of the photopolymerizable monomer upon irradiation with actinic radiation, and the transparency of the resulting polymer is increased. Those that do not inhibit are preferred, and specific examples include polymerization initiators that generate radicals by acetophenone-based or benzophenone-based actinic radiation. In particular, it is preferable to use 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin ethyl ether, or the like.

  The content of these polymerization initiators is preferably in the range of 0.01 to 2 parts by mass with respect to 100 parts by mass of the photopolymerizable monomer mixture. If the content of the polymerization initiator is 0.01 parts by mass or more, the polymerization reaction can be completed in a short time, and if it is 2 parts by mass or less, the optical properties and weather resistance of the resulting resin laminate are lowered. More preferably, it is the range of 0.05 mass part or more and 1 mass part or less.

  In addition to thermal polymerization initiators, antioxidants, ultraviolet absorbers, dyes / pigments, mold release agents, polymerization inhibitors, etc., use as necessary to the photopolymerizable monomer mixture as long as the functions of the above substances are not impaired. can do.

  As a method of supplying the photopolymerizable monomer mixture to the lower support sheet, a method of supplying the translucent resin sheet on the lower support sheet from a pipe or a hose after the functional layer is disposed inside Any method such as various coating methods may be used, but it is preferable that the photopolymerizable monomer mixture is continuously supplied while being uniformly spread on the lower support sheet. For this purpose, a method using a die having a discharge port with a width corresponding to the width of the lower support sheet, or a layer of the upper support sheet is laminated on the mixture while supplying the photopolymerizable monomer mixture on the lower support sheet. In doing so, a method of expanding the photopolymerizable monomer mixture with a roll through both side support sheets can be applied, or a combination thereof may be applied.

  X-rays, ultraviolet rays, electron beams, and the like can be used as active rays for polymerizing the photopolymerizable monomer mixture. Ultraviolet rays are particularly preferred because of the simplicity of the apparatus. Ultraviolet rays radiated from various ultraviolet irradiation devices can be used as the ultraviolet rays, and examples of such ultraviolet irradiation devices include high pressure mercury lamps, low pressure mercury lamps, metal halide lamps, xenon lamps, chemical lamps, germicidal lamps, black lights, An ultraviolet LED etc. can be mentioned.

The irradiation intensity of the actinic radiation is determined according to the type and concentration of the polymerization initiator contained in the photopolymerizable monomer mixture, and the irradiation time, and a desired polymerization rate is obtained. preferably adjusted to be suppressed to varying, for example, a 1 mW / cm ² or more 500 mW / cm ² or less.

  The temperature condition at the time of irradiation with actinic radiation can be selected depending on the polymerization rate, viscosity condition, etc., but is preferably not higher than the boiling point of the photopolymerizable monomer. For example, the photopolymerizable monomer mixture is methyl methacrylate. When it contains 30 mass% or more, it is preferable that it is 100 degrees C or less.

  For polymers in which photopolymerizable monomers are polymerized by actinic radiation, the remaining monomers are reduced, and the residual stress in the resin laminate is reduced, resulting in a glass transition of the resulting polymer. Heat treatment can be performed at a temperature of Tg or higher. When methyl methacrylate is used as the monomer, heat treatment is preferably performed at 100 ° C. or higher. The timing for performing the heat treatment can be selected from the heat resistance of the translucent resin sheet to be used, either in a state of being sandwiched between the upper and lower support sheets or after being peeled from between the upper and lower support sheets.

  The production speed of the resin laminate, that is, the moving speed of the upper and lower support sheets is preferably 0.1 to 15 m / min, and more preferably 1 to 10 m / min. If the production rate is 0.1 m / min or more, the production amount of the resin laminate can be secured, and if it is 15 m / min or less, the active ray irradiation section can be prevented from extending over a long distance.

  The thickness of the resin laminate is not particularly limited, but the heat of polymerization is efficiently removed, and bubbles are formed in the resin laminate due to boiling of the unreacted monomer, or the translucent resin sheet Is preferably within the range in which the deformation can be suppressed by being heated to the glass transition temperature or higher, for example, 5 mm or less.

