JP2017165044A - Windshield plate and vehicle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a windshield plate that has excellent durability against ultraviolet rays, and as a result, in which scratch resistance against impact is kept over a long period of time, and to provide a vehicle with the windshield plate having excellent reliability.SOLUTION: A windshield plate 100 has a base material 1 formed by using a material containing a thermoplastic resin and a coat layer 2 that is provided on at least one surface side of the base material 1 and is formed by using a resin composition containing a silicon-modified (meth)acrylic resin. The windshield plate 100 satisfies the following requirement A after the coat layer 2 has been irradiated with ultraviolet rays for 3,000 hours using a sunshine weatherometer. Requirement A: when the windshield plate 100 is subjected to a cross-cut method in accordance with JIS K 5600-5-6, adhesion of the coat layer cut into a lattice shape to a base material is 90% or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a windshield plate and a vehicle.

  Windshields used for motorcycles, golf carts, forklifts, and other vehicles, and windshields (visors) used for head-mounted items such as helmets and goggles are lightweight, transparent, workable, and crackable. Various plastic materials are used from the viewpoints of hardness and safety in case of cracking.

  In particular, in recent years, the surface of a windshield has been proposed to improve the transparency and scratch resistance while maintaining the thermoformability of a windshield for vehicles using plastic materials. ing.

  For example, Patent Document 1 discloses an ultraviolet curable resin composition that is used by being applied to the surface of a windshield such as a helmet visor or goggles.

  Patent Document 2 discloses a windshield for a vehicle provided with a coating film made of a thermosetting resin composition having a melamine skeleton.

JP 2005-298619A International Publication No. 2009/057799 Specification

  However, the windshield with the coating treatment applied to the surface as described above has a reduced resistance to scratches such as sand dust and stepping stones due to the long-term irradiation of ultraviolet rays contained in sunlight. There was a problem that the transparency of the windshield was lowered.

  Therefore, an object of the present invention is to provide a windshield having excellent durability against ultraviolet rays and, as a result, maintaining scratch resistance against impacts over a long period of time, and a highly reliable vehicle having such a windshield. It is to provide.

Such an object is achieved by the present invention described in the following (1) to (11).
(1) A base material formed using a material containing a thermoplastic resin and a resin composition containing a silicon-modified (meth) acrylic resin provided on at least one surface side of the base material A coating layer,
A windshield board that satisfies the following requirement A after the coating layer is irradiated with ultraviolet rays for 3000 hours using a sunshine weatherometer.
Requirement A: The windshield has an adhesion of 90% or more to the base material of the coating layer cut in a lattice shape by the cross-cut method defined in JIS K 5600-5-6.

  (2) In the above (1), the base material has a yellowing degree measured in accordance with JIS K 7105 of 6.0 [ΔYI] or less after the coating layer is irradiated with the ultraviolet rays for 3000 hours. Windshield as described.

  (3) The windshield plate according to (1) or (2), wherein the resin composition further includes urethane (meth) acrylate.

  (4) Content of the said urethane (meth) acrylate is a windshield as described in said (3) which is 10 to 75 mass parts in 100 mass parts of said resin compositions.

  (5) The windshield plate according to any one of (1) to (4), wherein the resin composition includes a (meth) acrylate monomer.

  (6) The windshield plate according to (5), wherein the content of the (meth) acrylate monomer is 15 parts by mass or more and 55 parts by mass or less in 100 parts by mass of the resin composition.

  (7) The windshield plate according to any one of (1) to (6), wherein the resin composition includes an isocyanate.

  (8) The windshield plate according to (7), wherein the content of the isocyanate is 3 parts by mass or more and 40 parts by mass or less in 100 parts by mass of the resin composition.

  (9) The content of the silicon-modified (meth) acrylic resin is 5 parts by mass or more and 45 parts by mass or less in 100 parts by mass of the resin composition, according to any one of (1) to (8). Windshield.

  (10) The windshield plate according to any one of (1) to (9), wherein a part or all of the windshield plate is formed into a curved shape.

  (11) A vehicle comprising the windshield plate according to any one of (1) to (10) above.

  ADVANTAGE OF THE INVENTION According to this invention, it can be set as the windshield which was equipped with the outstanding durability with respect to an ultraviolet-ray, As a result, the abrasion resistance with respect to an impact was maintained over the long term. Therefore, a vehicle including such a windshield plate can have excellent reliability.

It is a longitudinal cross-sectional view which shows 1st Embodiment of the windshield board of this invention. It is a longitudinal cross-sectional view which shows 2nd Embodiment of the windshield board of this invention.

  Hereinafter, the windshield plate and vehicle of this invention are demonstrated in detail based on preferred embodiment shown to an accompanying drawing.

  The windshield 100 of the present invention includes a base material 1 formed using a material containing a thermoplastic resin, and a resin composition that is provided on at least one surface side of the base material 1 and contains a silicon-modified (meth) acrylic resin. After the coating layer 2 is irradiated with ultraviolet rays for 3000 hours using a sunshine weatherometer, the following requirement A is satisfied. Requirement A: The windshield has an adhesion of 90% or more to the base material of the coating layer cut in a lattice shape by the cross-cut method defined in JIS K 5600-5-6. In this way, if the adhesion of the windshield 100 after irradiation with ultraviolet rays is 90% or more by the cross-cut method, the windshield 100 has excellent durability against ultraviolet rays, and as a result, scratch resistance against impacts. It can be said that the property is maintained over a long period of time, and the windshield 100 can exhibit excellent transparency over a long period of time.

