JP5621233B2 - panel - Google Patents

Description

  The present invention relates to a panel in which a frame-like portion is integrally provided on the entire periphery of the rear surface of the panel main body, and more particularly to a panel suitable for use as a transparent panel-like member for a roof or window of a vehicle such as an automobile.

  JP-A-2005-103907 and JP-A-2008-94087 describe resin window plates for automobiles, which are made of a two-color molded product in which a transparent resin panel has a border formed with an opaque resin.

  Japanese Patent Application Laid-Open No. 2005-103907 discloses an automobile provided with a transparent portion (panel body) formed in a rectangular flat plate shape and a frame portion integrally formed on the outer peripheral end of one surface of the front and back surfaces of the transparent portion. Windows are listed. In the outer peripheral part of the transparent part, the transparent part and the frame part are laminated in the thickness direction, and the central part of the transparent part has a single layer structure in which the frame part is not laminated. This two-color molded product is manufactured by two-color injection molding in which the frame portion is molded with an opaque material and then the transparent portion is molded with a transparent material.

  Japanese Patent Application Laid-Open No. 2008-94087 discloses a panel made of a two-color molded product in which a frame-like part is provided at the peripheral part of the panel body, by reducing the thickness of the inner peripheral side of the frame-like part toward the inner peripheral side. It describes that the distortion of the main body is prevented. In JP 2008-94087 A, the panel main body is first injection molded, and then the frame-shaped portion is injection molded.

JP-A-2005-103907 JP2008-94087

  A synthetic resin panel provided with a frame-like portion on the rear surface of the panel body is subjected to annealing treatment at 120 ° C. to 130 ° C. for about 2 hours for the purpose of removing residual strain after injection molding. During this annealing treatment, for example, a non-crystalline material such as polycarbonate resin undergoes secondary shrinkage due to molecular chain relaxation or rearrangement, and the crystalline material undergoes secondary shrinkage due to recrystallization, and is made of a resin material. The panel main body and the frame-shaped part contract again. When a hard coating made of a thermosetting synthetic resin is provided on a synthetic resin panel, a thermal history is applied again at the time of forming the hard coating, so re-shrinkage equivalent to or higher than the annealing treatment may occur. .

  This frame-like part is provided at the peripheral edge of the rear surface of the panel body. If the frame-like part constrains the shrinkage of the panel body or conversely exceeds the shrinkage of the panel body, The body will be deformed.

  In general, the vehicle window panel is configured to be convexly convex toward the outside of the vehicle, and the frame-like portion is disposed at the peripheral portion on the vehicle interior side of the panel body. As described above, when the panel is deformed with the thermal history such as the annealing treatment, an error exceeding the allowable value may occur in the convex curved shape of the panel body.

  The present invention relates to a synthetic resin panel in which a frame-like portion is integrally provided on the rear surface of the panel body, and the panel is curved so as to be convex toward the front side. An object is to provide a panel with good shape accuracy.

The panel according to claim 1 is an automotive window panel made of a synthetic resin material that has a front surface and a rear surface, and is curved so that the front surface is convex, and the panel body and the entire rear surface of the panel body. A frame-like portion provided integrally with the panel body over the periphery, the panel body is made of a translucent synthetic resin, and the area of the transparent region (3) of the panel body is 400 cm ² or more, In the panel in which the width of the frame-shaped portion is 30 to 200 mm and the panel main body is injection-molded, and then the frame-shaped portion is integrally formed with the panel main body by injection molding on the entire periphery of the rear surface of the panel main body. , the volume of the panel main body ^{(m 3)} _{V 1,} the volume of the frame-shaped portion ^{(m 3)} _{V 2,} a 100 mm × 100 mm flat plate of 3mm thickness molded of a material constituting the panel body 130 ° C. When held for 2 hours Shrinkage ratio (%) of _{S 1,} shrinkage when held 2 hours 100 mm × 100 mm flat plate of 3mm thickness molded with the material constituting the said frame-shaped portion at 130 ° C. (percent) when the _{S 2} ,
0.38 ≦ V ₂ / V ₁ ≦ 0.75
1.0 <S ₂ / S ₁ <3.0
0.38 <(S ₂ · V ₂ ) / (S ₁ · V ₁ ) <1.1
, And the case where the flexural modulus of the material constituting the panel body a (MPa) and F _1, the flexural modulus of the material constituting the frame-shaped portion (MPa) was F _2,
0.35 <(S ₂ · V ₂ · F ₂ ) / (S ₁ · V ₁ · F ₁ ) <1.5
, And the case where molding shrinkage during injection molding of the material forming the framelike part (%) as I _2, the linear expansion coefficient of the material constituting the panel body was alpha _1,
0.8 × 10 ⁻² <α ₁ / I ₂ <2.3 × 10 ⁻²
It is characterized by being.

The panel of claim 2 is characterized in that Oite to claim 1, the main component of the synthetic resin of the main component and a frame-like portion of the synthetic resin constituting the panel body is the same.

The panel of claim 3 is the panel according to claim 1 or 2, wherein the material constituting the frame portion is selected from the group consisting of glass fiber, carbon fiber, aramid fiber, biodegradable fiber, talc, mica, and wollastonite. It is a composite reinforced thermoplastic synthetic resin material containing at least one kind.

A panel according to a fourth aspect is characterized in that, in any one of the first to third aspects, a hard film is formed on the front surface of the panel main body.

The panel of claim 5 is characterized in that, in any one of claims 1 to 4 , a hard film is formed on the front surface of the panel main body and the inner region of the frame-shaped portion of the rear surface of the panel main body. It is what.

The panel of claim 6 is characterized in that, in claim 4 or 5 , the thickness of the hard coating is 1/100 or less of the thickness of the panel body.

A panel according to a seventh aspect is characterized in that, in any one of the fourth to sixth aspects, the hard film is composed of a cured layer of an active energy ray-curable composition or a thermosetting organosiloxane.

The panel of claim 8 is characterized in that, in any one of claims 1 to 7 , the translucent synthetic resin is an aromatic polycarbonate resin.

In the panel of the present invention, the volume of the frame-shaped portion is smaller than the volume of the panel body (0.01 <V ₂ / V ₁ <1.0), and the material constituting the frame-shaped portion is 130 ° C. × 2 Hr. The ratio S ₂ / S ₁ between the shrinkage rate S ₂ and the 130 ° C. × 2 Hr shrinkage rate S _{1 of} the material constituting the panel body is 1.0 <S ₂ / S ₁ <3.0. Thus, by setting the S ₂ / S ₁ ratio to more than 1.0 and less than 3.0, the shrinkage of the panel body during the annealing process is prevented from being constrained by the frame-shaped portion or conversely assisted (suppressed). The same applies hereinafter), and the shape accuracy of the panel after annealing is improved.

