JP2007223126A - Synthetic resin molded body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded body which is made by laminating a surface resin layer on a synthetic resin base material with an adhesive layer placed between them, causes no wrinkle even when the molded body is subjected to a secondary thermal process such as thermo-bending, and shows good flaw resistance. <P>SOLUTION: In the molded body made by laminating the surface resin layer 3 on the synthetic resin base material 1 with the adhesive layer 2 placed between them, the adhesive layer 2 is composed of a polyurethane-based resin prepared by compounding a polyisocyanate and a polyol, the molar equivalent of the isocyanate group of the polyisocyanate being larger than the molar equivalent of the hydroxyl group of the polyol, and reacting them. The ratio of the molar equivalent of the isocyanate group of the polyisocyanate to the molar equivalent of the hydroxyl group of the polyol (the molar equivalent of the isocyanate group/the molar equivalent of the hydroxyl group) satisfies 1.0<(the molar equivalent of the isocyanate group)/(the molar equivalent of the hydroxyl group)≤5.0 in order to let the isocyanate group remain in the adhesive layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a synthetic resin molded article having an abrasion-resistant layer having no bubbles or wrinkles, and particularly to a synthetic resin molded article that can be subjected to secondary processing.

  Molded bodies made of thermoplastic resins such as polycarbonate and polyethylene terephthalate are used in various applications as building materials, industrial materials, etc., taking advantage of the transparency and impact resistance of the resins. However, these resin moldings have the disadvantage that the surface hardness is poor and the surface is easily scratched. Therefore, in order to prevent the surface of the resin molded body, particularly the transparent resin molded body, from being scratched, a hard coat layer made of a silicone resin or an acrylic resin is formed on the surface to improve the surface hardness. There is something.

For example, a transparent resin molded body is known in which a hard coat layer such as urethane acrylate resin is formed on a thermoplastic synthetic resin base material through a primer layer made of an adhesive resin containing a filler (Patent Document 1). . The transparent resin molded body of Patent Document 1 is a heat-bending product that has a good appearance by absorbing the stress during bending without causing the primer layer to be too flexible even when the molded body is subjected to heat-bending. It can be processed.
JP 2005-178035 A

However, the transparent resin molded body of the above-mentioned Patent Document 1 cannot exhibit the original adhesiveness of the adhesive resin because the primer layer is formed by including a filler in the adhesive resin, and the molded body cannot be exhibited. In the boiling water test to measure the adhesion between each layer of the base material, adhesive layer and hard coat layer, bubbles and wrinkles are generated and partly peeled off, so further improvement of adhesion between each layer is desired It was.
The present invention solves the above problems, and is a synthetic resin molding excellent in scratch resistance, which is laminated and integrated by an adhesive layer which has excellent adhesion between a base material and a surface layer and does not generate bubbles or wrinkles. The purpose is to provide a body.

  Therefore, the synthetic resin molded body according to the present invention is a molded body in which a surface resin layer is formed on at least one surface of a synthetic resin substrate via an adhesive layer, and the adhesive layer is a mole of an isocyanate group of polyisocyanate. It is formed from a polyurethane-based resin obtained by mixing and reacting a polyisocyanate and a polyol so that the equivalent is greater than the molar equivalent of the hydroxyl group of the polyol.

In the present invention, it is preferable that the isocyanate group of the polyisocyanate blended in the adhesive layer remains in the adhesive layer, and the molar equivalent of the isocyanate group of the polyisocyanate forming the adhesive layer and the hydroxyl group of the polyol. The molar equivalent ratio with respect to the molar equivalent (isocyanate group molar equivalent / hydroxyl molar equivalent) is preferably 1.0 <isocyanate group molar equivalent / hydroxyl molar equivalent ≦ 5.0.
Moreover, it is also preferable that the said surface resin layer is formed with urethane acrylate resin.

  Furthermore, the transfer film used for the formation of these synthetic resin moldings is formed on the surface of the release film so that the molar equivalent of the resin layer and the isocyanate group of the polyisocyanate is larger than the molar equivalent of the hydroxyl group of the polyol. It is characterized in that an adhesive layer formed of a polyurethane resin obtained by mixing and reacting an isocyanate and a polyol is laminated.

