JP5167240B2 - Synthetic resin molded body and laminate film or transfer film for molding the molded body - Google Patents

Description

  The present invention is a synthetic resin molded body excellent in self-healing property, particularly a synthetic material that can be subjected to secondary heat processing, having a self-repairing property that has a flawless adhesive layer that is promptly repaired even if the surface is scratched. The present invention relates to a resin molded body.

  A molded body made of a thermoplastic resin such as polycarbonate or polyethylene terephthalate is used for various applications as a building material, an industrial material, etc. by utilizing the transparency and impact resistance of the resin itself. 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.

  As such a silicone hard coat molded body with improved surface hardness, for example, a translucent film in which a silicone hard coat film is provided on a silicon oxide modified film formed on the surface of a translucent resin base material such as polycarbonate resin. Resin products are known (Japanese Patent Laid-Open No. 2005-305310: Patent Document 1). In Patent Document 1, since a silicon oxide-modified film is formed, a translucent resin product having good adhesion of the silicone-based hard coat film and excellent scratch resistance can be obtained.

  Moreover, as an acrylic hard-coat molded object, the hard-coat film which apply | coated and hardened the active ray hardening or the thermosetting acrylic composition to the film which consists of polyester or a polycarbonate is known, for example (Japan Unexamined-Japanese-Patent No. 2006-231845). : Patent Document 2). In Patent Document 2, an acrylic polymer having a low molecular weight is added to an acrylic composition to reduce the surface viscosity of the coating liquid and improve the surface smoothness.

JP 2005-305310 A JP 2006-231845 A

  However, although the translucent resin product of Patent Document 1 has a silicone-based hard coat layer, it has excellent hard coat properties. However, once scratched, the scratch exists for a long time without self-healing. Thus, the appearance was deteriorated and the product could not be subjected to secondary heat processing.

  Moreover, also in the hard coat film of the above-mentioned Patent Document 2, it is possible to obtain a film having good wear resistance, recoat property, and leveling property and excellent visibility. However, the acrylic hard coat layer is activated by active rays or heat. Since it was cured, once it was damaged, it could not be self-repaired and could not be subjected to secondary heat processing.

  An object of the present invention is to solve the above-mentioned problems, and to provide a synthetic resin molded article excellent in self-healing property, which recovers transparency by self-healing the scratch even if the surface is scratched. To do. It is another object of the present invention to provide a synthetic resin molded article excellent in self-healing property, which is laminated and integrated with an adhesive layer which is excellent in adhesion between a substrate and a surface resin layer and does not generate bubbles or wrinkles. Furthermore, it aims at providing the synthetic resin molded object which does not generate | occur | produce inconveniences, such as a crack and a flaw, even if a molded object is secondary-heat-processed.

Therefore, the synthetic resin molded body according to the present invention is 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,
The synthetic resin substrate is a substrate formed of a thermoplastic resin,
The surface resin layer is a layer formed of urethane acrylate resin, and this layer contains silica having an average particle diameter of 1 to 200 nm,
The molded article has a transparency with a total light transmittance of 75% or more and a haze of 5% or less, and the amount of change between the haze before the test for scratching the surface resin layer and the haze immediately after the test is 0. 3% or more, and after 5 minutes of the test, the synthetic resin molding for secondary heat processing is characterized by showing a haze at which the recovery rate obtained based on the following formula (1) is 50% or more. It is a body.
Here, the “secondary heat processing” synthetic resin molded body means a synthetic resin molded body “used for applications in which thermal processing is performed later”.

  This scratch imparting test is preferably performed only on the surface resin layer and is preferably performed using a brass brush.

In the present invention, the haze before the scratch imparting test of the molded product is 0.1 to 1.0%, the haze immediately after the test is 0.3 to 5.0%, and the change in haze before and immediately after the test is 0. in the range of .2～4.0%, it is not preferable haze recovery rate after 5 minutes elapsed wounds imparting test is 70% or more.

  Furthermore, the adhesive layer of the molded body in the present invention is formed from 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. It is preferable that Moreover, it is preferable that the isocyanate group of the polyisocyanate blended in the adhesive layer remains in the adhesive layer. Furthermore, the molar equivalent ratio between the molar equivalent of the isocyanate group of the polyisocyanate forming the adhesive layer and the molar equivalent of the hydroxyl group of the polyol is preferably 1.0 <isocyanate group molar equivalent / hydroxyl molar equivalent ≦ 5.0. .

The laminate film of the present invention is a laminate film used for molding these synthetic resin moldings for secondary heat processing, wherein the molar equivalent of the isocyanate group of the polyisocyanate is the hydroxyl group of the polyol on the surface of the adhesive film. An adhesive layer formed from a polyurethane-based resin obtained by mixing and reacting a polyisocyanate and a polyol and a silica having an average particle diameter of 1 to 200 nm were included so as to exceed the molar equivalent. The surface resin layer is laminated.

The transfer film of the present invention is a transfer film used for molding these synthetic resin moldings for secondary heat processing, and is formed of urethane acrylate resin on the surface of the release film and having an average particle diameter of 1 to 200 nm. It was formed from a surface resin layer containing silica and 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. The adhesive layer is laminated.

  The synthetic resin molded body of the present invention is a transparent molded body formed by forming a surface resin layer on the surface of a synthetic resin substrate, and before and after performing a scratching test using a brass brush or the like on the surface resin layer The haze change amount is 0.3% or more, and the haze recovery rate obtained by the above formula (1) is 50% or more. Therefore, sand or the like is rubbed against the transparent synthetic resin molded body by wind. If it hits, the surface resin layer will be scratched, haze will increase, it will become cloudy and the appearance will deteriorate. However, after a lapse of time, the scratches are self-repaired so that the appearance is not damaged, the haze is recovered, and a molded product having almost original transparency without any cloudiness is obtained. Therefore, the synthetic resin molded body of the present invention is a molded body having good scratch resistance. This self-healing property is considered to be that the wound is closed and restored by the elasticity of the resin around the wound over time, and the original transparency is restored by eliminating white turbidity due to light scattering. It is done.

  Further, the haze before the scratching test on the surface resin layer of the synthetic resin molded body is 0.1 to 1.0%, the haze immediately after the test is 0.3 to 5.0%, and the change in haze before and immediately after the test. When the amount is 0.2 to 4.0% and the recovery rate of haze after 5 minutes of the scratch application test is 70% or more, the molded article exhibits good transparency, and according to the scratch application test. If the surface resin layer is scratched, the haze increases and becomes cloudy and temporarily loses transparency, but after 5 minutes, it almost recovers to the haze before the test and has good transparency without the original cloudiness. A molded body having Therefore, even if the synthetic resin molded body is scratched by sand or the like and becomes cloudy, the cloudiness is temporary, and the scratches are closed by self-restoration over time, and the transparency is restored. Can be made into a molded body that exhibits for a long period of time.

