JP5680941B2 - Resin glazing laminate - Google Patents

Description

  The present invention relates to a resin glazing laminate that has excellent adhesiveness necessary for fixing to a structural member and can achieve good design.

  Conventionally, attempts to replace glass glazing with glazing made of transparent thermoplastic resin have been extensively carried out in order to achieve weight reduction, improved safety, and utilization in a manner impossible with glass. In the field of transportation equipment represented by automobiles, in particular, attempts are being made to replace glass glazing with polycarbonate resin glazing having good impact resistance. In the field of transport aircraft, weight reduction is an essential and urgent issue. As a result, attempts to replace such glass are spurred further. However, while there are numerous proposals, its replacement, especially in the automotive field, has not made much progress. One of the main reasons why substitution has not progressed while there is a strong demand for weight reduction is the high cost of resin glazing.

  The present applicant has already made a method of manufacturing a member in which a frame member attached to a structural member such as a vehicle body is integrated with a resin window by a multicolor molding method, wherein the frame member is made of a polycarbonate resin and a polyethylene terephthalate resin. The manufacturing method which is a composition was proposed (refer patent document 1). While this method is excellent in productivity, it requires a mold for multicolor molding. The initial investment for manufacturing the mold is large. Thus, this method is suitable for mass production but not very suitable for small-scale production.

  In recent years, due to the increase in environmental awareness, there is a tendency for the use of resin glazing for the purpose of weight reduction even in a relatively small-volume production vehicle or a limited number of vehicles such as an electric vehicle. Accordingly, there is a demand for a resin glazing laminate that can be used in small-volume production. In the case of resin glazing, there are a hard coat layer for improving the scratch resistance, and an ink layer for protecting and concealing the urethane adhesive layer (in the case of black, it may be referred to as a blackout layer). Needed.

  As a configuration of the laminate, a configuration in which a hard coat layer is provided on a resin substrate and then a blackout layer is provided on the layer (referred to as “configuration-A” in this description) has been proposed (Patent Literature). 2 and 3). However, in the case of glazing having a curved shape, in Configuration-A, a hard coat layer and a blackout layer are provided after a predetermined curved surface is formed. There was a problem that formation was difficult.

  In addition, a configuration in which a blackout layer is provided on a resin substrate and then a hard coat layer is provided on the layer (referred to as “configuration-B” in this description) has been proposed (see Patent Documents 4 to 6). . In the configuration-B, it is possible to perform heat bending after providing the blackout layer on the sheet molded product, and the designability and accuracy of the blackout layer are improved. Patent Document 4 and Patent Document 6 using Configuration-B propose a specific coloring ink having hard coat liquid resistance, and Patent Document 5 discloses a specific hard coat composition having good adhesion to the blackout layer. Things have been proposed. However, when an adhesive layer is provided for fixing to a structural member, an adhesive layer is provided on the hard coat layer, and when trying to obtain good adhesion, the hard coat agent is limited, while the hard coat agent There was a trade-off problem, such as a decrease in adhesiveness when performance was increased.

On the other hand, after providing a hard coat layer on the resin base material as a laminate that can be directly provided with an adhesive layer on the ink layer, after performing a blast treatment in a state of masking other than the adhesive portion, and removing the hard coat layer A method of providing an ink layer at the removed portion has been proposed (see Patent Document 7). However, this method has a problem that the blasting process increases the number of steps, and a general inorganic blasting agent has a problem that the blasting surface is whitened and it is difficult to obtain a laminate having excellent design properties. It was.
Therefore, a resin glazing laminate that has excellent adhesiveness necessary for fixing to a structural member and can achieve good design has not yet been provided.

JP 2004-359220 A Japanese Patent Laid-Open No. 01-159246 JP 2006-289932 A Japanese Patent Publication No. 07-025910 JP 2006-255928 A JP-T-2006-523157 Japanese Utility Model Publication No. 61-078628

  An object of the present invention is to provide a resin glazing laminate that has excellent adhesion necessary for fixing to a structural member and can achieve good design.

  As a result of intensive studies, the present inventors have found that an ink layer made of acrylic polyurethane, a primer layer for adhesion containing a polyisocyanate compound and an acetate solvent, and a urethane adhesive on at least a part of the resin substrate. An ink layer made of acrylic polyurethane on a resin base material and a specific part between a part where the adhesive layer is formed in this order and a part where a specific hard coat layer is formed in this order on the resin base material By adopting a configuration in which a hard coat layer is formed, a resin glazing laminate is obtained that has excellent adhesion necessary for fixing to a predetermined structural member and can achieve good design. The present invention has been investigated.

That is, the present invention is as follows.
1. A glazing laminate in which the following (B) layer, (C) layer, (D) layer, and (E) layer are laminated on at least one surface of the following (A) layer,
When the cross section along the thickness direction of the laminated body is seen, the laminated structure 1 laminated in the order of (A) layer- (B) layer- (C) layer- (D) layer, and (A) layer- ( B) a laminated structure 2 laminated in the order of layer- (E) layer, and a laminated structure 3 laminated in the order of (A) layer- (E) layer, and laminated between laminated structures 1 and 3 A glazing laminate, wherein the structure 2 is interposed.
(A) Layer: a light-transmitting base material layer made of polycarbonate resin.
(B) Layer: A two-component curable ink layer made of acrylic polyurethane formed by reaction of an acrylic polyol resin and a polyisocyanate compound.
(C) Layer: An adhesive primer layer formed from a primer composition containing a polyisocyanate compound and an acetate solvent.
(D) Layer: An adhesive layer made of a urethane adhesive.
(E) layer: It is a hard coat layer consisting of only one layer or at least two layers (E1) and (E2). In (E layer) consisting of only one layer, the polyfunctional acrylic polymer is the main component. In the (E layer) composed of at least two layers, the (E1) layer comprises the (A) layer and (B). It is a primer layer made of an acrylic resin directly laminated with a layer, and the (E2) layer is a top made of a silicone resin laminated on the surface of the (E1) layer that is not in contact with the (A) layer or the (B) layer. Is a layer .
2. 2. The glazing laminate according to 1 above, wherein the layer (B) has a thickness of 3 μm to 60 μm.
3. Two-component curability obtained by reacting the acrylic polyurethane with an acrylic polyol resin, a polyol having a number average molecular weight of 100 to 2,000 other than the acrylic polyol resin, and hexamethylene diisocyanate and / or a polyisocyanate compound derived from the isocyanate. The glazing laminated body in any one of said 1-2 which is an ink layer.
4). 4. The glazing laminate according to 3 above, wherein the polyol other than the acrylic polyol resin is a polyether polyol.
5. The layer (E) is formed of a coating liquid in which the raw material for the hard coat layer is dissolved or / and dispersed in an organic solvent, and the coating liquid organic coating is directly applied on at least the (A) layer and the (B) layer. The glazing laminate according to any one of the above 1 to 4, wherein the solvent has a compatibility parameter (SP value) in the range of 18.5 to 22 (MPa) ^0.5 .
6). 6. The glazing laminate according to 5 above, wherein the organic solvent of the coating liquid directly applied to the layer (A) and the layer (B) is at least one selected from the group consisting of alcohols and ketones.
7). The glazing laminate according to any one of 1 to 6 , wherein the layer (A) is formed by injection compression molding.
8). A method for producing a glazing laminate comprising the following steps (i) to (iv):
(I) a step of forming the following (B) layer on a part of at least one surface of the following (A) layer (step (i)),
(Ii) On the side of the light-transmitting substrate obtained in step (i) and partially formed with the (B) layer, (B) from the surface of the (A) layer where the layer is not formed (B ) A step of forming the following (E) layer continuous over part of the surface of the layer (step (ii)),
(Iii) a step (step (iii)) of forming the following (C) layer on at least a part of the surface of the (B) layer in which the (E) layer obtained in the step (ii) is not formed; and (iv) ) A step of forming the following (D) layer on the surface of the (C) layer obtained in the step (iii) (step (iv)).
(A) Layer: a light-transmitting base material layer made of polycarbonate resin.
(B) Layer: A two-component curable ink layer made of acrylic polyurethane formed by reaction of an acrylic polyol resin and a polyisocyanate compound.
(C) Layer: An adhesion primer layer comprising a primer composition containing a polyisocyanate compound and an acetate solvent.
(D) Layer: An adhesive layer made of a urethane adhesive.
(E) layer: It is a hard coat layer consisting of only one layer or at least two layers (E1) and (E2). In (E layer) consisting of only one layer, the polyfunctional acrylic polymer is the main component. In the (E layer) composed of at least two layers, the (E1) layer comprises the (A) layer and (B). It is a primer layer made of an acrylic resin directly laminated with a layer, and the (E2) layer is a top made of a silicone resin laminated on the surface of the (E1) layer that is not in contact with the (A) layer or (B) layer Is a layer .
9. 9. The manufacturing method according to 8 above, wherein in step (i), after forming the layer (B) on the layer (A), the layer is heated and deformed, and then the step (ii) is performed.

  The resin glazing laminate of the present invention comprises an ink layer made of acrylic polyurethane on a part of at least one surface on a resin substrate, an adhesive primer layer containing a polyisocyanate compound and an acetate solvent, and a urethane adhesive An ink layer made of acrylic polyurethane on a resin base material and a part between a part where an adhesive layer made of this part is formed in this order and a part where a specific hard coat layer is formed in this order on the resin base material By adopting a configuration in which the portion where the hard coat layer is formed is interposed, it has excellent adhesiveness necessary for fixing to the structural member, and good design can be obtained. Therefore, the industrial effect that it produces is exceptional.

It is a longitudinal cross-sectional view of the mold clamping apparatus which shows the state at the time of the start of a shaping | molding cycle. It is a longitudinal cross-sectional view of the mold clamping apparatus which shows the state before the start of injection compression molding. It is a longitudinal cross-sectional view of the mold clamping apparatus which shows the state which is carrying out injection compression molding. It is a figure which shows an example of a structure of an ink layer, a hard-coat layer, and an contact bonding layer. It is a figure which shows the shape of sheet | seat-(alpha) created in the Example. It is a figure which shows the shape of the sheet | seat -beta produced in the Example. It is a schematic diagram which shows the sheet molded product after printing, thermal bending, and a hard-coat process (a gate part is not shown in figure). It is a schematic diagram which shows the glazing molded article obtained after the trimming process (a figure shows a left rear quarter window). It is a schematic diagram which shows the vehicle body attachment state of a glazing molded product.

Hereinafter, the present invention will be described in detail.
<Laminate>
(I) Base material layer ((A) layer)
The (A) layer according to the present invention is a light-transmitting substrate layer made of a polycarbonate resin. The polycarbonate resin forming the light transmissive substrate layer may be hereinafter referred to as “resin material-A”. Further, the base material layer molded from the resin material-A may be referred to as molded product-A below. The molded product A may have light diffusibility in which a fluoroscopic image cannot be clearly observed when light is passed through, but it is more preferable that the molded product A has transparency that allows the fluoroscopic image to be observed. Therefore, the total light transmittance of the molded product-A is preferably 15% or more, more preferably 20% or more, and further preferably 25% or more. A higher total light transmittance is preferable. Although the upper limit of the total light transmittance depends on the thickness of the molded product, it is preferably 92% in consideration of the thickness commonly used for glazing. Here, the total light transmittance of the molded product-A is a value measured by a method according to JIS K7105. The haze of the molded product-A is preferably in the range of 0.1 to 20%. The upper limit of haze is more preferably 10%, still more preferably 5%. Details of the resin material-A will be described later.

The thickness of the molded product-A is preferably 1 to 9 mm. The lower limit of the thickness is more preferably 2 mm, still more preferably 3 mm. The upper limit of the thickness is more preferably 7 mm, still more preferably 6 mm. The preferred thickness range here refers to the thickness of the main light-transmitting surface used as glazing, and does not include steps or holes provided for the purpose of reinforcing, fixing, and positioning the glazing. And Further, the thickness does not need to be uniform, and a shape in which the thickness continuously changes, a shape having a steep thickness change, a shape in which the thickness changes regularly, and the like can be taken. Examples of the shape in which the thickness changes regularly include a shape in which lenses and prisms are regularly arranged. An embodiment having a substantially uniform thickness is suitable for practical use. In the case of such a uniform thickness, the thickness difference is preferably within 1 mm, more preferably within 0.6 mm. Moreover, the maximum projected area of the molded product-A is preferably 200 to 60,000 cm ² , more preferably 1,000 to 40,000 cm ² .

  Examples of the molding method of the molded product-A include injection molding, extrusion molding, compression molding, blow molding, and rotational molding. In particular, injection molding is preferable, and injection compression molding is particularly preferable. Details of the injection compression molding will be described later. Further, the molded product-A may be a product whose shape is determined by performing secondary processing such as bending, trimming, and perforation after molding. Details of the secondary processing will be described later.

The more preferable aspect of the molded article-A of the present invention satisfies the following conditions in terms of viewing a fluoroscopic image in the molded article. That is, when the surface roughness (Ra): 0.06 μm or less, the average amplitude y of the surface waviness component: 0.5 μm or less, and the average wavelength x of the surface waviness component are detected on both surfaces of the molded product-A, y Preferably satisfies the following formula (1).
y ≦ 0.0004x ² + 0.0002x (1)
(In Formula (1), y represents the average amplitude Wa of the filtered waviness curve defined in JIS B0610 of the sheet, the unit thereof is μm, and x represents the average wavelength WSm of the filtered waviness curve of the sheet, The unit is mm.)

  Here, Ra is the arithmetic average roughness measured according to JIS B0610. In the above, preferably Ra: 0.05 μm or less and y: 0.4 μm or less, more preferably Ra: 0.03 μm or less and y: 0.3 μm or less, more preferably Ra: 0.02 μm or less y: 0.2 μm or less. On the other hand, from the viewpoint of compatibility between the reduction in production cost and the currently required surface properties, the lower limit of Ra is preferably 0.001 μm, more preferably 0.002 μm, and still more preferably 0.005 μm, and the lower limit of y is Preferably it is 0.05 micrometer, More preferably, it is 0.1 micrometer. In order to produce a molded product having such a surface property, it is preferable to perform injection molding (including injection compression molding) using a mold satisfying similar properties. Details of such surface properties are described in Japanese Patent Application Laid-Open No. 2002-128909, the contents of which are incorporated herein.

(Ii) Details of Resin Material-A The polycarbonate resin used for the resin material-A is preferably a bisphenol A type polycarbonate resin, but in addition to the bisphenol A type polycarbonate, it is polymerized with other dihydric phenols. Various polycarbonate resins may be used. The polycarbonate resin may be produced by any production method, and in the case of interfacial polycondensation, a terminal stopper of a monohydric phenol is usually used. The polycarbonate resin may also be a branched polycarbonate resin obtained by polymerizing trifunctional phenols, and further includes a polyester carbonate resin copolymerized with an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid, a divalent aliphatic or alicyclic alcohol. It may be a polymerized or copolymerized polycarbonate or a copolymerized polycarbonate. Isosorbide is preferably used as the alicyclic alcohol. Further, it may be a copolymerized polycarbonate in which units other than polycarbonate such as polyorganosiloxane units, polyalkylene units, and polyphenylene units are copolymerized.

  When the viscosity average molecular weight of the polycarbonate resin is in the range of 13,000 to 40,000, it can be applied to a wide range of fields. When the viscosity average molecular weight is 20,000 or more, it is excellent in strength and suitable for a vehicle resin window. In the polycarbonate resin of the present invention, the lower limit of the viscosity average molecular weight is more preferably 22,000, and still more preferably 23,000. The upper limit of the viscosity average molecular weight of the polycarbonate resin is more preferably 35,000, still more preferably 30,000 from the viewpoint of versatility. In addition, the viscosity average molecular weight should just be satisfied as the whole polycarbonate resin, and what satisfy | fills this range by 2 or more types of mixtures from which molecular weight differs is included.

The viscosity average molecular weight (M) of the polycarbonate resin is obtained by inserting the specific viscosity (ηsp) obtained at 20 ° C. from a solution of 0.7 g of the polycarbonate resin in 100 ml of methylene chloride into the following equation. Details of the polycarbonate resin are described in, for example, JP-A-2002-129003.
ηsp / c = [η] + 0.45 × [η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

The polycarbonate resin in the present invention can contain various conventionally known additives as long as the transparency is not impaired. Examples of such additives include heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, colorants, mold release agents, sliding agents, infrared absorbers, light diffusing agents, fluorescent whitening agents, and antistatic agents. Examples include agents, flame retardants, flame retardant aids, plasticizers, reinforcing fillers, impact modifiers, photocatalytic antifouling agents, acid inhibitors, hydrolysis stabilizers, and photochromic agents. In addition, the heat stabilizer, antioxidant, ultraviolet absorber, light stabilizer, colorant, mold release agent, and the like can be blended with known appropriate amounts in conventional polycarbonate resins. This is because such an amount rarely inhibits the transparency of the resin.
Among the above, the polycarbonate resin in the present invention preferably contains a heat stabilizer, an antioxidant, an ultraviolet absorber, an infrared absorber and the like.

(Heat stabilizer)
As the heat stabilizer, a phosphorus stabilizer is preferably exemplified. Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Specific examples of phosphites among such phosphorus stabilizers include (a-1) trialkyl phosphites such as tris (isodecyl) phosphite, (a-2) aryl dialkyl phosphites such as phenyl diisodecyl phosphite, (a -3) diaryl monoalkyl phosphites such as diphenyl mono (isodecyl) phosphite, (a-4) triaryl phosphites such as tris (2,4-di-tert-butylphenyl) phosphite, (b) distearyl Pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-Bis (1-methyl-1-phenylethyl) fur Nyl} pentaerythritol diphosphite and the like, and (c) cyclic structures by reacting with dihydric phenols such as 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite Suitable examples include phosphites having the following. Of the phosphorus stabilizers, preferred examples of phosphate include trimethyl phosphate and triphenyl phosphate. Specific examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite. Illustrated. A specific example of the tertiary phosphine is preferably triphenylphosphine.

  As the antioxidant, a hindered phenol compound is preferably exemplified. For example, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] Undecane is preferably used.

  Other heat stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), and glycerol-3-stearyl thiopropionate, And lactone stabilizers.

  The blending amount of the heat stabilizer and the antioxidant is 0.0001 to 1% by weight, preferably 0.01 to 0.3% by weight, based on the weight of the resin material-A. However, the upper limit of the lactone stabilizer is preferably 0.03% by weight.

(UV absorber)
Examples of the ultraviolet absorber in the present invention include known benzophenone compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, cyclic imino ester compounds, cyanoacrylate compounds, and malonic ester compounds. More specifically, for example, benzotriazole compounds include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4- (1,1 , 3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- [5-chloro (2H) -Benzotriazol-2-yl] -4-methyl-6-tert-butylphenol and 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3) -Tetramethylbutyl) phenol] and the like are preferably exemplified. For example, as the hydroxyphenyltriazine-based compound, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 2- [4-[(2 -Hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy -3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy- 3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, and 2- (2-hydroxy-4) Preferred examples include-[1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine. For example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) is preferably exemplified as the cyclic imino ester compound. Further, for example, as a cyanoacrylate compound, 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy ] As a malonic ester compound, methyl] propane is preferably exemplified by tetraethyl-2,2 '-(1,4-phenylenedimethylidyne) bismalonate.

  Furthermore, the ultraviolet absorber is a polymer type copolymer obtained by copolymerizing such a UV-absorbing monomer and a monomer such as alkyl (meth) acrylate by taking the structure of a monomer compound capable of radical polymerization. An ultraviolet absorber may be sufficient. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The

  Among these, from the viewpoint of having good thermal stability, a cyclic imino ester compound can be mentioned as a more preferable ultraviolet absorber. Other compounds having a relatively high molecular weight can provide better heat resistance. For example, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3 , 3-tetramethylbutyl) phenol], 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, and 1,3-bis [( 2-Cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane is preferably exemplified. The content of the ultraviolet absorber is preferably 0.005 to 5% by weight, more preferably 0.01 to 3% by weight, still more preferably 0.05 to 0.5% by weight, based on the weight of the resin material-A. %.

  The resin material-A of the present invention and the E layer described later can also contain a hindered amine light stabilizer typified by bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. The combined use of the hindered amine light stabilizer and the ultraviolet absorber effectively improves the weather resistance. In such a combination, the weight ratio (light stabilizer / ultraviolet absorber) of both is preferably in the range of 95/5 to 5/95, more preferably in the range of 80/20 to 20/80. You may use a photostabilizer individually or in mixture of 2 or more types. The content of the light stabilizer is preferably 0.0005 to 3% by weight, more preferably 0.01 to 2% by weight, still more preferably 0.05 to 0.5% by weight, based on the weight of the resin material-A. It is.