  The panel of the present invention is suitable for use as a vehicle panel.

It is sectional drawing of the panel which concerns on embodiment. It is a top view of the panel of FIG.

  Hereinafter, embodiments will be described with reference to the drawings. FIG. 1 is an overall sectional view of a panel according to an embodiment, and FIG. 2 is a plan view of the panel. 1 is a cross-sectional view taken along the line II of FIG.

  The panel 4 is a resin window glass of a vehicle, and includes a plate-like panel main body 1 and a frame-like portion 2 provided so as to go around the entire periphery of the rear surface of the panel main body 1. In addition, the inner peripheral side of the frame-shaped portion 2, that is, the panel plate central portion where the frame-shaped portion 2 does not overlap is a transparent region 3.

The panel body 1 is transparent with a thickness t ₁ of about ₂ to 10 mm, and the frame-like portion 2 is opaque with a thickness t ₂ of about 0.5 to 5 mm. t ₁ / t ₂ is preferably 0.75 to 5.0, particularly preferably about 1.5 to 4.0.

  The panel 4 is curved so that the front surface (upper surface in FIG. 1) side of the panel body 1 is convex.

The panel 4 has a substantially rectangular shape, but the size is not particularly limited, and may be appropriately selected and determined according to the application. Usually, when used as a window material for automobiles, the area of the transparent window layer portion is about 400 cm ^{2 to 2} m ² , and the width of the window frame layer portion is about 30 to 200 mm. Among them, the area of the transparent window layer portion is preferably 800 cm ² to 1 m ^2, the width of the window frame layer portion is 30 to 150 mm. Similarly, the curved height (interval with the outermost peripheral edge on the rear surface side of the frame-like part 2) c, the length a of the long side, and the length b of the short side of the front surface of the panel body 1 are also used. The R in the long side length a direction is usually 5000R to 20000R, particularly about 10000R to 20000R, and the R in the short side length b direction is 1000R to 15000R, especially 5000R to The value is preferably about 10,000R.

  Although illustration is omitted, in order to mold the panel 4, a transparent resin material is injected into a cavity formed between the fixed mold of the mold and the first movable mold, and the panel body 1 is molded. Next, the first movable mold is opened, the second movable mold is matched, the resin is injected into the cavity formed between the second movable mold and the panel body 1, and the frame-shaped portion 2 is Form. Thereafter, the second movable mold is opened and the molded panel 4 is removed. Next, the molded product is subjected to an annealing treatment for holding at 1 to 5 hours, particularly 1 to 2 hours, preferably at 100 to 130 ° C., particularly 120 to 130 ° C., to remove the strain.

  In addition, after apply | coating a hard-coat stock solution to the whole front surface of the panel main body 1 of this panel 4, and the transparent area | region 3 among the rear surfaces of the panel main body 1, it hardens by UV irradiation or a heating, and a hard film (hard-coat layer) ) May be formed.

  When this hard film is formed, the heat curing process and the annealing process at the time of forming the hard film using a thermosetting resin may be combined.

  Next, materials suitable for applying the panel of the present invention to automobile window glass and the like will be described.

  If the constituent material of the panel main body 1 is a transparent resin, it can be suitably selected from conventionally well-known arbitrary things. Here, the term “transparent” is generally 10% or more, preferably 20% or more, more preferably 30%, as the total light transmittance in a plate-shaped molded product having a smooth surface thickness of 3 mm measured according to JIS K7105. This means that the Haze value is usually 10% or less, preferably 5% or less, and more preferably 3% or less. In a transparent resin containing a dye or pigment, the proportion of the dye or pigment used is usually 0.001 to 2 parts by weight, preferably 0.005 to 1 part by weight, with respect to 100 parts by weight of the thermoplastic resin. More preferably, it is 0.005-0.5 weight part.

  Examples of the transparent resin include polystyrene resin, high impact polystyrene resin, hydrogenated polystyrene resin, polyacryl styrene resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, polyalkyl methacrylate resin, poly Methacryl methacrylate resin, polyphenyl ether resin, polycarbonate resin, amorphous polyalkylene terephthalate resin, polyester resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, amorphous polyarylate resin, poly Heat of ether sulfone, styrene thermoplastic elastomer, olefin thermoplastic elastomer, polyamide thermoplastic elastomer, polyester thermoplastic elastomer, polyurethane thermoplastic elastomer, etc. Plastic elastomers Kyora. Among these, from the viewpoint of impact resistance and heat resistance, a polycarbonate resin (PC), particularly, an aromatic polycarbonate resin as a main constituent resin is preferable. The main constituent resin means that the ratio of the aromatic polycarbonate resin is usually 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more.

  Examples of resins used in combination with PC as the main constituent resin include polystyrene resin, ABS resin, AS resin, AES resin, ASA resin, polyphenylene ether resin, polymethacryl methacrylate resin, and polyester resin. An alloy or a copolymer may be used as long as the properties are maintained.

  The PC used in the present invention is, for example, a linear or branched thermoplastic polymer obtained by reacting an aromatic dihydroxy compound and a carbonate precursor, or a small amount of a polyhydroxy compound in combination therewith. Or a copolymer. PC can be produced by a known method, and examples of the production method include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. .

  Examples of aromatic dihydroxy compounds used as raw materials include 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane ( Also known as: tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4 -Hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4- Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, , 2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) Propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-trichloropropane, 2 , 2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3- Bis (hydroxyaryl) alkanes such as hexafluoropropane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydride) Bis (hydroxyaryl) cycloalkanes such as xylphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; 9,9-bis (4-hydroxyphenyl) fluorene; Cardiostructure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; dihydroxy diphenyls such as 4,4′-dihydroxydiphenyl ether and 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether Aryl ethers; dihydroxydiaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide, 4,4 '-Dihydroxy-3,3'- Dihydroxydiaryl sulfoxides such as dimethyldiphenyl sulfoxide; dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like.

  Among the above, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A) is particularly preferable from the viewpoint of impact resistance. Two or more kinds of these aromatic dihydroxy compounds may be used in combination.

  As the carbonate precursor to be reacted with the aromatic dihydroxy compound, carbonyl halide, carbonate ester, haloformate and the like are used. Specifically, phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dimethyl carbonate And dialkyl carbonates such as diethyl carbonate; and dihaloformates of dihydric phenols. Two or more of these carbonate precursors may be used in combination.