  Note that the windshield 100 is, for example, a windshield (vehicle windshield) used in a vehicle, and the vehicle refers to a person or an entire vehicle on which an object is moved or operated. For example, a vehicle, a truck, a ship, a railway vehicle, an airplane, a bus, a motorcycle, a bicycle, a forklift, a work vehicle that performs a predetermined work on a construction site, a golf cart, a toy vehicle, various vehicles in an amusement park, and the like.

  Further, the windshield for a vehicle refers to a plate-like structure that is arranged between a person or an object on the vehicle and the outside and shields the person or an object on the vehicle and the outside in at least one direction. . For example, it includes a windshield (screen) for motorcycles and bicycles, and other window materials provided in vehicles.

  Further, the windshield 100 can be applied to, for example, a windshield (visor) used for a head-mounted article such as a helmet and goggles in addition to the vehicle windshield.

  Therefore, by providing the windshield plate 100 for the vehicle and the head-mounted object, excellent reliability can be achieved.

Hereinafter, the windshield 100 will be described in detail.
<< First Embodiment >>
The windshield 100 of the present invention includes the base material 1 and the coat layer 2 as described above. However, in the present embodiment, the coat layer 2 is selectively provided on one surface side of the base material 1. ing.

  FIG. 1 is a longitudinal sectional view showing a first embodiment of a windshield of the present invention. Hereinafter, for convenience of explanation, the upper side of FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.

<Coat layer>
In this embodiment, the coat layer 2 (hard coat layer) is formed on the upper surface of the substrate 1 and formed using a resin composition, as shown in FIG. It is provided for imparting weather resistance, durability, scratch resistance, and thermoformability.

  Thus, in the windshield 100, when the coat layer 2 is formed on the upper surface (one surface) of the base material 1, when the windshield 100 is applied to a vehicle windshield, a person who uses the vehicle. It is preferable to dispose the substrate 1 on the person and / or the object side and the coat layer 2 on the outside of the vehicle.

  More specifically, when the windshield plate 100 is used as a windshield (screen) for a motorcycle or a bicycle, the coat layer 2 is preferably provided on the front surface. Moreover, when using the windshield 100 as a window material with which a vehicle is provided, it is preferable that the coat layer 2 is provided in the outdoor side (surface side exposed outside).

  In the present invention, the coat layer 2 is composed of a material excellent in weather resistance and scratch resistance, that is, a material satisfying the following requirement A after being irradiated with ultraviolet rays for 3000 hours using a sunshine weatherometer. .

  Requirement A: The windshield plate has an adhesion of 90% or more to the base material 1 of the coat layer 2 cut into a lattice shape by the cross-cut method defined in JIS K 5600-5-6.

  Here, as one of the problems in using the windshield for a long period of time, as described above, the impact of sand dust, stepping stones, etc. is caused by irradiating ultraviolet rays contained in sunlight for a long time. As a result, the transparency of the windshield may be reduced.

  As a result of repeated studies on the problem, the present inventors approximated the scratch resistance against impacts such as sand dust and stepping stones in accordance with the cross-cut method defined in JIS K 5600-5-6. It was found that the coating layer 2 cut in a lattice shape can be evaluated by observing the adhesion of the coating layer 2 to the substrate 1.

  As a result of further investigations, the present inventors have conducted a cross-cut method defined in JIS K 5600-5-6 after irradiating the coat layer 2 with ultraviolet rays using a sunshine weatherometer for 3000 hours. Therefore, if the adhesion of the coat layer 2 cut into a lattice shape to the base material 1 is 90% or more, the windshield 100 is irradiated with ultraviolet rays contained in sunlight for a long time. However, the present inventors have found that it can be said to have excellent scratch resistance against impacts such as sand dust and stepping stones, and have completed the present invention.

  More specifically, the adhesion by the cross-cut method is a value calculated as follows.

  First, a windshield plate 100 of 60 mm long × 60 mm wide × 8 mm thick is prepared, and the windshield 100 is irradiated with ultraviolet rays for 3000 hours using a sunshine weatherometer. Next, in accordance with the cross-cut method defined in JIS K 5600-5-6, a rectangular grid (25 squares) cut (cut) at intervals of 2 mm on the coat layer 2 side using a single blade. )I do. Subsequently, a tape having an adhesion strength of 10 ± 1 N per 25 mm width is applied to a 25-mass grid, and the tape is attached within 0.5 minutes at an angle close to 60 ° within 0.5 to 1.0 seconds. Pull apart. The number of grids peeled off along the cut edges and / or at the intersections of the coating layer 2 is measured, and the ratio of the grids (coat layer 2) adhering to the substrate 1 is calculated.

  In the present invention, the resin layer used for forming the coating layer 2 having such a structure, that is, the coating layer 2 that maintains excellent scratch resistance even after the use of the windshield 100 is used in the present invention. ) A thing containing an acrylic resin is used. Hereinafter, this resin composition will be described in detail.