  The adhesive layer of the synthetic resin molded body of the present invention is formed from a polyurethane resin obtained by mixing and reacting a polyisocyanate and a polyol so that the molar equivalent of the isocyanate group of the polyisocyanate is larger than the molar equivalent of the hydroxyl group of the polyol. Therefore, unreacted isocyanate groups react with active hydrogen such as hydroxyl groups, amino groups, imino groups, carboxyl groups, urethane bonds and urea bonds between the synthetic resin substrate and the surface resin layer to form covalent bonds. It can occur and adhesion can be improved. Furthermore, the urethane bond generates intermolecular force such as hydrogen bond, and solidifies in a state where the adhesive layer enters each other at the interface between the synthetic resin base material and the surface resin layer, and can exhibit good adhesiveness.

In addition, since the hydroxyl group of the polyol and the isocyanate group of the polyisocyanate corresponding to the molar equivalent form a urethane bond, the adhesive layer has stability against heat, water, and the like. No wrinkles or partial detachment occurs, and there is no delamination during actual use, and it can be used for a long time.
Furthermore, the adhesive layer uses a polyurethane-based resin, and exhibits plasticity by heating for secondary heat processing. Moreover, as described above, an unreacted isocyanate group is a synthetic resin base material or surface resin layer. As the adhesiveness is improved by forming a covalent bond with the substrate, it is possible to maintain the adhesion between the layers by heating and prevent the synthetic resin base material and the resin surface layer from peeling off, and heat bending. Secondary heat processing such as can be performed satisfactorily.

  The molar equivalent ratio of the isocyanate group of the polyisocyanate forming the polyurethane resin of the adhesive layer to the molar equivalent of the hydroxyl group of the polyol (isocyanate group molar equivalent / hydroxyl molar equivalent) is 1.0 <isocyanate group molar. When the equivalent / hydroxyl molar equivalent ≦ 5.0, almost all hydroxyl groups react with each other, so that the compatibility with water is deteriorated, and the adhesion at the boiling water test can be improved. When the molar equivalent ratio is 1.0 or less, the hydroxyl group remains even after the urethane bond is formed, and the residual hydroxyl group and water show good compatibility, so the adhesion in the boiling water test May cause delamination. On the other hand, if the molar equivalent ratio is larger than 5.0, the cohesive force of the adhesive layer is weakened, so that the adhesion during the boiling water test is also deteriorated. Thus, if the adhesion during the boiling water test is poor, problems such as cracks and delamination occur during actual outdoor use. Therefore, 1.0 <isocyanate group molar equivalent / hydroxyl molar equivalent ≦ 5.0 It is preferable to eliminate the problem.

  In addition, when the surface resin layer is a urethane acrylate resin, the scratch resistance is inferior to that of a hard coat layer made of a conventional silicone resin, but the surface hardness is superior to that of a thermoplastic resin such as polycarbonate or polyethylene terephthalate. Abrasion resistance can be imparted to the body. Moreover, since this urethane acrylate resin has a stretching property, it can also provide heat workability.

  In particular, since this urethane acrylate resin has elasticity even at room temperature, even if the surface resin layer (molded body surface) made of this resin is scratched, the scratch is blocked by the elasticity of the resin. It can be restored to its original appearance and visually observed as a surface state without scratches. If the molded body is transparent, light is irregularly reflected due to scratches or the like, and temporarily becomes cloudy, but after a while, the scratches are closed and restored to the original flat shape, and the light is not irregularly reflected, and the original transparent Can demonstrate its sexuality.

  The transfer film of the present invention is formed of a polyurethane-based resin obtained by mixing and reacting a polyisocyanate and a polyol so that the molar equivalent of the isocyanate group of the polyisocyanate is larger than the molar equivalent of the hydroxyl group of the polyol. Therefore, it can be sufficiently softened by heat during transfer, sufficiently adhered to the soft surface of the resin base material, and can be bonded and bonded satisfactorily by the anchor effect, covalent bond, intermolecular force and the like. further. Since this adhesive layer has flexibility, even if the transfer film is wound around a paper tube or the like, it is possible to prevent each layer from peeling off or wrinkling.

  Hereinafter, specific embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to these.

  FIG. 1 is a sectional view showing a synthetic resin molded body according to an embodiment of the present invention, and FIG. 2 is a sectional view of a transfer sheet for forming the synthetic resin molded body.