  In the present invention, the PC may be a branched aromatic polycarbonate resin obtained by copolymerization of a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6- Tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, 1, In addition to polyhydroxy compounds such as 1,1-tri (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxyindole (also known as isatin bisphenol), 5-chloroisatin, Examples include 5,7-dichloroisatin and 5-bromoisatin. Among these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferable. The polyfunctional aromatic compound is used by substituting a part of the aromatic dihydroxy compound, and the amount used is usually 0.01 to 10 mol%, preferably 0.1%, based on the aromatic dihydroxy compound. ~ 2 mol%.

  Although the molecular weight of PC used for this invention is arbitrary, it is 10,000-35,000 normally as viscosity average molecular weight [Mv] converted from solution viscosity. By setting the viscosity average molecular weight to 10,000 or more, the mechanical strength is improved and it is suitable for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is 35,000 or less, the fluidity is lowered and the molding process becomes easy. In addition, when forming hard films, such as a hard coat, in a post process, a viscosity average molecular weight becomes like this. Preferably it is 18,000-35,000, More preferably, it is 20,000-30,000. By setting the viscosity average molecular weight to 18,000 or more, it is possible to suppress a decrease in impact strength when a cured film is formed on the surface. Two or more types of PCs having different viscosity average molecular weights may be mixed.

Here, the viscosity average molecular weight [Mv] means that the intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. is obtained with an Ubbelohde viscometer using methylene chloride as a solvent, and the Schnell viscosity formula (η = 1.23 × 10 ⁻⁴ M ^0.83 ).

  The terminal hydroxyl group concentration of the PC used in the present invention is usually 2,000 ppm or less, preferably 1,500 ppm or less, more preferably 1,000 ppm or less. In addition, the lower limit is usually 10 ppm, preferably 30 ppm, more preferably 40 ppm, especially for PC produced by the transesterification method.

  By setting the terminal hydroxyl group concentration to 10 ppm or more, a decrease in molecular weight can be suppressed, and the mechanical properties of the resin composition tend to be further improved. Moreover, it exists in the tendency which the residence heat stability and color tone of a resin composition improve more by making terminal group hydroxyl group density | concentration into 2,000 ppm or less. When forming a cured film such as a hard coat, by applying a terminal hydroxyl group concentration of 100 to 2,000 ppm, preferably 200 to 1,000 ppm, and more preferably 300 to 1,000 ppm, with a high terminal hydroxyl group concentration, Its adhesion and durability are improved. The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm with respect to the weight of PC, and the measurement method is a colorimetric determination by the tetrachloride / acetic acid method (Macromol. Chem. 88 215 (1965)). Method).

  Further, in order to improve the appearance of the molded product and the fluidity, the PC used in the present invention may contain an aromatic polycarbonate oligomer. The aromatic polycarbonate oligomer has a viscosity average molecular weight [Mv] of usually 1,500 to 9,500, preferably 2,000 to 9,000. The usage-amount of an aromatic polycarbonate oligomer is 30 weight% or less normally with respect to PC.

  Furthermore, the PC used in the present invention may contain not only virgin PC but also PC regenerated from used products, so-called material recycled PC. Used products include optical recording media such as optical discs, light guide plates, vehicle transparent parts such as automobile window glass, automobile headlamp lenses, and windshields, containers such as water bottles, eyeglass lenses, soundproof walls, glass windows, and waves. Examples include building members such as plates. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The use ratio of the regenerated PC is usually 80% by weight or less, preferably 50% by weight or less based on virgin PC.

  In addition to the above-mentioned dyes or pigments, any conventionally known auxiliary agent can be added to the constituent material of the panel body. Examples thereof include mold release agents, heat stabilizers, antioxidants, and weather resistance improvements. Agents, alkali soaps, metal soaps, plasticizers, fluidity improvers, nucleating agents, flame retardants, anti-dripping agents and the like. The usage-amount of these adjuvants is suitably selected from a well-known range.

  The constituent material of the frame-like portion 2 is not particularly limited, and various known arbitrary thermoplastic resins can be used. Specifically, for example, polycarbonate resin; thermoplastic polyester resin such as polyethylene terephthalate resin, polytrimethylene terephthalate, polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin) ), Styrene-based resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin); Polyolefin resins such as polyethylene resins and polypropylene resins; Polyamide resins; Polyimide resins; Polyether resins; Polyurethane resins; Polyphenylene ether resins; Id resins; polysulfone resins; and polymethacrylate resins and the like, which may be used in combination of two or more. Among these, PC and thermoplastic polyester resin are preferable from the viewpoint of thermal stability, rigidity, and adhesion to the design part (1), and among them, PC-based materials, particularly thermoplastic polyester resins. Use in combination is preferred.

  Of the constituent resin materials of the panel main body 1 and the frame-like portion 2, it is desirable that the main components blended in an amount of 10% by weight or more are the same in order to enhance the bonding property between them.

  When a polymer alloy composed of PC and a thermoplastic polyester resin is used as the constituent material of the frame-like portion 2, the ratio of PC to the total amount of both components is usually 50 to 95% by weight.

  The thermoplastic polyester resin is a polymer or copolymer obtained by condensation reaction of a dicarboxylic acid component composed of a dicarboxylic acid or a reactive derivative thereof and a diol component composed of a diol or an ester derivative thereof.

  In general, the thermoplastic polyester resin is produced by reacting a dicarboxylic acid component with a diol component in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc. This is done by discharging out of the system. The condensation reaction may be either a batch type or a continuous type, and the degree of polymerization may be increased by solid phase polymerization.

  The dicarboxylic acids may be either aromatic dicarboxylic acids or aliphatic dicarboxylic acids, but aromatic dicarboxylic acids are preferred from the viewpoints of heat resistance and dimensional stability. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylether dicarboxylic acid 4,4′-biphenylmethanedicarboxylic acid, 4,4′-biphenylsulfonedicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-ter-phenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid and the like can be mentioned. In addition, alkyl group-substituted products such as 5-methylisophthalic acid; reactive derivatives such as alkyl ester derivatives such as dimethyl terephthalate and diethyl terephthalate can also be used.

  Among the above, terephthalic acid, 2,6-naphthalenedicarboxylic acid and their alkyl ester derivatives are preferable, and terephthalic acid and its alkyl ester derivatives are more preferable. Two or more of these aromatic dicarboxylic acids may be used in combination, and together with the aromatic dicarboxylic acid, an aliphatic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, or a fatty acid such as cyclohexanedicarboxylic acid. It is also possible to use a cyclic dicarboxylic acid in combination.

  The diols include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, deca Aliphatic diols such as methylene glycol and 2,2-dimethyl-1,3-propanediol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanediol, trans- or cis-2,2, Alicyclic diols such as 4,4-tetramethyl-1,3-cyclobutanediol; aromas such as p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether) Group diols. These substitution products can also be used.