(Infrared absorber)
In order to enhance the efficiency of the vehicle air conditioner, the resin material-A in the present invention preferably contains an infrared absorber. As a result, the resin glazing produced according to the present invention is not only effective in reducing the weight, but also further reducing carbon dioxide by improving the efficiency of the air conditioner, particularly when applied to resin windows for vehicles. Reduction of the environmental load represented Preferred examples of the infrared absorber of the present invention include inorganic near infrared absorbers such as metal oxides, metal borides, and metal nitrides, organic near infrared absorbers such as phthalocyanine-based near infrared absorbers, and carbon fillers. Is done.

  The inorganic near-infrared absorber preferably has an average particle diameter of 1 to 200 nm, more preferably 2 to 80 nm, and still more preferably from the viewpoints of compatibility between transparency and near-infrared absorptivity, suitability for dispersion in a resin, and the like. 3-60 nm. The inorganic material is not particularly limited as long as the effects of the present invention are achieved, and examples thereof include metal oxides, metal borides, and metal nitrides.

Examples of the metal oxide in the inorganic near infrared absorber include tungsten oxide compounds, titanium oxide, zirconium oxide, tantalum oxide, niobium oxide, zinc oxide, ruthenium oxide, indium oxide, tin-doped indium oxide (ITO), and tin oxide. Antimony-doped tin oxide (ATO), cesium oxide, and the like. As the metal boride (boride), a metal boride compound is preferable. Specifically, lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride ( CeB ₆ ), yttrium boride (YB ₆ ), titanium boride (TiB ₆ ), zirconium boride (ZrB ₆ ), hafnium boride (HfB ₆ ), vanadium boride (VB ₆ ), tantalum boride (TaB ₆₎ ), Chromium boride (CrB, CrB ₆ ), molybdenum boride (MoB ₆ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ), and the like. Examples of the metal nitride include titanium nitride, niobium nitride, tantalum nitride, zirconium nitride, hafnium nitride, and vanadium nitride.

Among these, a tungsten oxide compound is preferable because it has a high near-infrared absorptivity and a high visible light transmittance, and a tungsten oxide compound represented by the following general formula (α) is particularly preferable.
MxWyOz (α)
Here, the element M is at least one selected from the group consisting of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn, W represents tungsten, and O represents oxygen. . Of the tungsten oxide compounds represented by the general formula (α), cesium-containing tungsten oxide, in which the M element is represented by Cs, is particularly preferable because of its high near infrared absorption ability.

In addition, in the general formula (α), the added amount of the M element satisfies the relationship of 0.001 ≦ x / y ≦ 1.1 as the value of x / y based on the tungsten content. In particular, x / y is preferably in the vicinity of 0.33 from the viewpoint of suitable near infrared absorption ability. Further, when x / y is around 0.33, a hexagonal crystal structure is easily obtained, and the use of this crystal structure is also preferable in terms of durability. In addition, the oxygen content in the general formula (α) preferably satisfies the relationship of 2.2 ≦ z / y ≦ 3.0 as the value of z / y based on the content of tungsten. More specifically, Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like can be mentioned. The said inorganic near-infrared absorber may be used individually by 1 type, or can also use 2 or more types together.

Organic near-infrared absorbers include anthraquinone compounds, naphthoquinone compounds, azo compounds, polymethine compounds, mercaptonaphthol compounds, cyanine compounds, squarylium compounds, dithiol metal complex compounds, diallylmethane compounds, triallylmethane Examples of such compounds include an imido compound, an imonium compound, a diimonium compound, an aminium compound, and a phthalocyanine compound. Among these, phthalocyanine compounds and dithiol metal complex compounds can be mentioned as suitable examples.
Examples of the carbon filler include carbon black, graphite, carbon nanotube, and fullerene, and carbon black is particularly preferable.

  The content of the metal oxide near-infrared absorber is preferably 10 to 2,000 ppm, more preferably 50 to 1,000 ppm, and still more preferably 100 to 700 ppm in the resin material-A: 100% by weight. It is. The content of the metal boride-based near-infrared absorber is preferably 1 to 200 ppm, more preferably 5 to 100 ppm, by weight, in the resin material-A: 100% by weight.

(II) Ink layer ((B) layer)
The layer (B) according to the present invention is a two-component curable ink layer made of acrylic polyurethane formed by reaction of an acrylic polyol resin and a polyisocyanate compound. This acrylic polyurethane may be obtained by further copolymerizing a polyol other than the acrylic polyol resin.

(II-i) Acrylic polyol resin component (hereinafter referred to as component (b-1))
The component (b-1) according to the present invention is a copolymer containing a hydroxyl group obtained by polymerizing a monomer having methyl methacrylate as a main component from the viewpoint of both heat resistance and weather resistance of the ink. preferable. The copolymer is more preferably a monomer comprising a hydroxyl group-containing monomer and a monomer not containing a hydroxyl group, the main component of which is methyl methacrylate, from the viewpoint of easy control of the amount of hydroxyl groups.

  As monomers not containing a hydroxyl group other than methyl methacrylate, styrene, α-methylstyrene, acrylic acid, methacrylic acid, methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate , Tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, and isopentanyl (meth) acrylate. It is done. Any of these may be used alone or in admixture of two or more. Here, the notation of (meth) acrylate means that both acrylate and methacrylate are included.

  The layer (B) in the present invention preferably has an appropriate flexibility, and by having an appropriate flexibility, it can absorb the difference in expansion between the base material A layer and maintain good adhesion. . Furthermore, since the followability to bending is excellent, it is easy to perform bending after forming the layer (B). These characteristics greatly contribute to good adhesiveness at the time of use at a high temperature or a low temperature after finally bonding the glazing laminate to the structural member. From the viewpoint of imparting such appropriate flexibility, it is preferable to contain (meth) acrylate having 4 or more carbon atoms in the alcohol residue as a monomer other than the above methyl methacrylate. Of these, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and n-butyl (meth) acrylate is particularly preferable.

  On the other hand, as a monomer containing a hydroxyl group, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxyethyl ( (Meth) acrylates such as ε-caprolactone adduct of (meth) acrylate, β-methyl-γ-valerolactone adduct of 2-hydroxyethyl (meth) acrylate, glycerol mono (meth) acrylate, and glycerol di (meth) acrylate And allyl compounds such as allyl alcohol, glycerol monoallyl ether, and glycerol diallyl ether. Among these, hydroxyalkyl (meth) acrylates are preferable from the viewpoint of easy availability and excellent reactivity, and 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate are more preferable.

  The OH group content of the acrylic polyol resin is preferably 0.5 to 7.4% by weight, more preferably 1 to 5% by weight, and still more preferably 1 to 3% by weight based on the total weight. The OH group equivalent (molecular weight per OH group) is preferably 230 to 3,400, more preferably 340 to 1,700, and still more preferably 570 to 1,700. The proportion of methyl methacrylate is preferably 25 to 85% by weight based on the total weight of (b-1).

  Moreover, the number average molecular weight of acrylic polyol resin becomes like this. Preferably it is 230-30,000, More preferably, it is 500-10,000, More preferably, it is 1,000-7,000. The number average molecular weight is a styrene-converted number average molecular weight measured by gel permeation chromatography.

(II-ii) Polyol component other than component (b-1) (hereinafter referred to as component (b-2))
As described above, in the present invention, the ink layer preferably has an appropriate flexibility. However, in order to further enhance the flexibility and shape followability, in the present invention, a polyol component other than the component (b-1) is added. It is preferable to contain. By forming a crosslinked structure containing a flexible and long-chain component described later, flexibility and shape followability can be improved.

  The polyol as the component (b-2) has two or more hydroxyl groups, and preferably has two or three hydroxyl groups in one molecule. Such a hydroxyl group may be bonded at any position in the molecule, but more preferably has two hydroxyl groups at the end of the molecule. As the polyol of component (b-2), polyester polyol, polyether polyol, polyether / ester polyol, polycarbonate polyol, polyolefin polyol, silicone polyol, and the like can be used. The number average molecular weight of such polyol is in the range of 100 to 2,000, preferably 100 to 1,000, and more preferably 150 to 600. As the component (b-2), polyether polyol can be most suitably used from the viewpoint of both heat resistance and flexibility.

  Preferred examples of the polyether polyol include those obtained by ring-opening polymerization of a cyclic ether, and reaction products of a polyhydric alcohol and a cyclic ether compound. Examples of such polyhydric alcohols include low molecular weight diols, triols such as trimethylolpropane and glycerin, and polysaccharides having more than three valences such as xylitol and sorbitol. Low molecular weight diols include ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, 2-ethyl-1,3-hexane glycol, 2,2,4-trimethyl-1,3-pentanediol, 3, Examples include 3-dimethylol heptane, 1,9-nonanediol, 2-methyl-1,8-octanediol, and cyclohexanedimethanol. As the cyclic ether compound, ethylene oxide and propylene oxide are preferably exemplified.

  More specifically, for example, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can be used as the polyether polyol. Examples of the polyethylene glycol include diethylene glycol that is a dimer, triethylene glycol that is a trimer, and pentaethylene glycol that is a pentamer. The polyether polyol is more preferably in the range of 2 to 10 mer, still more preferably 3 to 5 mer, particularly preferably trimer.

  As the polyester polyol, those obtained by polycondensation of dicarboxylic acid or its anhydride and a low molecular weight diol can be used. Examples of such dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and phthalic acid. Further, as the low molecular weight diol, the exemplified compounds of the polyether polyol can be similarly used. Furthermore, diethylene glycol and triethylene glycol are also included. Examples of the polyester polyol include polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, polybutylene sebacate, and the like, and those obtained by ring-opening polymerization of a lactone to a low molecular weight diol, for example, Polycaprolactone, polymethylvalerolactone and the like can be used.

  Examples of polyether ester polyols include those obtained by ring-opening polymerization of a cyclic ether to polyester glycol, those obtained by polycondensation of polyether glycol and dicarboxylic acid, such as poly (polytetramethylene ether) adipate.

  As the polycarbonate polyol, polybutylene carbonate, polyhexamethylene carbonate, poly (3-methyl-1,5-pentylene) carbonate obtained by deglycolization or dealcoholization from low molecular weight diol and alkylene carbonate or dialkyl carbonate is used. Can do.

  Polyolefin polyol, hydrogenated polybutadiene polyol, polyisoprene polyol and the like can be used as the polyolefin polyol, and polydimethylsiloxane polyol and the like can be used as the silicone polyol.

(II-iii) Polyisocyanate compound (hereinafter referred to as component (b-3))
The component (b-3) according to the present invention means one having two or more isocyanate groups. For example, as a diisocyanate compound,
(1) Tolylene diisocyanate (usually abbreviated as “TDI”, including 2,4-TDI and 2,6-TDI), diphenylmethane diisocyanate (abbreviated as “MDI”, 4,4′-MDI, 2 , 4'-MDI, and 2,2'-MDI), 1,5-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate ("XDI") And includes o-XDI, m-XDI, and p-XDI), tetramethylxylylene diisocyanate (abbreviated as “TMXDI”), 4,4′-diphenyl ether diisocyanate, 2-nitrodiphenyl-4, 4'-diisocyanate, 2,2'-diphenylpropane-4,4'-di Aromatic diisocyanates such as socyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4′-diphenylpropane diisocyanate, and 3,3′-dimethoxydiphenyl-4,4′-diisocyanate;
(2) Tetramethylene diisocyanate, hexamethylene diisocyanate (abbreviated as “HDI”), 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate Aliphatic diisocyanates such as (abbreviated "TMDI" and includes 2,2,4-TMDI, and 2,4,4-TMDI);
(3) Isophorone diisocyanate (abbreviated as “IPDI”), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate (abbreviated as “H ₁₂ MDI”), hydrogenated xylylene diisocyanate (abbreviated as “H ₆ XDI”) And alicyclic diisocyanates such as hydrogenated tetramethylxylylene diisocyanate and cyclohexyl diisocyanate. Examples of triisocyanate compounds include triphenylmethane-4,4,4-triisocyanate and tris (p- Isocyanatophenyl) thiophosphate and the like.

  These can be used alone or in combination of two or more. Among these, from the viewpoint of light resistance required for glazing products, polyisocyanate compounds containing no aromatic ring such as aliphatic diisocyanate and alicyclic diisocyanate are preferable, and HDI is particularly preferable.

  (B-3) The polyisocyanate compound of component (b-3) is further modified with the above-mentioned polyisocyanate compound, urethane modified product, allophanate modified product, urea modified product, biuret modified product, uretdione modified product, uretoimine modified product, isocyanurate modified product, adduct modified product. And modified products such as carbodiimide modified products.

  Specific examples of such modified products include adduct modified products of TDI and trimethylolpropane, isocyanurate modified products of TDI, isocyanurate modified products of TDI and HDI, adduct modified products of HDI and trimethylolpropane, and HDI Examples include uretdione-modified products, HDI biuret-modified products, HDI isocyanurate-modified products, and IPDI isocyanurate-modified products. Among them, HDI biuret-modified products are preferred. The NCO content of the polyisocyanate compound is preferably in the range of 15 to 25% by weight because of excellent reaction efficiency.

  The polyisocyanate compound may be blocked as necessary. Examples of blocking agents for such blocked polyisocyanates include alcohols such as methanol, ethanol, propanol, butanol, and isobutanol; phenols such as phenol, cresol, xylenol, p-nitrophenol, and alkylphenol; methyl malonate Active methylene compounds such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone; acid amides such as acetamide, acrylamide, and acetanilide; acid imides such as succinimide and maleic imide; Imidazoles such as 2-ethylimidazole and 2-ethyl-4-methylimidazole; Lactams such as 2-pyrrolidone and ε-caprolactam; Shim, methyl ethyl ketoxime, cyclohexanone oxime, and ketone or aldehyde oximes, such as acetoacetic aldoxime; other ethyleneimine, and the like bisulfite and the like. The equivalent ratio of the isocyanate group (NCO group) to the hydroxyl group (OH group) (NCO group / OH group) is preferably in the range of 1/5 to 5/1, more preferably 1/3 to 3/1, still more preferably. It is in the range of 1/2 to 2/1, particularly preferably in the range of 1/1 to 2/1.

  The above components (b-1) and (b-3), and if necessary, the component (b-2) are used as inks, preferably in a form in which they are dissolved in a solvent. The ink is laminated, dried and cured to form a two-component curable ink layer which is a B layer. Solvents in such inks include esters such as butyl acetate, ethyl acetate, 2-methoxypropyl acetate, 3-methoxybutyl acetate, and butyl diethylene glycol acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, toluene, xylene, and solvesso. Preferred examples include aromatic hydrocarbon solvents such as 100 and Solvesso 150, and aliphatic hydrocarbon solvents such as hexane. In the present invention, the ink for forming the B layer is mainly composed of an aromatic hydrocarbon solvent in the state of the ink so as not to deteriorate the polycarbonate of the A layer more than necessary and to obtain good adhesion. And a solvent containing the above-mentioned ester as a subcomponent. More specifically, the composition preferably contains 50 to 97% by weight of an aromatic hydrocarbon solvent and 3 to 50% by weight of esters in 100% by weight of the solvent component of the ink.

  As a representative example of the two-component curable ink containing the above components (b-1) and (b-3), and the component (b-2) and satisfying preferred embodiments of the respective components, Teikoku Ink Manufacturing ( A POS screen ink manufactured by Kogyo Co., Ltd. is exemplified.

(II-iv) Other components that can be blended in the ink The ink for forming the layer (B) of the present invention includes a curing accelerating catalyst, a pigment, a leveling agent, an antifoaming agent, a rheology modifier, an antioxidant, and an ultraviolet ray. Various additives used in the technical field such as an absorbent, a light stabilizer, various functional particles, a plasticizer, and a dispersant can be mixed and used. Examples of curing accelerator catalysts include dibutyltin dilaurate, di-n-octyltin dilaurate, tin 2-ethylhexanoate, zinc 2-ethylhexanoate, and cobalt salts, and triethylamine, pyridine, Methylpyridine, benzyldimethylamine, triethylenediamine, N, N-dimethylcyclohexylamine, N-methylpiperidine, N-methylmorpholine, pentamethyldiethylenetriamine, 1,4-diazabicyclo [2.2.2] octane, and N, N And tertiary amines such as' -dimethylpiperazine. These may be used alone or in combination of two or more. Such a catalyst is preferably in the range of 0.01 to 1% by weight for metal salts and in the range of 0.1 to 5% by weight for tertiary amines per 100% by weight of the ink solid content.

  As the pigment, various dyes and pigments used in printing inks can be used. As the pigment, any of inorganic pigments and organic pigments can be used. Both lake pigments and toner pigments can be used as such organic pigments, and aluminum hydroxide, calcium carbonate, titanium oxide, and the like can be used as extender pigments for lake pigments. Examples of the inorganic pigment include (i) metal oxides such as titanium dioxide (including white pigment, titanium yellow and titanium black), zinc oxide, iron oxide, chromium oxide, iron black, and cobalt blue, (ii) ) Metal hydroxides such as alumina white, iron oxide yellow, and viridian; (iii) chromates such as chrome yellow, molybdate orange, zinc chromate, and strontium chromate; (iv) white carbon, clay, talc, and Silicates such as ultramarine, (v) sulfates such as precipitated barium sulfate and barite powder, (vi) carbonates such as calcium carbonate, (vii) other inorganic pigments such as ferrocyanide (bitumen), phosphates ( Examples thereof include manganese violet) and carbon (carbon black).

  Organic pigments include basic dyes such as rhodamine lake and methyl violet lake, acidic dyes such as quinoline yellow lake, vat dyes such as malachite green lake, mordant dyes such as alizanin lake, various azo pigments (carmine 6B and (Including soluble azo pigments such as permanent 2B, insoluble azo pigments such as diazo and monoazo), phthalocyanine pigments such as phthalocyanine blue, condensed polycyclic pigments such as thioindigobordeaux, perinone red and quinacridone red, and other nitro Illustrative examples include pigments, nitroso pigments, fluorescent pigments such as Lumogen (registered trademark) manufactured by BASF, livestock pigments such as Luminova manufactured by Nemoto Special Chemicals, and aniline black.

  The glazing laminate of the present invention is used for glazing for vehicles in its preferred mode, and the blackout treatment for shielding and protecting the adhesive portion is usually black, but may be colored other than black. In the case of black, carbon black can be suitably used as the main component of the pigment. The oil absorption amount of carbon black is not particularly limited. In terms of shielding properties, a high oil absorption amount and a developed structure are preferable. However, since the ink tends to thicken, it can be adjusted in consideration of this point.

  The ink in the present invention can be imparted with various functions to the ink layer by including not only a pigment having a coloring function but also a component imparting other functions. Such functions include, for example, conductive functions (functions such as heat generation, electromagnetic wave absorption, and antistatic), water and oil repellency functions, hydrophilic functions, ultraviolet absorption functions, infrared absorption functions, self-healing functions, and crack prevention functions. Is exemplified. For example, after forming the ink layer for the purpose of coloring, the aspect which forms the ink layer which has such a function on it or another part is illustrated. In particular, the glazing laminate of the present invention may be required to have a conductive function, an ultraviolet absorption function, an infrared absorption function, and the like without significantly impairing transparency. By blending particles having these functions in the ink layer, such functions can be improved.

  As a compounding component used for obtaining such a conductive function, conductive particles such as metal particles are preferably exemplified. Examples of such conductive particles include an element selected from the group consisting of silver (Ag), palladium (Pd), platinum (Pt), gold (Au), ruthenium (Ru), copper (Cu), and nickel (Ni). Fine particles such as metals or alloys containing oxides or oxides. These conductive particles may be used alone or in combination of two or more. The average particle diameter of such metal particles is preferably 0.001 μm to 5 μm, more preferably 0.001 μm to 2 μm. Particularly preferably, metal nanoparticles are suitable, and the average particle size is preferably 0.001 to 0.01 μm. Metal nanoparticles are preferable in that a metal coating can be easily created.

  As a compounding component used for obtaining the ultraviolet absorbing function, various ultraviolet absorbers described in “silicone resin-based top layer” described later can be used. More preferably, various metal oxides can be used, and titanium oxide, zinc oxide, and cerium oxide are particularly preferable. As a compounding component utilized in order to obtain the said infrared absorption function, the various infrared absorbers demonstrated as a component which can be mix | blended in resin material-A can be utilized.

