JP2014205294A - Resin laminate for thermoforming and method for molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate that can be molded into a three-dimensional shape by thermoforming while having a surface protective layer with sufficient scratch resistance.SOLUTION: The resin laminate for thermoforming has a rigid resin layer A produced by curing a three-dimensional crosslinking type curable composition and a thermoplastic resin layer B comprising a thermoplastic resin having a glass transition temperature of less than 200°C. The thickness of the rigid resin layer A is not less than 0.05 mm to less than 0.5 mm. The total thickness of the resin laminate is not less than 0.1 mm to less than 5 mm. The thickness ratio A/B of the rigid resin layer A to the thermoplastic resin layer B is less than 1. At least the outermost surface of the rigid resin layer A is formed by using a three-dimensional crosslinking type curable composition showing a pencil hardness of 7H or more when cured into a sheet form of 0.2 mm in thickness and the outermost surface of the rigid resin layer A shows a pencil hardness of 6H or more when forming a resin laminate including the thermoplastic resin layer B.

Description

  The present invention relates to a resin laminate for thermoforming and a molding method capable of giving a shape to a resin laminate having a tertiary cross-linkable curable resin layer, which was difficult to give by thermoforming, and a three-dimensional cross-linking type The present invention relates to a thermoforming resin laminate capable of being shaped by heat while having excellent characteristics of a curable resin layer, and a method for molding the resin laminate.

  There are various methods for forming resin sheets and films that are brought into close contact with molds while being heated and melted, such as vacuum forming, vacuum pressure forming, and press forming, and are widely used in the production of food containers and miscellaneous goods. ing.

Conventionally, resin materials used in these molding methods are sheets made of general-purpose plastics such as polyethylene, polypropylene, polystyrene, polymethyl methacrylate, and vinyl chloride, and thermoplastic resins called general-purpose engineering plastics represented by polyethylene terephthalate and polycarbonate. It was common to use a film.

  Nowadays, for such a three-dimensional molded product, there is a demand to increase the durability and design of the surface, and for that purpose, a film having a transfer layer is preliminarily thermoformed into the outer shape of the molded product, A method has been proposed in which the mold is closed, the mold is closed, the cavity is heated and filled with molten resin, the mold is opened after cooling, and a molded product having a transfer layer (surface protective layer) is obtained. (See Patent Documents 1 to 3). These provide decorative molded products with excellent weather resistance, scratch resistance, and chemical resistance, but the surface protective layer is pre-crosslinked so that it can provide follow-up to three-dimensional shapes. As a result, the thickness of the surface protective layer was limited, which was insufficient for imparting scratch resistance.

  As another method for obtaining a molded article having a three-dimensional shape having a surface protective layer, means for applying a hard coat to an injection molded article is also disclosed (see Patent Document 4). In this method, a three-dimensional molded article is injected. A step of molding and a step of coating the surface protective layer are required, resulting in poor productivity, and at the same time, it is difficult to decorate.

JP 2000-079796 A JP2012-081628A JP 2012-213928 A JP 2004-035610 A

  The present invention has been made in view of the above-mentioned problems of the prior art, and is a resin laminate having a surface protective layer having sufficient scratch resistance, and can be molded into a three-dimensional shape by thermoforming. Is to provide.

  The present inventors originally provided a resin laminate capable of imparting an arbitrary shape by thermoforming while making the three-dimensional cross-linkable curable resin, which is difficult to thermoform, to have a thickness that exhibits sufficient scratch resistance. As a result of intensive studies on a molding method using the same, the present invention has been completed.

  That is, the present invention comprises a hard resin layer A obtained by curing a three-dimensional crosslinkable curable composition, and a thermoplastic resin layer B made of a thermoplastic resin having a glass transition temperature of less than 200 ° C. A resin laminate for thermoforming, wherein the thickness of the hard resin layer A is 0.05 mm or more and less than 0.5 mm, the total thickness of the resin laminate is 0.1 mm or more and less than 5 mm, the hard resin layer A and the thermoplastic resin layer Three-dimensional cross-linking type curing in which the thickness ratio A / B to B is less than 1, and at least the outermost surface of the hard resin layer A has a pencil hardness of 7H or more when cured into a plate shape having a thickness of 0.2 mm. And the outermost surface of the hard resin layer A when formed into a resin laminate including the thermoplastic resin layer B has a pencil hardness of 6H or more. Resin laminate.