  Moreover, when the surface resin layer is a urethane acrylate resin, the surface hardness is inferior to a hard coat layer made of a conventional silicone resin or acrylic resin, but is superior to a thermoplastic resin substrate such as polycarbonate or polyethylene terephthalate. Thus, scratch resistance can be imparted to the molded body. Moreover, since this urethane acrylate resin has a stretching property, it can also provide heat workability. Therefore, when the synthetic resin base material is formed of a thermoplastic resin, secondary heat processing such as thermal bending, pressure forming, and stamping can be performed.

  Since such a urethane acrylate resin has elasticity even at room temperature, even if a surface resin layer (molded body surface) made of this resin is scratched, the scratch is easily closed by the elasticity of the resin. It can be easily restored and restored to its original appearance, and can be visually observed as a scratch-free surface state. Therefore, even if the molded body is scratched and the light is irregularly reflected and temporarily clouded, after a while, the scratches are closed and restored to the original state, and the light is not irregularly reflected and the original white turbid transparent Can demonstrate its sexuality.

Moreover, the includes silica having an average particle diameter 1~200nm urethane acrylate resins or Ranaru surface resin layer, to a surface hardness is hardly scratched slightly improved, in the production by the laminate film press Peeling from molds and molding rolls is performed well, and the surface resin layer is peeled off from the release film at the time of manufacturing with a transfer film, so that a synthetic resin molded body having a good surface condition is obtained. In addition , transparency and silica dispersibility are also improved .

  On the other hand, the polyurethane resin obtained by mixing and reacting the polyisocyanate and the 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 in the adhesive layer of the synthetic resin molded body of the present invention. If formed, unreacted isocyanate groups react with active hydrogens 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, and are shared. Bonding can occur to improve adhesion. In addition, urethane bonds generate intermolecular forces such as hydrogen bonds to further improve the adhesion, and the adhesive layer solidifies in a state where the adhesive layer enters each other at the interface between the synthetic resin substrate and the surface resin layer. Adhesion can be demonstrated.

  In addition, this adhesive layer has a urethane bond between the hydroxyl group of the polyol and the isocyanate group of the polyisocyanate corresponding to the molar equivalent, so that it has stability against heat, water, etc. No wrinkles, wrinkles, etc., partial peeling, no delamination during actual use, and long-term use.

  Furthermore, by using a polyurethane-based resin for the adhesive layer, plasticity is exhibited by heating for secondary heat processing, and as described above, unreacted isocyanate groups are formed on the synthetic resin substrate and the surface resin layer. As the adhesiveness is improved by forming a covalent bond between the layers, it is possible to maintain the adhesion between the layers by heating and prevent the synthetic resin base material and the surface resin layer from peeling off, such as thermal bending. The secondary heat processing 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 is 1.0 <isocyanate group molar equivalent / hydroxyl molar equivalent ≦ 5.0. If so, the hydroxyl group reacts almost entirely, so the compatibility with water becomes poor, the adhesion at the boiling water test can be improved, and has a very good adhesion, the synthetic resin substrate and the surface resin It can be set as the synthetic resin molding which does not peel from a layer.

  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, when the adhesiveness at the time of boiling water test is bad, the problem of a crack and delamination will generate | occur | produce at the time of actual use outdoors. Therefore, it is preferable that the molar equivalent ratio is 1.0 <isocyanate group molar equivalent / hydroxyl molar equivalent ≦ 5.0 because the above problem can be eliminated.

The laminate film of the present invention comprises an adhesive layer formed from 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 greater than the molar equivalent of the hydroxyl group of the polyol. Since the laminate is laminated with a surface resin layer made of urethane acrylate resin and containing silica having an average particle diameter of 1 to 200 nm , the laminate film has flexibility and each layer is peeled even when wound on a paper tube There will be no wrinkles or traps. Further, since the adhesive layer is well bonded to the adhesive film by an anchor effect, a covalent bond, an intermolecular force, and the like, peeling, wrinkles, bubbles, and the like do not occur due to heat during lamination.

In the transfer film of the present invention, the molar equivalent of the isocyanate group of the polyisocyanate and the surface resin layer formed of urethane acrylate resin and containing silica having an average particle diameter of 1 to 200 nm is larger than the molar equivalent of the hydroxyl group of the polyol. In addition, it has an adhesive layer formed from a polyurethane-based resin that has been reacted by blending polyisocyanate and polyol, so the transfer film is flexible, and even if the transfer film is wound around a paper tube, each layer is peeled off It is possible to prevent dripping or wrinkles. The adhesive layer is sufficiently softened by heat at the time of transfer, sufficiently adhered to the soft surface of the resin base material, and can be bonded and bonded satisfactorily by an anchor effect, a covalent bond, an intermolecular force, and the like.

Because the the surface resin layer contains silica having an average particle diameter 1~200nm of such a laminate film or transfer film, Ya press die to which the silica-containing surface resin layer is used in the production by the laminate film Since it peels favorably from the forming roll and favorably peels off from the release film used in the production by the transfer film, a synthetic resin molded article having a good surface condition can be produced.

FIG. 1 is a cross-sectional view of a synthetic resin molded body showing one embodiment of the present invention. FIG. 2 is a cross-sectional view of a transfer film used in the production of the synthetic resin molding of the present invention. FIG. 3 is a cross-sectional view of a synthetic resin molded body showing another embodiment of the present invention. FIG. 4 is a cross-sectional view of a laminate film used in the production of the synthetic resin molding of the present invention. FIG. 5 is a perspective view of a heat-processed molded body obtained by hot stamping the synthetic resin molded plate of the present invention.

Explanation of symbols

P1, P2 Synthetic resin molding 1 Resin substrate 2 Adhesive layer 3 Surface resin layer 4 Release film 5 Adhesive resin layer F1 Transfer film F2 Laminate film

  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 molding according to an embodiment of the present invention, and FIG. 2 is a sectional view of a transfer film used for forming the synthetic resin molding.

The transparent synthetic resin molded product P1 of this embodiment has a thickness 0.1 in which the adhesive layer 2 and the surface resin layer 3 are laminated and integrated in this order on the surface of one side of the transparent plate-shaped resin substrate 1. The molded body has a total light transmittance of 75% to 98% and a haze of 5% to 0.1% or more. The surface resin layer 3 was subjected to a scratching test, and the amount of change in haze before and immediately after the test was 0.3% or more, and after 5 minutes of the test, the following formula (1) Is a molded article having a self-repairing property that exhibits a haze of 50% or more. Here, the haze immediately after the test refers to a haze obtained by measurement within 40 seconds after the scratch application test.

  When the above scratch imparting test is performed using a brass brush, only the surface resin layer can be easily scratched, which is preferable in measuring the self-healing property of the surface resin layer. Note that the adhesive layers 2 and 2 and the surface resin layers 3 and 3 may be laminated and integrated on both surfaces of the resin base material 1 to form a synthetic resin molded body having self-healing performance on both surfaces.