  Among the above, ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferable from the viewpoint of thermal stability, impact resistance, rigidity, and the like. 1,3-propanediol and 1,4-butanediol are more preferable, and ethylene glycol is particularly preferable. Two or more of these may be used in combination. Further, as the diol component, a long chain diol having a molecular weight of 400 to 6,000, that is, one or more of polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like are used in combination with the above diols. It may be copolymerized.

  Further, the thermoplastic polyester resin used in the present invention can be branched by introducing a small amount of a branching agent. Examples of the branching agent include trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, pentaerythritol and the like.

  Preferable specific examples of the thermoplastic polyester resin used in the frame-shaped part 2 include polyethylene terephthalate resin (PET), polypropylene terephthalate resin (PPT), polybutylene terephthalate resin (PBT), polyhexylene terephthalate resin, polyethylene-naphthalate. Examples include resin (PEN), polybutylene naphthalate resin (PBN), poly (1,4-cyclohexanedimethylene terephthalate) resin (PCT), polycyclohexylcyclohexylate (PCC), and the like. Among these, polyethylene terephthalate resin (PET), polypropylene terephthalate resin (PPT), and polybutylene terephthalate resin (PBT) are preferable in terms of fluidity and impact resistance.

  The polyethylene terephthalate resin is a saturated polyester polymer or copolymer obtained by a condensation reaction of terephthalic acid as a main component as a dicarboxylic acid component and ethylene glycol as a diol component as a main component. The proportion of the ethylene terephthalate unit as the repeating unit is usually 70 mol% or more, preferably 80 mol% or more. In addition, in the polyethylene terephthalate resin, diethylene glycol, which is a side reaction product during polymerization, may be included as a copolymerization component. The amount of diethylene glycol is usually based on the total amount of the diol component used in the polymerization reaction. 0.5 to 6 mol%, preferably 0.5 to 5 mol%.

Specific examples of other thermoplastic polyester resins include, for example, polypivalolactone resins obtained by ring-opening polymerization of lactone, poly (ε-caprolactone) resins, and liquid crystal polymers that form liquid crystals in the molten state (Thermotropic).
Liquid Crystal Polymer (TLCP). Specifically, commercially available liquid crystal polyester resins include “X7G” manufactured by Eastman Kodak Company, “Xyday” manufactured by Dartco Company, “Econol” manufactured by Sumitomo Chemical Co., Ltd., “ Vector "and the like.

  The intrinsic viscosity of the thermoplastic polyester resin used in the present invention is usually 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g. Here, the intrinsic viscosity means a value measured at 30 ° C. in a solvent of phenol / tetrachloroethane = 50/50 (weight ratio). When the intrinsic viscosity is less than 0.4, the impact resistance tends to decrease, and when it exceeds 1.5, the fluidity tends to decrease. The amount of terminal carboxyl groups of the thermoplastic polyester resin is usually 5 to 50 μeq / g, preferably 10 to 30 μeq / g. When the terminal carboxyl group amount is less than 5 μeq / g, the impact resistance tends to decrease, and when it exceeds 50 μeq / g, the moist heat resistance and the thermal stability tend to be insufficient.

  Furthermore, as the thermoplastic polyester resin used in the present invention, not only virgin raw materials but also thermoplastic polyester resins regenerated from used products, so-called material recycled thermoplastic polyester resins can be used. . As used products, containers, films, sheets, fibers, and the like are mainly exemplified, and containers such as PET bottles are preferable. In addition, as the recycled thermoplastic polyester resin, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.

  Moreover, it is preferable to mix | blend a filler with the structural material of the frame-shaped part 2 in order to improve rigidity, dimensional stability, and heat resistance. Examples of such fillers include titanium oxide, zinc oxide, barium sulfate, silica, calcium carbonate, iron oxide, alumina, calcium titanate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium sulfate, and sulfuric acid. Sodium, calcium sulfite, magnesium silicate (talc), aluminum silicate (mica), calcium silicate (wollastonite), clay, glass beads, glass powder, glass fiber, carbon fiber, aramid fiber, component defibered fiber, silica sand, silica Stone, quartz powder, shirasu, diatomaceous earth, white carbon, iron powder, aluminum powder and the like. Among these, glass fiber, carbon fiber, aramid fiber, biodegradable fiber, magnesium silicate (talc), aluminum silicate (mica), and calcium silicate (wollastonite) are preferable. Two or more kinds of fillers can be used in combination.

  The shape of the filler may be any of spherical, cubic, granular, needle-like, plate-like, and fiber-like, but improves the dimensional stability of the finally obtained thermoplastic resin composition. From the viewpoint of high rigidity and good appearance, a plate shape or a needle shape is preferable, and a filler having a laser diffraction particle size (D50) of 10 μm or less is preferable.

  The usage-amount of a filler is 2-50 weight part normally with respect to 100 weight part of constituent materials of a frame-shaped part, Preferably it is 5-40 weight part. When the amount of the filler is less than 2 parts by weight, the effect of improving rigidity, dimensional stability and heat resistance is small, and when it exceeds 50 parts by weight, the impact resistance is lowered.

  The above fillers may be left untreated, but for the purpose of increasing the affinity with the resin component or the interfacial binding force, surface treatment agents, higher fatty acids or their derivatives, derivatives such as salts, coupling agents, etc. It is preferable to treat with. When the surface treatment is performed in combination with various surfactants such as nonionic, cationic, and anionic types and dispersants such as various resins, the mechanical strength and kneadability are preferably improved. .

  Conductive carbon black and / or hollow nanocarbon fibers can be blended in the constituent material of the frame-like portion 2 for the purpose of imparting antistatic properties and conductivity capable of electrostatic coating. Examples of the conductive carbon black include acetylene black obtained by thermally decomposing acetylene gas, and Ketjen black produced by crude incomplete combustion using crude oil as a raw material. Hollow nanocarbon fibers have an outer region consisting of an essentially continuous multi-layer of regularly arranged carbon atoms and an inner hollow region, with each layer and the hollow region being arranged substantially concentrically. There are essentially cylindrical fibrils. Furthermore, the regularly arranged carbon atoms in the outer region are graphite-like. The diameter of the hollow region is usually 2 to 20 nm. Such hollow nanocarbon fibers are sold by Hyperion Catharsis under the trade name “graphite fibrils” and are readily available.