  This embodiment shows a transparent plate-shaped synthetic resin molded body, and an adhesive layer 2 and a surface resin layer 3 are laminated and integrated in this order on the surface of one side of a transparent plate-shaped resin substrate 1. This is a transparent laminated molded body. The adhesive layer 2 and the surface resin layer 3 may be laminated and integrated on both surfaces of the resin base material 1.

  This resin substrate 1 is formed by molding a transparent thermoplastic resin or a transparent curable resin into a plate shape. Examples of such thermoplastic resins include olefin resins such as polyethylene, polypropylene, and cyclic polyolefin, vinyl resins such as polyvinyl chloride, polymethyl methacrylate, and polystyrene, cellulose resins such as nitrocellulose and triacetyl cellulose, polycarbonate, Amorphous / crystalline polyethylene terephthalate, ester resins such as aromatic polyester, ABS resin, copolymer resins of these resins, mixed resins of these resins, and the like are used. In addition, as the curable resin, a resin that is cured by heat, ultraviolet rays, electron beams, or the like, such as an epoxy resin, a polyimide resin, or an acrylic resin is used. Since the thermoplastic resin is softened by heating and can be subjected to secondary heat processing, it is preferably used as a base resin for a resin molded body capable of secondary heat processing. In particular, polycarbonate has good impact resistance and transparency, and is preferably used mainly as a resin for base materials for outdoor use. Amorphous polyethylene terephthalate has good workability and provides deep drawing. It is preferably used as a base resin for use in performing secondary heat processing. And since this polycarbonate and amorphous polyethylene terephthalate have poor surface hardness and are easily scratched, it is possible to further expand the application by increasing the surface hardness and exhibiting scratch resistance as in the present invention. it can.

  The resin base material 1 is appropriately mixed with plasticizers, stabilizers, antioxidants, ultraviolet absorbers and the like that are generally added to the molding of each of the resins, thereby improving moldability, thermal stability, weather resistance, and the like. It has been. Although the thickness of this resin base material 1 is suitably changed according to a use, it is normally used by the thickness of about 0.1-20 mm.

  In this embodiment, the resin base material 1 is formed into a transparent plate-like body, but it may be formed into other irregular shapes, and is made opaque or translucent by blending a filler or a colorant. Also good.

  The adhesive layer 2 is for integrally bonding the resin base material 1 and the surface resin layer 3 and is made of a polyurethane resin. The polyurethane-based resin is blended so that the hydroxyl group of the polyol and the isocyanate group of the polyisocyanate have a molar equivalent (hereinafter referred to as equivalent), and all are urethane-bonded to form a three-dimensional structure, The polyisocyanate and the polyol are mixed so that the isocyanate group equivalent of the polyisocyanate is larger than the hydroxyl group equivalent of the polyol, in other words, the number of isocyanate groups contained in the polyisocyanate is larger than the number of hydroxyl groups contained in the polyol. Almost all of the hydroxyl groups are reacted with isocyanate groups, but the isocyanate groups of the excess polyisocyanate remain unreacted and form a polyurethane resin in the state of remaining inside the adhesive layer 2 is doing. Therefore, the adhesive layer 2 contains a urethane-bonded urethane resin and unreacted polyisocyanate.

  The polyurethane-based resin is not particularly limited, but the thermoplastic polyurethane-based resin is softened by heating. Therefore, the polyurethane-based resin is preferably used as an adhesive layer resin for a transfer film or a resin molded body capable of secondary heat processing. As the polyol that forms this polyurethane resin, ether-based, ester-based, carbonate-based, aliphatic-based polyol, and the like are used, and as the polyisocyanate, bifunctional, trifunctional, modified isocyanate, and the like are used. Specific polyols include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, various types of ethylene oxide / propylene oxide copolymers, polydimethylsiloxane diol, polyethylene adipate, polybutylene adipate, Polyhexamethylene adipate, polyhexamethylene carbonate diol, hydroxyl-terminated liquid polybutadiene, hydroxyl-terminated liquid polyisoprene, etc., and specific polyisocyanates are tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, etc. Preferably used.

  And it is preferable to mix | blend polyisocyanate and a polyol so that the equivalent ratio of the isocyanate group and a hydroxyl group may be set to 1.0 <isocyanate group equivalent / hydroxyl group equivalent <= 5.0. When blended in this way, unreacted polyisocyanate groups react with active hydrogen such as hydroxyl groups, amino groups, imino groups, carboxyl groups, urethane bonds, and urea bonds between the synthetic resin substrate or the surface resin layer and share. By producing a bond and improving the adhesion, the adhesive bonding between the resin base material 1 and the resin surface layer 3 can be maintained, and the adhesion between layers by heating for secondary heat processing is maintained and peeling is prevented. Can do. Furthermore, since it is partially urethane-bonded and cross-linked, it can be prevented from being too soft and generating bubbles and wrinkles, and the water resistance is improved and water stability is obtained.