  The dispersoids in the ink such as the pigments and functional particles are preferably used in combination with or combined with various dispersants in order to improve the dispersibility in the ink. As such a dispersant, a surfactant, a polymer dispersant, and the like can be used. Among such surfactants, examples of the anionic surfactant include acylmethyl taurine salts, fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts. , Naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salt and the like. Further, among the surfactants, nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl Examples include amines and glycerin fatty acid esters.

  Polymeric dispersants include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial formalized product, polyvinyl alcohol-partial butyral , Vinyl pyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyamide, polyallylamine salt, condensed naphthalenesulfonate , Styrene-acrylate copolymer, styrene-methacrylate copolymer, acrylate-acrylate copolymer, acrylate-methacrylate Salt copolymer, Methacrylate-acrylate copolymer, Methacrylate-methacrylate copolymer, Styrene-itaconate copolymer, Itaconic acid-itaconate copolymer, Vinylnaphthalene- Examples include acrylate copolymers, vinyl naphthalene-methacrylate copolymers, vinyl naphthalene-itaconate copolymers, cellulose derivatives, and starch derivatives. Other examples include natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum, and lignin sulfonate. The above dispersants can be used alone or in combination of two or more.

(II-v) Printing Method and Ink Layer Thickness The method for forming the two-component curable ink layer in the present invention is not particularly limited, and can be formed on a flat or curved molded product surface by a conventionally known method. The method is preferred. Examples of the printing method include methods such as offset printing, flexographic printing, gravure printing, screen printing, and inkjet printing. Among these, screen printing is most preferably applied in the present invention. This is because screen printing has the following advantages. First, the advantage is that it is excellent in productivity and is easy to cope with a large print target. Secondly, since the multilayer coating is easy, the allowable range of the thickness of the printing layer is wide. Third, it is relatively easy to handle curved surfaces.

  In the present invention, the thickness of the two-component curable ink layer is preferably in the range of 3 to 60 μm, more preferably in the range of 5 to 40 μm, and most preferably 6 to 35 μm. In the above-mentioned range, not only the adhesion performance between the resin glazing and the structural member, which is a rigid body to be fixed, is improved, but also the intended purpose of the printing layer such as light shielding properties, and work efficiency and printing appearance are compatible. Is possible. Furthermore, printing can be applied not only to a single layer but also to a multilayer coating of two or more layers. In the multi-layer coating, it is preferable to overlap each layer with a thickness of 6 to 12 μm, and a method in which only the air-drying is performed and the multi-layer coating is repeated, and the baking process is performed after all the coating is completed. As the printing screen plate, a plate made of fibers such as cotton, nylon, and polyester, and an electroformed plate can be used, but a plate made of nylon fibers or polyester fibers is particularly preferable. These fibers may include yarn surface treated with carbon. As the fiber, either monofilament or multifilament can be used, but monofilament is preferable. As the yarn type, any of S, T, and HD can be used. Furthermore, these plates are made of highly water- and oil-repellent fibers and surface treatment agents with such properties for the purpose of good ink separation and prevention of clogging and as a result the formation of a smooth printing surface. A plate made of treated fibers can also be used.

(III) Adhesive primer layer ((C) layer)
The (C) layer in the present invention is formed from a primer composition containing a polyisocyanate compound and an acetate solvent. Such a primer composition may further contain a filler, a catalyst, a desiccant, a resin component, and optionally other compounds that are usually blended.

(III-i) Polyisocyanate compound used for layer (C) (hereinafter referred to as component (c-1))
As the polyisocyanate compound used for the layer (C) in the present invention, the same compounds as those exemplified in the above-mentioned section “(II-iii) polyisocyanate compound” can be used, but more preferably aromatic compounds. The main component is a polyisocyanate containing a ring. Such polyisocyanates are excellent in reactivity. More preferably, at least one polyisocyanate compound selected from the group consisting of MDI, TDI, triphenylmethane-4,4,4-triisocyanate, and tris (p-isocyanatephenyl) thiophosphate is (c -1) In 100 mol% of the polyisocyanate compound used as a component, it is preferably 50 mol% or more, more preferably 55 to 90 mol%.

  In the component (c-1), other polyisocyanate compounds such as an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound can be used in combination. Examples of other compounds used in combination include isocyanurate-modified products of TDI and HDI, adduct-modified products of HDI and trimethylolpropane, isocyanurate-modified products of HDI, and isocyanurate-modified products of IPDI. An isocyanurate-modified product with HDI is preferable because the reactivity can be easily adjusted.

  Particularly preferred is a combination consisting of MDI, tris (p-isocyanatephenyl) thiophosphate, and a modified isocyanurate of TDI and HDI, especially tris (p-isocyanatephenyl) thiophosphate. It is preferable to set it as the range of 50-70 mol% in 100 mol%. By adopting such a configuration, both the reaction activity and the product life of the primer are excellent, and good adhesiveness and man-hour reduction during production can be obtained.

(III-ii) Solvent used for layer (C) (hereinafter referred to as component (c-2))
The solvent used for the (C) layer in the present invention contains acetate as a main component. As the other components, any of various known solvents can be used as long as they are inert with respect to the isocyanate group. Such an acetate is preferably ethyl acetate and butyl acetate, and these are preferably contained in an amount of 70% by weight or more, more preferably 80% by weight or more in 100% by weight of the solvent in the primer composition. As other components, methyl ethyl ketone (MEK), acetone, and toluene are preferably exemplified, but further saturated carbonization having 5 to 12 carbon atoms such as pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane. A hydrogen compound can also be used in combination. The ratio of the saturated hydrocarbon compound having 5 to 12 carbon atoms during the combined use is preferably 1 to 15% by weight in 100% by weight of the solvent.

  The addition amount of the solvent in the primer composition is appropriately determined depending on the type of the isocyanate compound and is not particularly limited, but is usually about 100 to 1,000 parts by weight with respect to 100 parts by weight of the isocyanate component. Preferably it is 200-700 weight part.

  Examples of the catalyst for accelerating the reaction of the isocyanate group include metal salts such as tin salts and amine catalysts exemplified as the curing accelerating catalyst in the section “(II-iv) Other components that can be blended in ink”. Among them, dibutyltin dilaurate is preferable as the metal salt, and 1,4-diazabicyclo [2.2.2] octane is preferable as the amine catalyst. In the primer composition, a tin salt such as dibutyltin dilaurate is essential, and an amine catalyst is preferably used in combination as necessary. The amount of the catalyst added is appropriately determined depending on the type of the isocyanate compound and is not particularly limited, but is usually 0.1 to 1 part by weight, preferably 0.1 to 100 parts by weight based on 100 parts by weight of the isocyanate component. 0.5 parts by weight.

(III-iii) Other components used for layer (C) (hereinafter referred to as (c-3) component)
As other components used in the layer (C) in the present invention, in order to obtain good workability, a urethane resin such as a polyester polyurethane resin, a polyether polyurethane resin, and an acrylic polyurethane resin, and a polyester resin may be used in combination. it can. As such a resin, a thermoplastic urethane resin and a polyester resin, both of which exhibit solvent solubility, are preferably used. More preferred is a thermoplastic polyurethane resin, and among these, a polyester polyurethane resin is preferred. The number average molecular weight of such a resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 15,000 to 50,000. In addition, the addition amount of this resin is about 10-30 weight part normally with respect to 100 weight part of isocyanate components, and 12-25 weight part is more preferable.

  Furthermore, in order to ensure the stability of the primer composition, a dehydrating agent inert to isocyanate groups such as synthetic zeolite can be used in combination. A filler is suitably blended in the primer composition for the purpose of improving adhesiveness, imparting light shielding properties, and preventing migration of a plasticizer contained in the adhesive of the urethane adhesive layer described later. Examples of the filler include calcium carbonate, silica, carbon black, clay, glass balloon, silica balloon, ceramic balloon, plastic balloon, talc, titanium oxide, quicklime, zeolite, and diatomaceous earth. Carbon black is particularly preferable, and the content thereof is preferably 5 to 30% by weight, more preferably 5 to 15% by weight in the primer composition. Within this range, the storage stability and the flexibility of the primer coating are excellent. Since carbon black blocks or absorbs ultraviolet rays and visible light, it contributes to improving the weather resistance of the resin glazing laminate. The carbon black is not particularly limited, and examples thereof include various types such as N110, N220, N330, N550, and N770 defined by the ASTM standard. These can be used alone or in combination of two or more. The proportion of the filler is 10 to 60% by weight, more preferably 30 to 55% by weight, in the solid content of 100% by weight of the primer for adhesion. Further, the primer composition may contain a phosphate such as aluminum hydrogen in tripolyphosphoric acid in order to improve the adhesion to the substrate.

(III-iv) Method for Producing Composition of Layer (C) As the method for producing the composition for forming the layer (C) in the present invention, any of various known methods that can sufficiently mix the components can be applied. For example, mixing by a ball mill is preferably exemplified.

The (C) layer is formed by applying the primer composition using various applicators and drying it at normal temperature. As the coating method, for example, a brush coating method, a spray coating method, a wire bar method, a blade method, and a roll coating method can be used. The thickness of the adhesion primer layer is preferably in the range of 2 to 40 μm, more preferably 3 to 30 μm, and more preferably 5 to 20 μm. In the said range, while suppressing the bad influence to the polycarbonate resin of the (A) layer of the solvent in a primer, favorable adhesion | attachment is attained. Furthermore, the primer can be applied not only by a single layer but also by a multilayer coating of two or more layers. The primer is sufficiently dried, but the urethane adhesive described below is applied within the time when the active ingredient does not disappear. Such time is preferably from 2 minutes to 24 hours, more preferably from 5 minutes to 30 minutes. In the case of multi-layer coating, this time is the time from the last layer coating.
As a typical example of the preferred embodiment of the primer composition, RC-50E and RC-50KE, which are body primers manufactured by Yokohama Rubber Co., Ltd., are exemplified.

(IV) Urethane adhesive layer (hereinafter referred to as (D) layer)
As the urethane adhesive in the present invention, either a moisture curable one-component urethane adhesive or a two-component urethane adhesive can be used, but the moisture curable one-component urethane adhesive is particularly excellent in production efficiency. Therefore, it is preferable. Moisture curable one-component urethane adhesives are usually composed mainly of isocyanate group-containing compounds, especially isocyanate group-terminated urethane prepolymers (hereinafter referred to as NCO-terminated prepolymers), and plasticizers, fillers and catalysts. , And optionally other compounds. The other compound is intended to impart desired properties to the composition, and includes, for example, an adhesive such as a silane coupling agent and a (meth) acrylate-based copolymer for imparting heat-resistant adhesion. It includes a polymer, and a foaming agent or a microballoon for imparting lightness, vibration damping and soundproofing. Here, the content of the prepolymer is usually preferably 15 to 50% by weight, more preferably 20 to 45% by weight, and further preferably 30 to 45% by weight in the total amount of the urethane adhesive composition. Is done. Representative examples of preferred embodiments of the urethane adhesive composition include various adhesives for direct glazing, such as WS-222 manufactured by Yokohama Rubber Co., Ltd. and # 560 manufactured by Sunstar Giken Co., Ltd. .

(IV-i) Isocyanate group-terminated urethane prepolymer (hereinafter referred to as component (d-1))
The isocyanate group-terminated urethane prepolymer of the layer (D) in the present invention is suitably used as a main component in the moisture-curable one-component urethane adhesive, and an excess amount of polyisocyanate compound is usually used with respect to various polyols. It can be produced by reacting by a method. Examples of the polyol include polyether polyols, polyester polyols, polyols whose main chain is a C—C bond, low molecular weight polyols, and other polyols. The number average molecular weight of such a urethane prepolymer is preferably in the range of 1,000 to 30,000, more preferably 2,000 to 10,000. The amount ratio of the polyol and the polyisocyanate compound used in producing the isocyanate group-terminated urethane prepolymer is 1.2 to 4 in the ratio of NCO group to OH group (NCO group / OH group (equivalent ratio)). The lower limit of the range is more preferably 1.5, and the upper limit of the range is more preferably 2.5, and even more preferably 2.2.

  Polyether polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, 1,4- Examples include polyols obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and polyoxytetramethylene oxide to polyhydric alcohols such as butanediol and pentaerythritol. In particular, the adhesive may contain a trifunctional or higher polyol obtained by adding alkylene oxides to a trifunctional or higher polyhydric alcohol such as glycerin, 1,1,1-trimethylolpropane, or pentaerythritol. It is preferable in that it is excellent in strength and can be easily manufactured with a widely used raw material. As the tri- or higher functional polyol, a polyoxyalkylene triol such as polyoxypropylene triol is particularly preferred from the viewpoint of low cost and adhesive strength. In addition, it is preferable to use a bifunctional polyol such as polypropylene glycol and polytetramethylene glycol in combination with such a trifunctional or higher functional polyol because the strength required for the adhesive can be easily adjusted. The ratio of the trifunctional or higher functional polyol to the bifunctional polyol is preferably 30 to 80% by weight, more preferably 50 to 70% by weight, with the trifunctional polyol being preferably 100% by weight. This ratio is the same for any polyol.

  Examples of the polyester polyol include condensed polyester polyols, lactone polyester polyols, and polycarbonate diols. Examples of the polyol having a C—C bond in the main chain include acrylic polyol, polybutadiene-based polyol, hydrogenated polybutadiene-based polyol, polyolefin-based polyol, and saponified ethylene-vinyl acetate copolymer. Examples of the low-molecular polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, and hexanediol. Examples of other polyols include flame retardant polyols, phosphorus-containing polyols, and halogen-containing polyols.

  The polyols used in the isocyanate group-terminated urethane prepolymer can be used alone or in combination of two or more. Among the polyols, polypropylene glycol is particularly preferable, and two or more types having different molecular weights can be used in combination.

  As the isocyanate compound used in the isocyanate group-terminated urethane prepolymer, the same compounds as those exemplified in the above-mentioned section “(II-iii) polyisocyanate compound” can be used. The main component is a polyisocyanate containing a ring, and MDI and TDI are preferable, and MDI is particularly preferable in terms of strength and versatility. Such isocyanate compounds may be used alone or in combination of two or more, and the terminal structure may be a biuret modified product.

(IV-ii) Other components Examples of the other components of the layer (D) in the present invention include a plasticizer, a filler, and a catalyst.
Plasticizers include diisononyl phthalate, dioctyl phthalate (DOP), dibutyl phthalate, dilauryl phthalate, butyl benzyl phthalate, dioctyl adipate, diisodecyl adipate, trioctyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, adipic acid Examples include propylene glycol polyester, butylene glycol adipate polyester, alkyl alkyl stearate, alkylbenzene, and epoxidized soybean oil. The blending amount of the plasticizer is usually preferably 10 to 30% by weight, more preferably 15 to 25% by weight in the total amount of the urethane adhesive composition.

  Examples of the filler include calcium carbonate, silica, carbon black, clay, glass balloon, silica balloon, ceramic balloon, plastic balloon, talc, titanium oxide, quicklime, zeolite, and diatomaceous earth. A combination of carbon black and other fillers is preferred, and clays such as kaolin and montmorillonite and calcium carbonate are particularly suitable as other fillers. The blending amount of the filler is usually preferably in the range of 30 to 65% by weight, more preferably in the range of 40 to 60% by weight, still more preferably in the range of 40 to 50% by weight in the total amount of the urethane adhesive composition. Can be selected. Among them, carbon black can be selected in the range of 10 to 40% by weight, more preferably 25 to 35% by weight, based on the total amount of the urethane adhesive composition.

  Examples of the catalyst include organic tin compounds (dibutyltin diacetylacetonate, dibutyltin dilaurate, tin octylate, dibutyltin dimaleate, etc.); 2,2′-dimorpholinodiethyl ether, di (2,6-dimethylmorpholinoethyl) ether; Bismuth carboxylates (bismuth 2-ethylhexanoate, bismuth octylate, bismuth neodecanoate, etc.); carboxylic acids (benzoic acid, phthalic acid, 2-ethylhexanoic acid, octylic acid, stearic acid, oleic acid, linoleic acid, etc.); Triethylenediamine and its salt; N, N-dimethylaminoethylmorpholine; bis (2-dimethylaminoethyl) ether; 1,8-diazabicyclo (5,4,0) undecene-7 and its salt (phenol salt, octylic acid Salt, oleate, p-toluenesulfonate, Formate, etc.); imidazole compounds (2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-Diamino-6- [2'-un Silimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4 -Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl- 4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazoline, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, etc.) Illustrated. The compounding quantity of a catalyst can be normally selected in the range of 0.005-0.5 weight% in the composition whole quantity in a urethane adhesive composition whole quantity.

  Further, if necessary, an adhesive [the polyisocyanate compound having an inner molecular weight of less than 1000, a silane coupling agent (mercaptopropyltrimethoxysilane, mercaptopropylmethyldimethoxysilane, γ-N-phenylaminopropyltrimethoxysilane, γ -Isocyanatopropyltrimethoxysilane or the like, or a reaction product of such a polyisocyanate compound and a silane coupling agent]; hexamethylene diisocyanate derivative (burette modified, isocyanurate modified, trimethylolpropane modified, etc.); titanate System coupling agents; solvents (xylene, toluene, etc.); in addition, anti-aging agents, antioxidants, foaming agents, ultraviolet absorbers and pigments other than those described above may be added in appropriate amounts.

(IV-iii) (D) Layer Thickness The thickness of the (D) layer in the present invention is as follows: Adhesives and Searants: General Knowledge, Application Techniques, New Curing Techniques page 27 It is preferable to determine in this area. However, since this figure is a relatively safe area setting, in view of various shapes and usage conditions, the area is less than 2 mm, preferably less than 1.5 mm, than the line that divides the area. It is also possible to reduce the thickness of the urethane adhesive. In particular, when the length of the molded product is less than 1 m, it is possible to design the thickness on a line extrapolating the line of Δα = 12 × 10 ⁻⁶ K.

(V) Hard coat layer (hereinafter referred to as (E) layer)
The layer (E) in the present invention is formed from a coating solution obtained by dissolving or / and dispersing a raw material for a hard coat layer in an organic solvent, and may be composed of only one layer or may be composed of two or more layers. Good. Such a coating liquid usually consists of a solid content that substantially forms a layer and an organic solvent, and may further contain water. The SP value (solubility parameter value) of the organic solvent of the coating liquid forming the layer (E) is preferably 18.5 to 22 (MPa) ^0.5 , and preferably 19.5 to 21.5 (MPa). More preferably, it is ^0.5 . In such a range, it is possible to achieve both a reduction in the adverse effect of the organic solvent on the polycarbonate resin and an improvement in solubility in the solid content. The SP value of the organic solvent in the present invention is determined by Yuji Harasaki; “Basic Science of Coating” p. 51 (1977) Calculated according to the calculation from the chemical composition of a bookstore. Preferred organic solvents include alcohols and ketones.

  In the (E) layer consisting of only one layer, various organic polymers conventionally used for coating can be used. In particular, in the present invention, a curable polymer mainly composed of a polyfunctional acrylic polymer, and an organic-inorganic composite composed of an organic polymer and metal oxide fine particles are preferably exemplified. As the polyfunctional acrylic polymer forming the layer (E), a polymer having a structural unit derived from methyl methacrylate as a main component and forming a cross-linked structure by self-crosslinking and reaction with other crosslinking components by various functional groups Is preferably exemplified. As the functional group contributing to the formation of such a crosslinked structure, various conventionally known functional groups can be used. For example, a double bond, a hydroxyl group (for example, crosslinking by reaction with methyl roll melamine or polyisocyanate), and a carboxyl group ( For example, cross-linking by reaction with polyepoxy and the like are exemplified. On the other hand, the organic-inorganic composite forming the layer (E) includes (i) a mixed composite of an organic polymer and a metal oxide that has been subjected to surface treatment that can be dispersed in the polymer, and (ii) an organic polymer. And (iii) a metal oxide surface-treated with a surface treatment agent having a functional group, and (iii) a metal oxide surface-treated with a surface treatment agent having a functional group capable of reacting with the polymer. Examples include composites in which a polymer matrix is formed by reaction between such functional groups or by reaction with other reactive monomers or polymers with respect to such functional groups, and may be a combination thereof. .