  The resin base material 1 of the transparent synthetic resin molding P1 of this embodiment is obtained by molding a transparent thermoplastic resin into a plate shape. Although this thermoplastic resin is not limited, for example, olefin resins such as polyethylene, polypropylene, and cyclic polyolefin, vinyl resins such as polyvinyl chloride, polymethyl methacrylate, and polystyrene, nitrocellulose, triacetyl cellulose, etc. Cellulose resins, polycarbonate, amorphous or crystalline polyethylene terephthalate, ester resins such as aromatic polyester, ABS resins, copolymer resins of these resins, mixed resins of these resins, and the like are 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 the synthetic resin molding of the present invention capable of secondary heat processing. In particular, thermoplastic polycarbonate has good impact resistance and transparency, and can be preferably used mainly as a base resin for outdoor use. Amorphous polyethylene terephthalate has good processability and is deep. It is preferably used as a base resin for use in secondary heat processing for drawing or the like. And since this polycarbonate and amorphous polyethylene terephthalate have poor surface hardness and are easily scratched, even if the surface resin layer 3 is provided on the surface to exhibit scratch resistance or scratches, as in the present invention, Applications can be further expanded by restoring the surface state by self-healing and restoring transparency.

  Additives such as plasticizers, stabilizers, antioxidants, ultraviolet absorbers and the like that are generally added to the molding of each resin are appropriately blended in the resin base material 1 to provide moldability, thermal stability, and weather resistance. Etc. are enhanced. 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. If it is the resin base material 1 of this invention synthetic resin molding which can be secondary-heat-processed, it is preferable when it is about 0.5-15.0 mm in order to exhibit the shaping | molding performance of secondary heat processing.

  In the transparent synthetic resin molded body P1 of this embodiment, the resin base material 1 is molded into a plate-like body, but may be molded into other irregular shapes. Further, the resin base material 1 may be a base material having transparency such as colored transparency or translucent by blending a filler or a colorant, but the total light transmittance of the synthetic resin molded body P1 is 75. % And haze of 5% or less are required, and therefore, the resin substrate 1 must have a total light transmittance of 75% or more and haze transparency of 5% or less. Preferably, the resin base material 1 has a total light transmittance of 85 to 98% and a haze of 0.1 to 1.0%.

  The adhesive layer 2 is for integrally bonding the resin base material 1 and the surface resin layer 3, and is made of thermoplastic resin such as acrylic resin, vinyl chloride resin, vinyl acetate, ethylene-vinyl acetate resin, polyurethane resin, epoxy It is made of a curable resin exhibiting plasticity such as a resin, an unsaturated polyester resin, or a silicone resin. These resins are appropriately added with additives such as ultraviolet absorbers, pigments, dyes, surface modifiers, polymerization initiators and the like that are generally added to each resin as necessary. It is preferable that these resins have translucency, particularly transparency, in producing the transparent synthetic resin molded product P1. However, even if the resin does not have translucency / transparency, by reducing the thickness, the adhesive layer 2 has translucency / transparency. It is not necessary to have sex. However, considering the integrated strength of adhesion between the resin base material 1 and the surface resin layer 3, a thickness of a certain level or more is required. Therefore, the transparent adhesive layer 2 having a total light transmittance of 75% or more and a haze of 5% or less. For this purpose, it is preferable to use a translucent resin. Further, in the case of the synthetic resin molded body P1 to be subjected to secondary heat processing, the adhesive layer 2 needs to be formed of a thermoplastic resin or a curable resin having a low crosslink density and having plasticity.

  In order for the curable resin to exhibit thermoplasticity, the thermosetting resin and the thermoplastic resin are copolymerized, or a curable monomer having a flexible group such as a long-chain alkyl group is polymerized. Thus, the crosslinking density is lowered.

  Among such adhesive layer resins, polyurethane resins, particularly polyurethane resins that are thermosetting resins that are not completely cross-linked and have low cross-link density and low plasticity, have heat resistance and water resistance. In addition to being softened by heating, it is preferably used as an adhesive layer resin for a laminate film, a transfer film, or a resin molded body capable of secondary heat processing. The polyurethane-based resin having a low crosslinking density is blended so that the hydroxyl group of the polyol and the isocyanate group of the polyisocyanate have a molar equivalent (hereinafter also referred to as equivalent), and all are urethane-bonded to form a three-dimensional structure. Polyisocyanate so that the isocyanate group equivalent of the polyisocyanate is greater than the hydroxyl equivalent of the polyol, in other words, the number of isocyanate groups contained in the polyisocyanate is greater than the number of hydroxyl groups contained in the polyol. And polyol are blended, and almost all of the hydroxyl groups are reacted with isocyanate groups, but the isocyanate groups of the polyisocyanate blended in excess remain unreacted and remain in the adhesive layer 2 in the polyurethane state. Those forming a resin are preferably used. Therefore, in the adhesive layer 2 using the polyurethane-based resin, urethane-bonded urethane resin and unreacted polyisocyanate are mixed.

  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 and the like are preferably used. As specific polyisocyanates, tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate and the like are preferably used.

  And it is preferable to mix | blend polyisocyanate and a polyol so that the molar equivalent ratio of the isocyanate group and a hydroxyl group may be 1.0 <isocyanate group molar equivalent / hydroxyl molar equivalent <= 5.0. When blended in this way, the unreacted polyisocyanate group is in contact with the synthetic resin substrate 1 and / or the surface resin layer 3 with active hydrogen such as hydroxyl group, amino group, imino group, carboxyl group, urethane bond, urea bond and the like. By reacting and generating a covalent bond to improve the adhesion, the adhesive bonding between the resin base material 1 and the surface resin layer 3 can be maintained, and the adhesion between the layers by heating for secondary heat processing is maintained and peeling is performed. Can be prevented. 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 2 even when the molded body is subjected to a boiling water test. Therefore, it is possible to obtain a synthetic resin molded article that does not cause peeling or poor appearance even when used for a long time.

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

  When the molar equivalent ratio (isocyanate group molar equivalent / hydroxyl molar equivalent) is 1.0, all of the isocyanate groups and hydroxyl groups react to form a three-dimensional structure, resulting in poor adhesion and lack of flexibility. In addition, when the molar equivalent ratio is less than 1.0, hydroxyl groups remain unreacted in the adhesive layer, and the hydroxyl groups have good compatibility with water, so the adhesion deteriorates due to boiling water during the boiling water test. However, there is a risk that bubbles, blisters, wrinkles, etc. are generated and peeled off. 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, there is a problem that cracks, delamination and appearance are deteriorated during actual use outdoors and the like, as described above, 1.0 <isocyanate group equivalent / It is preferable to satisfy the hydroxyl group equivalent ≦ 5.0 because the above problem can be eliminated. A more preferred 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 it is 0.1 μm or less, it is difficult to maintain the adhesive strength and the flexibility becomes poor, which is not desirable, and even if it is 10 μm or more, further improvement in adhesive strength and shape retention cannot be expected. It is a waste of money and transparency is also worsened.

  The surface resin layer 3 of the transparent synthetic resin molding P1 is formed of a thermoplastic synthetic resin, a curable resin that is cured by heat, ultraviolet rays, an electron beam, moisture, or the like, a synthetic resin that joins the cut end surfaces, rubber, or the like. It has a self-repairing property. As these synthetic resins, resins having resilience such as urethane resins, soft vinyl chloride, thermoplastic elastomers such as styrene, polyester, olefin, and fluorine are appropriately selected and used.