(Silicon-modified (meth) acrylic resin)
Silicon-modified (meth) acrylic resin (siloxane-modified (meth) acrylate) is connected to a main chain in which a structural unit derived from a (meth) acryl monomer having a (meth) acryloyl group is repeated, and this main chain is linked to siloxane. It is a polymer (prepolymer) having a repeating body (subchain) in which structural units having a bond are repeated.

  That is, it is a polymer (prepolymer) in which a (meth) acrylic compound as a main chain and a compound having a siloxane bond (—Si—O—Si—) as a sub chain are linked.

  The silicon-modified (meth) acrylic resin provides the coating layer 2 with excellent transparency by having the main chain, and also has a repeating body in which the structural unit having the siloxane bond is repeated. The layer 2 can be provided with excellent scratch resistance and weather resistance.

  Specifically, the main chain of the silicon-modified (meth) acrylic resin is constituted by repeating structural units derived from a monomer having at least one (meth) acryloyl group of the following formula (1) and formula (2). What has the chemical formula shown by following formula (12) as what is equipped with the repetition of the structural unit derived from both of these monomers is mentioned.

（式（１）中、ｎは、１以上の整数を示し、Ｒ１は、独立して炭化水素基、有機基、または水素原子を示し、Ｒ０は、独立して炭化水素基または水素原子を示す。）

(In the formula (1), n represents an integer of 1 or more, R 1 independently represents a hydrocarbon group, an organic group, or a hydrogen atom, and R 0 independently represents a hydrocarbon group or a hydrogen atom. .)

（式（２）中、ｍは、１以上の整数を示し、Ｒ２は、独立して炭化水素基、有機基、または水素原子を示し、Ｒ０は、独立して炭化水素基または水素原子を示す。）

(In Formula (2), m represents an integer of 1 or more, R2 independently represents a hydrocarbon group, an organic group, or a hydrogen atom, and R0 independently represents a hydrocarbon group or a hydrogen atom. .)

（式（１２）中、ｍ、ｎは、１以上の整数を示し、Ｒ１、Ｒ２、Ｒ３は、それぞれ独立して炭化水素基、有機基、または水素原子を示し、Ｒ０は、独立して炭化水素基または水素原子を示す。）

(In the formula (12), m and n each represent an integer of 1 or more, R1, R2, and R3 each independently represent a hydrocarbon group, an organic group, or a hydrogen atom, and R0 is independently carbonized. Represents a hydrogen group or a hydrogen atom.)

  Moreover, it is preferable that the terminal or side chain of the main chain has a hydroxyl group (—OH). That is, in the case of the formula (1), formula (2) or formula (12), it is preferable that R1 and / or R2 is hydrogen. Thereby, when polycarbonate-type resin is used as the base material 1 mentioned later, the adhesiveness of the coating layer 2 and polycarbonate-type resin can be improved. For this reason, the adhesiveness with respect to the base material 1 of the coating layer 2 increases, and it can prevent that the coating layer 2 peels from the base material 1 unintentionally. Therefore, the scratch resistance and weather resistance of the windshield 100 can be further improved. Moreover, when the isocyanate (hardening agent which has an isocyanate group) mentioned later is contained in a resin composition, the said hydroxyl group reacts with the isocyanate group which a hardening | curing agent has, and forms the crosslinked structure by a urethane bond. Thereby, hardening of a resin composition can be accelerated | stimulated and it can contribute to formation of the coating layer 2. FIG.

  In addition, at least one terminal or side chain of the main chain having such a structure is bonded to a repetitive body (sub-chain) in which a structural unit having a siloxane bond is repeated.

  Since the siloxane bond has a high bonding force, the silicon-modified (meth) acrylic resin has a repeating body in which a structural unit having a siloxane bond is repeated, thereby obtaining a coat layer 2 with better heat resistance and weather resistance. be able to. Moreover, since the hard coat layer 2 can be obtained because the bonding strength of the siloxane bond is high, it is possible to further increase the scratch resistance of the windshield 100 with respect to impacts such as sand dust and stepping stones. As a result, the windshield 100 after irradiating with ultraviolet rays can surely satisfy the requirement A.

  Specific examples of the repeating body in which the structural unit having a siloxane bond is repeated include those composed of repeating a structural unit having at least one siloxane bond of the following formula (3) and formula (4). It is done.

（式（３）中、Ｘ_１は、炭化水素基または水酸基を示す。）

(In formula (3), X ₁ represents a hydrocarbon group or a hydroxyl group.)

（式（４）中、Ｘ_２は、炭化水素基または水酸基を示し、Ｘ_３は、炭化水素基または水酸基から水素が離脱した２価の基を示す。）

(In Formula (4), X ₂ represents a hydrocarbon group or a hydroxyl group, and X ₃ represents a divalent group in which hydrogen is removed from the hydrocarbon group or hydroxyl group.)

  Specific examples of the repeating product in which the structural unit having a siloxane bond is repeated include those having polyorganosiloxane and those having silsesquioxane. The structure of silsesquioxane may be any structure such as a random structure, a cage structure, or a ladder structure (ladder structure).

  Examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group, a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, a phenyl group, a naphthyl group, and 2 -An aryl group such as a methylphenyl group, an aralkyl group such as a benzyl group, a diphenylmethyl group, and a naphthylmethyl group, a phenyl group, and a biphenyl group.

  Moreover, it is preferable that the unsaturated double bond is introduce | transduced into the terminal or side chain of the repeating body in which the structural unit which has a siloxane bond was repeated. Thereby, when the later-described urethane (meth) acrylate is contained in the resin composition, it is bonded to the (meth) acryloyl group of the urethane (meth) acrylate to form a silicon-modified (meth) acrylic resin and urethane (meth). A network with acrylates can be formed. Therefore, in the coat layer 2, the silicon-modified (meth) acrylic resin and the urethane (meth) acrylate are more uniformly dispersed, and as a result, the coat layer 2 can express the above-described characteristics more uniformly throughout. it can.

  The content of the silicon-modified (meth) acrylic resin in the resin composition is not particularly limited, but is preferably 5 parts by mass or more and 45 parts by mass or less in 100 parts by mass of the resin composition, and 11 parts by mass. As mentioned above, it is more preferable that it is 28 mass parts or less. When the content of the silicon-modified (meth) acrylic resin in the resin composition is less than the lower limit, the hardness of the coat layer 2 obtained from the resin composition may be reduced. Further, when the content of the silicon-modified (meth) acrylic resin in the resin composition exceeds the upper limit, the content of materials other than the silicon-modified (meth) acrylic resin in the resin composition is relatively reduced. Therefore, the flexibility of the coat layer 2 formed using the resin composition may be reduced.

  Examples of the silicon-modified (meth) acrylic resin having the above configuration include compounds represented by the following formulas (5) and (6).

（式（５）中、Ｍｅは、メチル基を示し、ｍ、ｎ、ｐは、それぞれ１以上の整数を示す。）

(In formula (5), Me represents a methyl group, and m, n, and p each represents an integer of 1 or more.)

（式（６）中、Ｍｅは、メチル基を示し、ｍ、ｎ、ｐは、それぞれ１以上の整数を示し、Ｒ１、Ｒ２、Ｒ３、Ｒ４は、それぞれ独立して炭化水素基、有機基、または水素原子を示す。）

(In the formula (6), Me represents a methyl group, m, n, and p each represents an integer of 1 or more, and R1, R2, R3, and R4 each independently represent a hydrocarbon group, an organic group, Or a hydrogen atom.)

(Urethane (meth) acrylate)
Moreover, it is preferable that a resin composition contains urethane (meth) acrylate further.

  When an unsaturated double bond is introduced into the terminal or side chain of a repeating product in which a structural unit having a siloxane bond, which is included in a silicon-modified (meth) acrylic resin, is repeated, urethane (meth) acrylate in the resin composition As a result, the (meth) acryloyl group of this urethane (meth) acrylate and the unsaturated double bond are combined to form a network of silicon-modified (meth) acrylic resin and urethane (meth) acrylate. The As a result, the resin composition is cured to obtain a cured product, whereby the coat layer 2 composed of the cured product is formed. In addition, hardening of the resin composition by this (meth) acryloyl group and an unsaturated double bond couple | bonding is performed by the photocuring hardened | cured by irradiating an energy ray like an ultraviolet-ray to a resin composition.

  By including urethane (meth) acrylate in the coat layer 2 formed as described above, the flexibility of the coat layer 2 can be improved, and the windshield 100 is partially or entirely curved. Since it can be applied to what has a shape, the occurrence of cracks on the surface of the coat layer 2 can be accurately suppressed when the windshield 100 is heat-bent, and thus excellent thermoformability is imparted to the windshield 100. Can do.

  Furthermore, by using a combination of the above-described silicon-modified (meth) acrylic resin and this urethane (meth) acrylate, it is possible to obtain a windshield 100 that is highly compatible with excellent scratch resistance and thermoformability. . Moreover, even if sand dust, stepping stones or the like collide with the coat layer 2 after being irradiated with ultraviolet rays contained in sunlight by using the windshield plate 100 due to the improvement of scratch resistance, the windshield plate 100 is It may be assumed that requirement A is satisfied.

  The urethane (meth) acrylate refers to a compound having a main chain having a urethane bond (—OCONH—) and a (meth) acryloyl group linked to the main chain. Urethane (meth) acrylate is a monomer or oligomer.

  The urethane (meth) acrylate having such a configuration has a urethane bond, and thus is a compound having excellent flexibility. For this reason, the coating layer 2 can give further flexibility (flexibility) to the coating layer 2 because it contains urethane (meth) acrylate. Therefore, it is possible to accurately suppress the occurrence of cracks in the bent portion when the windshield 100 is formed into a curved shape.

  In addition, the number of (meth) acryloyl groups in one molecule of urethane (meth) acrylate is preferably 2 or more.

  When the number of (meth) acryloyl groups in one molecule of the urethane (meth) acrylate is 2 or more, the urethane (meth) acrylate can be bonded to the silicon-modified (meth) acrylic resin to form a network. Curing of the coat layer 2 can be promoted. Thereby, the crosslinking density of the coat layer 2 is increased, and the hardness of the coat layer 2 can be increased to some extent. For this reason, the characteristics of the coating layer 2 such as scratch resistance, solvent resistance, and weather resistance can be improved.