  In the present invention, the outermost surface of the hard resin layer A is obtained by curing a three-dimensional crosslinkable curable resin composition containing a polyfunctional (meth) acrylic monomer having a cage silsesquioxane structure. It is preferable.

  Further, the present invention is characterized in that the thermoforming resin laminate is thermoformed by any one of a vacuum forming method, a pressure forming method, a vacuum / pressure forming method, or a press forming method. This is a method for molding a thermoformed resin laminate.

  The thermoformed resin laminate of the present invention can be molded into a three-dimensional shape from a film / sheet while having sufficient scratch resistance, and can provide a high surface hardness molded product with excellent design. And Further, the thermoforming resin laminate according to the present invention can use a vacuum forming method, a pressure forming method, a vacuum / pressure forming method, and a press forming method as a forming method, and has excellent productivity and a stable shape. Can be held with high accuracy.

It is explanatory drawing which showed typically the laminated body of 1st aspect invention of this invention. It is explanatory drawing which showed typically the laminated body of 2nd aspect invention of this invention. It is a top view which shows the resin laminated body after a shaping | molding in this invention. It is A-A 'sectional view of the resin layered product after fabrication in the present invention.

  Hereinafter, the present invention will be described in detail.

  For the three-dimensional crosslinkable curable composition (hereinafter referred to as curable composition) constituting the hard resin layer A according to the thermoforming resin laminate of the present invention, a compound having an unsaturated double bond is used. It may be contained. However, at least the outermost surface of the hard resin layer A needs to be formed using a three-dimensional crosslinkable curable composition having a pencil hardness of 7H or more when cured into a plate having a thickness of 0.2 mm. . Here, examples of the compound having an unsaturated double bond include vinyl compounds and (meth) acrylate compounds. Among these, as the vinyl compound, monofunctional vinyl compounds such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, maleic anhydride and maleimide, and bifunctional vinyl such as divinylbenzene, divinylbiphenyl and divinylnaphthalene. Examples are compounds.

  As one (meth) acrylate compound, monofunctional, bifunctional, trifunctional or higher (meth) acrylates can also be used. As monofunctional (meth) acrylate compounds, methyl acrylate, ethyl acrylate, n-butyl acrylate, Isobutyl acrylate, sec-butyl acrylate, t-butyl acrylate, pentyl acrylate, neopentyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl acrylate, iso Nonyl acrylate, decyl acrylate, isodecyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate Alkyl acrylates such as tetradecyl acrylate, pentadecyl acrylate, isomyristyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, eicodecyl acrylate, n-lauryl acrylate, stearyl acrylate, acryloylmorpholine, cyclohexyl Acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3- Phenyloxypropyl acrylate, 1,4-butane Monoacrylate, 2-hydroxyalkylacryloyl phosphate, 4-hydroxycyclohexyl acrylate, 1,6-hexanediol monoacrylate, neopentyl glycol monoacrylate, and cyclic esters such as ε-caprolactone in the above hydroxyl group-containing acrylic ester compounds Compound added, compound obtained by addition reaction of glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate and acrylic acid, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, tetrahydrofurfuryl acrylate, Isobornyl acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl acrylate (2-isobutyl-2-methyl-1,3-dioxolan-4-yl) methyl acrylate.

  Examples of the bifunctional acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol (meth) acrylate, long chain aliphatic di (meth) acrylate, and neopentyl glycol di (meth) acrylate. , Hydroxypivalate neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, propylene di (meth) acrylate, glycerol (meth) acrylate, triethylene glycol di (meth) acrylate tetraethylene glycol di ( (Meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, poly Ethylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, methoxylated cyclohexyl di ( (Meth) acrylate, acrylated isocyanurate, bis (acryloxyneopentyl glycol) adipate, bisphenol A di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol di (meth) ) Acrylate, phthalic acid di (meth) acrylate, phosphoric acid di (meth) acrylate, zinc di (meth) acrylate, and the like.

  Further, as the trifunctional or higher functional (meth) acrylate, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Tri (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, tri (meth) acrylate phosphate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate Dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, carboxylic acid-modified dipentaerythritol penta (meth) ) Acrylate, urethane tri (meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ester hexa (meth) acrylate, and the like.