  The surface resin layer 3 can be formed by adding inorganic particles such as silica and glass, synthetic resin particles such as polymethyl methacrylate and silicone, and metal particles such as titanium oxide and aluminum oxide to these synthetic resins. preferable. The particles can improve the surface hardness of the surface resin layer 3 and improve the releasability from a press die and a molding roll when a synthetic resin molded product P1 is produced using a laminate film. The surface state of the surface resin layer 3 can be improved by improving the releasability from the release film when the synthetic resin molded body P1 is produced using. In particular, since silica has transparency, it is preferably used for forming the transparent surface resin layer 3. These particles are desirably contained in the surface resin layer 3 in an amount of 1 to 20% by mass, preferably about 3 to 10% by mass. Further, from the viewpoint of transparency and dispersibility, the average particle diameter is preferably 1 to 200 nm.

  In addition to the above particles, the surface resin layer 3 includes an ultraviolet absorber, a surfactant, a monomer, a polymerization initiator, a surface modifier, an antistatic agent, a pigment, a dye, a fluororesin, a silicone resin, and the like. It is formed by adding a general additive necessary for making a coating material or an additive for improving performance.

  Among these synthetic resins, urethane resins, after curing, have both surface hardness due to urethane-bonded hard segments and flexibility due to soft segments that are the remaining organic components of urethane-bonded polyol and polyisocyanate. Therefore, it is preferably used as a resin for the surface resin layer 3 of the molded body having a self-repairing function and having scratch resistance and secondary heat processing.

  Among the urethane-based resins, when the surface resin layer 3 is formed of a urethane acrylate resin or a urethane methacrylate resin, the surface hardness can be increased by the acrylate component or the methacrylate component, and the scratch resistance can be further imparted. Even if the surface resin layer 3 is scratched, it is particularly preferable because the surface resin layer 3 has a self-repairing property in which the scratch is closed by the elasticity of the soft segment of the surrounding resin and restored to the original surface state. In the description of the urethane-based resin used for the surface resin layer 3 below, the term (meth) acrylate is used to include both acrylate and methacrylate.

  As this urethane (meth) acrylate resin, (a) a urethane (meth) acrylate resin obtained by reacting an organic isocyanate having a plurality of isocyanate groups in one molecule and a polycaprolactone-modified alkyl (meth) acrylate, or (B) containing urethane (meth) acrylate obtained by reacting an organic isocyanate having a plurality of isocyanate groups in one molecule with polycaprolactone-modified alkyl (meth) acrylate, A urethane (meth) acrylate resin composed of two or more urethane (meth) acrylates having different numbers of repeating caprolactone units per caprolactone-modified alkyl (meth) acrylate residue, or (c) a plurality of urethane (meth) acrylate resins in one molecule Isocyanate Urethane (meth) acrylate resin obtained by reacting an organic isocyanate having a group with two or more polycaprolactone-modified alkyl (meth) acrylates having different numbers of repeating caprolactone units, or Urethane (meth) acrylate obtained by reacting organic isocyanate having an isocyanate group with polycaprolactone-modified alkyl (meth) acrylate, organic isocyanate having a plurality of isocyanate groups in one molecule, and hydroxyalkyl (meth) acrylate It is preferable that it is urethane (meth) acrylate resin containing urethane (meth) acrylate obtained by making these react. As the polycaprolactone-modified alkyl (meth) acrylate, polycaprolactone-modified hydroxyalkyl (meth) acrylate is particularly preferably used.

  Among these urethane (meth) acrylate resins, (e) an organic isocyanate having a plurality of isocyanate groups in one molecule, a polycaprolactone-modified hydroxy (meth) acrylate and a hydroxy (meth) acrylate different from this (particularly 1 A urethane (meth) acrylate resin obtained by reacting a hydroxy (meth) acrylic resin copolymerized with a polymer having a secondary hydroxyl group is preferably used. When this urethane (meth) acrylate resin (e) has a hydroxyl value of 125 to 145, the reactivity with the isocyanurate group of the organic isocyanurate is improved, and the contamination resistance and appearance of the surface resin layer are improved. This is preferable.

  Among the organic isocyanates, organic isocyanates having two isocyanate groups per molecule include tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2. Diisocyanate monomers such as 1,4-trimethylhexamethylene diisocyanate, methyl-2,6-diisocyanate hexanoate, norbornane diisocyanate are preferably used. In addition, as an organic isocyanate having three or more isocyanate groups in one molecule, a compound represented by the following structural formula (A) in which a diisocyanate monomer is isocyanurate-modified, and a structural formula in which a diisocyanate monomer is adduct-modified (in the following structural formula) B), isocyanate compounds such as a compound represented by the following structural formula (C) obtained by biuret modification of a diisocyanate monomer, 2-isocyanatoethyl-2,6-diisocyanate caproate, triaminononane triisocyanate, etc. A polymer is preferably used.

  On the other hand, the polycaprolactone-modified alkyl (meth) acrylate or polycaprolactone-modified hydroxyalkyl (meth) acrylate is a compound represented by the following structural formula (D). As specific examples, polycaprolactone-modified hydroxyethyl (meth) acrylate, polycaprolactone-modified hydroxypropyl (meth) acrylate, polycaprolactone-modified hydroxybutyl (meth) acrylate, and the like are preferably used. As the caprolactone used in these, ε-caprolactone, trimethylcaprolactone and the like are preferably used.

  Furthermore, the hydroxyalkyl (meth) acrylate is a compound represented by the following structural formula (E), and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like are preferably used. .

  Furthermore, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. are preferably used as the hydroxy (meth) acrylate having a primary hydroxyl group.

  These urethane (meth) acrylates may contain two or more urethane (meth) acrylates having different numbers of repeating caprolactone units per polycaprolactone-modified alkyl (meth) acrylate residue. Furthermore, the urethane (meth) acrylate may contain urethane (meth) acrylate obtained by reacting an organic isocyanate having a plurality of isocyanate groups in one molecule with hydroxyalkyl (meth) acrylate. Furthermore, it is preferable to improve the scratch resistance by adding a monomer having a cyclic skeleton such as styrene, or to adjust the polymerization reactivity by adding a monomer such as methyl (meth) acrylate, A polymerization initiator is added.

  The surface resin layer 3 made of a urethane acrylate resin obtained by reacting such a monomer or copolymer resin has self-healing properties, and is used for surface resin with sand, pebbles, rags, brushes, scrubbing brushes, sponges, etc. Even if the surface of the layer 3 is scratched, the scratch is blocked by the elasticity of the surrounding resin, particularly the soft segment in the resin, and recovers to the original surface state over time, so that the scratch becomes invisible. Even if the hardness is inferior to the surface resin layer formed of a silicone hard coat agent or an acrylic resin hard coat agent, the surface resin layer 3 is hardly scratched, and the molded body having the surface resin layer 3 has scratch resistance. It will have. Moreover, since the surface resin layer 3 made of urethane acrylate resin has elasticity, if the resin base material 1 is formed of a heat-processable thermoplastic resin, it can be formed into a heat-processable molded body. It is particularly useful as the surface resin layer 3 of the plate for outdoor secondary heat processing for forming a deformed shape to be used outdoors.