  In addition, this urethane (meth) acrylate can be obtained as a reaction product of, for example, an isocyanate compound obtained by reacting a polyol and diisocyanate and a (meth) acrylate monomer having a hydroxyl group.

  Examples of the polyol include polyether polyol, polyester polyol, and polycarbonate diol.

  The polyether polyol is preferably a polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide random copolymer having a number average molecular weight of less than 1300. When a polyether polyol having a number average molecular weight of 1300 or more is used, depending on the type of the polyether polyol, the flexibility of the coating layer 2 is too high, and the coating layer 2 is scratched by the impact of sand dust or stepping stones. Etc., and the requirement A may not be satisfied.

  The polyester polyol can be obtained, for example, by subjecting a diol and a dicarboxylic acid or dicarboxylic acid chloride to a polycondensation reaction, or esterifying a diol or a dicarboxylic acid to cause an ester exchange reaction. Examples of the dicarboxylic acid include adipic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, maleic acid, terephthalic acid, isophthalic acid, and phthalic acid. Examples of the diol include ethylene glycol, Examples include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, and tetrapropylene glycol.

  Further, as polycarbonate diol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene Glycol, 2-ethyl-1,3-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, polyoxyethylene glycol, and the like are used. Two or more kinds can be used in combination.

  Examples of the (meth) acrylate monomer having a hydroxyl group include trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3 -Hydroxybutyl acrylate, polyethylene glycol monoacrylate and the like.

Furthermore, the weight average molecular weight of urethane (meth) acrylate is not particularly limited, but is preferably 1.0 × 10 ³ or more and 2.0 × 10 ³ or less, 1.1 × 10 ³ or more, 1.5 It is more preferable that it is 10 ³ or less. When the weight average molecular weight of the urethane (meth) acrylate is within the above range, the balance between the flexibility and hardness of the coat layer 2 becomes good, and the bent portion when the windshield 100 is formed into a curved shape. The occurrence of cracks in can be suppressed.

  In addition, the weight average molecular weight of urethane (meth) acrylate can be measured by GPC (gel permeation chromatography), for example.

  Further, the content of urethane (meth) acrylate in the resin composition is not particularly limited, but is preferably 10 parts by mass or more and 75 parts by mass or less, and preferably 17 parts by mass or more and 50 parts by mass or less in 100 parts by mass of the resin composition. It is more preferable that the amount is not more than part by mass. If the content of urethane (meth) acrylate in the resin composition is less than the lower limit, the flexibility of the coat layer 2 may be poor depending on the type of urethane (meth) acrylate. Moreover, when content of urethane (meth) acrylate in a resin composition exceeds the said upper limit, depending on the kind of urethane (meth) acrylate, content of materials other than urethane (meth) acrylate in a resin composition There is a risk that the relative resistance decreases, the scratch resistance of the windshield 100 decreases, and the requirement A cannot be satisfied.

((Meth) acrylate monomer)
Moreover, it is preferable that a resin composition further contains a (meth) acrylate monomer.

  When an unsaturated double bond is introduced into the terminal or side chain of a repeating product in which a structural unit having a siloxane bond, which is included in a silicon-modified (meth) acrylic resin, is repeated, a (meth) acrylate monomer is contained in the resin composition As a result, the (meth) acryloyl group of this (meth) acrylate monomer and the unsaturated double bond are combined to form a network of the silicon-modified (meth) acrylic resin and the (meth) acrylate monomer. As a result, the resin composition is cured to form the coat layer 2.

  In the coating layer 2 formed as described above, the adhesion between the substrate 1 and the coating layer 2 is improved, and when the windshield 100 is applied to, for example, a curved surface, the windshield 100 is subjected to thermal bending. When it does, peeling from the base material 1 of the coating layer 2 becomes difficult to occur. In addition, the surface hardness of the coat layer 2 is increased, and as a result, excellent scratch resistance can be imparted to the coat layer 2, so that even if the coating layer 2 is irradiated with ultraviolet rays contained in sunlight, The windshield 100 may satisfy the requirement A. Furthermore, since the (meth) acrylate monomer also functions as a reactive diluent, the viscosity of the resin composition is reduced, and other constituent materials contained in the resin composition are uniformly distributed in the (meth) acrylate monomer. Demonstrate the function to disperse.

  The (meth) acrylate monomer is not particularly limited. For example, pentaerythritol tetraacrylate, ditrimethylolpropane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate , Ethoxylated pentaerythritol triacrylate, ethoxylated pentaerythritol tetraacrylate, polyethylene glycol diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated hydrogenated bisphenol A diacrylate, ethoxylated cyclohexane dimethanol diacrylate, tricyclodecane dimethanol di Acrylate, 2-hydroxyethyl acrylate , 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, isobornyl acrylate and the like, can be used singly or in combination of two or more of them. Among these, from the viewpoint of improving the weather resistance of the windshield 100, a resin containing no aromatic is preferable.