  A typical example of the (E) layer comprising two or more layers is at least a primer layer ((E1) layer) and a top layer ((E2) layer). Generally, the (E1) layer strongly bonds the (A) layer and the (E2) layer, and contains a high concentration of an ultraviolet absorber, so that the (E1) layer and the (E2) layer are bonded. And (A) improve the weather resistance in the layer. Furthermore, it has a role of relieving the difference in thermal expansion between the (E2) layer and the (A) layer and preventing cracks in the (E2) layer. In order to further enhance the function of the (E1) layer, a structure of three or more layers containing a layer capable of further improving the adhesion and relaxing the thermal expansion difference between the (E1) layer and the (E2) layer. Is also possible.

  As described later, the (E) layer of the present invention preferably has a laminated structure comprising a primer layer made of an acrylic resin as the (E1) layer and a top layer made of a silicone resin as the (E2) layer. Is widely known in the field of polycarbonate resin glazing, especially in the glazing field of transportation equipment. Also in this invention, conventionally well-known various structures can be taken.

  Two or more laminated hard coat layers are generally composed of layers having different chemical structures or functions, so that adhesion, hardness, weather resistance, and the like can be combined at a high level, which is more preferable in the present invention. It is an aspect. (E) Each of the layers forming the layer can be selected from either a thermosetting type or an active energy ray curable type such as an ultraviolet curable type, and in the case of two or more layers, a method of sequentially curing each layer, and lamination Any post-curing method can be selected.

  In the case of one layer, the coating liquid for forming the (E) layer is two layers or more. In the case of two or more layers, the coating liquid for forming the (E1) layer is the (A) layer and, if necessary, a part of the (B) layer. Will be applied directly.

  The layer (B) in the present invention has a good resistance to the solvent, particularly the solvent having the above-mentioned SP value, and can be used for the light-transmitting substrate layer. Can be used as it is. With such a feature, there is no problem in the configuration in which the coating liquid of the (E) layer is applied to a part of the (B) layer. Therefore, in the present invention, the (E) layer can be formed on the (B) layer in which the (C) layer and the (D) layer are not laminated, more preferably the (C) layer and the (D) layer. (E) layer, or two or more layers including the (E1) layer and the (E2) layer can be formed on the (B) layer in which is not laminated.

(Vi) Primer layer in hard coat layer ((E1) layer)
A more preferable (E1) layer in the hard coat layer of the present invention is formed by copolymerizing a monomer having an ultraviolet absorbing group and / or a photostable group and an alkyl (meth) acrylate monomer. Is.

(V-i-1) Acrylic copolymer used for primer layer The primer layer in the preferred hard coat layer must have the following formula (A-1) unit, (A-3 unit) and (A-4) unit. And the total of these three units and the unit (A-2) is at least 70 mol% in 100 mol% of all repeating units of the acrylic copolymer. And the units (A-1) to (A-4) satisfy the following ratio. That is, based on the number of moles of all repeating units of the acrylic copolymer,
i) The sum of the units (A-1) and (A-2) is in the range of 40 to 90 mol%,
ii) (A-3) units are in the range of 1-30 mol%,
iii) (A-4) units are in the range of 5 to 30 mol%, and iv) (A-) when based on the total number of moles of (A-1) units and (A-2) units (A- 1) It is preferable that a unit is 30 mol% or more.

（上記式（Ａ−１）中、Ｒ^１はメチル基またはエチル基を表す。）

(In the above formula (A-1), R ¹ represents a methyl group or an ethyl group.)

（上記式（Ａ−２）中、Ｒ^２はシクロアルキル基であり、Ｘ^１は水素原子またはメチル基を表わす。）

(In the above formula (A-2), R ² represents a cycloalkyl group, and X ¹ represents a hydrogen atom or a methyl group.)

（上記式（Ａ−３）中、Ｘ^２は水素原子またはメチル基を表わし、Ｗは、トリアジン構造、ベンゾトリアゾール構造、およびベンゾフェノン構造からなる群から選択される少なくとも１種の紫外線吸収性基、または環状ヒンダードアミン構造を有する光安定性基を表わす。）

(In the formula (A-3), X ² represents a hydrogen atom or a methyl group, and W represents at least one ultraviolet absorbing group selected from the group consisting of a triazine structure, a benzotriazole structure, and a benzophenone structure, Or represents a photostable group having a cyclic hindered amine structure.)

（上記式（Ａ−４）中、Ｒ^３は炭素数２〜５のアルキレン基を表わし、Ｘ^３は水素原子またはメチル基を表わし、Ｚはヒドロキシ基、アルコキシシリル基、グリシジルオキシ基、イソシアネート基からなる群から選ばれる少なくとも１種の置換基を表わす。）

(In the above formula (A-4), R ³ represents an alkylene group having 2 to 5 carbon atoms, X ³ represents a hydrogen atom or a methyl group, Z represents a hydroxy group, an alkoxysilyl group, a glycidyloxy group, an isocyanate group. Represents at least one substituent selected from the group consisting of:

More preferably, the ratio of the units (A-1) to (A-4) is based on the number of moles of all repeating units of the acrylic copolymer.
i) The sum of the units (A-1) and (A-2) is preferably in the range of 50 to 90 mol%, more preferably 55 to 87 mol%,
ii) (A-3) units are preferably in the range of 3-25 mol%, more preferably 4-20 mol%,
iii) (A-4) units are preferably in the range of 7 to 28 mol%, and iv) in a total of 100 mol% of (A-1) units and (A-2) units, (A-1) The unit is preferably 40 mol% or more, more preferably 40 to 90 mol%.

  Examples of the monomer for deriving the unit (A-1) include methyl methacrylate or ethyl methacrylate, which can be used alone or in combination. The unit (A-2) is not particularly limited as long as it is an acrylate or methacrylate having at least one cycloalkyl group in the molecule. The cycloalkyl group preferably has 5 to 12 carbon atoms. As the monomer for deriving the unit (A-2), cyclohexyl acrylate, 4-methylcyclohexyl acrylate, 2,4-dimethylcyclohexyl acrylate, 2,4,6-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, adamantyl Acrylate, dicyclopentadienyl acrylate, cyclohexylmethyl acrylate, 4-methylcyclohexylmethyl acrylate, 2,4-dimethylcyclohexylmethyl acrylate, 2,4,6-trimethylcyclohexylmethyl acrylate, 4-t-butylcyclohexylmethyl acrylate, cyclohexyl Methacrylate, 4-methylcyclohexyl methacrylate, 2,4-dimethylcyclohexyl methacrylate, 2,4 6-trimethylcyclohexyl methacrylate, 4-t-butylcyclohexyl methacrylate, adamantyl methacrylate, dicyclopentadienyl methacrylate, cyclohexylmethyl methacrylate, 4-methylcyclohexylmethyl methacrylate, 2,4-dimethylcyclohexylmethyl methacrylate, 2,4,6- Examples include compounds such as trimethylcyclohexylmethyl methacrylate and 4-t-butylcyclohexylmethyl methacrylate. These can be used alone or in admixture of two or more. Of these, cyclohexyl methacrylate is most preferably employed.

  Among the above units (A-3), as a monomer for deriving a unit containing a benzotriazole structure, 2- (2′-hydroxy-5 ′-(meth) acryloxyphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloxymethylphenyl) -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(2- (meth) acryloxyethyl) ) Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(2- (meth) acryloxyethyl) phenyl] -5-chloro-2H-benzotriazole, and 2- [2′-hydroxy-3′-methyl-5 ′-(8- (meth) acryloxyoctyl) phenyl] -2H-benzotriazole and the like. Rukoto can.

  Among the units (A-3), examples of the monomer for deriving a unit containing a benzophenone structure include 2-hydroxy-4- (2- (meth) acryloxyethoxy) benzophenone, 2-hydroxy-4- (4- (Meth) acryloxybutoxy) benzophenone, 2,2'-dihydroxy-4- (2- (meth) acryloxyethoxy) benzophenone, 2,4-dihydroxy-4 '-(2- (meth) acryloxyethoxy) benzophenone 2,2 ′, 4-trihydroxy-4 ′-(2- (meth) acryloxyethoxy) benzophenone, 2-hydroxy-4- (3- (meth) acryloxy-2-hydroxypropoxy) benzophenone, and 2- Hydroxy-4- (3- (meth) acryloxy-1-hydroxypropoxy) benzophenone, etc. It can be mentioned.

  Among the above units (A-3), as a monomer for deriving a unit containing a triazine structure, an acrylic monomer represented by the following formula (A-3-i) or formula (A-3-ii) is preferably used. Is done.

（上記式（Ａ−３−ｉ）中、Ｒ^４は炭素数２〜６のアルキレン基であり、Ｒ^５は水素原子、炭素数１〜１８のアルキル基または炭素数１〜１８のアルコキシ基を表し、Ｒ^６、Ｒ^７は同一または互いに独立して水素原子、ハロゲン原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、または炭素数１〜１８のアルキル基もしくはハロゲン原子で置換されていてもよいフェニル基を表し、Ｒ^８は炭素数１〜１８のアルキル基を表し、Ｘ^４は水素原子またはメチル基であり、Ｙ^１は水素原子、ＯＨ基または炭素数１〜１２のアルキル基を表す。）

(In the above formula (A-3-i), R ⁴ represents an alkylene group having 2 to 6 carbon atoms, and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. And R ⁶ and R ⁷ are the same or independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkyl group or halogen atom having 1 to 18 carbon atoms. Represents a phenyl group which may be substituted with, R ⁸ represents an alkyl group having 1 to 18 carbon atoms, X ⁴ represents a hydrogen atom or a methyl group, Y ¹ represents a hydrogen atom, an OH group or 1 to 1 carbon atoms. Represents 12 alkyl groups.)

（上記式（Ａ−３−ｉｉ）中、Ｒ^９は水素原子、炭素数１〜１８のアルキル基または炭素数１〜１８のアルコキシ基を表し、Ｒ^１０、Ｒ^１１は同一または互いに独立して水素原子、ハロゲン原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、または炭素数１〜１８のアルキル基もしくはハロゲン原子で置換されていてもよいフェニル基を表し、Ｒ^１２は炭素数１〜１８のアルキル基を表し、Ｘ^５は水素原子またはメチル基であり、Ｙ^２は水素原子、ＯＨ基または炭素数１〜１２のアルキル基を表す。）

(In the above formula (A-3-ii), R ⁹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ¹⁰ and R ¹¹ are the same or independently of each other. a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an alkyl group or a phenyl group which may be substituted by a halogen atom having 1 to 18 carbon atoms, having 1 to 18 carbon atoms having 1 to 18 carbon atoms, R ¹² Represents an alkyl group having 1 to 18 carbon atoms, X ⁵ represents a hydrogen atom or a methyl group, and Y ² represents a hydrogen atom, an OH group, or an alkyl group having 1 to 12 carbon atoms.)

  Specifically, 2-acryloxyethylcarbamic acid 1- [3-hydroxy-4- {4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl} phenyloxy ] -3- (2-ethylhexyloxy) -2-propyl, 2-methacryloxyethylcarbamic acid 1- [3-hydroxy-4- {4,6-bis (2,4-dimethylphenyl) -1,3 5-Triazin-2-yl} phenyloxy] -3- (2-ethylhexyloxy) -2-propyl, 2-acryloxy-1- [3-hydroxy-4- {4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazin-2-yl} phenyloxy] -3- (2-ethylhexyloxy) -2-propane, and 2-methacryloxy-1- [3-hydroxy-4- {4 Such as 3,6-Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl} phenyl oxy] -3- (2-ethylhexyl) -2-propane.

  Among the above units (A-3), examples of the monomer for deriving a unit containing a cyclic hindered amine structure include 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6, 6- Pentamethyl-4-piperidyl methacrylate, 1-ethyl-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-propyl-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-t -Butyl-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-cyclohexyl-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1- (4-methylcyclohexyl) -2, 2,6,6-tetramethyl-4-piperidyl methacrylate, 1-t-octyl-2,2,6,6-tetramethyl-4-pi Lysyl methacrylate, 1-decyl-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-dodecyl-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-methoxy-2,2 , 6,6-tetramethyl-4-piperidyl methacrylate, 1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-propoxy-2,2,6,6-tetramethyl-4- Piperidyl methacrylate, 1-t-butoxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1- (4 -Methylcyclohexyloxy) -2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-oct Cis-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-t-octoxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-decyloxy-2,2,6, Examples include 6-tetramethyl-4-piperidyl methacrylate and 1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl methacrylate, and these may be used alone or in admixture of two or more. .

  Specific examples of the acrylate or methacrylate monomer having a functional group corresponding to the above formula (A-4) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, Such as 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, and 2-hydroxybutyl methacrylate Monomers having a hydroxy group, 3-trimethoxysilylpropyl acrylate, and 3-trimethoxysilylpropyl methacrylate Monomers having alkoxysilyl group, 3-glycidoxypropyl acrylate, and 3-glycidoxypropyl monomer having a glycidyl group such as methacrylate and the like, which can be used alone or in combination. Of these, a monomer having a hydroxy group is preferable, and 2-hydroxyethyl methacrylate is particularly preferable.

  The molecular weight of the acrylic copolymer is preferably 20,000 or more and more preferably 50,000 or more in terms of a weight average molecular weight calculated from GPC measurement in terms of standard polystyrene. Further, those having a weight average molecular weight of 10 million or less are preferably used. Therefore, the weight average molecular weight of the acrylic copolymer is preferably 50,000 to 10,000,000, more preferably 50,000 to 1,000,000, and even more preferably 50,000 to 500,000. An acrylic copolymer having such a molecular weight range is preferable because it exhibits sufficient performance such as adhesion and strength as the first layer.

(V-i-2) Other components for forming the (E1) layer The acrylic resin composition for forming the (E1) layer preferably contains a blocked polyisocyanate compound. A blocked polyisocyanate compound is one in which a blocking agent is reacted with an isocyanate group to eliminate almost any free isocyanate group, thereby suppressing the reactivity at room temperature. It means a compound that becomes reactive.

  As blocked polyisocyanate compounds, active methylene compounds such as oximes such as acetooxime and methyl ethyl ketoxime, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone Addition of blocking agents represented by alcohols such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol, and 2-ethyl-1-hexanol, and phenols such as phenol, cresol, and ethylphenol The blocked isocyanate compound obtained by letting it be used.

  Examples of the polyisocyanate compound to which the blocking agent is added include polyisocyanate, adduct-modified product of polyisocyanate and polyhydric alcohol, isocyanurate-modified product of polyisocyanates, and isocyanate burette. As the polyisocyanate, the compounds exemplified in the above-mentioned “(II-iii) polyisocyanate compound” can be used.

  These blocked polyisocyanate compounds can be used alone or in admixture of two or more. Blocked aliphatic and / or alicyclic polyisocyanate compounds are particularly preferred because of excellent weather resistance. The blocked aliphatic and / or alicyclic polyisocyanate compound is obtained by reacting (i) a hydroxy compound having 2 to 4 hydroxy groups with an aliphatic and / or alicyclic diisocyanate compound. An adduct-type polyisocyanate compound obtained by blocking an adduct-type polyisocyanate compound with a blocking agent; and (ii) an isocyanurate obtained by blocking an isocyanurate-type polyisocyanate compound derived from an aliphatic and / or alicyclic diisocyanate compound with a blocking agent. Type polyisocyanate compounds are preferred. Among them, aliphatic diisocyanate compounds and / or alicyclic diisocyanate compounds having 4 to 20 carbon atoms are preferable, and those having 4 to 15 carbon atoms are more preferable. By setting the number of carbon atoms of the isocyanate compound in such a range, a coating film having excellent durability is formed.

  The blocked polyisocyanate compound preferably has a converted isocyanate group ratio of 5.5 to 50% by weight, more preferably 6.0 to 40% by weight, and still more preferably 6.5 to 30% by weight. The converted isocyanate group ratio is a value that represents the weight of the isocyanate group to be produced as a percentage of the weight of the component (B) when the component (B) is heated to separate the blocking agent. When the isocyanate group ratio is in the preferred range, it is possible to satisfactorily achieve both adhesion to the substrate and prevention of cracks in the (E2) layer. The converted isocyanate group ratio (% by weight) is determined by a method in which an isocyanate group is ureated with a known amount of amine and an excess amine is titrated with an acid. Further, the content of the blocked polyisocyanate compound is such that the isocyanate group is 0.8 to 1.5 equivalents, preferably 0. 1 equivalent to 1 equivalent of the reactive group with the isocyanate present in the acrylic copolymer. The amount is 8 to 1.3 equivalents, most preferably 0.9 to 1.2 equivalents. More preferably, as the reactive group with isocyanate, the unit (A-4) contains a unit in which Z of the unit is a hydroxy group, and the isocyanate group is 0.8 to 1.5 with respect to 1 equivalent of the hydroxy group. The amount is equivalent, preferably 0.8-1.3 equivalent, and most preferably 0.9-1.2 equivalent.

  Furthermore, the acrylic resin composition forming the (E1) layer promotes the dissociation of the blocking agent of the blocked polyisocyanate compound and the urethanization reaction between the regenerated isocyanate group and the hydroxy group of the acrylic copolymer. Therefore, it is preferable to contain a curing catalyst. Examples of the curing catalyst include an organic tin compound, a quaternary ammonium salt compound, a tertiary amine compound, an organic titanium compound, and an organic zirconium compound. These compounds are used alone or in combination of two or more. Of these curing catalysts, organotin compounds are preferably used. Details of such a curing catalyst are described in JP-A-2008-231304.

  Furthermore, the acrylic resin composition forming the (E1) layer can contain a silane coupling agent, an ultraviolet absorber, a light stabilizer, and the like. Details of these agents are also described in JP-A-2008-231304. The compounding amount of such an agent is 0.2 to 8% by weight for the silane coupling agent, 0.2 to 20% by weight for the UV absorber, and 0 for the light stabilizer in 100% by weight of the acrylic resin composition. .05 to 10% by weight is preferred. Since the ultraviolet absorber and the light stabilizer have a synergistic effect, when any one of the units (A-1) to (A-4) is not included, they are contained so as to complement each other. It is preferable. Also in the case of an ultraviolet absorber, since the absorption wavelength varies depending on the type, different types of ultraviolet absorbers can be blended for the purpose of complementing the effect. As such different types of ultraviolet absorbers, both organic ultraviolet absorbers and inorganic ultraviolet absorbers can be used. As the inorganic ultraviolet absorber, single or composite oxide fine particles contained in the later-described (E2) layer are preferably exemplified, and titanium oxide, cerium oxide, and zinc oxide are particularly preferable. In the use of such an inorganic ultraviolet absorber, it is preferable to maintain a good dispersion in the hard coat layer by using various dispersants in the same manner as the dispersant in the printing ink. As such dispersants, modified polyurethanes, modified polyacrylates, modified polyesters, polycarboxylic acids, phosphate esters, alkylene oxides, silicones, and the like can be used as polymer systems. Any of a system, a cationic system, and a nonionic system may be used. An example of a dispersant suitable for the hard coat layer of the present invention, particularly the primer layer, is a polymer dispersant having an amino group and a molecular weight of 5,000 to 50,000. And high molecular weight dispersants having a molecular weight of 5,000 to 50,000. Such polymeric dispersants may be in the form of block or graft copolymers. Furthermore, after the treatment of such a dispersant, it can be further treated with another dispersant such as a modified polyacrylate. Examples of modified polyacrylates include (meth) acrylic acid and (meth) acrylic acid alkyl esters, and copolymers with other vinyl monomers such as styrene as necessary. The (meth) acrylic acid alkyl ester is an alkyl group having 1 to 35 carbon atoms, a (meth) acrylate having a monocyclic saturated alicyclic group such as cyclohexyl (meth) acrylate, and two or more such as isobornyl (meth) acrylate. (Meth) acrylate having a saturated alicyclic group having a ring of The amount of such a dispersant used is preferably 3 to 80% by weight, more preferably 3 to 30% by weight, out of a total of 100% by weight with the inorganic ultraviolet absorber.

(Vi-3) (E1) Layer Film Thickness of a suitable primer layer of the present invention obtained by thermosetting the acrylic resin composition is preferably 1 to 15 μm, and more preferably 2 to 10 μm. When the film thickness is less than 1 μm, the transmittance of ultraviolet rays is increased, and the polycarbonate substrate is yellowed and the adhesiveness with the silicone resin-based top layer is lowered, resulting in poor weather resistance. When the film thickness exceeds 15 μm, the internal stress increases, and the crosslinking reaction does not proceed sufficiently at the time of thermosetting, so that the coating layer has poor durability. Moreover, volatilization of the solvent used for dissolving the acrylic resin composition becomes insufficient, the solvent remains in the coating film, and the hot water resistance and weather resistance are impaired.