  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, and even the surface resin layer 3 made of urethane acrylate resin has poor self-repairing properties. On the other hand, even when the thickness is 100 μm or more, further improvement in self-repairability cannot be expected, which is undesirable because it wastes material. More preferably, it is 5-20 micrometers.

  And since the resin base material 1, the adhesive layer 2, and the surface resin layer 3 are all transparent synthetic resin moldings P1 which are translucent or transparent, light is irregularly reflected by the said damage | wound etc., and becomes cloudy temporarily. Loss of transparency, but as time passes, the scratches are closed and restored to the original surface state, so that there is no irregular reflection, so that the original transparency can be almost exhibited, and the transparency is maintained over a long period of time. It becomes the transparent molded object P1 which can do. However, when the scratch reaches the adhesive layer 2 and further to the resin substrate 1, the scratch on the surface resin layer 3 is restored to the original state, but the scratch on the adhesive layer 2 and the resin substrate 1 can be repaired. Since it is still scratched, it is diffused by the scratch and becomes cloudy, so that it does not have a self-repairing property as a molded body. Further, when the surface resin layer 3 disappears due to friction, wear, or the like, the self-repairing property does not exist.

  In particular, since the synthetic resin molded product P1 has transparency with a total light transmittance of 75% or more and a haze of 5% or less, the self-repairing function is effectively exhibited, and the surface resin layer 3 is made of sand or the like. Even if it becomes scratched and becomes cloudy, it self-repairs with the passage of time, resulting in a transparent synthetic resin molded product having substantially the same total light transmittance and haze. The preferable total light transmittance of the synthetic resin molding P1 is 80% or more, the haze is 3% or less, the most preferable total light transmittance is 85 to 98%, and the haze is 0.1 to 1.0%.

  Then, when a scratching test is performed on the surface resin layer 3 of the transparent synthetic resin molded body P1 having the above-described configuration, the surface resin layer 3 is formed of a resin, particularly a urethane acrylate resin. The surface (surface resin layer 3) is scratched and light is diffusely reflected to increase haze. The amount of change in haze before and immediately after the test (the haze before the test was subtracted from the haze measured within 40 seconds after the test). Value) is 0.3% or more. The increased haze is also damaged by the urethane acrylate resin forming the surface resin layer 3 with time, the surface state is restored to the original state, and the irregular reflection of light is reduced. After 5 minutes of the application test, it almost recovers to the haze before the test. In this recovery, by making the recovery rate obtained by the formula (1) 50% or more, the self-repairing property is surely exhibited and the transparency can be almost recovered. A more preferable recovery rate is 70% or more, most preferably 85% or more.

  This scratch imparting test needs to be a test for scratching only the surface resin layer 3, and in the test reaching the adhesive layer 2 and further to the resin base material 1, the scratches on the adhesive layer 2 and the resin base material 1 are damaged. This is because the transparency cannot be restored because it cannot be repaired. Specifically, for example, a brass material having a cylindrical shape with a diameter of 0.08 to 0.2 mm, a brass brush in which a large number of these brass materials are uniformly arranged, and a plurality of bundling materials in which a large number of brass materials are bundled. Using a brass brush arranged individually, a brass brush with many brass materials attached to the handle, brass wool made of brass fibers, blades such as knives, steel wool, cloth, taber wear wheels, sandpaper, etc. Only the surface resin layer 3 is damaged by these. Particularly preferable is the above-mentioned one made of brass, particularly a brass brush, and other materials are too hard and may damage the adhesive layer 2 and the resin base material 1.

  As the brass brush, for example, “Brass Brush 4 Lines” which are brass brushes made by TRUSCO NAKAYAMA CORPORATION (the brass material is round, the diameter is about 0.15 mm, and the length of the brass material is about 16 mm). , A brush in which 58 bundles of about 60 brass materials are arranged in 4 rows and fixed to a wooden handle, and the present inventors press this against the surface resin layer 3 with a force of 1 kg. Thus, only the surface resin layer 3 could be damaged by sliding back and forth. Many other brass brushes such as those manufactured by Topman Co., Ltd., Kyoto Machine Tool Co., Ltd., and MonotaRO Co., Ltd. are commercially available.

  Even if the haze of the molded product before performing the scratching test on the surface resin layer 3 in the synthetic resin molded product P1 is 0.1 to 1.0%, the surface resin layer Since 3 is formed of a resin, particularly a urethane acrylate resin, the haze measured within 40 seconds after the test becomes as high as 0.3 to 5.0% and becomes cloudy, and the amount of change in haze before and after the test. Is 0.2 to 4.0%. Thus, the synthetic resin molded product P1 having the surface resin layer 3 formed of urethane acrylate resin is easily damaged and inferior in surface hardness than the surface resin layer formed of a hard coating agent such as silicone. However, the surface hardness of the resin base material 1 is improved, and a molded body having a certain surface hardness or more is obtained. After 5 minutes after the scratch application test, the scratches were closed as described above and the original state was restored, and the transparency was restored. The recovery rate of the haze was 70% or more, and the transparency before the test was Is almost maintained.

  And if the resin base material 1 is formed of a thermoplastic resin and the surface resin layer 3 is a transparent resin molded product P1 formed of a urethane acrylate resin, the synthetic resin molded product P1 has scratch resistance. It is hard to be scratched and / or self-healing properties are exhibited even if scratched, and the scratch is repaired, so that the original total light transmittance and haze can be substantially restored, and thermal processing can be performed. Therefore, the window glass and windshield of vehicles such as automobiles and motorcycles that are rubbed by the wind being blown away by the wind, or the machine tool cover where the machine tool hits, the inspection window of the machine tool room, or the construction used outdoors For applications that require transparency and scratch resistance, such as protective plates for machine windows or touch panels for human touch panels, especially for applications that require secondary heat workability in addition to the above. It becomes a useful molded object. As the thermal processing, in addition to the above-described hot stamping processing, known thermal processing methods such as pressure forming, vacuum forming, and hot bending are appropriately used.

  In order to obtain the synthetic resin molding P1 having the above-described configuration, for example, a transfer method, a direct coating method, or the like can be used.

  When using the transfer method, as shown in FIG. 2, after forming a release layer on one side of a release film 4 such as biaxially stretched polyethylene terephthalate, if necessary, a surface made of a synthetic resin such as the above urethane acrylate resin The surface resin layer 3 is formed by applying a resin layer coating, heating and drying, and curing, and then, on this surface resin layer 3, a polyol and a polyisocyanate are mixed so that more isocyanate groups are contained than hydroxyl groups. An adhesive layer 2 is formed by applying a coating for the adhesive layer, heating and drying to cure, and a transfer film F1 in which the release film 4, the surface resin layer 3, and the adhesive layer 2 are laminated in this order is produced. Take up the tube. Then, the transfer film F1 is stacked on the surface of the extruded synthetic resin sheet 1 (resin base material 1) so that the adhesive layer 2 is on the synthetic resin sheet 1 side, and heat-pressed, and the release film 4 is peeled off. Thus, by transferring the adhesive layer 2 and the surface resin layer 3, it is possible to manufacture a synthetic resin molded body P1 in which the resin base material 1, the adhesive layer 2, and the surface resin layer 3 are laminated and integrated.