  In addition, among these, by using the polyfunctional (meth) acrylate monomer which has a 3 or more (meth) acryloyl group, in the coat layer 2 obtained from a resin composition, polyfunctional (meth) acrylate monomer mutually bridge | crosslinks. Then, due to the formation of the three-dimensional crosslinked structure, the hardness of the coat layer 2 becomes higher. As a result, since the coating layer 2 can be provided with excellent scratch resistance, even if the coating layer 2 is irradiated with ultraviolet rays contained in sunlight, the windshield 100 satisfies the requirement A. It can be.

  In addition, since the polyfunctional (meth) acrylate monomer having two (meth) acryloyl groups has a lower viscosity than the polyfunctional (meth) acrylate monomer having three or more (meth) acryloyl groups, the resin Contributes as a diluent for the composition. For this reason, by including a polyfunctional (meth) acrylate monomer having two (meth) acryloyl groups, the viscosity of the resin composition can be further reduced, and the handleability of the resin composition can be further improved. Can do.

  Although content of the (meth) acrylate monomer in a resin composition is not specifically limited, It is preferable that they are 15 mass parts or more and 55 mass parts or less in 100 mass parts of said resin compositions, 27 mass parts or more, 55 It is more preferable that the amount is not more than part by mass.

  When the content of the (meth) acrylate monomer in the resin composition is less than the lower limit, depending on the type of the (meth) acrylate monomer, the adhesion between the base material 1 and the coating layer 2 is insufficient, and the coating layer is subjected to heat bending. 2 may be easily peeled off from the substrate 1. Furthermore, the crosslink density of the coat layer 2 may be reduced, and the scratch resistance of the windshield 100 may be reduced. Moreover, when content of the (meth) acrylate monomer in a resin composition exceeds the said upper limit, depending on the kind of (meth) acrylate monomer, the coating layer 2 may break without extending at the time of heat bending.

(Isocyanate)
Moreover, it is preferable that a resin composition contains isocyanate further.

  Thereby, in the resin composition, isocyanate functions as a crosslinking agent that bonds (crosslinks) the silicon-modified (meth) acrylic resin between molecules. That is, by including an isocyanate as a crosslinking agent, a silicon-modified (meth) acrylic resin has a hydroxyl group with a main chain in which a structural unit derived from a (meth) acrylic monomer having a (meth) acryloyl group is repeated. The isocyanate group of the isocyanate reacts to form a crosslinked structure composed of urethane bonds, and as a result, the coat layer 2 composed of a cured product of the resin composition is formed. In addition, hardening of the resin composition by this hydroxyl group and an isocyanate group couple | bonding is performed by the thermosetting hardened | cured by heating a resin composition.

  In the coating layer 2 formed as described above, since a network formed by bonding hydroxyl groups and isocyanate groups can be constructed, the scratch resistance and weather resistance of the coating layer 2 can be further improved. Can do. Therefore, the windshield 100 after irradiating with ultraviolet rays can surely satisfy the requirement A.

  Although this isocyanate is not specifically limited, For example, the polyisocyanate etc. which have 2 or more of isocyanate groups are mentioned, It is more preferable that the polyfunctional isocyanate which has 3 or more of isocyanate groups is also included especially. Thereby, the scratch resistance and weather resistance of the coat layer 2 can be further improved.

  Although content of the isocyanate in a resin composition is not specifically limited, It is preferable that they are 3 mass parts or more and 40 mass parts or less in 100 mass parts of the said resin composition, and they are 10 mass parts or more and 25 mass parts or less. More preferably. If the isocyanate content in the resin composition is less than the lower limit, the scratch resistance of the coat layer 2 may be lowered depending on the type of isocyanate. Also, if the isocyanate content in the resin composition exceeds the upper limit, depending on the type of isocyanate, unreacted isocyanate remains as an impurity in the coating film. And durability (coating adhesion) may be reduced.

(Other materials)
Furthermore, in addition to the various materials described above, other materials may be included in the resin composition.

  Examples of other materials include, but are not limited to, resin materials other than the silicon-modified (meth) acrylic resin, photopolymerization initiators, ultraviolet absorbers, colorants, sensitizers, stabilizers, surfactants, oxidation agents, and the like. Examples thereof include an inhibitor, an anti-reduction agent, an antistatic agent, a surface conditioner, a hydrophilizing additive, a filler, a solvent, and the like, and one or more of these can be used in combination.

((UV absorber))
In addition, the resin composition can further improve the weather resistance of the coat layer 2 obtained from the resin composition by including an ultraviolet absorber. Therefore, even if sand dust, stepping stones or the like collide with the coat layer 2 after the coating layer 2 is irradiated with ultraviolet rays contained in sunlight by using the windshield plate 100, the windshield plate 100 is surely made to meet the above requirements. A may be satisfied.