  In this way, by partly urethane bonding, the adhesive layer 2 exhibits heat resistance and water resistance, and bubbles, blisters and wrinkles are generated in the adhesive layer 3 even when the molded body is subjected to a boiling water test. Therefore, the molded article can be used for a long time.

  Further, this urethane bond has an intermolecular force such as a hydrogen bond with a molecule of the resin base material 1 or the resin surface layer 3, and improves the adhesion between them and further prevents peeling. .

  When the isocyanate group equivalent / hydroxyl group equivalent is 1.0 or less, the hydroxyl group remains unreacted, and the hydroxyl group has good compatibility with water. There is a risk of peeling due to blisters or wrinkles. On the other hand, when the equivalence ratio is larger than 5.0, the cohesive force of the adhesive layer becomes weak, so that the adhesion during the boiling water test is also poor and may be peeled off. If the adhesiveness during the boiling water test is poor as described above, problems such as cracks and delamination occur during actual outdoor use. As described above, 1.0 <isocyanate group equivalent / hydroxyl group equivalent ≦ 5.0 This is preferable because the above problem can be eliminated. A more preferable equivalent ratio is 1.0 <isocyanate group equivalent / hydroxyl group equivalent ≦ 2.0.

  The thickness of the adhesive layer 2 is preferably 0.1 to 10 μm. If the thickness is 0.1 μm or less, it is difficult to maintain the adhesive strength and the flexibility is poor, which is not desirable. Even if the thickness is 10 μm or more, further improvement in the adhesive strength and shape retention cannot be expected. It will be a waste of money.

  The surface resin layer 3 is formed of a known hard coat agent, for example, a hard coat agent such as an inorganic type, an organic type, or an organic-inorganic hybrid type, and is cured by active energy rays such as heat, ultraviolet rays, or electron beams. It is formed by the coated film. Examples of the inorganic resin include trialkoxysilane, tetraalkoxysilane, colloidal silica-containing organotrialkoxysilane, methyltrialkoxysilane, and phenyltrialkoxysilane, which are resins having a siloxane bond. As the organic hard coat agent, acrylic, melamine, urethane, alkyd, fluorine-containing resin, acrylic radical, photocationic resin, etc. are used. As the organic-inorganic hybrid, inorganic fine particle dispersion is used. Acrylic radical, inorganic fine particle dispersed organic polymer, inorganic fine particle dispersed organoalkoxysilane, organic polymer dispersed silica, acrylic silicone, organoalkoxysilane, organoalkoxysilane / alkoxyzirconium, fluorine-containing resin / organoalkoxy Silane-based, silicate / organic polymer resins and the like are appropriately selected and used.

  Among these resins, silicone resins are preferably used because of their high surface hardness and excellent weather resistance. In addition, the urethane-based resin retains the surface hardness and flexibility of the hard segment of the urethane bond after curing, and the flexibility of the soft segment that is the organic component of the remaining polyol and polyisocyanate bonded to the urethane. And is preferably used as the resin of the surface resin layer 3 of the heat-processable molded body having scratch resistance.

  In particular, when the surface resin layer 3 is formed of a urethane acrylate resin, the surface hardness can be increased and scratch resistance can be imparted, and even if the surface layer 3 is scratched, the soft segment has elasticity. The urethane acrylate resin has a self-repairing property that closes the scratches and restores the original appearance, which is particularly preferable. As this urethane acrylate resin, a urethane acrylate resin comprising an organic isocyanate having a plurality of isocyanate groups in one molecule and a hydroxy-modified methacrylate and polycaprolactone-containing polyfunctional alcohol has high surface hardness and elasticity. In addition, since it also has self-repairing properties, it is particularly preferably used.