(Vi-4) (E1) Layer Formation Method As a method of forming the (E1) layer comprising the acrylic resin composition, a volatile solvent that does not react with the substrate and does not dissolve the substrate is used. The acrylic resin composition is dissolved, the acrylic resin coating is applied to the substrate surface, the solvent is then removed by heating, and further heated to react the hydroxyl group and the isocyanate group produced by heating. It is formed by crosslinking. Such solvents are preferably ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane, ethyl acetate, butyl acetate, Acetates such as 3-methoxybutyl acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethoxyethyl acetate, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-ethoxyethanol, 1-meth Alcohols such as cis-2-propanol (propylene glycol monomethyl ether), diacetone alcohol, propylene glycol monoethyl ether, propylene glycol n-butyl ether, and 2-butoxyethanol can be used, and n-hexane, n- Examples include hydrocarbons such as heptane, isooctane, benzene, toluene, xylene, gasoline, light oil, and kerosene, acetonitrile, nitromethane, and water. These can be used alone or in combination of two or more. Preferably, the mixing ratio is adjusted so as to satisfy the above SP value range. In such an acrylic resin coating, the concentration of the acrylic resin composition (solid component) is preferably 1 to 50% by weight, and more preferably 3 to 30% by weight.

  The base material on which the acrylic resin coating is applied is usually cured by heating after the solvent is dried and removed at a temperature from room temperature to a temperature lower than the heat distortion temperature of the base material. The thermosetting is preferably in the range of 80 to 160 ° C, more preferably in the range of 100 to 140 ° C, most preferably in the range of 110 to 130 ° C, preferably 10 minutes to 3 hours, more preferably 20 minutes to 2 hours. By heating, the crosslinkable group is crosslinked, and a molded product in which the acrylic resin layer is laminated as the first layer is obtained. When the heat curing time is shorter than 10 minutes, the crosslinking reaction does not proceed sufficiently, and a coating layer having poor durability and weather resistance in a high temperature environment may be obtained. Moreover, the heat curing time is sufficient within 3 hours in view of the performance of the coating film.

(V-ii) Silicone resin-based top layer ((E2) layer) in the hard coat layer
The (E2) layer of the present invention is preferably a coating layer formed by thermally curing an organosiloxane resin composition containing a hydrolyzed condensate of colloidal silica and alkoxysilane. Preferably, it is formed by using a coating material for coating comprising an organosiloxane resin solid content comprising the colloidal silica and alkoxysilane hydrolysis condensate, an acid, a curing catalyst, and a solvent. For forming a cured resin layer having a siloxane bond, a partial hydrolysis-condensation product of a compound mainly composed of a compound corresponding to a trifunctional siloxane unit (trialkoxysilane compound or the like), preferably a tetrafunctional siloxane unit. Partially hydrolyzed condensate containing a compound corresponding to (e.g., tetraalkoxysilane compound) and / or a compound corresponding to a bifunctional siloxane unit, and further partially hydrolyzed condensate filled with metal oxide fine particles such as colloidal silica Etc. are exemplified. The silicone resin hard coat agent may further contain a monofunctional siloxane unit. These include alcohol generated during the condensation reaction (in the case of a partially hydrolyzed condensate of alkoxysilane), etc., but if necessary, may be dissolved or dispersed in any organic solvent, water, or a mixture thereof. Good. Examples of the organic solvent for this purpose include lower fatty acid alcohols, polyhydric alcohols and ethers thereof, and esters. A leveling agent can be added to the hard coat layer in order to obtain a smooth surface state. JP-A-2008-231304 also describes details of specific embodiments, blending amounts, and adjustment conditions of such colloidal silica, alkoxysilane, acid, curing catalyst, and solvent. When the weather resistance is more important, it is preferable to contain an inorganic ultraviolet absorber typified by a metal oxide and an organic ultraviolet absorber. Examples of the ultraviolet absorber include inorganic oxides such as titanium oxide, cerium oxide, zinc oxide, tin oxide, zirconium oxide, antimony oxide, tungsten oxide, antimony-containing tin oxide, and tin-containing indium oxide. These composite metal oxide fine particles and a mixture thereof are exemplified. Of these, titanium oxide, cerium oxide, and zinc oxide are preferable, and cerium oxide is particularly preferable. Such a combination improves all the hardness, transparency, and weather resistance of the hard coat. The particle diameter of such fine particles is preferably 1 to 500 nm, more preferably 10 to 100 nm.

  As other ultraviolet absorbers, metal chelate compounds such as titanium, zinc, and zirconium, and (partial) hydrolysis condensates thereof, and as organic ones, the main skeleton is hydroxybenzophenone, benzotriazole, Examples include cyanoacrylate-based or triazine-based compound derivatives, and polymers or copolymers such as vinyl polymers containing these ultraviolet absorbers in the side chain.

  The (E2) layer is obtained by applying a coating for coating obtained by dissolving the organosiloxane resin composition in a solvent onto the (E1) layer formed on a transparent plastic substrate, and then curing by heating. Is formed. The amount of the solvent to be used is preferably 50 to 1900 parts by weight, more preferably 150 to 900 parts by weight with respect to 100 parts by weight as a total of the hydrolyzed condensate of colloidal silica and alkoxysilane. The concentration of the solid content is preferably 5 to 70% by weight, more preferably 7 to 40% by weight. It is desirable that the coating organosiloxane resin paint is adjusted to a pH of preferably 3.0 to 6.0, more preferably 4.0 to 5.5 by adjusting the contents of the acid and the curing catalyst. By adjusting the pH within this range, gelation of the organosiloxane resin coating at room temperature can be prevented, and storage stability can be increased. The organosiloxane resin paint usually becomes a stable paint by further aging for several hours to several days.

  The formation of the (E2) layer is preferably performed continuously following the formation of the (E1) layer. The substrate coated with the organosiloxane resin composition is usually cured by heating after drying and removing the solvent at a temperature from room temperature to a temperature lower than the heat distortion temperature of the substrate. The thermosetting is preferably performed at a high temperature within a range where there is no problem in the heat resistance of the base material because the curing can be completed earlier. At normal temperature, thermosetting does not proceed and a cured film cannot be obtained. This means that the organosiloxane resin composition in the coating organosiloxane resin coating is partially condensed. In the process of thermosetting, the remaining Si—OH undergoes a condensation reaction to form a Si—O—Si bond, resulting in a coat layer with excellent wear resistance. The thermosetting temperature is preferably 50 to 200 ° C, more preferably 80 to 160 ° C, and still more preferably 100 to 140 ° C. The heat curing time is preferably 10 minutes to 4 hours, more preferably 20 minutes to 3 hours, and further preferably 30 minutes to 2 hours.

  The thickness of the (E2) layer is preferably 2 to 10 μm, more preferably 3 to 8 μm. If the thickness of the coating layer is within such a range, cracks may occur in the coating layer due to stress generated during thermosetting, or the adhesion between the (E2) layer and the (E1) layer may be reduced. Thus, a coating layer having sufficient wear resistance as the object of the present invention can be obtained.

(V-iii) Method of Laminating Hard Coat Layer The method of laminating the hard coat layer in the present invention is not particularly limited, and is a dip coat method, a flow coat method, a blade coat method, a knife coat method, a squeeze coat method, a transfer. A roll coating method, a gravure roll coating method, an air spray coating method, an electrostatic spray coating method, a spin coating method, or the like can be used. Among these, the dip coating method and the flow coating method are preferable. When the hard coat layer is a single layer, it is usually air-dried after coating and then subjected to a curing reaction. In the case of two or more layers, a method of air-drying and curing for each layer is suitable, but a method of applying a coating solution for the next layer only by air-drying and curing two or more layers at once is adopted. You can also.

  As a method other than the application of the coating component, a transfer method may be mentioned. In such a method, a laminate sheet provided with a hard coat layer and a layer for adhering the layer and the molded product on the release layer is prepared, and the sheet and the molded product are laminated to form a laminate on the molded product. A hard coat layer can be provided. Furthermore, as another method, the hard coat layer laminated on the film and the thin sheet is bonded to the molded product-A by insert molding of the film and the sheet, thermal lamination, and various adhesives. The structure used as the hard-coat layer of molded article-A can also be taken.

  When there is a trim process as described later, providing a hard coat lamination process before the trim process has the advantage of facilitating the elimination of uneven hard coat film thickness and accumulation of hard coat liquid at the end of the product. .

  Furthermore, in the present invention, the hard coat layer may be provided by a method other than the above. Examples of such other methods include vapor deposition and thermal spraying. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method. Examples of the thermal spraying method include an atmospheric pressure plasma spraying method and a low pressure plasma spraying method. A hard film such as diamond-like carbon can be formed by the above method.

(VI) Laminated structure The glazing laminated structure of this invention laminated | stacked the following (B) layer, (C) layer, (D) layer, and (E) layer on the at least one surface of the following (A) layers. When it is a structure and the cross section along the thickness direction of a laminated body is seen, the laminated structure 1 laminated | stacked in order of (A) layer-(B) layer-(C) layer-(D) layer, There are a laminated structure 2 laminated in the order of A) layer- (B) layer- (E) layer, and a laminated structure 3 laminated in the order of (A) layer- (E) layer. The laminated structure 2 is interposed between the three.
(A) Layer: a light-transmitting base material layer made of polycarbonate resin.
(B) Layer: A two-component curable ink layer made of acrylic polyurethane formed by reaction of an acrylic polyol resin and a polyisocyanate compound.
(C) Layer: An adhesive primer layer formed from a primer composition containing a polyisocyanate compound and an acetate solvent.
(D) Layer: An adhesive layer made of a urethane adhesive.
(E) Layer: Hard coat layer.

  The (E) layer is laminated on the light transmitting portion of the (A) layer and the (B) layer laminated on the (A) layer. Examples of the lamination of the (E) layer on the (B) layer include lamination on a blackout treatment portion where no adhesive layer is provided, a conductive functional layer provided without significantly reducing transparency, and ultraviolet absorption. Examples include a functional layer and lamination on various functional layers such as an infrared absorption functional layer. Since the (E) layer is also formed on the (B) layer, the design is excellent, which is preferable. The (E) layer is preferably laminated before being bonded and fixed.

The manufacturing method of the glazing laminated body of this invention comprises the following process (i)-(iv).
(I) a step of forming the (B) layer on a part of at least one surface of the (A) layer (step (i)),
(Ii) On the side of the light-transmitting substrate obtained in step (i) and partially formed with the (B) layer, (B) from the surface of the (A) layer where the layer is not formed (B A step of forming the (E) layer continuous over a part of the surface of the layer (step (ii)),
(Iii) a step of forming the (C) layer on at least a part of the surface of the (B) layer in which the (E) layer obtained in the step (ii) is not formed (step (iii)),
(Iv) A step of forming the (D) layer on the surface of the (C) layer obtained in the step (iii) (step (iv)).
In the present invention, it is preferable that the step (ii) is performed after the layer (B) is formed on the layer (A) in the step (i) and then heat-deformed.

  Such a laminated structure is schematically shown in FIG. The step (step-1) proceeding sequentially with [1-a], [1-b], and [1-c] is a step of removing only the adhesion portion after providing the hard coat layer including the adhesion portion. is there. Such a method can be applied when the adhesion between the hard coat layer and the print layer is relatively low. For example, the removal of the hard coat layer can be carried out by a method of applying a strongly adhesive tape at a predetermined position and peeling the tape. In the step (step-2) proceeding sequentially with [2-a], [2-b], and [2-c], the adhesive portion is previously covered with a masking material, and a hard coat layer is provided thereon, and then the masking material. In which the primer and the adhesive can be applied on the ink layer. Since the hard coat process may be baked multiple times, such a masking material makes it possible to perform a good hard coat process without significant deformation at the time of baking, and the adhesive residue as much as possible after removing the mask. Less is required. The masking material satisfying such properties is preferably a material having a polyolefin as a base material and an adhesive strength in the range of 1 to 6 N / 10 mm. Such adhesive strength is more preferably in the range of 1 to 3 N / 10 mm. Specific examples of such a preferred masking material include, for example, parting masking tapes Nos. 4240 and 4241 manufactured by Tessa Tape Co., Ltd., and 4241 is particularly preferable. The step of proceeding in the order of [3-a] and [3-c] is a step (step-3) in which a hard coat liquid is applied by avoiding the adhesive portion and a hard coat layer is provided. Steps 1 to 3 can be used in combination with each other. Among these, the method including Step-2 is preferable because it can be applied to a wide range of configurations. FIG. 4 shows a configuration in which the ink layer is mainly covered and shielded and the ink layer is partially covered. In the glazing structure of the present invention, as described above, the functional ink having translucency is shown. Or the like may be printed on a part or all of the light-transmitting portion, and a hard coat layer may be provided thereon.

<Molded product-A molding method and secondary processing>
Examples of the molding method of the molded product-A in the present invention include injection molding, extrusion molding, compression molding, blow molding, and rotational molding. In particular, injection molding is preferable, and injection compression molding is particularly preferable. Further, the molded product-A may be a product whose shape is determined by performing secondary processing such as bending, trimming, and perforation after molding. The final shape of the laminated body may be determined at the time of manufacturing the molded body-A, or may be determined through a bending process and / or a trimming process after the lamination. Further peripheral members can be attached to members not yet coated with urethane adhesive as required. By attaching such peripheral members, a final part for the resin glazing laminate is formed. The purpose of the peripheral member includes, for example, positioning at the time of adhesion and fixing, and temporary fixing until the adhesive is completely cured. Examples of the peripheral member include a frame, a pin, a screw, a fastener, a cushioning material, a seal material, a hinge, and a lock mechanism. Such a peripheral member is preferably attached to a printed molded body having a hard coat layer and a final shape, using fixing means such as adhesion, adhesion, screwing, welding, fitting, ultrasonic welding, and laser welding, The final part. The final part with or without the peripheral member attached thereto is fixed to a structural member made of a rigid body such as a vehicle body by adhesion.

  A structural member is a structure or a structural component of a building, and refers to a support material that bears the load of other objects or parts. Examples include various window frames disposed on the body. Such transportation equipment includes automobiles, trucks, trains, aircraft, ships, motorcycles, bicycles, and wheelchairs, construction equipment, tractors, and the like. Buildings as structural members include, for example, buildings such as buildings, outdoor stadiums, gymnasiums, arcades, carports, greenhouses, and houses, road facilities such as soundproof walls, windbreak walls, and snow fences, signs, signs, and Display equipment such as a large outdoor monitor, and a power generation device such as a solar power generation device are included. The glazing bonded body referred to in the present invention refers to a structure in which the glazing structure of the present invention is combined with the structural member and integrated. Structural members include metals, glass, ceramics, ceramic composites, fiber reinforced plastics, fiber reinforced composites (composite materials such as FRP, SMC, and RTM made of glass fibers, aramid fibers, ceramic fibers, and carbon fibers), and wood Etc. are formed. As a metal member, the member formed from steel materials (steel plate), an aluminum alloy, a magnesium alloy, a titanium alloy, etc. is illustrated. The trim process will be described later.

(VII) Injection Compression Molding of Molded Product-A Injection compression molding according to the present invention includes so-called injection press molding and narrowly injection compression molding. Here, injection press molding refers to supplying molten thermoplastic resin into a mold cavity having a capacity larger than the target molded article capacity at least when the supply is completed, and after completing the supply, the mold cavity capacity is reduced. It refers to a molding method in which the molded product is reduced to a target molded product volume and the molded product is taken out after cooling to a temperature at which the molded product in the mold cavity can be taken out. The reduction of the mold cavity capacity may be started before or after the completion of the resin supply, but is preferably started before the completion of the supply. That is, a mode in which the step of reducing the cavity capacity and the step of filling the resin overlap is preferable. On the other hand, injection compression molding in the narrow sense is a molding method in which the expansion of the cavity capacity is at a level almost equal to the volume of the molten thermoplastic resin, and the volume fraction that compresses the molten thermoplastic resin is cooled and contracts. Point to. In the present invention, injection press molding which has a small distortion and excellent mold transfer property even in a large molded product is preferable.

  Furthermore, in the present invention, injection compression molding that maintains parallelism between the fixed side mold and the movable side mold is preferable. As a method for maintaining parallelism, a conventionally known method can be used. However, a preferred embodiment of the present invention is Method-1a: adjusting expansion / contraction of a plurality of mold clamping mechanisms arranged on a mold fixing plate. Injection compression molding method for controlling parallelism by performing the method, or method-1b: expansion and contraction of a plurality of correction force applying mechanisms for applying a correction force to the mounting surface of the mold against the mold clamping force by the mold clamping mechanism This is an injection compression molding method in which parallelism is controlled by adjusting. Method-1a is more suitable in the present invention because the parallelism control means of method-1a can maintain more precise parallelism and can sufficiently cope with a large molded article. The parallelism control means of the method-1b can be easily attached to an existing injection molding machine to exert its function, and as a result, the method-1b is advantageous in that the capital investment cost can be suppressed. .

  Details of Method-1a are described below. One of the preferable aspects of the above-mentioned method-1a is that the degree of parallelism between the fixed mold and the movable mold is adjusted by a mold clamping mechanism at four corners of the mold fixing plate. This is an injection compression molding method that maintains the parallelism.

In the method of detecting, calculating, and controlling parameters necessary for maintaining the parallelism, the following two points can be cited as preferred embodiments of the present invention.
A first preferred aspect is that the relative position between the movable plate and the fixed plate detected when the movable die is translated with respect to the fixed die by the mold clamping mechanism at four corners of the mold fixed plate. The average distance between the movable mold and the fixed mold is calculated from the detected value, and the difference between the detected value of each mold clamping mechanism and the average distance is added to or subtracted from the command value to each mold clamping mechanism as a correction amount. This is an injection compression molding method that maintains the parallelism between dies by controlling the integrated value of the difference by feedback.

  The second preferred mode is that when the movable mold moves parallel to the fixed mold by the mold clamping mechanism at the four corners of the mold fixing plate, the mold clamping in the mold clamping mechanism at the four corners is performed. The force is detected, the average value of the detected clamping force is calculated, and the difference between the target clamping force preset for the clamping mechanism set in the command value for each clamping mechanism and the average value of the detected clamping force is calculated. This is an injection compression molding method that maintains the parallelism between the molds by adding and subtracting as a correction amount and controlling the difference integrated value by feedback.

The flow length from the gate to the flow end of the molded article-A is preferably 15 to 300 cm, more preferably 30 to 250 cm. Furthermore, it is preferable that the molded product-A is flat, but by forming a predetermined curved surface already at the stage of the sheet manufacturing process, if the entire process can be seen comprehensively and cost can be reduced, It can also have a curved shape. Similarly, the thickness of the molded product-A is most preferably excellent in general versatility. However, if it is advantageous to have a thickness distribution, it may have a thickness distribution.
Further details of injection compression molding will be described with reference to the drawings.

(VII-i) Configuration of molding machine FIG. 1 is a longitudinal sectional view of a mold clamping device showing a state at the start of a molding cycle, and FIG. 2 is a longitudinal section of the mold clamping device showing a state before the start of injection compression molding of a molded product. FIG. 3 is a longitudinal sectional view of the mold clamping device showing a state in which the molded product is injection compression molded.
The mold clamping device 10 constitutes an injection molding machine together with the first injection device 11. The sheet to be produced may be a multilayer sheet as required, but is preferably a single layer sheet. Hereinafter, the details in producing the single-layer sheet will be described.

  The mold clamping device 10 includes: (a) a fixed plate 21 that is a mold fixing plate for mounting the fixed mold 13; (b) a movable plate 22 that is a mold fixing plate facing the fixed plate 21 for mounting the movable mold 14; (C) A mold clamping mechanism 16 including a hydraulic cylinder device and the like provided in the vicinity of the four corners which are the corners of the movable plate 22 and including a pressure clamping chamber 27 and an opening chamber 28; and (d) a hydraulic cylinder device of the mold clamping mechanism 16. A tie bar 23 formed by extending a rod; (e) provided at four corners of a fixed plate 21 on the extension of the tie bar 23 and provided at an opening of a through hole that freely penetrates the fixed plate 21 side end of the tie bar 23; (F) Mold opening / closing of a hydraulic cylinder device or a servo motor and a ball screw mechanism which are provided as a pair on the upper and lower surfaces or front and back side surfaces of the fixed plate 21 and move the movable plate 22 toward and away from the fixed plate 21. Device 18, and (g) solid Composed of a position sensor 24 that slides fixed to the guide 25 above between the plate 21 and the support plate 26.