  Although this ultraviolet absorber is not specifically limited, A triazine type | system | group, a benzophenone type | system | group, a benzotriazole type | system | group, and a cyanoacrylate type ultraviolet absorber are mentioned, Among these, it can use combining 1 type or 2 types. Among these, a triazine-based ultraviolet absorber is preferably used, and among the triazine-based ultraviolet absorbers, a hydroxyphenyl triazine-based ultraviolet absorber is more preferable. Here, the hydroxyphenyltriazine-based ultraviolet absorber has a hydroxyl group. Therefore, when an isocyanate functioning as a crosslinking agent is included in the resin composition, a crosslinked structure composed of a urethane bond formed by a reaction between a hydroxyl group of the silicon-modified (meth) acrylic resin and an isocyanate group of the isocyanate. In the (network structure), a hydroxyphenyltriazine-based ultraviolet absorber is also incorporated. That is, it is firmly held in the coat layer 2 obtained from the resin composition. Therefore, leakage (bleed out) of the ultraviolet absorber from the coat layer 2 due to deterioration of the coat layer 2 due to ultraviolet rays can be more reliably prevented or suppressed, and the weather resistance of the windshield 100 can be further increased. it can. Therefore, even if sand dust, stepping stones or the like collide with the coat layer 2 after the coating layer 2 is irradiated with ultraviolet rays contained in sunlight by using the windshield plate 100, the windshield plate 100 is more reliably It may be assumed that requirement A is satisfied.

  In addition, the content of the ultraviolet absorber in the resin composition includes a silicon-modified (meth) acrylic resin contained as an essential component in the resin composition, and a urethane (meth) acrylate and (meth) acrylate contained as optional components. When the monomer and isocyanate are combined as a main component, although not particularly limited, it is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the main component of the resin composition. More preferably, it is 1 part by mass or more and 10 parts by mass or less. If the content of the ultraviolet absorber in the resin composition is less than the lower limit, the weather resistance of the coat layer 2 may be lowered depending on the type of the ultraviolet absorber. In addition, even if the content of the ultraviolet absorber in the resin composition exceeds the upper limit, no further improvement in weather resistance is seen, and depending on the type of the ultraviolet absorber, the transparency of the coat layer 2, There is a possibility that the adhesion of the coat layer 2 to the substrate 1 may be impaired.

((Photopolymerization initiator))
In addition, the resin composition further includes a photopolymerization initiator. When the resin composition includes at least one of urethane (meth) acrylate and (meth) acrylate monomer, the resin composition is subjected to photopolymerization. The degree of cure of the coat layer 2 obtained by curing can be made more excellent. Therefore, the coat layer 2 can have more excellent scratch resistance.

  The photopolymerization initiator is not particularly limited. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and other benzoin or benzoin alkyl ethers, benzophenone, benzoylbenzoic acid and other aromatic ketones, benzyl Such as alpha-dicarbonyls, benzyl ketals such as benzyl dimethyl ketal and benzyl diethyl ketal, acetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl Ketone, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, 2-methyl-1 − [ Acetophenones such as-(methylthio) phenyl] -2-morpholinopropanone-1, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2,4-dimethylthioxanthone, 2-isopropyl Thioxanthones such as thioxanthone and 2,4-diisopropylthioxanthone, phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1-phenyl-1,2-propanedione-2- ( Examples include alpha-acyl oximes such as o-ethoxycarbonyl) oxime, amines such as ethyl p-dimethylaminobenzoate and isoamyl p-dimethylaminobenzoate, and among these, 1- (4-dodecylphenyl) is particularly preferable. ) -2-Hyd Xyl-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy Acetophenones such as 2-methyl-propan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 are preferred. Thereby, hardening of a resin composition can be advanced more rapidly by photopolymerization.

  Further, the content of the photopolymerization initiator in the resin composition is not particularly limited, but is 0.5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the main component of the resin composition. Is preferably 1 part by mass or more and 10 parts by mass or less. When the content of the photopolymerization initiator in the resin composition is less than the lower limit, depending on the type of the photopolymerization initiator, it may be difficult to sufficiently cure the resin composition, and the resin composition Even when the content of the photopolymerization initiator exceeds the upper limit, no further improvement is observed.

((Surface conditioner))
Furthermore, the surface conditioner is added for the purpose of improving the wettability and uniformity of the coating film to the substrate, the smoothness of the surface, and the surface slip property of the cured coating film. Silicone and acrylic regulators can be used. Among these, those containing at least one of fluorine-based and modified silicone-based materials are preferable. These are preferably composed of a polyether-modified product, an alkyl-modified product, and a polyester-modified product, and more preferably those composed of a polyether-modified product.

  Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propanol, and butanol, methyl ethyl ketone, 2-pentanone, isophorone, Examples include ketones such as diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate, cellosolve solvents such as ethyl cellosolve, glycol solvents such as methoxypropanol, ethoxypropanol, and methoxybutanol. These can be used alone or in combination. Among these, alcohols, cellosolves, and glycols may react with isocyanates in the resin composition, so it is desirable not to use them alone. It is more preferable to use hydrocarbon, ketone, or ester as the main component of the solvent.

  The average thickness of the coat layer 2 composed of the cured product of the resin composition as described above is not particularly limited, but is preferably 1 μm or more and 40 μm or less, and more preferably 2 μm or more and 30 μm or less. More preferably, it is 5 μm or more and 20 μm or less. When the thickness of the coat layer 2 is less than the lower limit, the weather resistance of the windshield 100 may be lowered. On the other hand, if the thickness of the coat layer 2 exceeds the upper limit, cracks may occur in the bent portion when the windshield 100 is formed into a curved shape.

<Base material>
The base material 1 is formed using a material including a thermoplastic resin, and the windshield 100 has lightness, transparency, workability, resistance to cracking (impact resistance), and safety when cracked. It is given.