  With such self-healing properties, even if scratches are made with sand, pebbles, rags, brushes, scrubbers, sponges, etc., the damage of the surrounding resin over time, especially the elasticity of the soft segments in the resin The surface shape is not so high and the surface resin layer 3 of urethane acrylate resin has elasticity. Therefore, if the resin substrate 1 and the adhesive layer 2 are formed of a heat-processable thermoplastic resin, a heat-processable molded body can be obtained. If the resin base material 1, the adhesive layer 2 and the surface resin layer 3 are all translucent and the molded body is transparent, the light is irregularly reflected by the scratches and the like, and becomes cloudy and temporarily transparent. However, when the time elapses, the scratches are closed and restored to the original shape and are not diffusely reflected, so that the original transparency can be exhibited, and this is a particularly useful function for transparent molded articles. .

  The thickness of the surface resin layer 3 is preferably 1 to 100 μm. If it is 1 μm or less, the surface hardness cannot be increased, and the required scratch resistance cannot be imparted. In particular, when the polyurethane acrylate surface resin layer is used, the self-healing property is poor. On the other hand, even when the thickness is 100 μm or more, improvement in scratch resistance cannot be expected, which is a waste of materials and is not desirable.

The resin molded body having the above-described configuration may be a transparent molded body or an opaque molded body, but in the case of a transparent molded body, the total light transmittance is 75% or more, the haze is 5% or less, Preferably, the total light transmittance is 85% or more and the haze is 3% or less. In particular, when the resin substrate 1 and the adhesive layer 2 are formed of a thermoplastic resin and the surface resin layer 3 is a transparent resin molded body formed of a urethane acrylate resin, the surface of the resin molded body has scratch resistance. It is hard to be scratched, and even if it is scratched, self-healing properties are demonstrated and the scratch disappears, so the above-mentioned total light transmittance and haze can be maintained, and heat processing can be performed, so cars, motorcycles, etc. Transparency, scratch resistance and thermal processing of vehicle window glass and windshields, machine tool covers, machine tool room viewing windows, construction machine window protection plates, touch panel protection plates, etc. Therefore, the molded article is useful for applications that require high properties.
As the thermal processing, in addition to the above bending processing, known thermal processing methods such as vacuum forming, pressure forming, and stamping are appropriately used.

  In order to obtain the resin molded body having the above-described configuration, for example, a transfer method, a lamination method, a direct coating method, or the like can be used.

  In the case of using the transfer method, as shown in FIG. 2, a resin paint made of a resin having the above-mentioned scratch resistance function is applied to one side of a release film 4 such as biaxially stretched polyethylene terephthalate, and the resin is dried by heating and solidified. The layer 3 was formed, and then an adhesive layer coating material in which a polyol and a polyisocyanate were mixed so that more isocyanate groups were contained than the hydroxyl group was applied on the resin layer 3 and then heated and dried to solidify the reaction. The layer 2 is formed, and a transfer film in which the release film 4, the resin layer 3, and the adhesive layer 2 are laminated in this order is produced and wound on a paper tube. Then, a transfer film is superimposed on the surface of the extruded synthetic resin sheet (resin base material 1) so that the adhesive layer 2 is on the synthetic resin sheet 1 side, and heat-pressed, and the adhesive layer 2 and the resin layer 3 Is transferred to produce the synthetic resin molded body of the present invention in which the resin base material 1, the adhesive layer 2 and the surface resin layer 3 are laminated and integrated.

  As described above, the adhesive layer 3 of this transfer sheet is sufficiently adhered to the soft surface of the sheet 1 when it is heat-pressed to the synthetic resin sheet 1 because some of the isocyanate groups remain unreacted. In addition to being integrated by the anchor effect, a good bonding force can be obtained by intermolecular forces such as hydrogen bonding. Also. Since the adhesive layer 3 has flexibility, even when the transfer film is wound around a paper tube or the like, it is possible to prevent the layer 2 from acting as a cushion and peeling off each layer or wrinkles. For this reason, the synthetic resin molding manufactured using the transfer sheet which has this contact bonding layer 3 has favorable contact | adherence, joining, and integration of each layer, and does not peel even if it uses it for a long period of time.

  When using the laminating method, the adhesive layer coating is applied to a film made of an adhesive resin such as an acrylic film, the adhesive layer 2 is formed by heat drying to react and solidify, and then the resin coating is applied. The resin layer 3 is formed by heating and solidifying to produce a laminate film. And the synthesis | combination of this invention which the resin base material 1, the acrylic film, the contact bonding layer 2, and the surface resin layer 3 laminated | stacked by laminating this laminated film on the synthetic resin sheet (resin base material 1) by which extrusion molding was carried out. A resin molding can be manufactured.