  An example of a resin laminate manufacturing apparatus to which the resin laminate manufacturing method of the present invention is applied is shown in FIG. The apparatus for producing a resin laminate shown in FIG. 1 includes a feeding device 1 that feeds the translucent resin sheet 2 and a winding device 11 that winds the translucent resin sheet. A tension of 20 kgf / m or more and 100 kgf / m or less per unit width is applied in the moving direction between the winding devices 11, particularly at the ultraviolet irradiation location where the ultraviolet irradiation device 4 is installed. A coater 3 connected to a functional layer molding coating solution supply device (not shown) is provided, and the functional layer molding coating solution is supplied from the coater 3 onto the translucent resin sheet fed from the feeding device. And applied. The ultraviolet curable monomer in the coating film is polymerized by ultraviolet rays emitted from the ultraviolet irradiation device 4 to form a functional layer, and a translucent resin sheet 2 ′ having a functional layer as an upper support sheet is formed.

  On the other hand, a die 5 for supplying the photopolymerizable monomer mixture 6 in a sheet form is provided on an endless belt 7 as a lower support sheet that is suspended on pulleys 13 and 14 and rotates in the direction of the arrow. A photopolymerizable monomer mixture 6 is supplied in a shape, and the photopolymerizable monomer mixture 6 is sandwiched between a translucent resin sheet having a functional layer and an endless belt by an upper surface pressing roller 8 and a lower surface pressing roller 8 ′. . Thereafter, the photopolymerizable monomer mixture 6 is polymerized and cured by ultraviolet rays emitted from the ultraviolet ray irradiating device 9 and then heat-treated by the heating means 10 to form a resin laminate 12 that is coated and integrated with the functional layer. . The heating means 10 is not particularly limited, and examples thereof include means for heating with warm water or hot air.

  The translucent resin sheet 2 and the endless belt 7 are peeled from the resin laminate, and the resin laminate is cut into a desired length by a cutter or wound into a roll to obtain a product. On the other hand, the translucent resin sheet 2 after the functional layer is transferred is wound up by the winding device 11, but the resin laminate is manufactured until the translucent resin sheet attached to the feeding device 1 is consumed. Can continue. In addition, before the light-transmitting resin sheet 2 is consumed, another new light-transmitting resin sheet 2 is connected to the supplied and moved sheet 2 to continuously manufacture the resin laminate. You can also. The upper and lower support sheets may be used without peeling depending on the use of the laminate.

  This manufacturing apparatus is formed by an in-line process connected to the production line of the resin laminate, while forming a functional layer on the translucent resin sheet by coating as an upper support sheet, without winding it. A translucent resin sheet having a functional layer formed in a separate process may be used, or a translucent resin sheet may be used instead of the endless belt as the lower support sheet.

  As described above, the method for producing a resin laminate of the present invention enables polymerization in a short time, so that productivity can be improved and equipment can be miniaturized. When the functional layer is a hard coat layer, It is possible to obtain a resin laminate coated with a hard coat layer having high scratch resistance and adhesion, excellent appearance, and high optical properties. The resulting resin laminate can be used for mobile phones, portable game machines, cars, etc. It is suitable as a transparent resin sheet for protecting a face plate of a liquid crystal display device such as a navigation system or a bootable AV device.

[Example 1]
UV decomposition polymerization initiator 1 with respect to 100 parts by mass of a mixture of 60 parts by mass of methyl methacrylate monomer and 40 parts by mass of methyl methacrylate polymer beads (BR-83: manufactured by Mitsubishi Rayon Co., Ltd.) at 80 ° C. for 30 minutes. 0.3 parts by mass of hydroxy-cyclohexyl-phenyl ketone (Irgacure 184: Ciba Japan), 0.05 parts by mass of sodium dioctyl sulfosuccinate (aerosol OT-100: manufactured by Mitsui Cyanamid Co., Ltd.) as a release agent Add, prepare photopolymerizable monomer mixture (methyl methacrylate content 99.7%), let stand for 6 hours at 50 ° C in order to remove bubbles generated at the time of preparation, then let it cool naturally to room temperature It was.

  As a coating liquid for forming a hard coat layer, 40 parts by mass of 1,6-hexanediol diacrylate (C6DA: Osaka Organic Chemical Co., Ltd.), 60 parts by mass of pentaerythritol triacrylate (M305: Toagosei Co., Ltd.), 1-hydroxy -Cyclohexyl-phenyl ketone (Irgacure 184: Ciba Japan Co., Ltd.) 4 parts by mass was mixed, and a coating containing an ultraviolet curable monomer was used.