  The panel body 1 is preferably made of non-reinforced synthetic resin, while the frame-like portion 2 is preferably made of composite reinforced synthetic resin. That is, it is preferable to add reinforcing fibers to the resin material of the frame-like portion 2. As the reinforcing fiber, for example, at least one selected from the group consisting of glass fiber, carbon fiber, aromatic polyamide fiber (aramid fiber), biodegradable fiber, talc, mica, and wollastonite can be used. In order to improve mechanical strength, dimensional accuracy, and heat resistance, the weight average fiber length of the fibers in the finished molded product is 0.1 to 5 mm, preferably 0.2 to 5 mm, more preferably 1 to 5 mm. . In addition, the weight average fiber length of the reinforcing fibers used in the production of such a molded product is arbitrary and may be appropriately selected and determined, but in general, the weight average fiber length of the raw material fibers is the strength and From the viewpoint of dispersibility, it is usually 1.5 to 10 mm, preferably 1.8 to 5 mm. In order to keep the weight average fiber length of the finished molded product high, the configuration of the injection cylinder of the injection molding machine is essential. Especially, the compression ratio of the screw is loosely compressed, the clearance is wide, and the clearance of the check ring is wide. It is effective. Moreover, as conditions at the time of injection molding, it is effective to mold the resin temperature at a high setting, the back pressure at the time of measurement is low, and the injection speed is low.

  Although not shown, in the present invention, a hard coat (hard coating) as a protective film may be provided in order to mainly prevent the panel body 1 from being damaged or deteriorated. Such a hard film may be provided only on the front surface opposite to the frame-like portion 2. The thickness of the hard coating is preferably 1/100 or less of the thickness of the panel body 1, and usually 1 to 50 μm, particularly 5 to 20 μm.

  The hard film may be a single layer, but may have a multilayer structure of at least two layers in order to enhance the protective function or weather resistance. In the multilayer structure, it is preferable to set the hardness of the outermost layer to the maximum. As the hard coating having a multilayer structure, for example, it has at least one function among a functional layer of each of heat ray shielding, ultraviolet absorption, thermochromic, photochromic, electrochromic, primer layer, colored decoration layer, etc. It is preferable.

  A transparent resin is suitable for the constituent material of the hard coating. As such a transparent resin, a known material known as a hard coat agent can be used as appropriate. For example, various hard coat agents such as silicone, acrylic, silazane, and urethane can be used. I can do it. In these, in order to improve adhesiveness and a weather resistance, the 2-coat type hard coat which provides a primer layer before apply | coating a hard-coat agent is preferable. Examples of the coating method include spray coating, dip coating, flow coating, spin coating, and bar coating. Moreover, the method by a film insert, the method of apply | coating and transferring the chemical | medical agent suitable for a transfer film, etc. can also be employ | adopted.

  Chemical films having various functions (heat ray shielding, ultraviolet absorption, thermochromic, photochromic, and electrochromic functions) may be formed on the outermost layer of the hard coating.

  A transparent resin layer may be provided between the surface of the panel body 1 and the hard coating.

  The present invention is suitable for application to windows of vehicles, particularly automobiles, and is particularly suitable for application to sunroofs, but is also applicable to quarter windows, rear windows, and the like.

  In the present invention, an uneven portion may be formed at the boundary between the rear surface of the panel main body 1 and the frame-shaped portion 2 to increase the bonding strength between the panel main body 1 and the frame-shaped portion 2. In the present invention, an attachment piece for attaching another component may be provided on the frame-like portion 2 in a protruding manner.

<Description of physical properties of panel body 1 and frame-like part 2>
In the present invention, the volume of the panel main body 1 is V ₁ , the volume of the frame-like portion 2 is V ₂ , and a 3 mm-thick 100 mm × 100 mm flat plate formed of the material constituting the panel main body 1 is heated to 130 ° C. When the shrinkage rate when held for a time is S ₁ , and the shrinkage rate when a 3 mm-thick 100 mm × 100 mm flat plate molded from the material constituting the frame-like portion 2 is held at 130 ° C. for 2 hours is S ₂ 0.01 <V ₂ / V ₁ <1.0, preferably 0.05 ≦ V ₂ / V ₁ ≦ 1.0, particularly preferably 0.1 ≦ V ₂ / V ₁ ≦ 0.75, 1.0 <S ₂ / S ₁ <3.0, preferably 1.1 ≦ S ₂ / S ₁ ≦ 3.0, particularly preferably 1.1 ≦ S ₂ / S ₁ ≦ 2.5.

Further, preferably 0.35 <(S ₂ · V ₂ ) / (S ₁ · V ₁ ) <1.1, particularly preferably 0.35 <(S ₂ · V ₂ ) / (S ₁ · V. ₁ ) ≦ 1.0.

When the bending elastic modulus of the panel body 1 is F ₁ and the bending elastic modulus of the frame-like portion is F ₂ , preferably 0.35 <(S ₂ · V ₂ · F ₂ ) / (S ₁ · V ₁ F ₁ ) <1.5, particularly preferably 0.35 <(S ₂ · V ₂ · F ₂ ) / (S ₁ · V ₁ · F ₁ ) ≦ 1.4.

When the molding shrinkage rate at the time of injection molding of the frame-like portion 2 is I ₂ and the linear expansion coefficient of the panel body is α ₁ , preferably 0.8 × 10 ⁻² <α ₁ / I ₂ <2.3 × 10 ⁻² and particularly preferably 0.8 × 10 ⁻² <α ₁ / I ₂ ≦ 2.0 × 10 ⁻² .

When the physical property values of the panel main body 1 and the frame-shaped part 2 are in the above range, the contraction behavior of the peripheral part of the panel main body 1 during the annealing process is restricted or assisted by the contraction behavior of the frame-shaped part 2. Is prevented, and the shape accuracy of the product panel 4 is improved. That is, as represented by 0.01 <V ₂ / V ₁ <1.0, when the volume of the frame-like part 2 is smaller than the volume of the panel body 1, the shrinkage rate S between the frame-like part 2 and the panel body 1. ₂ and S ₁ are 1.0 <S ₂ / S ₁ <3.0, the degree of contraction of the convexly curved panel body 1 and the degree of contraction of the frame-like portion 2 are substantially equal, and the convexity of the panel 4 The curvature radius of the curve is substantially the same before and after the annealing process, and the shape accuracy of the product panel 4 is improved.

In this case, if S ₂ / S ₁ is 1 or less, the contraction of the panel body 1 is restrained by the frame-shaped portion 2. In other words, the deformation behavior of the panel main body 1 to be contracted is hindered by the frame-like portion 2. As a result, the radius of curvature of the convex curvature of the panel 4 becomes larger than the allowable range, and the panel 4 becomes close to a flat (flat plate shape) or has a concave curvature. On the other hand, when S ₂ / S ₁ is 3 or more, the frame-like portion 2 tends to contract and deform beyond the contraction deformation of the panel body 1, and the convex warpage of the panel body 1 becomes strong. That is, the radius of curvature of the panel 4 is smaller than the allowable range.