  One of these vinyl compounds and (meth) acrylate compounds may be used alone, or two or more thereof may be used in combination. Further, the hard resin layer A may be a single layer of one type of cured product, or a plurality of layers made of a plurality of types of curable compositions may be laminated to constitute the hard resin layer A. As a method of laminating, a plurality of layers may be formed by sequentially coating and curing on a film-like substrate, or a film having a plurality of layers formed by an extrusion method using a multilayer die can be obtained.

In the resin laminate of the present invention, the curable composition forming the hard resin layer A preferably contains a cage-type silsesquioxane resin. In particular, the curable composition that forms the outermost surface of the hard resin layer A is preferably one containing a cage silsesquioxane resin. In a cured product made of a curable composition containing a cage silsesquioxane resin, the pencil hardness is improved and the scratch resistance is excellent. Here, the cage silsesquioxane resin is represented by the following formula (1).
(R ¹ SiO _3/2 ) _n (R ² R ³ SiO _2/2 ) _m (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _l (1)
(Wherein R ^{1 to} R ⁶ are groups having an alkyl group having 1 to ⁶ carbon atoms, a phenyl group, a (meth) acryl group, a (meth) acryloyloxyalkyl group, a vinyl group, or an oxirane ring. A group or different groups, but having at least two (meth) acrylic groups in the formula, and n, m, and l are average values, and n is 6-14. It is a number, m is a number from 0 to 4, and l is a number from 0 to 4 and satisfies m ≦ l.

  The curable composition used in the present invention becomes a three-dimensional cross-linked resin by radical polymerization thereof. Various additives can be added to the curable composition of the present invention for the purpose of improving the properties of the three-dimensional crosslinked resin or promoting radical polymerization. Examples of the additive that accelerates the reaction include a thermal polymerization initiator, a thermal polymerization accelerator, a photopolymerization initiator, a photoinitiation assistant, and a sharpening agent. When blending a photopolymerization initiator or a thermal polymerization initiator, the amount added is preferably in the range of 0.1 to 5 parts by weight with respect to a total of 100 parts by weight of the curable composition. A range of 3 parts by weight is preferred. If the added amount is less than 0.1 parts by weight, curing is insufficient, and the strength and rigidity of the resulting hard resin layer are lowered. On the other hand, if it exceeds 5 parts by weight, problems such as coloring of the hard resin layer occur. There is a fear.

  As the photopolymerization initiator used when the curable composition is a photocurable composition, an acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, acylphosphine oxide-based compound, or the like can be preferably used. . More specifically, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2 -Methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1-one, bis-2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide, benzophenone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, Examples thereof include isopropylthioxanthone and 1-chloro-4-propoxythioxanthone, and these can be used alone or in combination of two or more.

  The curable composition used in the present invention is processed into a sheet film by blending a radical polymerization initiator, applying and casting on a steel belt or a base film by heating or light irradiation, and curing. . When curing by heat, the curing conditions can be selected from a wide range from room temperature to around 200 ° C., depending on the selection of the thermal polymerization initiator and accelerator.

  Moreover, when manufacturing a hard resin layer by light irradiation, it can obtain by irradiating the ultraviolet rays with a wavelength of 10-400 nm, or visible light with a wavelength of 400-700 nm. The wavelength of the light to be used is not particularly limited, but near ultraviolet light having a wavelength of 200 to 400 nm is particularly preferably used. As a lamp used as an ultraviolet ray generation source, a low-pressure mercury lamp (output: 0.4 to 4 W / cm), a high-pressure mercury lamp (40 to 160 W / cm), an ultra-high pressure mercury lamp (173 to 435 W / cm), a metal halide lamp (80-160 W / cm), a pulse xenon lamp (80-120 W / cm), an electrodeless discharge lamp (80-120 W / cm), etc. can be illustrated. Each of these ultraviolet lamps is characterized by its spectral distribution, and is therefore selected according to the type of photoinitiator used.

  The curable composition is formed into a film / sheet using the above-mentioned means. As described above, at least the outermost surface of the hard resin layer A has a pencil hardness of the cured resin of 7H or more. is necessary. When the pencil hardness of the cured resin is less than 7H, the pencil hardness of the resin laminate is lowered. Here, the pencil hardness of the cured resin is a value measured in accordance with JIS K 5600 by creating a plate-like cured product with a thickness of 0.2 mm using the curable composition.