  The position sensor 24 is attached in the vicinity of each mold clamping mechanism 16 of the movable plate 22 so that the distance of the movable plate 22 to the fixed plate 21 at each corner can be detected. The mold clamping mechanism 16 may be provided on any mold fixing plate of the fixed plate 21 and the movable plate 22. Moreover, although the mold apparatus 15 is comprised by the fixed mold 13 and the movable mold 14, you may attach the position sensor 24 to four places, the said fixed mold 13 and the movable mold 14. FIG.

  As described above, when the second injection device is appropriately provided, as an arrangement method thereof, for example, a method of arranging two injection devices horizontally in parallel, one injection device is set up vertically and the other is arranged horizontally And a method of arranging two injection devices horizontally and orthogonally. Both can be molded by setting independent molding conditions in each injection device.

  As a resin flow path in the mold, in addition to a method of injecting resin from an injection device and filling the cavity through the hot runner manifold and gate, a method of filling the cavity through the cold runner and gate can be used. . The runner and gate may be single or plural, but a method of filling the cavity with a single gate is more preferable. In particular, a method of filling the cavity through a single hot runner manifold and gate is preferable.

  Also in the case of a plurality of gates, a method of filling the cavity through a plurality of hot runner manifolds and gates is preferable. In such a case, a method of filling the mold cavity by a cascade molding method using a sequential valve gating method (SVG method) is preferable. In such a method, the gate that normally passes the resin first is removed, and in each subsequent gate, after the molten resin that has flowed from the previous gate has passed, the gate is opened and the gate is placed on the flow of the molten resin. The resin from is filled. This operation is performed step by step at each gate to supply molten resin. As a result, it is possible to suppress the weld line as much as possible while using a plurality of gates.

  Since this method can reduce the amount of molten resin from one hot runner, it is preferable in that it can suppress shear heat generation of the resin and heat storage in the hot runner portion. Therefore, this method is suitable when the thermal stability of the resin material-A is slightly inferior. On the other hand, compared to the case of a single runner and gate, the resin flow inside the cavity is more complicated, so that inhomogeneity such as resin intimacy and orientation in the sheet is likely to occur, and the sheet quality is simple. One gate is more advantageous.

  As a hot runner gate system, either an internal heating method or an external heating method may be used. In the case of an external heating method, any of an open gate method, a hot edge gate method, a valve gate method, etc. is used. However, the valve gate method is preferable because a wider range of molding conditions can be obtained. When using a hot runner of the valve gate type, a packing member is used to prevent the molten thermoplastic resin from leaking from the sliding portion of the valve gate. Here, specific examples of the material constituting the packing member include acrylic rubber, silicone rubber, ethylene-propylene rubber, nitrile rubber, and fluorine-based resin. Rubber and fluorine resin are preferred.

(VII-ii) Cavity Formation for Molding Next, a molding example of a molded product will be described in the order of steps with reference to FIGS. In FIG. 1, it is in the state at the start of the molding cycle. In FIG. 2, the mold is closed by the mold opening / closing device 18 and the tie bar 23 and the fixed plate 21 are coupled by the lock device provided on the fixed plate 21. The intermediate clamping state is opened by an amount corresponding to the compression stroke, which is the difference between the state and the final clamping state, and is the starting point of the molding cycle. Here, the injection process refers to a process from when the molten resin is filled into the mold cavity corresponding to the product until the supply of the resin filled into the cavity is completed.

  The width of the compression stroke in the intermediate clamping state is such that the cavity capacity in the intermediate clamping state is preferably in the range of 1.05 to 10 times, more preferably in the range of 1.1 to 5 times the cavity capacity in the final clamping state. More preferably, the range is set to 1.2 to 2 times. Since the width of the compression stroke in the intermediate mold clamping state is widened as described above, the injection rate can be reduced, the distortion of the molded product can be improved, and the injection device 11 is also cost of the high-speed and high-pressure injection type. It is not necessary to use a high injection device. If the cavity capacity in the intermediate clamping state is less than 1.05 times the cavity capacity in the final clamping state, high pressure is concentrated on the resin near the gate when the resin is filled in the cavity in the injection process. The distortion and thickness variation of the molded product are likely to occur, and if it exceeds 10.0 times, molding defects such as jetting are likely to occur.

  In addition, the stop position of the movable mold 14 in the intermediate mold clamping state is not limited to the intermediate mold clamping state that is opened excessively by the compression stroke until the final mold clamping process when the thickness of the molded product is a certain thickness or more. The movable mold 14 may be moved forward. Then, the movable die 14 is retracted by receiving the injection pressure in the injection step, and the volume of the cavity is enlarged, so that the subsequent compression stroke is ensured, whereby the injection compression molding can be performed.

(VII-iii) Injection process and compression process In FIG. 3, molten resin is inject | emitted from the injection apparatus 11 to the cavity formed in FIG. This step is an injection step, and the compression step is performed next as a continuous step or a step in which the latter half and a part of the injection step are continued in parallel. Note that the period (t _O (seconds)) in which the compression operation and the resin injection supply are simultaneously performed is generally referred to as an overlap time. When the compression process is started in parallel in the latter half of the injection process, the screw advance position is detected, and when the screw advance position reaches the set position, compression by the mold clamping mechanism is started. The compression process is performed by compressing the molten material injected in the injection process so that the volume of the cavity is reduced by each mold clamping mechanism 16, and filling the cavity by spreading the molten material in the cavity. And the molded product 31 is shape | molded. The overlap time (t _O ) is preferably 2 seconds or less, more preferably 1 second or less. Further, t _O is preferably 0.05 seconds or more, more preferably 0.1 seconds or more, and an overlap time is preferably provided. Further, the compression start time at the time of overlapping is such that the resin filling ratio per total resin filling amount is preferably 90 to 99.9%, more preferably 95 to 99.5%, and still more preferably 97 to 99 by volume. % Is preferable in the present invention.

(VII-iv) Injection rate of molten resin in injection step In the injection step, the injection rate of filling the molten resin from the injection device 11 into the cavity formed in FIG. 2 is preferably 50 to 2,000 cm ³ / sec. 100~1,800cm more preferably ³ / sec, more preferably 150～1,500Cm ³ / sec. When the injection rate is less than 50 cm ³ / sec, the time for filling the cavity with the molten resin becomes longer, and the resin temperature decreases and the melt viscosity becomes too high before the transition from the injection process to the compression process. In the process, it tends to cause appearance defects such as short shots and flow marks, and poor accuracy in thickness and dimensions. On the other hand, when the injection rate exceeds 2,000 cm ³ / sec, distortion tends to remain in the obtained molded product, and appearance defects such as silver streaks due to air entrainment tend to occur. The injection rate referred to here is the resin volume injected into the mold cavity divided by the time required from the start of injection to the end of injection, and does not necessarily have to be a constant speed.

(VII-v) Parallel control between molds in compression process In the compression process, the mold is adjusted by adjusting the parallelism between the fixed mold and the movable mold by the mold clamping mechanism at the four corners of the mold fixing plate. Parallelism between molds is maintained. An average distance between the movable mold 14 and the fixed mold 13 is calculated from the detected value of the relative position between the movable plate 22 and the fixed plate 21 detected by the position sensor 24, and a command value to each mold clamping mechanism 16 is calculated. By adding and subtracting the difference between the detected value of each mold clamping mechanism and the average distance as a correction amount and feeding back and controlling the integral value of the difference, the parallelism between the movable mold 14 and the fixed mold 13 is increased. It is preferred to use a method of maintaining. As a result, the molten material flows at high speed and uniformly in the cavity, so that the molded product 31 has low distortion as an effect of compression molding, and a uniform and high accuracy as a parallel control effect.

  In the compression process, the parallelism between the molds is not maintained based on the detected value of the relative position between the movable plate 22 and the fixed plate 21 by the position sensor 24, but the movable molds are moved by the mold clamping mechanisms 16. When the mold 14 moves in parallel with respect to the fixed mold 13, the mold clamping force in each mold clamping mechanism 16 is detected, the average value of the detected mold clamping forces is calculated, and the command value to each mold clamping mechanism 16 is calculated. The degree of parallelism between dies is controlled by adding and subtracting the difference between the target clamping force of the mold clamping mechanism set in advance and the average value of the detected clamping force as a correction amount and feeding back the integrated value of the difference. It is also preferred to use a method of maintaining. Furthermore, it is also preferable to use both in combination in order to control the parallelism between the molds with higher accuracy. When both position control and mold clamping force control (pressure control) are used together, the average distance between the movable mold 14 and the fixed mold 13 advances from the intermediate mold clamping position to a predetermined distance, or The parallel control based on the position control may be performed until the average value of the detected clamping force reaches a predetermined pressure, and the pressure control may be performed after a predetermined distance or a predetermined pressure is detected. Further, after performing parallel control by position control, position control and pressure control may be used simultaneously. When the position control and the pressure control are used simultaneously, the position control is used only for the feedback control, and the pressure control performs at least one of the feedback control and the feedforward control.

  In the case where only position control is performed, the average distance between the movable mold 14 and the fixed mold 13 is calculated from the detected value of the relative position between the movable plate 22 and the fixed plate 21 detected by the position sensor 24. In addition to adding and subtracting the difference between the detected value of each mold clamping mechanism and the average distance as a correction amount to the command value to each mold clamping mechanism 16 and feeding back and controlling the integrated value of the difference, each mold clamping Feed forward control may be added to the mechanism 16 to perform mold clamping with emphasis on speed while maintaining parallelism between the movable mold 14 and the fixed mold 13.

  In the compression process, in order to maintain the parallelism between the molds by adjusting the parallelism between the fixed mold and the movable mold with the mold clamping mechanisms at the four corners of the mold fixing plate, It is also preferable to use a master slave system in which the mold clamping mechanism at one part is the master and the rest is the slave, but in the case of a large molded product that requires highly accurate parallel control, it is more preferable than the master slave system. The above two methods are more preferable.

  In the compression process of the present invention, particularly when a large sheet is formed, it is important to maintain the degree of parallelism between dies during the intermediate clamping state and the intermediate clamping state to the final clamping state. It is. In order to obtain a large sheet, there are many cases in which molding is performed by attaching a heavy metal mold to the movable plate 22 and the fixed plate 21, and each mold clamping mechanism of the molding machine is accompanied by an increase in the mold weight. It is difficult to maintain the parallelism at 16. Further, the uneven load generated by the pressure at the time of resin filling also causes the thickness non-uniformity of the molded product, but this effect is particularly noticeable in a large sheet. Furthermore, maintaining parallelism between molds achieves a more uniform pressure load on the resin within the mold. As a result, the pressure applied to the resin achieves a low pressure as a whole, and it is possible to provide a molded product with less distortion. When the parallelism between the molds is not sufficient, a local difference occurs in the pressure applied to the molded product during molding, which becomes one of the factors of distortion and also causes the warp of the sheet. Further, from the viewpoint of productivity, the misalignment of parallelism causes mold galling and the like, making it difficult to mass-produce products.

(VII-vi) Movement speed of movable mold in compression process In the compression process, each mold clamping mechanism 16 compresses the cavity to reduce the volume, and fills the cavity by spreading the molten material in the cavity. When moving, the moving speed of the movable mold is preferably 5 mm / second or more, more preferably 7.5 mm / second or more, and still more preferably 10 mm / second or more. A molded article having a higher L / D requires a higher mold capacity enlargement ratio and requires a higher moving speed. This is because in order to reduce the distortion of the molded product, it is important to end the compression process up to a predetermined final clamping state while the thermal distribution of the molten resin in the cavity is narrow. The higher the moving speed, the larger the compression stroke can be handled. Therefore, it is preferable that the moving speed is as high as possible, but at present, about 40 mm / sec is practically a limit on the apparatus. If the level is 35 mm / second, sufficiently precise speed control is possible. The moving speed is obtained by dividing the compression stroke from the intermediate clamping state to the final clamping state by the time required for compression, and does not necessarily have to be a constant speed. As described above, the larger the compression stroke and the higher the moving speed of the mold, the easier the galling of the mold occurs. Therefore, maintaining the parallelism between the molds is also an important and essential condition here.

(VII-vii) Pressure holding step In the compression step, each mold clamping mechanism 16 compresses the cavity to reduce the volume, and the molten material is spread in the cavity to fill the cavity. The repulsive force rises rapidly. At this time, the control by the mold clamping mechanism 16 may be switched from the position control to the pressure control. When switching to pressure control, it is desirable to control the pressure in the cavity (surface pressure) to be 7 to 20 MPa. Usually, the hydraulic pressure of the hydraulic cylinder or its piping is detected, and the surface pressure is obtained by dividing the mold clamping force by the projected area of the molded product, but a resin pressure sensor may be provided in the cavity.

  In order to maintain the cavity capacity in the final clamping state with an appropriate pressure that overcomes the repulsive force, the process is continued as a process that has continued in the compression process, or a process that has continued in parallel with the latter half of the compression process. A pressure process is performed. By this pressure-holding step, an extremely appropriate amount of resin is filled with a uniform density into the target molded product volume by the injection device 11, and the molded product is preferable because of its excellent shape accuracy and extremely low distortion. The application of pressure to the resin (pressurization) is due to the force by which the movable mold advances by each mold clamping mechanism 16. Further, such pressure transmission is usually performed by direct contact between these advancing members and the resin, but pressure transmission media such as fluid may be interposed between them.

The appropriate holding time of the pressure depends on the thickness of the molded product, and the appropriate time becomes longer as the thickness increases. However, this tendency is particularly noticeable in the case of a large molded product. In the case of a large molded product intended by the present invention, the holding time X (seconds) when the molded product thickness is t (mm) is appropriately within the range satisfying the following formula (I). For example, in the thickness of 5 mm which is an intermediate value in the range of 1 mm to 9 mm which is a preferable sheet thickness in the present invention, the range of 160 ± 30 seconds is preferable. However, this does not apply when a system that rapidly heats and cools the mold temperature typified by the heat and cool molding method is used.
X = (30 × t + 10) ± 30 (seconds) (I)

  In the invention, a method of partially raising the temperature of the cavity surface represented by such a rapid heating and cooling system and delaying the development of the solidified layer at the time of molding can be used in combination. By such combined use, although the molding cycle is increased, it becomes possible to further improve the transferability of the mold surface and form a high-quality design surface. Examples of such methods include a method of providing a heat insulating layer formed of a heat-resistant resin, ceramic, glass and the like on the cavity surface, and a heat and cool molding method. A method for controlling the mold temperature is preferably exemplified.

(VII-viii) Cooling step A cooling step is performed following the pressure holding step. The molded product in the cavity is taken out after cooling to a temperature at which it can be taken out from the cavity. When the mold is opened for removal, the above parallel control is performed up to a predetermined intermediate position. Such an intermediate position is usually the above-described intermediate mold clamping position. In order to suppress the occurrence of deflection due to the weight of the resin plate, the resin plate is cooled to a temperature lower than the load deflection temperature of the resin material-A, more preferably 30 to 60 ° C. lower than the load deflection temperature, and the resin material is taken out from the cavity. For example, in the case of a bisphenol A type polycarbonate resin, a range of 75 to 105 ° C is preferable, and a range of 80 to 100 ° C is more preferable. During the cooling process, the pressure in the pressure-holding process may be kept, may be in a state where no pressure is applied, or may be lowered stepwise during the cooling process. Further, the mold clamping mechanism 16 controls the position by the position control or the pressure control during the cooling process, so that sink marks and thickness unevenness of the molded product can be prevented.

  Here, the bending includes both hot bending and cold working. In the thermal bending process, the molded body before processing is heated to the softening temperature of the resin material-A or higher, preferably the glass transition temperature of the resin that is the main component of the resin material-A, and then the bending process is performed. In cold working, bending is performed at a temperature lower than that, and drawing, pressing, and the like are included in addition to bending. Further, such bending is preferably performed in advance in order to match the shape of the rigid body to which the molded product-A is to be fixed. However, it is possible to adopt a mode in which the bending is forcibly bent and fixed to the shape of the rigid body.

(VIII) Bending of Molded Product-A (VIII-i) Heating Step The thermal bending of the molded product-A in the present invention can be suitably used. In particular, a manufacturing method in which the molded article-A is formed into a sheet shape, and subjected to hot bending before the hard coat treatment and trim processing after the printing process can be preferably used. In the thermal bending process, when the glass transition temperature of the resin material-A is Tg (° C.), the molded product-A is preheated and softened in a temperature range of [Tg + 5] ° C. to [Tg + 70] ° C. To be served. The molded product-A taken out from the mold cavity is preferably subjected to a predetermined inspection of the molded product, and is usually masked for surface protection during storage or transportation, and is carried to the next step. The same is generally true when other processes such as a printing process are performed first. Prior to the heating step in thermoforming, the masking film is preferably removed.

  As the heating method, various conventionally known heating methods can be used. For example, an air forced circulation heating furnace, an infrared heater, and microwave heating are exemplified. Among these, even if the molded product-A represented by the sheet molded product is large, the whole is easily heated uniformly and the burden on the equipment cost is small. Is preferred. A plurality of heating methods can be used sequentially and simultaneously.

  The heating temperature is set to [Tg + 5] ° C. to [Tg + 70] ° C. with respect to Tg (° C.) of the resin material-A as described above. In the air forced circulation heating furnace, the temperature of the heating furnace is adjusted to such a temperature range, the treatment is performed for a predetermined time, and the molded product-A is brought to a temperature suitable for thermoforming. The molded product-A does not necessarily reach the temperature of the heating furnace. The temperature range is preferably [Tg + 10] ° C. to [Tg + 55] ° C., more preferably [Tg + 15] ° C. to [Tg + 50] ° C. For example, in the case of a bisphenol A type polycarbonate resin material having a Tg of 150 ° C. (including an additive of about 1% by weight), the temperature is 155 to 220 ° C., preferably 160 to 205 ° C., more preferably 160 to 200 ° C. If the temperature is less than the lower limit of the above temperature range, it takes too much time to achieve sufficient softening and the production efficiency is reduced, or the molded product is distorted or the dimensional accuracy is reduced by forced bending. On the other hand, when the upper limit of the temperature range is exceeded, relaxation of molecular chains occurs rapidly particularly on the sheet surface, and the initial high quality surface properties cannot be maintained. On the other hand, when there is little disorder of the molecular chain due to the resin flow on the surface of the molded product-A, the defects to the surface properties are reduced even by such relaxation, and it becomes easier to be subjected to higher temperature thermal bending. Bending at a high temperature is advantageous in terms of manufacturing efficiency and accuracy after bending. Therefore, the above temperature range is suitable for achieving both the production efficiency and the surface state and dimensional accuracy of the thermoformed product, and the molded product-A formed from a uniform resin flow is more suitable for bending. Yes.

If the heating time is too long, there will be a considerable decrease in surface accuracy and a significant amount of sagging deformation due to its own weight. Further, the thicker the sheet, the longer the time required for uniform heating. Therefore, the thicker the thickness, the more preferable the temperature range. The difference between the atmospheric temperature in the heating furnace and the Tg of the resin material-A is x (° C.) and the processing time y (seconds) is as follows. When the sheet thickness is z (mm),
^{y = [(0.28x 2 -34x +} 1250) × (z / 4.5) 2] ± 50
It is preferable to use the range of Further, the sheet to be heated may be placed horizontally or suspended vertically. In addition, the glass transition temperature (Tg (° C.)) of the resin material-A is measured by a method defined in JIS K7121, and refers to a glass transition temperature that can be recognized in a chart such as DSC.

(VIII-ii) Step of Forming Curved Surface by Bending In the present invention, a predetermined curved surface can be formed by applying various external forces to molded product-A represented by a sheet softened by heating. In the following description, a flat sheet which is a representative shape of the molded product-A is assumed. Here, in the heating step, heating is performed in a state where the high-quality design surface obtained in the manufacturing process of the molded product-A is maintained, and the curved surface forming step does not impair the design surface. Is preferably deformed.

  The degree of the curved surface in the present invention is represented by a radius of curvature (mm), preferably in the range of 500 to 30,000 mm, more preferably 1,000 to 25,000 mm, and more preferably 1,500 to 10,000 mm. is there. With such a relatively gentle curved surface, the effect of the manufacturing method of the present invention is more exhibited.