  Furthermore, when using the direct application method, a synthetic resin plate (resin substrate 1) is prepared in advance by extrusion molding or press molding, and the adhesive layer coating material is applied to the synthetic resin plate (resin substrate 1). By forming the adhesive layer 2 that has been heat-dried and reacted and solidified, and then applying the resin coating thereon, and solidifying by heat-drying and forming the resin layer 3, the resin base material 1 and the adhesive layer 2 The synthetic resin molding of the present invention in which the surface resin layer 3 is laminated can be easily produced.

  Hereinafter, the present invention will be described more specifically with reference to examples.

(Examples 1, 2, 3 and Comparative Examples 1, 2, 3)
A urethane acrylate coating solution in which a urethane acrylate resin was dissolved in a solvent was applied to a biaxially stretched polyethylene terephthalate film having a thickness of 50 μm, followed by heating and drying to form a surface resin layer (thickness 10 μm). Next, an ester-based polyol coating solution (resin content: 30.0%) obtained by dissolving an ester-based polyol having a hydroxyl group equivalent of 3206 in a solvent, and a polyisocyanate (resin component: 100.0%) having an isocyanate group equivalent of 198, Are mixed with 100: 0, 100: 1, 100: 2, 100: 3, 100: 4, 100: 5, 100: 10 at different mixing ratios (weight ratios), and the molar equivalent of isocyanate group and hydroxyl group Seven types of urethane coating solutions having ratios (isocyanate groups / hydroxyl groups) of 0.00, 0.54, 1.08, 1.62, 2.16, 2.70, and 5.41 were obtained. Seven types of transfer films were prepared by forming an adhesive layer (thickness: 2 μm) obtained by applying the liquid to the surface resin layer and heating and drying to solidify the reaction.

  Then, while extruding the polycarbonate resin into a transparent sheet having a thickness of 5 mm, the adhesive layer of each transfer film is pressed against the sheet surface and heat-pressed, and the biaxially stretched polyethylene terephthalate film is peeled to peel off the adhesive layer and the surface. The resin layer was transferred to obtain a transparent polycarbonate resin molded plate having a three-layer structure in which a polycarbonate resin base material, an adhesive layer, and a surface resin layer were laminated in this order. These are referred to as Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3, Example 4, and Comparative Example 3.

  Based on JIS K7361-1, the transparency of the transparent polycarbonate resin molded plate of each Example and each Comparative Example was measured using a direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. I investigated. The results are listed in Table 1. The total light transmittance of only the polycarbonate resin substrate having a thickness of 5 mm was 90.5%, and the haze was 0.4%.

  Further, the abrasion resistance of each molded plate is subjected to Taber abrasion based on JIS K6735 using a rotary ablation tester manufactured by Toyo Seiki Seisakusho, TYPE-t (wear wheel CS-10F, load 500 gf, 100 rotations). The total light transmittance and haze after the Taber abrasion were examined in the same manner as described above, and the haze change before and after the Taber abrasion was examined. The results are also shown in Table 1.

  In addition, using a surface property measuring machine manufactured by Shinto Kagaku Co., Ltd., TYPE-HEIDON-14, the brass brush was pressed with a force of 1 kg, and the self-healing property was scratched 10 times at a speed of 5 m / min. The surface state after 5 minutes was observed to determine whether or not the scratch was visible. The results are also shown in Table 1. A circle was marked on the molded plate where the scratch was not visible, and an X was marked on the molded plate where the scratch was visible.

Further, the cross-plate adhesion of each molded plate was examined based on JIS K5600-5-6. A cross-cut test was performed on each molded plate after being immersed in boiling water for 60 minutes, and the number of unexfoliated pieces was examined, and the appearance of each molded plate after being immersed in boiling water was visually examined. The results are also shown in Table 1. ◯ was marked on the molded plate where defects such as wrinkles, blisters and bubbles were not visible, and the state of the defect was marked on the molded plate where the defects were visible.
In addition, the cross-cut test and the appearance of each molded plate before dipping in boiling water were similarly examined. As a result, all the molded plates were not peeled off by the cross-cut test and the appearance was good.