  On the other hand, in the resin laminated body of this invention, it is necessary to have the thermoplastic resin layer B which consists of a thermoplastic resin whose glass transition temperature is less than 200 degreeC. Examples of the thermoplastic resin having a glass transition temperature of less than 200 ° C. include polystyrene (PS), polypropylene (PP), polyethylene (PE), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Examples thereof include acetyl cellulose (TAC), polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin polymer (COP) and cycloolefin copolymer (COC). In order to maintain the shape of the thermoformed product, one having a high elastic modulus at normal temperature is desirable, and PS, PMMA, biaxially stretched PET, biaxially stretched PENTAC, PC, COP, and COC are preferable.

  Here, as described above, the hard resin layer A constituting the resin laminate may be a single layer of one type of cured product, or may be a plurality of layers composed of a plurality of types of curable compositions. Although it is good, the thickness of the hard resin layer A needs to be 0.05 mm or more and less than 0.5 mm. If the thickness of the layer A is less than 0.05 mm, the pencil hardness of the resin laminate is lowered, and the original scratch resistance cannot be improved. If the thickness is 0.5 mm or more, problems such as cracking occur when a three-dimensional shape is imparted by thermoforming. From the viewpoint of ease of imparting a shape at the time of thermoforming, a thinner one is preferable, and a sufficient thickness is required to ensure scratch resistance typified by pencil hardness. The thickness is more preferably 0.05 mm or more and less than 0.25 mm.

  Moreover, in this invention, the total thickness of a resin laminated body is 0.1 mm or more and less than 5 mm. If it is less than 0.1 mm, it becomes difficult to maintain the shape after thermoforming. If it exceeds 5 mm, it takes a long time for thermoforming, resulting in poor productivity. From the viewpoint of the thermoforming cycle, the thickness of the resin laminate is preferably 0.1 mm or more and less than 2 mm.

  In the present invention, the thickness ratio A / B between the hard resin layer A and the thermoplastic resin layer B needs to be less than 1. When A / B exceeds 1, it becomes difficult to maintain the shape after thermoforming. A / B is preferably 0.02 or more and 0.8 or less from the viewpoint of easiness of thermoforming and shape retention after thermoforming.

  In the present invention, the pencil hardness of the resin laminate is required to be 6H or more. That is, in the resin laminate including the hard resin layer A and the thermoplastic resin layer B, the outermost surface of the hard resin layer A has a pencil hardness of 6H or more. If it is less than 6H, it will be easily damaged when used as an exterior material, resulting in a decrease in appearance quality.

  The thermoplastic resin layer B constituting the resin laminate may be a single layer of one kind of thermoplastic resin, or may be a plurality of layers made of a plurality of types of thermoplastic resins, which are directly laminated. It may be laminated or may be laminated via a binder layer. In addition, for the purpose of protecting the hard resin layer A during thermoforming, a thermoplastic resin layer B can be provided on the outer side of the hard resin layer A, but such a protective layer is peeled off and removed after thermoforming. Assuming The thickness of this protective layer is also included in the thickness of the thermoplastic resin layer B.

  Although the thickness of the binder layer used when using two or more layers of the thermoplastic resin layer B is not specifically limited, It is preferable that the thickness is 0.01-30 micrometers. If it is less than 0.01 μm, a sufficient adhesive effect may not be obtained, and if it is 30 μm or more, when used for layer A, the pencil hardness of the laminate may not be sufficiently obtained. When a binder layer is provided as an adhesive or an easy adhesion treatment agent between the hard resin layer A and the thermoplastic resin layer B when the thermoplastic resin layer B is made into a plurality of layers. This is also included in the thickness of the thermoplastic resin layer B.

  Moreover, as what comprises the binder layer as an adhesive layer, an adhesive adhesive, a pressure sensitive adhesive, a photocurable adhesive, a thermosetting adhesive, and a hot-melt-adhesive can also be used. As such, acrylic adhesive, urethane adhesive, epoxy adhesive polyester adhesive, polyvinyl alcohol adhesive, polyolefin adhesive, modified polyolefin adhesive, polyvinyl alkyl ether adhesive, rubber adhesive, vinyl chloride / vinyl acetate adhesive Adhesive, styrene / butadiene / styrene copolymer (SBS copolymer) adhesive, hydrogenated product (SEBS copolymer) adhesive, ethylene / vinyl acetate copolymer, ethylene-styrene copolymer, etc. Adhesives, ethylene / methyl methacrylate copolymers, ethylene / methyl acrylate copolymers, ethylene / ethyl methacrylate copolymers, acrylic ester adhesives such as ethylene / ethyl acrylate copolymers, etc. , Especially if the adhesion, transparency and workability are good Not shall.