  Examples of the thermoforming method for forming the curved surface include vacuum forming, pressure forming, and press forming, and any of them can be applied. Among these, press molding that can be applied to a relatively thick sheet without impairing the surface of the sheet is preferable. Here, press molding refers to a method of obtaining a predetermined shape by applying pressure using a mold or a frame when deforming a heated sheet. Typically, a mechanical drive is used to move the mold and other required mechanical devices. As such a driving device, a pneumatic or hydraulic piston, a pneumatic or hydraulic motor, an electric motor, an ultrasonic motor, or the like can be used. As the electric motor, a servo motor capable of controlling the position of the motor itself can be used according to the purpose in addition to a normal motor. In the case of a motor, the rotary motion is usually converted into a linear motion using a conversion mechanism such as a combination of a ball screw and a screw. Among these, a hydraulic piston is most widely used and is preferable in the present invention. The mold may be only a male mold, but in order to increase the dimensional accuracy after thermoforming, it is preferable to have a structure for engaging the male and female molds. That is, it is preferable to perform press molding with a sheet sandwiched between both male and female molds. Here, the surface properties of both male and female types may not satisfy the formula (1) described in the section “(I) Base material layer ((A) layer)”. By preparing a high-quality sheet molded product in advance and bending it without damaging the design surface of the sheet as much as possible, glazing with excellent surface accuracy can be obtained. In order to perform such bending, it is preferable to apply a pressing pressure so that the pressure from the mold surface in the design surface portion is buffered when the sheet is deformed using the mold. As the molding method, the following (a) to (e) are preferably exemplified.

(A) A method represented by grease molding; that is, a mold is covered with an elastic flexible sheet that can be impregnated with a liquid material such as felt or flannel, and impregnated with a liquid material such as grease. How to buffer pressure from.
(B) A method represented by the method described in JP-B-6-79961; that is, impregnating and curing using a curable liquid elastomer component such as a curable liquid silicone rubber as the liquid in (a) above. A method using a mold having a coating layer.
(C) A method using a mold having an elastomer coating layer directly on the mold surface.
(D) a method referred to as ridge forming; that is, using a mold consisting of a skeletal frame rather than a solid mold at least on the mold surface, contacting the skeletal frame over a portion of the non-design surface; A method in which there is no mold contact on the non-design surface.
(E) A method of forming a curved surface by applying a higher pressing pressure to the non-design surface portion than the design surface portion.

  While the method (a) is preferable in terms of a high degree of freedom in shape, a washing step after molding is required. In the method (d), the degree of freedom in shape is likely to be limited. Therefore, among the above, the methods (b), (c) and (e) are more preferable, and the simpler method (e) is more preferable.

Here, as a method of forming the curved surface by applying a higher pressing pressure to the non-design surface portion than the design surface portion,
(E-1): A method of providing a hard coating layer on the non-design surface portion and providing a soft coating layer on the design surface portion,
(E-2): A method of providing a coating layer that increases the contact area on the non-design surface portion, and providing a coating layer that reduces the contact area by roughening the surface or interspersing contact points on the design surface portion, And (e-3): The method etc. which make the thickness of the coating layer of a non-design surface part larger than the thickness of the coating layer of a design surface part, and reduce the pressure of a design surface part etc. are illustrated.

  Among these, the simplest method (e-3) is preferable. Examples of the coating layer include an elastomer layer and an elastic layer, and the elastic layer is particularly preferable because it can be most easily used. Examples of the elastic layer include layers made of knitted fabrics such as natural fibers, synthetic fibers, and inorganic fibers, woven fabrics, and nonwoven fabrics, layers in which such short fibers are flocked, and porous foamed resin layers. In particular, a layer made of flannel or felt is preferred.

  A more preferable method of the method (e-3) described above is a non-design in which an elastic flexible sheet is adhered to at least one of the mold surfaces and a higher press pressure is applied. This is a method using a mold in which the thickness of the elastic flexible sheet in the surface portion is made larger than the thickness of the design surface portion. The thickness difference between the sheets is preferably 0.1 to 3 mm, more preferably 0.2 to 2 mm, and still more preferably 0.3 to 1 mm. In such a method, the pressing pressure at the portion where a high pressing pressure is applied is preferably 0.05 to 2 MPa.

  The mold used for press molding may be any of a wooden mold, a gypsum mold, a resin mold, and a metal mold. In general, the mold life is increased in this order, but the mold manufacturing cost is also increased. Therefore, the mold material can be selected in consideration of these. As the wooden mold, any of a single plate, a laminated plywood and a hard board can be used, and it is preferable that the surface treatment is performed with various varnishes for protecting the mold surface. The resin mold is preferably a thermosetting resin and may be a reinforced resin containing a reinforcing agent or a reinforcing agent-free resin. As the thermosetting resin, unsaturated polyester resin, phenol resin, epoxy resin, and polyurethane resin can be suitably used. As the metal mold, an aluminum mold excellent in machinability is suitable. The mold temperature at the time of press molding can be used at normal temperature without particularly controlling the temperature, but it is also possible to appropriately control the temperature using a heater, a heating medium, or the like.

  A method for positioning the sheet on the mold will be described. In particular, when printing is performed on the sheet, the sheet needs to be accurately placed at a predetermined position of the mold. As such a positioning method, the position of the sheet attached to the clamp and the position of the mold are accurately input in advance to the program of the conveying device, and the method is achieved by accurately attaching the sheet to the clamp using a jig or the like. In addition, when setting the sheet on the mold, a method of controlling the clamp position by reading the position of the sheet or the printing position with a sensor and feeding back the position is preferably exemplified. Any of the methods can be used in the present invention, but the former method is preferable from the viewpoint of simplicity of the entire apparatus.

(IX) Trimming Step of Molded Product-A The final shape of the molded product-A in the present invention may be determined after being trimmed in the trim step. When bending the molded product-A, it is preferably performed before trimming. On the other hand, such a trimming process is an application in which the projection surface having the maximum projection area is mainly a rectangle, such as a carport, an arcade, a solar battery cover, and a sound insulation board, and the required size matches. Is not necessarily required. Such a trim step is performed at once, and is divided into two or more steps such as a rough trim and a final trim, and includes any of printing, thermal bending, and hard coat treatment in the middle of the trim step. There may be. From the viewpoint of production efficiency and expansion of the degree of freedom in hard coating, a method of performing trim processing in accordance with the final product shape at a time is preferable.

  In this trim step, known methods for processing conventional resins such as a cutting method, a cutting method, and a punching method can be used, and these can be combined as appropriate. Examples of the cutting method include a method of cutting with an NC lathe, a milling machine, a machining center, or the like using various cutting tools such as a router, an end mill, a milling cutter, and a rotary tool. In the cutting method, cutting with a blade, cutting with abrasive grains, shear cutting, cutting by heating / melting, electric discharge cutting, and the like can be used. Among the above, the apparatus is widely used, and the cutting method is preferable in terms of excellent cutting accuracy and speed. The cutting may be performed by any method of complete dry cutting, wet cutting, and semi-dry cutting.

  In order to ensure the accuracy in the trimming process, it is preferable that the trimming part is clearly specified in the printing process in advance. If the trimming part is clearly indicated by printing, whether or not the trimming accuracy is possible can be inspected at least visually. Therefore, it is preferable to perform border printing corresponding to the final member and trim the portion outside the outer edge as long as the design of the final product is not affected. In addition, when providing a hole and a notch in the design surface, it is preferable to use a method in which the position is clearly indicated by printing.

<Material adjustment>
(I) Production of transparent substrate made of polycarbonate resin (I-1) Production of polycarbonate resin-A1 A production method of polycarbonate resin-A1 will be described according to the following raw material notation. 9.5 parts by weight PC, 0.08 parts by weight VPG, 0.02 parts by weight SA, 0.03 parts by weight PEPQ, 0.05 parts by weight IRGN, 0.32 parts by weight UV1577, and 1 × 10 ^-4 parts by weight of BL was uniformly mixed with a super mixer. With respect to 10.0101 parts by weight of the mixture, 90 parts by weight of PC was uniformly mixed with a V-type blender to obtain a premix for feeding to the extruder.
The resulting premix was fed to the extruder. The extruder used was a vent type twin screw extruder (manufactured by Nippon Steel, Ltd .: TEX77CHT (completely meshing, rotating in the same direction, two-thread screw)) having a screw diameter of 77 mmφ. The extruder has a kneading zone comprising a combination of a feeding kneading disc and a reverse feeding kneading disc in order at an L / D of about 8 to 11 when viewed from the screw root, and thereafter an L / D of about 16 It had a kneading zone consisting of a feeding kneading disk in the portion -17. Further, the extruder had a reverse flight full flight zone of L / D 0.5 length immediately after the latter kneading zone. One vent port was provided in the portion of L / D of about 18.5-20. The extrusion conditions were a discharge rate of 320 kg / h, a screw rotation speed of 160 rpm, and a vent vacuum of 3 kPa. In addition, the extrusion temperature was a temperature configuration in which the first supply port was gradually raised from 230 ° C. to the die portion 280 ° C.
The strand extruded from the die was cooled in a hot water bath, cut by a pelletizer and pelletized. The pellets immediately after being cut passed through the vibrating sieve portion for about 10 seconds, thereby removing the long pellets that were insufficiently cut and those that could be removed.

(I-2) Production of polycarbonate resin-A2 9.43 parts by weight of PC, 0.1 part by weight of VPG, 0.02 part by weight of SA, 0.03 part by weight of PEPQ, 0.05 part by weight of IRGN 0.3 parts by weight of UV234, 0.07 parts by weight of IRA, and 1 × 10 ⁻⁴ parts by weight of BL were uniformly mixed with a super mixer. 90 parts by weight of PC is uniformly mixed with a V-type blender with respect to 10.001 parts by weight of the mixture, and the same procedure as in the production of polycarbonate resin-A1 is obtained except that a premix for supplying to the extruder is obtained. In this way, a pellet-like polycarbonate resin-A2 was obtained.

The raw materials used are as follows.
PC: Polycarbonate resin powder having a viscosity average molecular weight of 25,000 produced from bisphenol A and phosgene by an interfacial condensation polymerization method (manufactured by Teijin Chemicals Ltd .: Panlite L-1250WQ (trade name))
VPG: Full ester of pentaerythritol and aliphatic carboxylic acid (mainly stearic acid and palmitic acid) (manufactured by Cognis Japan Co., Ltd .: Roxyol VPG861)
SA: fatty acid partial ester (Riken Vitamin Co., Ltd. product: Riquemar S-100A)
PEPQ: Phosphonite heat stabilizer (manufactured by Sandoz: Sandstub P-EPQ)
IRGN: Hindered phenol antioxidant (Ciba Specialty Chemicals: Irganox 1076)
UV1577: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol (manufactured by Ciba Specialty Chemicals: Tinuvin 1577)
UV234: 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by Ciba Specialty Chemicals: Tinuvin234)
BL: Brewing agent (manufactured by Bayer: Macrolex Violet B)
IRA: Infrared shielding agent (Sumitomo Metal Mining Co., Ltd.) comprising an organic dispersion resin and Cs _0.33 WO ₃ (average particle diameter 5 nm) as an inorganic infrared absorber, and an inorganic infrared absorber content of about 23% by weight. YMDS-874 manufactured)

(II) Manufacture of Sheet Molded Product (II-1) Manufacture of Sheet-α A large molding machine capable of injection press molding the resin material -A1 or -A2 pellets with a platen 4-axis parallel control mechanism ) Manufactured by Meiki Seisakusho: MDIP2100, maximum clamping force 33540 kN), and a sheet molded product having a thickness of 4.5 mm and a length × width of 1000 mm × 600 mm shown in FIG. 5 was produced. As shown in this figure, the molding was carried out at one hot runner and gate. The mold was made to have the same level of surface properties on both the front and back surfaces of the plate.
Such a molding machine is equipped with a hopper dryer facility capable of sufficiently drying the resin raw material, and the dried pellets are supplied to the molding machine supply port by pneumatic transportation and used for molding. Molding is cylinder temperature 300 ° C, hot runner set temperature 300 ° C, mold temperature is 110 ° C on both fixed and movable sides, press stroke: 1.5mm, pressurization holding time: 120 seconds, press pressure is 17MPa, and over The lapping time was 0.12 seconds, and the movable mold parting surface was not in contact with the fixed mold parting surface at the final advanced position. Immediately after completion of filling, the valve gate was closed so that the molten resin did not flow backward from the gate to the cylinder. In both the mold compression and mold opening processes in this molding, the parallelism between the molds was maintained at about 0.000025 or less as tan θ representing the tilt amount and the twist amount by the four-axis parallel control mechanism.

(II-2) Manufacture of Sheet-β As shown in FIG. 6, the sheet was formed in the same manner as in the case of the sheet-α by changing to a mold having five hot runner gates on the long side. The five gates were cascade-formed by the SVG method in the order of the first hot runner gate, the second hot runner gate, and the third hot runner gate to form a sheet without a weld portion.

(II-3) Production of Sheet-γ After the resin material -A1 or -A2 is dried with hot air at 120 ° C. for 5 hours, the thickness is 4.5 mm and 1,200 mm according to the extrusion method described in JP-A-2005-081757. Manufactures an extruded sheet with a width of 100 mm at both ends to make a long side of 1,000 mm, cut at a length of 600 mm in the extrusion direction, cut to a thickness of 4.5 mm, and length x width is 1 A sheet molded product of 1,000,000 mm × 600 mm was manufactured.

(III) Printing on Sheet As shown in FIG. 7, a two-window window frame design was screen-printed on the sheet obtained in (II) above with black ink having a light shielding function. Printing was performed in an atmosphere of 23 ° C. and 50% relative humidity with clean air. The screen plate used 200 mesh, and the thickness of the obtained printing layer was about 8 μm. In the case of three-layer coating, the printing was carried out by printing the next layer after air-drying for 90 minutes in such an atmosphere after printing one layer. The film thickness in the multilayer coating was almost proportional to the number of layers. For example, in the three-layer coating, a film thickness of about 24 μm was obtained. In printing, after ink was placed by screen printing, air drying was performed for 30 minutes in such an atmosphere, and then the ink layer was dried and fixed by treatment at 90 ° C. for 60 minutes. In the case of multi-layer coating, this processing was performed after the final printing. The inks used in the printing are as follows (the following are only types, but all are black inks).

(ink)
POS: A polyol component composed of an acrylic polyol composed of an acrylic polyol copolymerized with methyl methacrylate, butyl methacrylate, and 2-hydroxyethyl methacrylate, and another polyol composed of triethylene glycol, and a curing agent composed of a modified HDI biuret. Two-part curable ink with urethane resin to be cured as binder (POS screen ink: 100 parts by weight, 210 curing agent: 5 parts by weight, and P-002 solvent: 15 parts by weight) Co., Ltd.) used as ink)
TAS: a two-component ink containing a urethane resin composed of polyester polyol and polyisocyanate as a binder (TAS screen ink: 100 parts by weight, 210 curing agent: 5 parts by weight, and G-002 solvent: 15 parts by weight of a uniform mixture ( (Employed from Teikoku Ink Co., Ltd.)
MRX: Two-component ink containing a urethane resin composed of polyester polyol and polyisocyanate as a binder (MRX screen ink: 100 parts by weight, 210 curing agent: 5 parts by weight, and G-002 solvent: 15 parts by weight of a uniform mixture ( (Employed from Teikoku Ink Co., Ltd.)
VK: One-component ink containing vinyl chloride-vinyl acetate copolymer resin as a binder (VK screen ink: 100 parts by weight and J-002 solvent: 15 parts by weight (both raw materials are manufactured by Teikoku Inc.)) Used as)
ISX: Polyester-based one-component ink (ISX screen ink: 100 parts by weight and Z-705 solvent: 10 parts by weight (both materials are manufactured by Teikoku Ink Co., Ltd.))
Of the above inks, POS is the ink of the example, and TAS, MRX, VK, and ISX are the inks of the comparative examples.

(IV) Hot bending of printed molded article After the above printing was completed, cotton flannel was attached to both surfaces of a female mold and a male mold made of wood using an adhesive using a hot press molding machine. At this time, after the thermoforming, two cotton flannels are overlapped and stuck on the outer side of the outer edge of the printing frame by 5 mm or more, and the pressing pressure from the mold is buffered at the inner side of the printing frame. I was able to do it. The thickness of one cotton flannel was 0.5 mm. The sheet was attached to the clamp at an accurate position using a jig, and then sent to an air forced circulation furnace having a furnace temperature of 170 ° C. by a conveying device. After the sheet stayed in the heating furnace for 10 minutes, it was immediately sent to the hot press molding process by a continuous conveyance device, and was sandwiched between the two molds and press molded. After being kept in the mold for 2 minutes, the sheet was taken out of the mold by the conveying device and removed from the clamp to obtain a sheet having a curved surface.
Note that the positioning of the sheet with respect to the mold was performed by accurately inputting in advance the position of the sheet to the clamp and the position of the mold into the program of the conveying device. The hot press molding was performed in a normal temperature atmosphere in which clean air circulated, and the wooden mold was used without temperature control (the temperature was about 45 ° C. by continuous molding).

(V) Hard Coat Treatment for Hot-Bending Molded Product The molded product printed and hot-bent molded as described above is subjected to the following hard coat treatment, and finally assumed to be attached to the vehicle body, urethane adhesive Was fixed to a stainless steel frame to obtain a resin glazing structure. Prior to the hard coat treatment, the surface including the printing surface was cleaned using a Bencot wiper impregnated with isopropyl alcohol. Next, a masking tape (TESA4241 manufactured by Tesa Tape Co., Ltd.) is used for the part to which the primer for urethane adhesive is applied, and then the flow coating method is used to prevent the following first layer acrylic resin paint from being pooled. The both sides including the masking part were applied by the above method, left standing in a suspended state for 20 minutes in a clean room at 25 ° C. and 50% relative humidity, and air-dried. Then, the cured film having an average thickness of about 5 μm was laminated in the central transparent portion by storing in an air forced circulation heating furnace at 125 ° C. for 60 minutes and thermally curing. Next, an organosiloxane resin coating for the second layer is applied on both sides of the cured film, and is left to stand in the same manner as the first layer and stored in an air forced circulation heating furnace at a furnace temperature of 125 ° C. for 60 minutes. The cured film was further cured, and a cured film having an average thickness of about 4 μm was laminated in the transparent portion at the center.
The flow coating was performed with a single nozzle, and the acrylic resin coating and the organosiloxane resin coating thereon were applied so that the liquid flow was in the opposite direction.

(VI) Preparation of acrylic resin paint and organosiloxane resin paint (VI-1) Preparation of acrylic resin paint HP-1 Ethyl methacrylate (hereinafter abbreviated as EMA) in a flask equipped with a reflux condenser and a stirrer and purged with nitrogen 74.2 parts by weight, 33.6 parts by weight of cyclohexyl methacrylate (hereinafter abbreviated as CHMA), 13.0 parts by weight of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), LA-82 (manufactured by Asahi Denka Kogyo Co., Ltd.) Hindered amine light-stable group-containing methacrylate; 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate 12.0 parts by weight, methyl isobutyl ketone (hereinafter abbreviated as MIBK) 132.8 parts by weight and 2-butanol (Hereinafter abbreviated as 2-BuOH) 66.4 parts by weight were added and mixed. The mixture was deoxygenated by bubbling nitrogen gas for 15 minutes, then heated to 70 ° C. under a nitrogen gas stream, 0.33 parts by weight of azobisisobutyronitrile (hereinafter abbreviated as AIBN) was added, and nitrogen was added. In a gas stream, the reaction was performed for 5 hours with stirring at 70 ° C. Further, AIBN: 0.08 part by weight was added, the temperature was raised to 80 ° C., the reaction was performed for 3 hours, and an acrylic having a non-volatile content of 39.7% by weight. The weight average molecular weight of the acrylic copolymer was 115,000 in terms of polystyrene from the measurement of GPC (column; Shodex GPCA-804, eluent: THF). MIBK: 68.6 parts by weight, 2-BuOH: 34.2 parts by weight, 1-methoxy-2-propanol (hereinafter abbreviated as PMA): 133 parts by weight are added to and mixed with TINUVIN. 400 (Ciba Specialty Chemicals Triazine UV Absorber) 4.24 parts by weight and Tinuvin 479 (Ciba Specialty Chemicals Triazine UV Absorber) 1.06 parts by weight in an acrylic copolymer solution 10.1 part by weight of VESTANAT B1358 / 100 (blocked polyisocyanate compound manufactured by Degussa Japan Co., Ltd.) so that the isocyanate group is 1.0 equivalent with respect to 1 equivalent of hydroxy group of the acrylic copolymer of Further, dimethyltin dineodecanoate: 0.015 part by weight was added and stirred at 25 ° C. for 1 hour to obtain an acrylic resin paint (HP-1).