  A stainless steel endless belt having a width of 500 mm is used as the endless belt 7, and a polyethylene terephthalate film having a width of 188 μm and a thickness of 188 μm is used as the endless belt 7 (Cosmo Shine A4100: Toyobo). The high-pressure mercury lamp of 9.6 kW was used as the ultraviolet irradiation device 4, the FL30S-BL lamp manufactured by Toshiba was used as the ultraviolet irradiation device 9, and hot air heating was used as the heating means 10.

  The translucent resin sheet is moved at a speed of 3 m / min, the applied tension is 40 kgf (80 kgf / m per unit width), and a die coater is used as the coater 2 so that the width is 380 mm and the thickness is 23 μm. The coating film formed in this manner was cured by irradiating with ultraviolet rays from the ultraviolet irradiation device 4 to obtain a hard coat layer.

  From the supply die, the previously prepared photopolymerizable monomer mixture was supplied in a sheet form having a width of 400 mm and a thickness of 1 mm, and the hard coat layer was entirely covered with the photopolymerizable monomer mixture.

Thereafter, ultraviolet rays are irradiated for 10 minutes with an irradiation intensity of 5 mW / cm ² by the ultraviolet irradiation device 9, heat treated at 130 ° C. for 5 minutes by the subsequent heating means 10, then air-cooled to 90 ° C., and the hard coat layer becomes the base resin The resin laminate integrated with was peeled off (Sample 1). The surface of the obtained resin laminate was smooth and had a good appearance.

  With respect to the obtained resin laminate, the total light transmittance, haze, and film thickness of the hard coat layer were measured by the following methods, and the appearance, scratch resistance, and comprehensive evaluation were evaluated by the following methods. The results are shown in Table 1.

[Total light transmittance and haze]
The total light transmittance was measured using HAZE METER NDH2000 (manufactured by Nippon Denshoku) in accordance with the measurement method shown in JIS K7361-1, and the haze was measured in accordance with the measurement method shown in JIS K7136.

[Hard coat layer thickness]
A sample was cut out with a microtome to a thickness of 100 nm and observed with a transmission electron microscope. The transmission electron microscope was measured using JEOL JEM-1010.

[Appearance of resin laminate]
The unevenness of the obtained resin laminate was visually observed and evaluated according to the following criteria.
○: There are few irregularities on the surface of the laminate, and there is no distortion even if the laminate is reflected or transmitted to see the image.
X: There are irregularities on the surface of the laminate, and when the image is viewed by reflecting or transmitting the laminate, the laminate appears distorted.

[Abrasion resistance]
A circular pad with a diameter of 25.4 mm with # 000 steel wool was placed on the hard coat layer surface of the resin laminate, and under a load of 2 kg, a 20 mm distance was reciprocally scratched 100 times, before and after the scratch. The difference in haze value was determined from equation (1).
Δhaze (%) = haze value after abrasion (%) − haze value before abrasion (%) (1)
[Comprehensive evaluation]
From the appearance of the resin laminate and the results of the scratch resistance test, the following evaluation was made.
◎: Initial appearance and scratch resistance are excellent ○: Initial appearance is good and scratch resistance is slightly inferior, but there is no problem as a product △: Initial appearance is good, but scratch resistance is a problem Yes, not a working product ×: The initial appearance is poor and does not become a working product.

[Example 2]
As a coating liquid for forming a hard coat layer, 50 parts by mass of 1,6-hexanediol diacrylate (C6DA: Osaka Organic Chemical Industry), trimethylolethane / acrylic acid / succinic anhydride condensation ester (TAS: Osaka Organic Chemical Industry) Co.) 50 parts by mass, 4 parts by mass of 1-hydroxy-cyclohexyl-phenyl ketone (Irgacure 184: Ciba Japan Co., Ltd.) were mixed, and a paint containing an ultraviolet curable monomer was used. A resin laminate was obtained in the same manner as in Example 1 except that coating was performed so that the tension applied to the translucent resin sheet was 35 kgf (70 kgf / m per unit width) and the thickness of the hard coat layer was 12 μm ( Sample 2) was evaluated. Like Sample 1, the surface of the obtained resin laminate was smooth and had a good appearance. The results are shown in Table 1.