Moreover, an easily bonding process is mentioned as binder layers other than the above. The easy adhesion treatment is a treatment for imparting chemical easy adhesion or physical easy adhesion to the surface of the resin layer which is difficult to adhere. The chemical easy adhesion ability is to obtain adhesion by forming a thin film layer of a resin having a functional group on the thermoplastic resin layer B and forming a chemical bond with the hard resin layer A. The adhesive ability is to form a resin thin film layer or an inorganic thin film layer having irregularities on the thermoplastic resin layer B, thereby obtaining an adhesive force with the hard resin layer by an anchor effect. Examples of the material having chemical easy adhesion include polyfunctional (meth) acrylates, epoxies, and thiol group-containing compounds. Examples of materials having physical easy adhesion include SiO ₂ , SiN, and SiC. A vapor deposition film etc. are mentioned.

  In order to give a three-dimensional shape to the resin laminate of the present invention, it is preferable to use any one of a vacuum forming method, a pressure forming method, a vacuum / pressure forming method, and a press forming method. Molded articles obtained by these molding methods have small residual strain during processing and excellent shape retention.

  The molding method will be described in more detail. FIG. 1 is a cross-sectional view showing a first embodiment of a thermoforming resin laminate. In FIG. 1, the hard resin layer A is laminated | stacked on both surfaces of the thermoplastic resin layer B through the easily bonding process layer. By setting it as such a layer structure, generation | occurrence | production of the curvature by the difference in the linear expansion coefficient of the thermoplastic resin layer B and the hard resin layer A can be reduced. In order to obtain such a thermoforming resin laminate, for example, a curable composition in which a photoradical initiator is blended with a thermosetting resin film (thermoplastic resin layer B) subjected to easy adhesion treatment on both sides is predetermined. After coating with a transparent cover film such as PET (not shown) that is not shown in the figure, the same curable composition is then applied to the opposite surface of the thermoplastic resin film. After coating, the curable composition is cured by irradiating ultraviolet rays from both sides, and the hard cover layer A1 and the hard resin layer A2 are made of hard resin cured by peeling and removing the transparent cover film. A resin laminate can be obtained. In addition, including the following FIG. 2, in the drawings, the hard resin layer A is simply referred to as layer A, and the thermoplastic resin layer B is simply referred to as layer B.

  Here, when the embodiment shown in FIG. 1 is used, for example, when the hard resin layer A1 is exposed as a surface and the hard resin layer A2 is used as a back surface in close contact with or adhered to another substrate, the outermost surface of the hard resin layer A1. When the hard resin layer A1 and the hard resin layer A2 are both exposed as the surface, both the hard resin layer A1 and the hard resin layer A2 have a pencil hardness of the outermost surface. It must be 7H or higher. That is, in the present invention, the outermost surface of the hard resin layer A that forms the exposed surface of the resin laminate is a three-dimensional cross-linking type in which the pencil hardness is 7H or more when cured to a plate shape having a thickness of 0.2 mm. What is necessary is just to be formed using the curable composition. In any case, the total thickness of the hard resin layer A1 and the hard resin layer A2 is the thickness of the hard resin layer A in the resin laminate of the present invention, and includes a plurality of hard resin layers A as shown in FIG. Will have a total thickness of 0.05 mm or more and less than 0.5 mm.

  The obtained thermoforming resin laminate can be formed by any one of a vacuum forming method, a pressure forming method, a vacuum / pressure forming method, and a press forming method. Among these, the vacuum forming method, the pressure forming method, the vacuum / pressure forming method, and the press forming method can be carried out by substantially the same procedure. That is, after preparing a pre-heated thermoforming resin laminate and arranging it along a mold of a desired shape, vacuuming from the mold side, pressurizing the facing atmosphere of the mold, or vacuum What is necessary is just to perform both drawing and pressurization, or to press with a press die paired with a forming die. The preheating temperature and the mold temperature at this time may be any temperatures that allow the thermoplastic resin layer to be sufficiently deformed following the mold. As a guideline, the thermoplastic resin layer has a Tg (glass transition temperature) to Tg + 50 °. It is. Thermoforming itself is possible even outside this range, but if the preheating temperature or the temperature of the mold is low, the molding time becomes long, or the vacuum must be evacuated or the pressure increased. Moreover, even if the temperature is too high, the cooling time of the mold for taking out the laminated body after molding becomes long and the productivity is lowered.