  If the transfer film F1 is applied to both surfaces of the synthetic resin sheet and transferred, a synthetic resin molded body in which the adhesive layers 2, 2 and the surface resin layers 3, 3 are laminated and integrated on both surfaces of the resin base material 1 is obtained. Can be manufactured. In addition, the synthetic resin molded body is formed by stacking the transfer film F1 on the upper surface or both upper and lower surfaces of the resin base material 1 made of a plurality of calendar sheets to be press-molded, and integrating them by hot pressing, and then the release film 4 is formed. It can also be manufactured by peeling.

  Since the surface resin layer 3 of the transfer film F1 is formed of urethane acrylate resin or the like, it has a certain degree of flexibility and can be wound on a paper roll or the like. Since the adhesive layer 2 remains part of the isocyanate group without reacting as described above, when the adhesive layer 2 is thermocompression bonded to the synthetic resin sheet 1, it adheres sufficiently to the soft surface of the sheet 1 and has an anchor effect. In addition, it is possible to obtain a good bonding force by intermolecular force such as hydrogen bonding. Further, since the adhesive layer 2 has flexibility, even if the transfer film F1 is wound around a paper tube or the like, the layer 2 can prevent a layer from peeling or wrinkling due to a cushioning action. . For this reason, the synthetic resin molding P1 manufactured using the transfer film F1 having the adhesive layer 2 has good adhesion, bonding and integration of each layer, and does not peel off even when used for a long time.

  When using the direct coating method, a synthetic resin plate (resin base material 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 base material 1) and dried by heating. Then, the cured adhesive layer 2 is formed, and then the surface resin layer coating material is applied thereon, heated and dried, and cured to form the surface resin layer 3, whereby the resin substrate 1 and the adhesive layer are formed. Synthetic resin molding P1 in which 2 and the surface resin layer 3 are laminated can be easily manufactured.

  FIG. 3 is a cross-sectional view showing a synthetic resin molded body according to another embodiment of the present invention, and FIG. 4 shows a laminate film used for forming the synthetic resin molded body.

  The synthetic resin molding P2 of this embodiment is a molding in which the adhesive resin layer 5, the adhesive layer 2, and the surface resin layer 3 are laminated and integrated in this order on the surface of one side of the transparent plate-shaped resin base material 1. The transparent synthetic resin molded product P2 has a total light transmittance of 75% to 98% and a haze of 5% to 0.1%. The surface resin layer 3 was subjected to a scratching test, and the amount of change in haze before and immediately after the test was 0.3% or more, and after 5 minutes of the test, the formula (1) Is a molded article having a self-repairing property that exhibits a haze of 50% or more. Since the resin base material 1, the adhesive layer 2, and the surface resin layer 3 of the transparent synthetic resin molded body P2 are the same as those of the synthetic resin molded body P1, the same reference numerals are given and description thereof is omitted.

  The adhesive resin layer 5 is a layer made of a resin excellent in adhesiveness with the base resin 1 such as an acrylic resin, a polycarbonate resin, a vinyl acetate resin, and an ethylene-vinyl acetate resin. It is preferable that the adhesive resin layer 5 has a thickness of 30 to 300 μm, a total light transmittance of 75% or more, and a haze of 5% or less so as to have transparency.

  In order to obtain the transparent synthetic resin molded product P2, for example, a method such as a laminating method or a direct coating method can be used.

  When the laminating method is used, as shown in FIG. 4, the adhesive layer 2 is obtained by applying the adhesive layer coating material to a film (adhesive resin layer) 5 made of an adhesive resin such as an acrylic film, and curing it by heating and drying. Next, the surface resin layer 3 is formed by applying the surface resin layer coating material, applying heat drying and curing, and the laminate film F2 is produced. Then, by laminating the laminate film F2 on the synthetic resin sheet 1 (resin base material 1) formed by extrusion, the resin base material 1, the adhesive resin layer 5 (acrylic film), the adhesive layer 2, and the surface resin layer 3 are obtained. Can be produced. In addition, it can manufacture also by laminating | stacking the laminate film F2 on the upper surface or both upper and lower surfaces of the resin base material 1 which consists of a some calendar sheet | seat for press-molding, and integrating by hot press molding. If the transfer film F2 is applied to both surfaces of the synthetic resin sheet and transferred, a synthetic resin molded body in which the adhesive layers 2, 2 and the surface resin layers 3, 3 are laminated and integrated on both surfaces of the resin base material 1 is obtained. Can be manufactured.

  When using the direct coating method, a synthetic resin plate (resin base material 1) is prepared in advance by extrusion molding or press molding, and an adhesive resin layer coating made of an adhesive resin such as an acrylic resin is applied, dried and bonded. The resin layer 5 is formed, and then the adhesive layer paint is applied thereon, heated and dried to form the adhesive layer 2, and then the surface resin layer paint is applied thereon and heated. By forming the dried and cured surface resin layer 3, the synthetic resin molded body P2 in which the resin base material 1, the adhesive resin layer 5, the adhesive layer 2, and the surface resin layer 3 are laminated can be easily manufactured. .

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

(Examples 1-7)
Urethane obtained by diluting a urethane methacrylate resin paint “Self-healing clear (trade name, registered trademark No. 4687902) No. 3000” with a solvent (methyl isobutyl ketone) on a biaxially stretched polyethylene terephthalate film having a thickness of 50 μm. A methacrylate coating solution was applied, dried by heating and cured to form a surface resin layer (dry thickness 10 μm). Next, an ester polyol coating solution (resin content: 30.0%) in which an ester polyol having a hydroxyl group molar equivalent of 3206 is dissolved in a solvent, and a polyisocyanate (resin component: 100.0%) having an isocyanate group molar equivalent of 198 ) And 100: 0, 100: 1, 100: 2, 100: 3, 100: 4, 100: 5, 100: 10, and mixed at different mixing ratios (mass ratio), and an isocyanate group and a hydroxyl group 7 equivalent urethane coating liquids having a molar equivalent ratio (isocyanate group / hydroxyl group) of 0.00, 0.54, 1.08, 1.82, 2.16, 2.70, and 5.41 were obtained. Seven types of transfer films were prepared by forming adhesive layers (thickness: 2 μm) obtained by applying each urethane coating solution to the surface resin layer, followed by drying by heating and curing.

  Then, while extruding the polycarbonate resin to a transparent sheet having a thickness of 5 mm (“Polycarbonate sheet PC1600” manufactured by Takiron Co., Ltd.), the adhesive layer of each transfer film is pressed against the sheet surface and thermocompression bonded to integrate the layers. After that, the biaxially stretched polyethylene terephthalate film is peeled off to transfer the adhesive layer and the surface resin layer, and the polycarbonate resin base material, the adhesive layer, and the surface resin layer are laminated in this order in a three-layer transparent polycarbonate resin molding I got a plate. These are referred to as Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, and Example 7.

  Based on JIS K7361-1, transparency of the transparent polycarbonate resin molded plate of each Example was examined for total light transmittance and haze using a direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. The results are shown in Tables 1 and 2.