[Example 3]
A polyethylene terephthalate film (A4100: Cosmo Shine manufactured by Toyobo Co., Ltd.) having a width of 500 mm and a thickness of 188 μm was used as the lower support sheet instead of the stainless steel endless belt. The translucent resin sheet is moved at a speed of 5 m / min, the applied tension is 15 kgf (30 kgf / m per unit width), and a die coater is used as the coater 3 so that the width is 380 mm and the thickness is 22 μm. A resin laminate was obtained (sample 3) and evaluated in the same manner as in Example 1 except that a hard coat layer was produced. Although a translucent resin sheet was used for the upper and lower support sheets, like the sample 1, the surface of the obtained resin laminate was smooth and had a good appearance. The results are shown in Table 1.

[Example 4]
The tension applied to the translucent resin sheet was 12.5 kgf (25 kgf / m per unit width), the air coat coating method was used for forming the hard coat layer, the thickness of the hard coat layer was 12 μm, and the width was 350 mm. A resin laminate was obtained in the same manner as in Example 1 (Sample 4) and evaluated. Like Sample 1, the surface of the obtained resin laminate was smooth and had a good appearance. The results are shown in Table 1.

[Example 5]
To 100 parts by mass of a mixture of 70 parts by mass of methyl methacrylate and 30 parts by weight of polybutylene glycol dimethacrylate (acrylic ester PBOM: manufactured by Mitsubishi Rayon Co., Ltd.), an ultraviolet decomposition polymerization initiator 1-hydroxy-cyclohexyl-phenyl ketone ( Ciba Japan, Irgacure 184) 0.3 parts by weight, 0.05 parts by weight of sodium dioctyl sulfosuccinate (Aerosol OT-100, Mitsui Cyanamid Co., Ltd.) as a release agent was added, and the photopolymerizable monomer A mixture was prepared (methyl methacrylate content 69.7%) and allowed to stand for 1 hour in order to remove bubbles generated during the preparation.

  Since the viscosity of the photopolymerizable monomer mixture is low, the following liquid seal was prepared in order to prevent side leakage from the lower support sheet. For 100 parts by mass of a mixture obtained by dissolving 40 parts by mass of methyl methacrylate polymer beads (BR-80: manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight 100,000) with heating at 60 ° C. for 30 minutes with respect to 60 parts by mass of methyl methacrylate. 0.03 parts by mass of ultraviolet decomposition polymerization initiator 1-hydroxy-cyclohexyl-phenyl ketone (Irgacure 184: Ciba Specialty Chemicals), sodium dioctyl sulfosuccinate (Aerosol OT-100: manufactured by Mitsui Cyanamid Co., Ltd.) as a release agent 0.05 parts by mass) and allowed to stand at room temperature for 24 hours in order to remove bubbles during preparation.

  As in Example 1, except that the translucent resin sheet was applied so that the moving speed was 2 m / min, the applied tension was 25 kgf (50 kgf / m per unit width), the width was 350 mm, and the thickness was 20 μm. A hard coat layer was prepared.

  After coating the liquid seal body in the feed direction at φ1.5 mm in the width direction of the endless belt 7 at a position of 50 mm from both ends, the photopolymerizable monomer mixture is fed from the supply die 5 to a width of 400 mm, A sheet having a thickness of 0.8 mm was supplied, and a translucent resin sheet was covered so that the entire surface of the hard coat layer was in contact with the photopolymerizable monomer mixture 6.

Thereafter, the ultraviolet irradiation device 9 irradiates ultraviolet rays at an irradiation intensity of 5 mW / cm ² for 25 minutes, heat-treats the heating means 10 at 130 ° C. for 5 minutes, air-cools to 90 ° C., and the hard coat layer becomes the base resin. The integrated resin laminate was peeled off (Sample 5). The obtained resin laminate had a smooth surface and a good appearance as in Sample 1. The results are shown in Table 1.

[Example 6]
A photopolymerizable monomer mixture was prepared in the same manner as in Example 5 except that 40 parts by mass of methyl methacrylate and 60 parts by weight of polybutylene glycol dimethacrylate were added as a photopolymerizable monomer mixture (containing methyl methacrylate). Amount 39.7%), and a resin laminate was obtained in the same manner as in Example 5 except that the irradiation time by the ultraviolet irradiation device 9 was changed to 10 minutes (sample 6) and evaluated. Compared with sample 1, the obtained resin laminate was mixed with a resin having higher flexibility than methyl methacrylate, and although a slight decrease in scratch resistance was confirmed, it could be used sufficiently as a product. It was a thing. The results are shown in Table 1.