  FIG. 2 shows a second embodiment of the thermoforming resin laminate of the present invention. In the embodiment of FIG. 2, a curable composition containing a photoradical initiator is applied to the easy-adhesion treated surface of the thermoplastic resin layer B2 made of an easily-adhesive thermoplastic resin film in the same manner as described above. After coating a transparent cover film (not shown) that has been peeled off, ultraviolet rays are applied to form the hard resin layer A, and the transparent cover film is peeled off, and another thermoplastic film is attached via a peelable adhesive. The thermoplastic resin layer B1 is laminated by laminating. With such a configuration, it is possible to reduce the occurrence of warpage of the laminate before the thermoforming treatment, and the thermoplastic resin layer B1 temporarily assists the thermoforming of the thermoplastic resin layer B2 during thermoforming. Can play the role of That is, by sandwiching the hard resin layer A, which is hard to be thermoformed, between the thermoplastic resin layers B1 and B2, it is caused by peeling of the thermoplastic resin layer B2 and the hard resin layer A that may occur immediately after thermoforming. This is because the thermoplastic resin layer B1 functions to suppress defects. Therefore, it is more desirable that the thermoplastic resin layer B2 and the thermoplastic resin layer B1 are the same kind of thermoplastic resin film. The molding method can be performed in the same manner as in the first embodiment, and finally the resin laminate having the hard resin layer A as the exposed surface of the resin laminate by peeling off and removing the thermoplastic resin layer B1. Can be obtained.

  In addition, as a peelable adhesive, a commercially available thing can be used suitably. Typical examples are acrylic adhesives, and those with weak adhesive strength can be peeled off physically and those that change the adhesive strength depending on the temperature. Can be selected.

  Moreover, when it is set as the structure of FIG. 2, the molded object which additionally formed the thermoplastic resin layer by insert molding can also be obtained. That is, the thermoforming resin laminate having the layer structure of FIG. 2 is arranged as close as possible to the mold on the receiving side of the insert-molding die and the thermoforming laminate of FIG. The injection molding resin is injected from the injection molding resin injection gate on the feed side into the closed mold. At this time, injection molding of the injection molding resin is performed, and the injection molding resin and the thermoforming resin laminate are integrated while being shaped. After removing the resin laminate from the mold, the thermoplastic resin layer B1 and the pressure-sensitive adhesive are removed to obtain a molded body in which an injection molding resin is further added to the thermoplastic resin layer B2. The thickness of the injection molding resin is not particularly limited, but the total thickness of the hard resin layer A, the thermoplastic resin layer B, and the injection molding resin is preferably 0.1 mm or more and less than 5 mm.

  The resin for injection molding at the time of insert molding is not particularly limited as long as it is a thermoplastic resin that can be integrated with the thermoplastic resin layer B and has transparency, but polycarbonate resin, acrylic resin, PET resin, styrene resin, etc. Desirably, they may be used alone or in combination.

  In this way, by using a process in which a thermoplastic resin layer B and an injection molding resin are integrated into a molded body by insert molding, a thin thermoforming resin molded body that can be easily thermoformed during thermoforming is used. By adding an injection molding resin, strength as a molded body can be imparted.

  The molded product having a three-dimensional shape obtained by the present invention can be used as a structural member as it is, and a film having a thickness of less than 0.3 mm can also be used as a film insert molding film for transferring a high surface hardness layer. it can.

  Hereinafter, the present invention will be described in more detail with reference to examples. The evaluation methods and symbols used in the present invention are as follows.

1) Pencil hardness: Measured according to JIS K 5600.
2) Film thickness of hard resin single layer and resin laminate: Measured using ID-SX manufactured by Mitutoyo Corporation.
3) Film thickness of each layer in the resin laminate: measured with an optical microscope with a scale.
4) Formability: The molded body obtained by molding was observed. If the crack was found to be cracked, cracked or fractured, x was only whitening was observed, and none was seen. ○.
5) Shape retention: after molding, the sample was allowed to stand for 24 hours, and the deviation of the shape immediately after molding was visually determined. The case where the shape hardly changed was marked with ◯, and the shape which changed clearly was marked with ×.