The deformation behavior of the panel 4 at the time of annealing treatment is the ratio S ₂ · V ₂ / S ₁ · V ₁ of the product of the volume of the panel body 1 and the frame-like portion 2 and the shrinkage rate at the time of annealing treatment, and the flexural modulus F _1, is also affected by the _{F 2.} Further, since the panel body 1 is injection-molded first, and after the panel body 1 has cooled to a certain degree to reach the allowable hardness, the frame-shaped part 2 is injection-molded on the rear surface of the panel body 1, so molding shrinkage I ₂ of _the linear expansion coefficient alpha ₁ of the panel body 1 also affect the deformation behavior of the panel 4. Therefore, the values of (S ₂ · V ₂ ) / (S ₁ · V ₁ ), (S ₂ · V ₂ · F ₂ ) / (S ₁ · V ₁ · F ₁ ), α ₁ / I ₂ are By setting the range, the shape accuracy of the product panel 4 can be increased.

The shrinkage rates S ₁ and S ₂ are average values of the shrinkage rate in the flow direction during injection molding and the shrinkage rate in the direction orthogonal to the flow direction. The linear expansion coefficient is also an average value in the flow direction and the direction orthogonal thereto.

  Hereinafter, examples and comparative examples will be described.

[Examples 1 to 6, Comparative Examples 1 and 2]
A panel having the shape shown in FIGS. 1 and 2 was formed. As the molding method, first, the panel body 1 was injection-molded (injection temperature 300 ° C.) into a cavity formed between a fixed mold and a first movable mold whose temperature was controlled at a mold temperature of 90 ° C. The injection speed was a single speed of 50 mm / sec, and the injection holding pressure switching position was 2 mm. Molding was performed with a valve gate type hot runner. Injection compression molding was performed, the mold was opened by 2 mm before injection, and 700 t was re-clamped at the injection holding pressure switching position. The holding time for re-clamping at this time was 15 seconds. Next, after the panel main body 1 is cooled for 60 seconds, the first movable mold is opened, and the second movable mold is controlled to a mold temperature of 90 ° C. with the panel main body held in the first movable mold. And filling the cavity formed between the second movable mold and the panel body 1 with the molding material of the frame-like portion 2 at a single rate of 40 mm / sec (injection resin temperature shown in Table 1) )did. The injection holding pressure switching position was set to 35 mm. A holding pressure of 25 MPa was applied for 5 seconds to form the frame-shaped part 2. After the cooling time of 60 seconds, the second movable mold was opened, and the molded body in which the molded panel body and the frame upper part were integrated was removed. After demolding, an annealing treatment of 130 ° C. × 3 Hr was performed.

The panel dimensions are as follows.
Long side a 750mm
Short side b 465mm
Curved height c As shown in Table 2 Width of the frame-like portion 2 (location along the long side, cross-section HH in FIG. 2) 90 mm
The width of the frame-like part 2 (location along the short side, cross-section II in FIG. 2) 97 mm
Panel body thickness 5mm
Frame thickness 3.5mm
Therefore, the volume V ₁ , V ₂ and V ₂ / V ₁ ratio of the panel main body and the frame-shaped portion are as follows.

V ₁ 1743.8 cm ³
V ₂ 666.0 cm ³
_{V 2} / V 1 0.38
A polycarbonate resin (manufactured by Mitsubishi Engineer Plastics; trade name “Iupilon S3000UR”) was used as a molding material for the panel body. The viscosity average molecular weight (Mv) was 21,000, and the linear expansion coefficient was 6.5 × 10 ⁻⁵ [/ ° C.]. The 3 mm thick 100 mm × 100 mm flat plate has a 130 ° C. × 2 Hr shrinkage S ₁ of 0.08% and a flexural modulus F ₁ of 2,300 MPa.

  The molding material for the frame-like part 2 was as shown in Table 1. In Table 1, PC is the above polycarbonate resin (Mitsubishi Engineering Plastics Co., Ltd .: Iupilon S-3000FN, viscosity average molecular weight Mv = 21,000), PET is polyethylene terephthalate resin (Mitsubishi Chemical Corporation: Novapex GG500), PE is Polyethylene resin (Nippon Polyethylene Co., Ltd .: Novatec HF310) and GF are glass fibers (Nippon Electric Glass Co., Ltd .: ECS03T-571, average fiber diameter 13 μm, average fiber length 3 mm). Talc (manufactured by Matsumura Sangyo Co., Ltd .: High Filler # 5000PJ) having an average particle size of 1.8 μm and a bulk density of 0.12 g / ml was used. After uniformly mixing the polycarbonate resin and the second component PET resin or PE resin with a tumbler mixer at the ratio shown in Table 1, a twin screw extruder (manufactured by Nippon Steel Works, TEX30XCT, L / D = 42, The barrel number is 12), the cylinder temperature is 280 ° C., the screw speed is 250 rpm, the barrel 1 (the most upstream barrel) is fed to the extruder and melt-kneaded, and the barrel 7 (the seventh from the upstream side) is further melted and kneaded. From the barrel), glass fibers were fed to the extruder at a ratio shown in Table 1 and melt kneaded to prepare pellets of the resin composition as molding materials. Moreover, the composite strong reinforcement | strengthening PBT (Intrinsic viscosity: 0.85, terminal COOH: 14) / PC resin of the comparative example 2 used the thing made from Mitsubishi engineering plastics. Table 1 also shows the physical properties of the injection-molded product with the blending.

V ₂ / V ₁ , S ₂ / S ₁ , (S ₂ · V ₂ ) / (S ₁ · V ₁ ), (S ₂ · V ₂ · F ₂ ) / (S ₁ · V ₁ · F of each panel ₁ ) Table 2 shows the bending height before and after annealing.

[Example 7]
In Example 4, the PC material constituting the panel molded body was colored with a pigment, the total light transmittance was set to 20%, and the thickness of the frame portion was set to 4.9 mm under the same conditions as in Example 4. Panels were molded. _{V 2} / V ₁ is 0.53. The measurement results of the physical properties are also shown in Table 2.

[Example 8]
A panel was produced under the same conditions as in Example 1 except that the annealing treatment after demolding was set to 130 ° C. × 1 Hr and the cured film coating treatment described below was performed. The measurement results of the physical properties are also shown in Table 2.
(Formation of cured film)
A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 93.0 g of propylene glycol monomethyl ether acetate, 60 g of glycidyl methacrylate, 2.0 g of mercaptopropyltrimethoxysilane and 2,2′-azobis (2,4 -Dimethylvaleronitrile) 0.62 g was added and reacted at 65 ° C. for 3 hours, and further 2,2′-azobis (2,4-dimethylvaleronitrile) 0.31 g was added and reacted for 3 hours. Next, 31.0 g of acrylic acid, 0.93 g of triphenylphosphine, 0.28 g of p-methoxyphenol, and 46.53 g of propylene glycol monomethyl ether acetate were added and reacted at 110 ° C. for 10 hours, and (meth) acryloyl group and A copolymer having an alkoxysilyl group was obtained. 25.69 g of silica sol (Nissan Chemical Co., Ltd .: IPA-ST) 25.69 g (solid content 30%), 0.5 g of water, and 0.1 g of dioctyltin dilaurate were added to the obtained copolymer. The mixture was reacted at 4 ° C. for 4 hours, and after completion of the reaction, 77.53 g of propylene glycol monomethyl ether acetate was added to obtain an organic-inorganic composite (solid content 30%).