[Comparative Example 1]
A resin laminate was obtained in the same manner as in Example 1 except that coating was performed so that the tension applied to the translucent resin sheet was 25 kgf (50 kgf / m per unit width) and the thickness of the hard coat layer was 5 μm (sample) 11) Evaluation was performed. The resulting resin laminate had a smooth surface and good appearance, but the base resin component permeated through the hard coat layer and flowed to the surface, resulting in low scratch resistance. Scratch resistance test with steel wool Resulted in numerous scratches. The results are shown in Table 1.

[Comparative Example 2]
A resin laminate was obtained in the same manner as in Example 1 except that the tension applied to the translucent resin sheet was 5 kgf (10 kgf / m per unit width) and the thickness of the hard coat layer was 15 μm (sample) 12) Evaluation was performed. Although the translucent resin sheet with the hard coat layer curled gently, it was acceptable in appearance, but the resulting resin laminate was uneven in thickness and distorted in appearance. It was not usable.

[Comparative Example 3]
A resin laminate was obtained in the same manner as in Example 1 except that the tension applied to the translucent resin sheet was 40 kgf (80 kgf / m per unit width) and the thickness of the hard coat layer was 30 μm (sample) 13) Evaluation was performed. The obtained resin laminate had a fine distortion and could not be used as a product. The results are shown in Table 1.

In the table, the MMA content of the photopolymerizable monomer mixture is expressed in mass% by removing the first decimal place of methyl methacrylate and polymethyl methacrylate contained in the photopolymerizable monomer mixture.

  The resin laminate obtained by the method of the present invention is suitable for applications requiring transparency, smoothness, adhesion, and scratch resistance as a protective plate for display devices such as mobile phones and liquid crystal displays.

1 Translucent resin sheet feeding device 2 Translucent resin sheet (upper support sheet)
2 'Translucent resin sheet having a hard coat layer 3 Coater 4 Ultraviolet irradiation device 5 Supply die 6 Photopolymerizable monomer mixture 7 Endless belt (lower support sheet)
8 Upper surface pressing roll 8 'Lower surface pressing roll 9 Ultraviolet irradiation device 10 Heating means 11 Translucent resin sheet winding device 12 Resin laminate 13 Main pulley 14 Main pulley

Claims (10)

  At least one of the lower support sheet and the upper support sheet that moves at the same speed in the same direction uses a translucent resin sheet on which a functional layer is formed, and the translucent resin sheet is arranged so that the functional layer side is on the inside. Then, while supplying the photopolymerizable monomer mixture on the lower support sheet, the upper support sheet is laminated on the photopolymerizable monomer mixture and irradiated with actinic radiation through the translucent resin sheet. A method for continuously producing a resin laminate, in which a photopolymerizable monomer mixture is polymerized and cured and integrated with a functional layer, and then a lower support sheet and an upper support sheet are peeled off to form a resin laminate.   The functional layer is a hard coat layer, and the hard coat layer is formed to a thickness of 10 μm or more and 25 μm or less on a translucent resin sheet loaded with a tension of 20 kgf / m or more and 100 kgf / m or less per unit width. Item 8. A continuous production method of a resin laminate according to Item 1.   The continuous manufacturing method of the resin laminated body of Claim 1 or 2 in which a hard-coat layer contains resin obtained by superposing | polymerizing an acryl-type monomer.   The continuous manufacturing method of the resin laminated body in any one of Claims 1-3 in which a photopolymerizable monomer mixture contains 30 mass% or more of methyl methacrylate.   The hard coat layer irradiates the coating film obtained by coating the translucent resin sheet with a coating liquid containing a monomer having at least two (meth) acryloyloxy groups in the molecule. The continuous manufacturing method of the resin laminated body in any one of Claims 1-4 formed.   The translucent resin sheet is a polyethylene terephthalate film, The continuous manufacturing method of the resin laminated body in any one of Claims 1-5.   The continuous manufacturing method of the resin laminated body in any one of Claims 1-6 which heat-processes 100 degreeC or more after superposition | polymerization of a photopolymerizable monomer mixture.   The continuous manufacturing method of the resin laminated body of Claim 1 in which a functional layer is formed in an in-line process.   The method for continuously producing a resin laminate according to any one of claims 1 to 8, wherein the lower support sheet is an endless belt.   The method for continuously producing a resin laminate according to any one of claims 1 to 9, wherein the lower support sheet is made of stainless steel.

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