[Synthesis example]
A reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer was charged with 400 ml of 2-propanol (IPA) as a solvent and 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst. Into the dropping funnel, 150 ml of IPA and 126.9 g of 3-methacryloxypropyltrimethoxysilane (MTMS: SZ-6030 manufactured by Toray Dow Corning Silicone Co., Ltd.) were added, and the IPMS solution of MTMS was added at room temperature while stirring the reaction vessel. It was added dropwise over 30 minutes. After completion of the dropwise addition of MTMS, the mixture was stirred for 2 hours without heating. After stirring for 2 hours, the solvent was removed under reduced pressure and dissolved in 500 ml of toluene. The reaction solution was washed with saturated brine until neutral, and then dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 86 g of a cage silsesquioxane compound having methacryloyl groups on all silicon atoms. This silsesquioxane was a colorless viscous liquid soluble in various organic solvents.

[Reference Example 1]
(Creation and evaluation of hard resin sheet)
Cage-type silsesquioxane compound having methacryloyl groups obtained in the above synthesis examples on all silicon atoms: 23 parts by weight, dipentaerythritol hexaacrylate: 39 parts by weight, dicyclopentanyl diacrylate: 32 parts by weight, 1 to 6 parts by weight of urethane acrylate oligomer and 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator were mixed to obtain a transparent curable composition.

Next, using a roll coater, a curable composition was cast on PET that had been peel-treated to a thickness of 0.2 mm, and another peel-treated PET was cast. The sheet-shaped three-dimensional cross-linking type is cured by using a 30 W / cm high-pressure mercury lamp after being laminated, cured at an accumulated exposure amount of 4000 mJ / cm ² , and peeled and removed all of the peeled PET. A cured product was obtained. About the obtained hardened | cured material, pencil hardness and film thickness were measured. The results are shown in Table 1.

In addition, the meaning of the symbol in Table 1 is as follows. A: Compound obtained in Synthesis Example 1
B ... Dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)
C: Pentaerythritol triacrylate (Kyoeisha Chemical Co., Ltd. light acrylate PE-3A)
D ... Caprolactone-modified dipentaerythritol hexaacrylate 2 (KAYARAD DPCA-30 manufactured by Nippon Kayaku Co., Ltd.)
E ... dicyclopentanyl diacrylate (Kyoeisha Chemical Co., Ltd. light acrylate DCP-A)
F ... Dicyclopentanyl dimethacrylate (NK ester DCP manufactured by Shin-Nakamura Chemical Co., Ltd.)
G ... Urethane acrylate oligomer 1 (UF-503 manufactured by Kyoeisha Chemical Co., Ltd .: number average molecular weight of about 8800)
H: Urethane acrylate oligomer 2 (Shin Nakamura Chemical Co., Ltd. NK oligo UA-122P: number average molecular weight of about 1100)
I ... 1-hydroxycyclohexyl phenyl ketone (polymerization initiator)

[Reference Examples 2 to 4]
As shown in Table 1, each reactive compound was blended at a weight ratio shown in Table 1 to obtain a curable composition, and then a sheet-like cured product having a predetermined thickness was obtained in the same manner as in Reference Example 1. Obtained. About the obtained hardened | cured material, pencil hardness and film thickness were measured. The results are shown in Table 1.

[Example 1]
Using a roll coater on 0.25 mm-thick biaxially stretched PET (Tg: 70 ° C., thermoplastic resin layer B1) on both surfaces of which the curable composition of Reference Example 1 was subjected to easy adhesion treatment, the thickness was 0. After laminating 0.1 mm biaxially stretched PET, which has been cast to 1 mm, to the cast curable composition, using a 30 W / cm high-pressure mercury lamp, 4000 mJ / cm ^The hard resin layer A1 was formed by curing with an accumulated exposure amount of ² . Furthermore, after the curable composition of Reference Example 1 was cast and photocured so as to have a thickness of 0.1 mm on the opposite easy-adhesive surface as well, a hard resin layer A2 was provided, and then the biaxially peeled The stretched PET was peeled off to obtain a thermoformed resin laminate. The obtained thermoforming resin laminate is placed in a mold having a heater and a pressure air mechanism, heated with a heater until the surface temperature of the resin laminate sheet reaches 200 ° C., and then has a pressure of 5 atm and upper and lower molds. Pressure molding was performed on the thermoforming resin laminate at a temperature of 150 ° C. to 250 ° C. under the conditions of a delay of 10 seconds until compressed air and a pressure holding time of 30 seconds. The mold used was a watch glass with a diameter of 50 mm and a depth of 5 mm. FIGS. 3 and 4 show a plan view and AA ′ cross-sectional view of the resin laminate after molding, respectively. Table 2 shows the pencil hardness, the film thickness of each layer, the film thickness ratio, the moldability during vacuum forming, and the shape retention of the obtained resin laminate.