In a flask equipped with a thermometer, a stirrer and a reflux condenser, 80 g of dipentaerythritol triacrylate, 4.0 g of isocyanate propyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE 9007), 0.08 g of p-methoxyphenol and dibutyltin dilaurate 0 0.04 g was added and reacted at 70 ° C. for 2 hours. When this reaction product was analyzed by an infrared absorption spectrum, absorption of 250 cm ⁻¹ of the isocyanate group was not recognized, and it was confirmed that the reaction was completed. Next, 211.23 g of silica sol (manufactured by Nissan Chemical Industries, Ltd .: MEK-ST), 0.84 g of water and 0.4 g of acetylacetone aluminum were added and reacted at 70 ° C. for 4 hours to obtain a polyfunctional acrylate. .

A benzozotriazole-based ultraviolet absorber (manufactured by Ciba Specialty Chemicals: TINUVIN PS) was added to the composition containing 30% by weight of the organic-inorganic composite component obtained above and 70% by weight of the polyfunctional acrylate component. 3 parts by weight, 3 parts by weight of a hindered amine light stabilizer (Sankyo LS765 manufactured by Sankyo Co., Ltd.) and 3 parts by weight of a stabilizer (manufactured by Ciba Specialty Chemicals: Irgacure 184) are added to 10 parts by weight of methyl etone ketone. It was dissolved to obtain an active energy ray-curable composition. This active energy ray-curable composition was flow-coated on a panel molded body so that the thickness of the coating film after drying was 6 μm, and was heat-dried at 80 ° C. for 2 minutes. Next, the coating film was cured by irradiating with an ultraviolet ray of 500 mJ / cm ² using a high-pressure mercury lamp having an output of 120 w / cm ² as a light source.

[Example 9]
A panel was produced under the same conditions as in Example 1 except that the annealing treatment after demolding was set to 130 ° C. × 1 Hr and the cured film coating treatment described below was performed. The measurement results of the physical properties are also shown in Table 2.

(Formation of cured film)
(Synthesis of polyorganosiloxane)
To a reactor equipped with a stirrer and a reflux condenser, 272 parts by weight of methyltrimethoxysilane and 160 parts by weight of methanol were added, and the mixture was cooled to 10 ° C. or less under a nitrogen atmosphere. Next, 400 parts by weight of a 0.1% acetic acid solution was dropped over 40 minutes to hydrolyze the alkoxysilane. After completion of the dropwise addition, the reaction was continued for 1 hour under ice cooling and then stirred for 3 hours at room temperature to complete the hydrolysis.

To the obtained silanol solution, 200 parts by weight of methanol silica sol (particle size 15 μm, silica solid content 30%) and 600 parts by weight of isopropanol were added, and stripped under a reduced pressure of 20 to 50 mmHg under an internal temperature of 35 ° C. or less. Methanol and residual water were removed. The finally obtained polyorganosiloxane solution (non-volatile substance (hereinafter referred to as NVM) 20%) was 650 parts by weight. Furthermore, this reaction solution was allowed to stand at 40 ° C. for 7 hours in the dark, and the condensation reaction was allowed to proceed gradually. As a result of GPC analysis of this polyorganosiloxane solution (H1), no 1-dimer was present, the trimer was 0.01%, the tetramer was 9.9%, and the pentamer was 11. 4%, hexamer or higher was 78.7%. The number average degree of polymerization was 10.8. During this oligomerization reaction, each molecule is considered to be linearly linked. The linear expansion coefficient in 60-90 degreeC of the hardened | cured material which hardened this solution at 125 degreeC for 2 hours was 10.0 * 10 < ^-5 > / ^degreeC .

(Synthesis of acrylic primer)
Add 100 parts by weight of diacetone alcohol to a reactor equipped with a stirrer, reflux condenser, nitrogen gas inlet tube, and dropping funnel, and thoroughly replace the inside of the reactor with nitrogen gas while stirring and heat to 80-90 ° C. did. On the other hand, 20 parts by weight of trimethoxypropyl methacrylate, 60 parts by weight of methyl methacrylate, 5 parts by weight of methyl acrylate, 5 parts by weight of vinyl acetate, 10 parts by weight of glycidyl methacrylate, 0.2 part by weight of ethylene glycol dimethacrylate and azobisiso as an initiator 3 parts by weight of butyronitrile (AIBN) was added to the dropping funnel, and this was gradually added from the dropping funnel into the reactor over 1 hour. During this time, stirring and introduction of nitrogen gas were continued. Thereafter, the reaction was continued at 90 ° C. for 3 hours. And, 20 parts by weight of polymethyl methacrylate having a molecular weight (Mw) of 150,000, 150 parts by weight of methyl isobutyl ketone as a solvent, 150 parts by weight of cellosolve acetate, 110 parts by weight of propylene glycol monomethyl ether, 110 parts by weight of isopropanol and 50 parts by weight of diacetone alcohol. Parts were added to make NVM 15%. To this reaction solution, 2,2′-dihydroxybenzophenone as an ultraviolet absorber was added at a ratio of 2% with respect to NVM to obtain a primer coating composition. The linear expansion coefficient in 60-90 degreeC of the hardened | cured material which hardened this primer coating composition at 125 degreeC for 2 hours was 24.0 * 10 < ^-5 > / degreeC.

(Formation of cured film)
The acrylic primer coating composition was applied on the panel structure, dried at room temperature for 20 minutes, and then cured and dried at 125 ° C. for 1 hour. Thereafter, the above-mentioned polyorganosiloxane solution (NVM 20%) paint was applied, allowed to air dry at room temperature for 20 minutes, and then cured at 120 ° C. for 1 hour to form a cured film on the panel structure.

  Evaluation methods in Examples and Comparative Examples are as follows.

(1) Linear expansion coefficient
3 g of each paint was weighed in an aluminum cup and allowed to stand on a hot plate at about 45 ° C. for 2 hours to remove volatile components. Subsequently, it was cured in a dryer at 125 ° C. for 2 hours, and this was used as a sample for measuring the linear expansion coefficient. The polycarbonate used as the primary material is a 10 mm long section of a thermoplastic resin injection molding test piece specified by ISO 294-1, and the linear expansion coefficient in the flow direction and its perpendicular direction is measured. Took its average value.