  Further, the surface hardness of the molded plate of each example was examined by pencil hardness based on JIS K5400. The results are also shown in Tables 1 and 2.

  In addition, a self-repairing property was measured using a brass brush (“Tsuco Nakayama Co., Ltd.” “Toki” manufactured by Shinto Kagaku Co., Ltd., using a surface property measuring instrument, TYPE-HEIDON-14, at an ambient temperature of 23 ° C. and a load of 1 kg. A scratch imparting test was conducted, in which four rows of handle brass brushes)) were pressed and scratched by reciprocating 10 times at a speed of 5 m / min. After about 30 seconds had passed after the scratch application test, the haze was examined in the same manner as described above, and this was defined as the haze immediately after the scratch application test. Further, the haze after 5 minutes from the test was examined in the same manner as described above, and this was defined as the haze after 5 minutes from the scratching test. These results are also shown in Tables 1 and 2. Further, before the scratch application test, about 30 seconds after the test, and from each haze when 5 minutes passed after the test, the amount of haze change before and after the test and the haze recovery rate were calculated according to the above formula (1). . The results are also shown in Tables 1 and 2.

  Moreover, the surface state of the molded plate when 5 minutes passed after the test was observed from a location 50 cm away, and it was examined whether or not the scratch was visible. The results are also shown in Tables 1 and 2. “No” was marked on the molded plate where the scratch was not visible, and “Yes” was marked on the molded plate where the scratch was visible. From these haze, haze change amount, haze recovery rate, and results of visual observation, self-repair performance was comprehensively determined.

  Further, the cross-layer adhesion of the surface resin layer 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 Tables 1 and 2. ◯ 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.

  Further, in order to investigate the thermal processability, a male mold and a female mold having a radius of 50 mm were prepared, each molded plate was dried and then heated (220 ° C., 5 minutes), and a surface resin layer was formed between the male mold and the female mold. Were pressed so as to be on the female mold side, and embossing was performed to obtain each heat-processed molded body P3 having a semicircular convex semi-cylindrical portion with a radius of 50 mm as shown in FIG. The surface of the convex semi-cylindrical portion of each heat-processed molded body P3 was observed and examined for the presence of defects such as whitening, wrinkles, bubbles, and cracks. The results are also shown in Tables 1 and 2. The mark was given to the molded product P3 having no defect, and the state was written to the molded product P3 having the problem.

(Examples 8, 9, and 10)
Colloidal silica ("MIBK-ST" manufactured by Nissan Chemical Industries, Ltd.) is blended with the urethane methacrylate resin paint 100 used in Example 1 so as to have a mass ratio of 5, 10 and 15, and these are used as solvents. Three types of silica-containing urethane methacrylate coating solutions diluted with (methyl isobutyl ketone) were prepared. A transfer film was prepared and transferred to a polycarbonate sheet in the same manner as in Example 4 except that each coating solution was used, thereby obtaining three types of three-layered transparent polycarbonate resin molded plates. These are referred to as Example 8, Example 9, and Example 10.

  About the transparent resin molding plate of each of these Examples 8, 9, and 10, each measurement and test of transparency, surface hardness, self-healing property, boiling water test, and embossing molding were performed in the same manner as in Example 1. The results are also shown in Tables 1 and 2.

(Example 11)
The ester-based 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 1.82, and further to the mixed solution 100 On the other hand, colloidal silica ("MEK-ST" manufactured by Nissan Chemical Industries, Ltd.) was added and mixed so as to have a mass ratio of 20 to prepare a silica-containing urethane coating liquid for an adhesive layer. Then, except that this silica-containing urethane coating liquid for the adhesive layer was used, a transfer film was prepared and transferred to a polycarbonate sheet in the same manner as in Example 4, thereby forming a transparent polycarbonate resin molded plate having a three-layer structure. Got. This is Example 11.

  For the transparent resin molded plate of Example 11, each measurement and test of transparency, surface hardness, self-healing property, boiling water test, and embossing was performed in the same manner as in Example 1. The results are also shown in Tables 1 and 2.

(Comparative Example 1)
The biaxially stretched polyethylene terephthalate film used in Example 1 was coated with an acrylic paint (UV-curable silicone-modified acrylic paint “UVHC3000” manufactured by GE Toshiba Silicone Co., Ltd.), dried, and then cured by irradiation with ultraviolet rays to obtain a surface resin. A layer (thickness 4 μm) was formed. Next, using the urethane coating liquid having an equivalent ratio of hydroxyl group and isocyanate group used in Example 4 of 1.82, the urethane coating liquid is applied on the surface resin layer, and is heated and dried to be cured. A transfer film was produced by forming an adhesive layer (thickness: 2 μm). Then, it transferred to the transparent polycarbonate sheet of thickness 5mm like Example 4, and obtained the transparent resin molding plate of the comparative example 1 of 3 layer structure.

  As with Example 1, the transparent resin molded plate of Comparative Example 1 was measured and tested for transparency, surface hardness, self-repairability, boiling water test, and embossing. The results are also shown in Tables 1 and 2.

(Comparative Example 2)
The biaxially stretched polyethylene terephthalate film used in Example 1 is coated with a silicone-based hard coat paint (polysiloxane-based hard coat treatment agent “NP730” manufactured by Nippon Dacro Shamrock Co., Ltd.), heat-dried and cured to provide a hard coat function. A surface resin layer having a thickness of 3 μm was formed. Next, in the same manner as in Comparative Example 1, a transfer film on which an adhesive layer (thickness 2 μm) was formed was produced. Then, it transferred to the transparent polycarbonate sheet of thickness 5mm like Example 4, and obtained the transparent resin molding plate of the comparative example 2 of 3 layer structure.

  As with Example 1, the transparent resin molded plate of Comparative Example 2 was measured and tested for transparency, surface hardness, self-repairability, boiling water test, and stamping. The results are also shown in Tables 1 and 2.

(Comparative Example 3)
A resin substrate made of transparent polycarbonate resin having a thickness of 5 mm extruded in each example (polycarbonate sheet PC1600 manufactured by Takiron Co., Ltd.) was produced, and the transparency, Each measurement and test of surface hardness, self-repairability, and stamping was performed. This is referred to as Comparative Example 3, and the results are also shown in Tables 1 and 2.

  As can be understood from Table 1 and Table 2, in all of the examples and comparative examples, the total light transmittance is 89% or more, and the haze is 0.7% or less. It has the performance as a molded plate.

  Further, the pencil hardness is 4B in Comparative Example 3 which is a polycarbonate sheet of a resin base material, whereas each Example in which the resin of the surface resin layer is a polyurethane methacrylate resin is 3B. It is better than the material. On the other hand, Comparative Example 1 in which the surface resin layer was made of silicone-modified acrylic resin was HB, and Comparative Example 2 made of silicone resin was 2B, and the surface hardness was higher than in each Example. As described above, the surface hardness of the surface resin layer made of the urethane methacrylate resin of each example is better than that of the polycarbonate resin base material, but is inferior to the surface resin layer made of the silicone-modified acrylic resin and the silicone resin. It turns out that it is easy to be attached.