  Furthermore, in order to investigate thermal workability, male and female dies with a radius of 50 mm were prepared, each molded plate was dried, heated (220 ° C., 5 minutes), sandwiched between the male and female dies, and stamped Molding was performed to obtain a semicircular heat-processed molded body having a radius of 50 mm. Each heat-processed molded body was observed and examined for defects such as whitening, wrinkles, bubbles, and cracks. The results are also shown in Table 1. A circle was indicated for a molded plate having no defect, and a state was indicated for a molded plate having a defect.

(Comparative Example 4)
The ester polyol and polyisocyanate used in Example 1 were mixed at a mixing ratio of 100: 3 and mixed so that the equivalent ratio of hydroxyl group to isocyanate group was 1.62, and further 20 mass of colloidal silica. %, A silica-containing urethane coating solution added and mixed so as to be% was prepared. And like Example 1, while forming the resin surface layer by a urethane acrylate coating liquid on a biaxially-stretched polyethylene terephthalate film, on this, the produced silica containing urethane coating liquid is apply | coated, heat-dried, and it reacts. A transfer film was produced by forming a solidified adhesive layer (thickness: 2 μm). Then, it transferred to the transparent polycarbonate sheet of thickness 5mm like Example 1, and obtained the transparent resin molding plate of the comparative example 4 of 3 layer structure.

  As in Example 1, this transparent resin molded article was examined for transparency, scratch resistance, self-healing property, adhesion, and heat processability, and the results are also shown in Table 1.

  As understood from this Table 1, in all examples and comparative examples, the total light transmittance shows a value of 90% or more, and the haze shows a value of 1.0 or less. It can be seen that Further, in the Taber abrasion test, the total light transmittance before and after the test showed almost no change, but the haze showed a change of about 5% before and after the test, but between each Example and each Comparative Example. There was no difference. Furthermore, in the self-repairing property, it can be seen that all the molded plates are self-repaired, and the molded plate having a surface layer made of urethane acrylate resin has self-repairing performance.

  However, in the boiling water test, the molded plate of each example did not peel at all before and after the test and showed sufficient adhesion, but the molded plate of each comparative example was peeled after the test and the adhesion was not perfect I understood. Moreover, it turned out that wrinkles generate | occur | produced after the test and comparative example 1,2,4 is inferior to an external appearance. In each example and each comparative example, the polycarbonate resin base material and the polyurethane acrylate surface resin layer are the same, and it is understood that the adhesiveness is inferior at a molar ratio of 5.41 or more with the hydroxyl group of the isocyanate group in the adhesive layer.

Further, in the stamping molding test, each example was able to be molded with a good appearance and excellent in heat workability, but Comparative Examples 1 and 2 were inferior in heat workability due to generation of bubbles.
In addition, Comparative Example 3 has a good appearance in a boiling water test and a stamping molding test, but cannot be used as a molded plate due to extremely poor adhesion.

It is sectional drawing of the synthetic resin molding which shows one Embodiment of this invention. It is sectional drawing of the transfer sheet used for manufacture of the synthetic resin molding of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Resin base material 2 Adhesive layer 3 Resin surface layer 4 Release film

Claims (5)

  A molded body formed by forming a surface resin layer on at least one surface of a synthetic resin base material via an adhesive layer so that the molar equivalent of the isocyanate group of the polyisocyanate is greater than the molar equivalent of the hydroxyl group of the polyol. And a synthetic resin molding characterized in that it is formed from a polyurethane resin obtained by mixing and reacting a polyisocyanate and a polyol.   The synthetic resin molded article according to claim 1, wherein the isocyanate group of the polyisocyanate blended in the adhesive layer remains in the adhesive layer.   The molar equivalent ratio of the isocyanate group of the polyisocyanate forming the adhesive layer to the molar equivalent of the hydroxyl group of the polyol (isocyanate group molar equivalent / hydroxyl molar equivalent) is 1.0 <isocyanate group molar equivalent / hydroxyl molar equivalent. The synthetic resin molding according to claim 1 or 2, wherein ≦ 5.0.   The synthetic resin molded body according to any one of claims 1 to 3, wherein the surface resin layer is formed of a urethane acrylate resin.   It is a transfer film used for formation of the synthetic resin molding in any one of Claims 1 thru | or 4, Comprising: On the surface of a peeling film, the molar equivalent of the isocyanate layer of polyisocyanate and a resin layer is a polyol. A transfer film comprising an adhesive layer formed of a polyurethane-based resin obtained by mixing and reacting a polyisocyanate and a polyol so that the molar equivalent of a hydroxyl group is increased.

Images