Measuring instrument: TMA100 (manufactured by Seiko Electronics Industry Co., Ltd.)
Temperature condition: Cured film 30-190 ° C, temperature rise at 10 ° C / min
PC resin 30-100 ° C, temperature rising at 10 ° C / min Load: -1 g
Atmosphere: Cured film N ₂ , 300 ml / min
PC resin In-air measurement: The data at the second and subsequent temperature increases were adopted (the first time was to erase the thermal history)
). The measurement was repeated 5 times and the values were averaged.

(2) GPC
5 g of the polyorganosiloxane composition solution was bathed in an ice bath, and volatile components (mainly water and organic solvents; alcohols, acetylacetone, etc.) were removed under a reduced pressure of 10 mmHg or less. Next, it was dissolved in THF to make a 0.1% concentration solution, passed through a 0.1 μ membrane filter, and then subjected to GPC analysis under the following conditions.

Measuring equipment: Shodex system 21 (Showa Denko)
Column (for low molecular weight): KF-803L x 1 + KF-802.5 x 1 + KF-
801 × 2 Molecular weight measurement range: 200 to 70,000
Sample concentration: 0.1% THF
Eluent: THF
Oven temperature: 40 ° C
Calibration curve reference material: polystyrene

(3) Mold shrinkage, secondary shrinkage
Each resin is injected and filled into a 100 mm x 100 mm x 3 mm thick flat plate mold for injection molding (mold temperature 80 ° C) where marks are installed at intervals of 90 mm in the flow direction and 90 mm in the perpendicular direction. A holding pressure of 50% of the peak pressure was attached for 10 seconds. Next, after holding the pressure, the molded body taken out from the mold after holding for 20 seconds was used as a flat test piece.

<Mold shrinkage>
The molded specimen was held for a whole day and night in an atmosphere of 23 ° C. and 50% Rh, and the interval between the marks was measured. The measured value was divided by the interval on the mold to calculate the molding shrinkage.

<Secondary shrinkage>
The test piece after the molding shrinkage measurement was subjected to heat treatment at 130 ° C. for 2 hours. The heat-treated test piece was kept for a whole day and night in an atmosphere of 23 ° C. and 50% Rh, and the interval between the marks was measured. The secondary shrinkage was calculated by dividing the measured value from the interval after molding used to calculate the molding shrinkage.

(4) Flexural modulus Measurement was carried out based on the ISO 178 plastic bending test method.

(5) Total light transmittance, Haze
A test piece having a size of 50 mm × 50 mm was cut out from the transparent part of the obtained panel-shaped molded body, and the total light transmittance and Haze were measured based on ISO 13468-1 and ISO 14782.

(6) Scratch resistance evaluation Based on JIS K-7105, after implementing the Taber abrasion test, Haze was measured with the haze meter, and the evaluation result was shown on the following conditions.

Wear wheel: CS-10F
Load: 500g
Evaluation: Measure Haze value at initial stage and after 100 cycles
○: ΔHaze <4%
Δ: ΔHaze = 4-10
×: ΔHaze> 10

(7) Curved height The obtained panel-shaped molded body was placed on a surface plate, and the height from the surface plate surface to the uppermost point was measured to obtain the curved height.

As is apparent from Table 2, in Examples 1 to 7, the ratio of the bending height before and after annealing is 0.93 to 1.09, which is close to 1. On the other hand, in Comparative Example 1 in which S ₂ / S ₁ is 1.00 and Comparative Example 2 in which S ₂ / S ₁ is 3.33, the change in bending height before and after annealing is large.

1 Panel body 2 Frame portion 3 Transparent area 4 Panel

Claims (8)

An automotive window panel made of a synthetic resin material having a front surface and a rear surface and curved so that the front side is convex,
A panel body, and a frame-like portion provided integrally with the panel body over the entire periphery of the rear surface of the panel body;
The panel body is made of translucent synthetic resin.
The area of the transparent region (3) in the panel body is 400 cm ² or more,
The width of the frame-shaped portion is 30 to 200 mm,
After the panel body is injection-molded, in the panel in which the frame-shaped part is formed integrally with the panel body by injection molding on the entire periphery of the rear surface of the panel body,
_{V 1} the volume ^{(m 3)} of the panel body, two volumes of the frame-shaped portion ^{(m 3)} _{V 2,} a 100 mm × 100 mm flat plate of 3mm thickness molded of a material constituting the panel body 130 ° C. The shrinkage rate (%) when held for a time is S ₁ , and the shrinkage rate (%) when a 3 mm-thick 100 mm × 100 mm flat plate molded from the material constituting the frame-like portion is held at 130 ° C. for 2 hours is S ₂
0.38 ≦ V ₂ / V ₁ ≦ 0.75
1.0 <S ₂ / S ₁ <3.0
0.38 <(S ₂ · V ₂ ) / (S ₁ · V ₁ ) <1.1
And
If the flexural modulus of the material constituting the panel body a (MPa) and F _1, the flexural modulus of the material constituting the frame-shaped portion (MPa) was F _2,
0.35 <(S ₂ · V ₂ · F ₂ ) / (S ₁ · V ₁ · F ₁ ) <1.5
And
Molding shrinkage during injection molding of the material forming the framelike part (%) as I _2, if the linear expansion coefficient of the material constituting the panel body was alpha _1,
0.8 × 10 ⁻² <α ₁ / I ₂ <2.3 × 10 ⁻²
A panel characterized by being.   2. The panel according to claim 1, wherein the main component of the synthetic resin constituting the panel main body is the same as the main component of the synthetic resin constituting the frame-like portion.   3. The composite according to claim 1 or 2, wherein the material constituting the frame-shaped portion contains at least one selected from the group consisting of glass fiber, carbon fiber, aramid fiber, biodegradable fiber, talc, mica, and wollastonite. A panel characterized by being a reinforced thermoplastic synthetic resin material.   4. The panel according to claim 1, wherein a hard film is formed on a front surface of the panel main body.   5. The panel according to claim 1, wherein a hard film is formed on a front surface of the panel main body and an inner region of the frame-shaped portion of the rear surface of the panel main body.   6. The panel according to claim 4, wherein the thickness of the hard coating is 1/100 or less of the thickness of the panel body.   The panel according to any one of claims 4 to 6, wherein the hard film comprises an active energy ray-curable composition or a cured layer of a thermosetting organosiloxane.   8. The panel according to claim 1, wherein the translucent synthetic resin is an aromatic polycarbonate resin.

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