  In the scratch application test for examining self-repairability, each example had a haze of 0.4 to 0.7% before the test, and a haze of 30 seconds after the test was 1.0 to 1.3%. The haze change amount was 0.5 to 0.8%, and scratches were attached, resulting in poor transparency. And when 5 minutes passed, it changed to 0.4-0.7%, and it has substantially recovered | restored even to the haze before a test. When the recovery rate was calculated based on the formula (1), it was 60 to 100%. Furthermore, in the visual observation of the surface state after 5 minutes from the test, it was found that in each example, the scratches were not observed and the transparency was recovered.

  Thus, it can be seen that in each example, the surface resin layer has self-healing performance, and the original transparency can be recovered and maintained even if the molded plate is damaged. And in Examples 8, 9, and 10 in which silica was added to the surface resin layer, the haze recovery rate of Example 10 was 60%, which was worse than that of the other examples. From this result, it is understood that up to 10 mass ratio is preferable when silica is added to the surface resin layer.

  However, Comparative Example 1 having a silicone-based acrylic resin surface resin layer had a haze of 0.5% before the test, 0.5% immediately after the test, and 0.5% even after 5 minutes of the test. There is no change, the surface resin layer is not scratched, and the self-healing performance is unknown. Comparative Example 2 having a silicone resin surface resin layer was a surface resin layer having a haze of 0.5% before the test and increased to 0.7% immediately after the test, and having a surface hardness but having scratches. It was. And even if 5 minutes of a test passes, it does not change with 0.7%, and it turns out that the damage | wound remains on the surface resin layer as it is, and it does not self-repair. Further, Comparative Example 3 of the polycarbonate resin base material showed transparency of 0.4% before the test, but it was very bad at 24.2% immediately after the test and was easily damaged. Even after 5 minutes of the test, it did not change to 24.2%, and the scratch remained on the surface of the resin base material and was not self-repaired.

  Moreover, in the boiling water test, 90 or more of 100 resin plates of each example except Example 7 did not peel, and showed practical adhesion. Although Example 7 was peeled off, it was not peeled off by the cross-cut test before the test, and had sufficient adhesion unless exposed to severe conditions similar to the boiling water test. Of the examples, Examples 2, 3, 4, 5, 6, 8, 9, and 10 are those in which 95 or more pieces are not peeled off, exhibit sufficient adhesion, and the laminated board on which the polycarbonate resin molded plate does not peel off. It can be seen that it is. In Examples 3, 4, 5, 6, 8, 9, and 10, defects such as wrinkles and cracks did not occur even in the appearance observation after the boiling water test. It was. However, Examples 1 and 11 were worse than the other examples in the appearance observation in the tape peeling results. On the other hand, both Comparative Examples 1 and 2 were peeled off in the tape peeling test, and in addition, wrinkles and cracks were observed in the appearance observation, indicating that they were not in close contact.

  From the results of these boiling water tests, it can be seen that each example has better adhesion than each comparative example. It turns out that it is excellent in adhesiveness especially when the molar equivalent ratio with the hydroxyl group of the isocyanate group in an contact bonding layer is 0.54 or more and less than 5.41. In particular, the resin molded plate having an adhesive layer having a molar equivalent ratio of 1.08 to 2.70 was a very excellent result in the tape peeling test and appearance observation.

  Furthermore, in the press-molding test, Examples 3 to 11 were excellent in thermoforming with good appearance and excellent in heat workability. In Examples 1 and 2, although heat processing was possible, bubbles were generated and slightly heat workability was achieved. It was inferior to. On the other hand, in Comparative Examples 1 and 2, cracks occurred, and the heat-processed molded bodies were clouded and did not have transparency, had poor appearance, and did not have scratch resistance.

  From the results of the above tests, a transparent polycarbonate resin molding in which the surface resin layer is formed of a urethane acrylate resin and the adhesive layer is formed of a urethane resin having a molar equivalent ratio of isocyanate groups to hydroxyl groups of 1.08 to 2.70. The plate has good self-healing properties, and even if the surface is scratched with sand, etc., the scratches are repaired and the transparency can be restored, the adhesion of each layer is also good and the delamination is difficult, and further, stamping molding etc. It can be seen that this is a practical resin molded plate that can be thermally processed.

  Even if the transparent synthetic resin molding of the present invention is scratched by sand or the like and the transparency is lowered, the scratch is self-repaired and the transparency is restored over time, and the transparency can be maintained for a long time. . Therefore, it can be used for window glass and windshields of vehicles such as automobiles and motorcycles, protective plates for construction machines, and inspection windows for machine tool rooms.

Claims (8)

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,
The synthetic resin substrate is a substrate formed of a thermoplastic resin,
The surface resin layer is a layer formed of urethane acrylate resin, and this layer contains silica having an average particle diameter of 1 to 200 nm,
The molded article has a transparency with a total light transmittance of 75% or more and a haze of 5% or less, and the amount of change between the haze before the test for scratching the surface resin layer and the haze immediately after the test is 0. 3% or more, and after 5 minutes of the test, the synthetic resin molding for secondary heat processing is characterized by showing a haze at which the recovery rate obtained based on the following formula (1) is 50% or more. body.

The haze of the molded body before scratching test is 0.1 to 1.0%, the haze immediately after the test is 0.3 to 5.0%, and the change in haze before and immediately after the test is 0.2 to 4%. The synthetic resin molding for secondary heat processing according to claim 1, wherein the synthetic resin molding is in the range of 0.0% and the haze recovery rate after 5 minutes of the scratching test is 70% or more. The synthetic resin molding for secondary heat processing according to claim 1 or 2, wherein the scratch imparting test is performed using a brass brush. The adhesive layer 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. The synthetic resin molding for secondary heat processing in any one of Claim 1 thru | or 3 . The synthetic resin molding for secondary heat processing according to claim 4 , wherein the isocyanate group of 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 is 1.0 <isocyanate group molar equivalent / hydroxyl molar equivalent ≦ 5.0. The synthetic resin molding for secondary heat processing of Claim 4 or Claim 5 . It is a laminate film used for shaping | molding the synthetic resin molding for secondary heat processing in any one of Claim 1 thru | or 6 , Comprising: The molar equivalent of the isocyanate group of polyisocyanate is on the surface of an adhesive film. An adhesive layer formed from a polyurethane-based resin obtained by mixing and reacting a polyisocyanate and a polyol so as to exceed the molar equivalent of the hydroxyl group of the polyol, and a silica formed from a urethane acrylate resin and having an average particle diameter of 1 to 200 nm A laminate film, wherein a surface resin layer containing is laminated. It is a transfer film used for shaping | molding of the synthetic resin molding for secondary heat processing in any one of Claim 1 thru | or 6 , Comprising: It forms on the surface of a peeling film from urethane acrylate resin, and average particle diameter and a surface resin layer silica was included in the 1 to 200 nm, so that the molar equivalent of the isocyanate groups of the polyisocyanate is greater than the molar equivalent of the hydroxyl groups of the polyol, polyurethane resin reacted by blending a polyisocyanate and a polyol A transfer film characterized in that an adhesive layer formed thereon is laminated.

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