[Examples 2 to 5]
Except having changed the film thickness of the curable composition and the hard resin layer A as shown in Table 2, the resin laminated body for thermoforming and the pressure-molded article were obtained in the same manner as in Example 1. Various evaluation results are shown in Table 2.

[Example 6]
A resin laminate for thermoforming and a compressed air molded product were obtained in the same manner as in Example 1 except that 0.5 mm PC (Tg: 150 ° C.) obtained by subjecting the thermoplastic resin layer B1 to easy adhesion treatment was used. Various evaluation results are shown in Table 2.

[Example 7]
Using the roll coater on the 0.1 mm thick PC (Tg: 150 ° C., thermoplastic resin layer B2) subjected to the easy adhesion treatment, the curable composition of Reference Example 1 has a thickness of 0.1 mm. Example 1 was prepared by laminating a separately prepared 0.1 mm PC (Tg: 150 ° C., thermoplastic resin layer B1), which was not easily adhered, onto the cast curable composition. The curable composition was cured in the same manner as described above to obtain a thermoforming resin laminate composed of three layers of a thermoplastic resin layer B2, a hard resin layer A, and a thermoplastic resin layer B1. Various evaluation results are shown in Table 2. In addition, a PC resin for injection molding (trade name “HFD1810” manufactured by Savic Co., Ltd.), which was previously dried at 120 ° C. for 24 hours by film insert molding using this thermoforming resin laminate, was obtained at a resin temperature of 320 ° C. After being integrated with a 0.5 mm thick PC resin for injection molding by injection under conditions of a mold temperature of 90 ° C. to 120 ° C., an in-mold pressure of 300-500 kg / cm ² and an injection time of 5 seconds, the thermoplastic resin layer B1 Was peeled to obtain a molded product. The pencil hardness of the surface of the hard resin layer A after peeling off the thermoplastic resin layer B1 was 6H.

[Comparative Examples 1-6]
Example 1 except that the curable composition type and film thickness of the hard resin layers A1 and A2 and the resin type and film thickness of the thermoplastic resin layer B1 (Tg are the same as those in the example) were changed as shown in Table 2. In the same manner as above, a thermoformed resin laminate and a vacuum molded product were obtained. Various evaluation results are shown in Table 2.

Claims (3)

  A resin laminate for thermoforming comprising a hard resin layer A obtained by curing a three-dimensional crosslinkable curable composition and a thermoplastic resin layer B made of a thermoplastic resin having a glass transition temperature of less than 200 ° C. A hard resin layer A having a thickness of 0.05 mm or more and less than 0.5 mm, a total thickness of the resin laminate of 0.1 mm or more and less than 5 mm, and a thickness ratio A between the hard resin layer A and the thermoplastic resin layer B. / B is less than 1, and at least the outermost surface of the hard resin layer A is a three-dimensional crosslinkable curable composition having a pencil hardness of 7H or more when cured into a plate having a thickness of 0.2 mm. A thermoforming resin laminate, wherein the outermost surface of the hard resin layer A, which is formed and includes a thermoplastic resin layer B, has a pencil hardness of 6H or more.   The outermost surface of the hard resin layer A is obtained by curing a three-dimensional crosslinkable curable resin composition containing a polyfunctional (meth) acrylic monomer having a cage silsesquioxane structure. The thermoformed resin laminate according to claim 1.   The thermoforming resin laminate according to claim 1 or 2 is thermoformed by any one of a vacuum forming method, a pressure forming method, a vacuum / pressure forming method, or a press forming method. A method for forming a thermoformed resin laminate.

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