(VI-2) Preparation of Organosiloxane Resin Paint HT-1 A water-dispersed colloidal silica dispersion (catalyst SN-30, solid content concentration 30% by weight, manufactured by Catalyst Chemical Industry Co., Ltd.) 133 parts by weight of 1 M hydrochloric acid: 1 .3 parts by weight was added and stirred well. The dispersion was cooled to 10 ° C., and 162 parts by weight of methyltrimethoxysilane was added dropwise with cooling in an ice-water bath. Immediately after the addition of methyltrimethoxysilane, the temperature of the mixture started to increase due to the reaction heat, and after 5 minutes from the start of the addition, the temperature rose to 60 ° C., and then the temperature of the mixture gradually decreased due to the cooling effect. When the temperature of the mixed solution reached 30 ° C., the mixture was stirred for 10 hours at 30 ° C., and a methanol solution having a choline concentration of 45% by weight as a curing catalyst: 0.8 part by weight, pH 5 parts by weight of acetic acid as an adjusting agent and 440 parts by weight of isopropyl alcohol as a diluting solvent were mixed to obtain an organosiloxane resin composition paint (HT-1).

(VI-3) Preparation of acrylic resin paint HP-2 In a flask equipped with a reflux condenser and a stirrer, MIBK: 443.4 parts by weight, 2- [4-[(2-hydroxy-3- (2′- Ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine (Cinubin 405, Ciba Specialty Chemicals) 350.3 parts by weight 2-isocyanatoethyl methacrylate: 93.1 parts by weight was added and mixed and heated to 80 ° C. Then, 0.1 part by weight of dibutyltin dilaurate was added and stirred at the same temperature for 30 minutes. After cooling to room temperature, the resulting solution was transferred into water, and after stirring, the reaction product was extracted with MIBK. The oily substance obtained by distilling MIBK was dropped into methanol and stirred to obtain a pale yellow powder. The powder was dried and 2-methacryloxyethylcarbamic acid 1- [3-hydroxy-4- {4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl} phenyl Oxy] -3- (2-ethylhexyloxy) -2-propyl (hereinafter abbreviated as MOI-405) was obtained.
Next, equipped with a reflux condenser and a stirrer, EMA: 62.1 parts by weight, CHMA: 168.2 parts by weight, HEMA: 26.0 parts by weight, MOI-T405: 41.4 Parts by weight, LA-82: 47.9 parts by weight, MIBK: 518.4 parts by weight were added and mixed. The mixture was deoxygenated by bubbling nitrogen gas for 15 minutes, then heated to 70 ° C. under a nitrogen gas stream, added with AIBN: 0.66 parts by weight, and stirred at 70 ° C. for 5 hours in the nitrogen gas stream. To react. Further, AIBN: 0.16 parts by weight was added, the temperature was raised to 80 ° C. and reacted for 3 hours. After cooling to near room temperature, 2-BuOH: 259.2 parts by weight was added, and the non-volatile content concentration was 30.4% by weight. A copolymer solution was obtained.
Furthermore, to 100 parts by weight of the acrylic copolymer solution, MIBK: 28.2 parts by weight, 2-BuOH: 14.1 parts by weight, PMA: 97.8 parts by weight were added and mixed, and the acrylic in the acrylic resin solution was mixed. VESTANATB 1358/100: 6.0 parts by weight was added so that the isocyanate group was 1.0 equivalent with respect to 1 equivalent of the hydroxy group of the copolymer, and TINUVIN 479: 0.53 part by weight, APZ-6633 (Toray Industries, Inc.) -Ethanol solution of silane coupling agent hydrolysis condensate manufactured by Dow Corning Co., Ltd .; solid content 5 wt%) 7.0 parts by weight, dimethyltin dineodecanoate: 0.011 part by weight and 1 at 25 ° C The mixture was stirred for a time to obtain an acrylic resin paint (HP-2).

(VI-4) Preparation of Organosiloxane Resin Paint HT-2 1.3 parts by weight of 1M hydrochloric acid was added to 133 parts by weight of the above catalloid SN-30 and stirred well. The dispersion was cooled to 10 ° C., and 216 parts by weight of methyltrimethoxysilane was added dropwise with cooling in an ice water bath. After completion of the dropwise addition of methyltrimethoxysilane, the mixture was stirred at 30 ° C. for 10 hours, then 1.1 parts by weight of choline methanol solution (containing 45% choline) as a curing catalyst, 6.7 parts by weight of acetic acid, and isopropyl alcohol as a diluent solvent: 550 parts by weight was mixed, and 3.4 parts by weight of 710T (IPA dispersion type titanium oxide dispersion manufactured by Teika Co., Ltd.) was further added to obtain organosiloxane resin paint HT-2.

(VII) Trimming of Unnecessary Parts The molded product subjected to the hard coating treatment of (V) was cut using an NC end mill to obtain a glazed molded product having the periphery black-out printed as shown in FIG. Prior to the trimming, the masking tape stuck for applying the adhesion primer was removed.
<Evaluation>
(I-1) Reference Examples 1 to 11 (Tables 1 and 2)
(Appearance visual evaluation of manufactured sheet)
The manufactured sheet (indicated as “front” in Tables 1 and 2; the same in (I-2) below) and the sheet after thermoforming (indicated as “after” in Tables 1 and 2) (indicated in the following (I-2) In the same manner, the appearance was observed based on the heterogeneity of the fluoroscopic image and the reflected image observed through the molded product. Evaluation criteria were as shown in the following A to D. The results are shown in Tables 1 and 2.
A: Level at which no defect is observed even when observed at a tight angle of about 10 to 20 degrees with respect to the surface.
B: Slight defects are observed when observed at a tight angle of about 10 to 20 degrees with respect to the surface. For example, a person other than the person in charge cannot easily identify a defect even if a defective part is pointed out, or a level at which a thin shadow can be confirmed with a projection image of direct sunlight on a clear day.
C: Defects are observed when observed at a tight angle of about 10 to 20 degrees with respect to the surface. For example, a person other than the person in charge in charge can discern a defect if a defective part is pointed out, or a level at which a relatively dark shadow can be confirmed with a projection image of direct sunlight in a sunny day.
D: Defects are observed even when observed at a relatively loose angle of about 30 degrees or more with respect to the surface. For example, a person who is not a preconceived person in charge, can observe defects without pointing out a defective part, or can identify a defect, or a dark shadow can be confirmed with a projection image of direct sunlight on a clear day.
(Note that the shade density of the projected image represents a relative degree when the samples having different appearance properties are compared under the same conditions).

(I-2) Reference Examples 1 to 5 (Table 1)
(Evaluation of surface properties of a sheet produced by injection compression molding and a sheet after thermoforming)
The surface of the sheet produced by injection compression molding and the sheet after thermoforming was measured as follows. That is, in accordance with JIS B0610, using a surface roughness shape measuring instrument (Surfcom 1400A manufactured by Tokyo Seimitsu Co., Ltd.), measurement is performed at any three locations on each sheet (a total of 6 locations on both sides) to determine the surface roughness Ra. Calculated. Further, the waviness amplitude Wa and waviness wavelength WSm of the waviness curve in the above formula (1) are also measured using the same measuring device, the reference length L is 90 mm, the cut-off wavelength is 2.5 mm from the surface uneven shape, and the cut-off type 2CR (phase non-compensation) and slope correction as least-square curve correction, and extracting and calculating a waviness curve. By measuring Wa and WSm in the same manner, measurement was performed at arbitrary three locations on the sheet (total of 6 locations on both sides). The results are shown in Table 1.

(I-3) Examples 1 to 7, Comparative Examples 1 to 4 (Table 3)
(Evaluation of resistance to coating liquid forming (E1) layer)
(E1) The acrylic resin paint used for the coating liquid for forming the layer is flow-coated on the blackout printed part of the printed and heat-bent molded product (molded product shown in FIG. 8), and air-dried at room temperature for 30 minutes. The surface appearance after the observation was observed. “◯” indicates that there is no change, and “X” indicates that a change such as a change in gloss or surface roughness occurs. The acrylic resin paint used was HP-1 and HP-2, which will be described later, and CP710 manufactured by SDC Technologies. The SP value of HP-1 and HP-2 is about 20.2 (MPa) ^0.5 , and CP710 consists of a mixed solvent of diacetone alcohol and 1-methoxy-2-propanol, and its SP value is about 21.5 (MPa) ^0.5 . The results are shown in Table 3.

(I-4) Examples 1 to 7, Comparative Examples 1 to 4 (Table 3)
(Evaluation of resistance to adhesive primer mainly composed of acetate solvent)
A primer for adhesion (RC-50E manufactured by Yokohama Rubber Co., Ltd.) containing an acetic ester solvent as a main component was applied to the blackout printing portion of a printed and heat-bent molded product (molded product shown in FIG. 8). The surface appearance after air drying for 10 minutes was observed. “◯” indicates that there was no change, and “X” indicates that a change such as swelling or roughness of the printed portion occurred. The adhesion primer was implemented as follows. Use a bencott wiper impregnated with isopropyl alcohol to clean the surface of the printed part, then thoroughly impregnate the primer solution, and then lightly squeeze the bencott wiper at a speed of about 1 cm / second to apply the primer. Worked. The thickness of the (E1) layer was about 5 μm. The results are shown in Table 3.

(I-5) Examples 1 to 7, Comparative Example 3 (Table 4)
(Resistance to urethane adhesive and adhesion evaluation)
Three test pieces on a strip with a length of 110 mm and a width of 30 mm were cut out from a printed part of a black-out printed and heat-bent molded product and used as test pieces for evaluation. Primer coating was applied to the printed part of the test piece, and about 5 minutes later, a bead of urethane adhesive having a diameter of 5 mmφ was applied on the primer. Thereafter, a release paper was placed on the bead, and a 3 mm thick spacer was used to crush the bead so that the thickness became 3 mm, thereby adhering the urethane adhesive to the test piece. Primer coating was carried out in the same manner as in the above evaluation (I-4).
After such adhesion, curing treatment for one week was performed in an atmosphere of 23 ° C. and 50% relative humidity, and the urethane adhesive was cured with moisture. The test piece after completion of the curing treatment was subjected to the following two types of acceleration treatment. That is,
(I): Acceleration treatment for 336 hours storage in an oven with a furnace temperature of 90 ° C., and (ii): No spilling of water droplets by squeezing after soaking in water, but with a sufficiently damp cotton cloth Covering, putting it in a sealed container in such a state, and storing it at 70 ° C. for 168 hours. The accelerated treatment (ii) is in accordance with the so-called Cataplasma test.
After such treatment, the appearance was confirmed, and the adhesiveness of the urethane adhesive bonded to the test piece was peeled off and evaluated by a test. In such a peeling test, it is generally required that the urethane adhesive cohesively fails and does not have a predetermined amount of adhesive failure. Therefore, the case where all the fractures in the peeling test are cohesive fractures is expressed as “CF-100” in Table 3. Such a result is the best result. The results are shown in Table 4.
In addition, this evaluation (I-5) was implemented only what was a favorable result by evaluation of the said evaluation (I-4).

(I-6) Examples 8 to 15 (Table 5)
(Adhesion to CFRP body frame and evaluation)
The above-mentioned trimmed glazed molded product is made of CFRP vehicle body frame material made from an epoxy resin-impregnated carbon fiber woven fabric pre-figure that assumes vehicle body attachment as shown in FIG. Adhesion was performed using a rubber product. At the time of adhesion, both the adhesion part of the glazing molded product (printed part protected by the masking tape) and the adhesion part of the frame material made of CFRP were wiped with a becot wiper impregnated with isopropyl alcohol to clean the surface. After that, body primer RC-50E (Yokohama Rubber Co., Ltd.) was applied to both the adhesive part of the glazing molded product (a little wider than the urethane adhesive bead finally being spread) and the adhesive part of the CFRP frame material. ) Made). Such coating was carried out using a Bencot wiper which was sufficiently impregnated with the primer solution and then lightly squeezed. The primer thickness was about 8 μm. Within 3 minutes from the application of the primer, a triangular urethane bead having a width of 8 mm and a height of 12 mm was applied. Such coating was performed by making one round so that the bead does not get on an area within 10 mm from the outer edge of the molded product. The molded product was fixed to a stainless steel frame so that the thickness of the urethane adhesive was 6 mm by a 6 mm thick spacer attached to the molded product side. After curing for 1 week at 23 ° C. and 50% RH, the entire frame was placed in a 90 ° C. hot air drying oven and treated for 1,000 hours. (Indicated by “◯” in Table 5). In addition, in any of the test pieces, no peeling was observed in any of the test pieces in the cello tape peeling test after the boiling water 3 hr treatment on both the polycarbonate resin surface and the blackout printing surface.

  As shown in Table 3, Table 4, and Table 5, the two-part curable ink layer of the present invention has (i) resistance to the hard coat liquid, so that the hard coat liquid comes into contact with the ink layer. In some cases, a good resin glazing structure is obtained, and (ii) it has resistance to a primer mainly composed of an acetate ester solvent, so that the primer can be applied and has good adhesion to a polycarbonate resin. A resin glazing structure having good adhesion, and (iii) excellent heat resistance of the ink itself. It can be seen that a glazing construct is obtained.

  A good design required for a glazing member of a transport machine such as an automobile and an excellent adhesion of a structural member are exhibited, and the manufacturing method thereof is a method by which the structure can be manufactured efficiently and at low cost. Therefore, as described above, glazing materials for vehicles that require these characteristics, such as back door windows, sunroofs, roof panels, detachable tops, window reflectors, winker lamp lenses (including covers), room lamp lenses (including covers). ), And a display display front plate. In addition to glazing materials for vehicles, window glass for construction machinery, window glass for buildings, houses, and greenhouses, roofs for garages and arcades, lighting lenses, traffic light lenses, optical equipment lenses, large mirrors, glasses , Goggles, sound barriers, motorcycle windshields, nameplates, lighting covers, solar cell covers or solar cell substrates, display device covers, touch panels, and parts for game machines (pachinko machines, etc.) (circuit covers, chassis, pachinko ball transport) It can be used for a wide range of applications such as guides. Therefore, the polycarbonate resin molded body of the present invention is useful for various applications such as various electronic / electrical equipment, OA equipment, vehicle parts, machine parts, other agricultural materials, fishery materials, transport containers, packaging containers, playground equipment and miscellaneous goods. The industrial effects that it plays are exceptional.

10 clamping device 11 first injection device 13 fixed mold 14 movable mold 15 mold device 16 mold clamping mechanism 18 mold opening / closing device 20 engagement device 21 fixed plate 22 movable plate 23 tie bar 24 position sensor 25 guide 26 support plate 27 pressure Clamping chamber 28 Open chamber 31 Molded product 41 obtained by molding Sheet base material 42 Hard coat layer (the opposite surface may not be shown)
43 Print layer (the opposite side may not be shown)
44 Adhesive primer layer 45 Urethane adhesive 46 Masking agent 51 Sheet-α (The size excluding the gate portion is 1,000 mm long × 600 mm wide × 4.5 mm thick)
52 Gate (width 120mm at the outer edge of the sheet, distance 100mm from the center of the hot runner gate to the outer edge of the sheet, thickness 4.5mm)
53 Hot Runner Gate 61 Sheet-β (The size excluding the gate is 1,000 mm long x 600 mm wide x 4.5 mm thick)
62 Gate (thickness 4.5mm)
63 1st hot runner gate 64 2nd hot runner gate 65 3rd hot runner gate 71 Sheet molded product 72 after printing, thermal bending, and hard coat treatment 72 Sheet molded product main body 73 Blackout printed window frame (printing is (It is made on the back side of this figure)
81 Grammed molded body after trimming (It is a quarter window on the left side of the car body)
82 Window translucent portion 91 Left-side rear fender 92 of the vehicle body to which 81 81 glazing molded product is mounted Left-side rear fender 93 of the vehicle body to which 81 glazing molded product is mounted Left-side rear combination lamp 94 81 of the vehicle body to which glazed molded product is mounted Openable and closable back door window 95 81 to which the glazing molded product is attached. Panorama window of the vehicle body to which the glazing molded product is attached.

Claims (9)

A glazing laminate in which the following (B) layer, (C) layer, (D) layer, and (E) layer are laminated on at least one surface of the following (A) layer,
When the cross section along the thickness direction of the laminated body is seen, the laminated structure 1 laminated in the order of (A) layer- (B) layer- (C) layer- (D) layer, and (A) layer- ( B) a laminated structure 2 laminated in the order of layer- (E) layer, and a laminated structure 3 laminated in the order of (A) layer- (E) layer, and laminated between laminated structures 1 and 3 A glazing laminate, wherein the structure 2 is interposed.
(A) Layer: a light-transmitting base material layer made of polycarbonate resin.
(B) Layer: A two-component curable ink layer made of acrylic polyurethane formed by reaction of an acrylic polyol resin and a polyisocyanate compound.
(C) Layer: An adhesive primer layer formed from a primer composition containing a polyisocyanate compound and an acetate solvent.
(D) Layer: An adhesive layer made of a urethane adhesive.
(E) layer: It is a hard coat layer consisting of only one layer or at least two layers (E1) and (E2). In (E layer) consisting of only one layer, the polyfunctional acrylic polymer is the main component. In the (E layer) composed of at least two layers, the (E1) layer comprises the (A) layer and (B). It is a primer layer made of an acrylic resin directly laminated with a layer, and the (E2) layer is a top made of a silicone resin laminated on the surface of the (E1) layer that is not in contact with the (A) layer or (B) layer Is a layer .   The glazing laminate according to claim 1, wherein the layer (B) has a thickness of 3 μm to 60 μm.   Two-component curability obtained by reacting the acrylic polyurethane with an acrylic polyol resin, a polyol having a number average molecular weight of 100 to 2,000 other than the acrylic polyol resin, and hexamethylene diisocyanate and / or a polyisocyanate compound derived from the isocyanate. It is an ink layer, The glazing laminated body in any one of Claims 1-2.   The glazing laminate according to claim 3, wherein the polyol other than the acrylic polyol resin is a polyether polyol. The layer (E) is formed of a coating liquid in which the raw material for the hard coat layer is dissolved or / and dispersed in an organic solvent, and the coating liquid organic coating is directly applied on at least the (A) layer and the (B) layer. The glazing laminate according to any one of claims 1 to 4, wherein the solvent has a compatibility parameter (SP value) in the range of 18.5 to 22 (MPa) ^0.5 .   The glazing laminate according to claim 5, wherein the organic solvent of the coating liquid directly applied to the (A) layer and the (B) layer is at least one selected from the group consisting of alcohols and ketones. The glazing laminate according to any one of claims 1 to 6 , wherein the layer (A) is formed by injection compression molding. A method for producing a glazing laminate comprising the following steps (i) to (iv):
(I) a step of forming the following (B) layer on a part of at least one surface of the following (A) layer (step (i)),
(Ii) On the side of the light-transmitting substrate obtained in step (i) and partially formed with the (B) layer, (B) from the surface of the (A) layer where the layer is not formed (B ) A step of forming the following (E) layer continuous over part of the surface of the layer (step (ii)),
(Iii) a step (step (iii)) of forming the following (C) layer on at least a part of the surface of the (B) layer in which the (E) layer obtained in the step (ii) is not formed; and (iv) ) A step of forming the following (D) layer on the surface of the (C) layer obtained in the step (iii) (step (iv)).
(A) Layer: a light-transmitting base material layer made of polycarbonate resin.
(B) Layer: A two-component curable ink layer made of acrylic polyurethane formed by reaction of an acrylic polyol resin and a polyisocyanate compound.
(C) Layer: An adhesion primer layer comprising a primer composition containing a polyisocyanate compound and an acetate solvent.
(D) Layer: An adhesive layer made of a urethane adhesive.
(E) layer: It is a hard coat layer consisting of only one layer or at least two layers (E1) and (E2). In (E layer) consisting of only one layer, the polyfunctional acrylic polymer is the main component. In the (E layer) composed of at least two layers, the (E1) layer comprises the (A) layer and (B). It is a primer layer made of an acrylic resin directly laminated with a layer, and the (E2) layer is a top made of a silicone resin laminated on the surface of the (E1) layer that is not in contact with the (A) layer or (B) layer Is a layer . The manufacturing method according to claim 8 , wherein the step (ii) is performed after the layer (B) is formed on the layer (A) in the step (i) and then heat-deformed.

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