  The thermoplastic resin is not particularly limited, and examples thereof include polystyrene resins, polyethylene resins, polypropylene resins, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate resins, and vinyl chloride. Resin, polyacetal resin, etc. are mentioned, Among these, it can be used 1 type or in combination of 2 or more types. Among these, polycarbonate resins are particularly preferable. Since the cured product of polycarbonate resin is rich in mechanical strength such as transparency (translucency) and rigidity, the transparency and impact resistance of the windshield 100 are improved by using the polycarbonate resin for the substrate 1. Can be made. In addition, the polycarbonate resin has a specific gravity of about 1.2 and is classified as a light resin material. Therefore, the base material 1 is composed of a polycarbonate resin as a main material. Thus, the substrate 1 and thus the windshield 100 can be reduced in weight. Further, when the silicon-modified (meth) acrylic resin contained in the coat layer 2 has a hydroxyl group, the adhesion between the substrate 1 containing the polycarbonate resin and the coat layer 2 can be improved. Thus, the coating layer 2 can be prevented from unintentionally peeling off. As a result, the scratch resistance and weather resistance of the windshield 100 can be further improved.

  The polycarbonate resin is not particularly limited, and various types can be used, and among them, an aromatic polycarbonate resin is preferable. The aromatic polycarbonate-based resin has an aromatic ring in its main chain, whereby the strength of the substrate 1 can be further improved.

  This aromatic polycarbonate resin is synthesized by, for example, an interfacial polycondensation reaction between bisphenol and phosgene, a transesterification reaction between bisphenol and diphenyl carbonate, or the like.

  Examples of the bisphenol include bisphenol A and bisphenol (modified bisphenol) that is the origin of the repeating unit of the polycarbonate represented by the following formula (1A).

（式（１Ａ）中、Ｘは、炭素数１〜１８のアルキル基、芳香族基または環状脂肪族基であり、ＲａおよびＲｂは、それぞれ独立して、炭素数１〜１２のアルキル基であり、ｍおよびｎは、それぞれ０〜４の整数であり、ｐは、繰り返し単位の数である。）

(In the formula (1A), X is an alkyl group having 1 to 18 carbon atoms, an aromatic group or a cyclic aliphatic group, and Ra and Rb are each independently an alkyl group having 1 to 12 carbon atoms. , M and n are each an integer of 0 to 4, and p is the number of repeating units.)

  Specific examples of the bisphenol that is the origin of the repeating unit of the polycarbonate represented by the formula (1A) include 4,4 ′-(pentane-2,2-diyl) diphenol, 4,4 ′-( Pentane-3,3-diyl) diphenol, 4,4 ′-(butane-2,2-diyl) diphenol, 1,1 ′-(cyclohexanediyl) diphenol, 2-cyclohexyl-1,4-bis ( 4-hydroxyphenyl) benzene, 2,3-biscyclohexyl-1,4-bis (4-hydroxyphenyl) benzene, 1,1′-bis (4-hydroxy-3-methylphenyl) cyclohexane, 2,2′- Bis (4-hydroxy-3-methylphenyl) propane and the like can be mentioned, and one or more of these can be used in combination.

  In particular, the polycarbonate-based resin is preferably composed mainly of a bisphenol-type polycarbonate-based resin having a skeleton derived from bisphenol. By using such a bisphenol-type polycarbonate resin, the base material 1 exhibits even more excellent strength.

  The content of the polycarbonate resin in the substrate 1 is not particularly limited, but is preferably 75 parts by mass or more, more preferably 85 parts by mass or more in 100 parts by mass of the substrate. By making content of polycarbonate-type resin into the said range, the base material 1 shall exhibit the outstanding intensity | strength.

  Moreover, the base material 1 contains various additives, such as antioxidant, a coloring agent, a filler, a plasticizer, a ultraviolet absorber, a heat ray absorber, other than the thermoplastic resin mentioned above as needed. You may go out.

  Further, for the purpose of improving the adhesion to the coating layer 2, the substrate 1 is subjected to surface roughening treatment by sandblasting or solvent treatment, or corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment. Surface oxidation treatment such as ozone / ultraviolet irradiation treatment and electron beam irradiation treatment may be performed.

  The thickness of the substrate 1 is preferably 0.1 mm or more and 18 mm or less, more preferably 1 mm or more and 10 mm or less, and further preferably 3 mm or more and 4 mm or less. When the thickness of the substrate 1 is less than the lower limit, depending on the type of thermoplastic resin, the mechanical strength of the windshield 100 may be reduced, and the thickness of the substrate 1 exceeds the upper limit. If it exceeds, depending on the type of the thermoplastic resin, it may be difficult to form the windshield 100 into a curved shape.

  Moreover, as the base material 1, the thing of the single layer structure obtained from the material containing a thermoplastic resin, or the thing of the multilayer structure which laminated | stacked two or more single layer films obtained from the material containing a thermoplastic resin is used. be able to.

  Here, when it is a multilayer structure, it may be comprised with the same material and may be comprised with a different material.

  For example, as the base material 1 having a multilayer structure, a first weather resistant layer excellent in weather resistance, a heat resistant layer excellent in heat resistance, and a second weather resistant layer excellent in weather resistance are laminated in this order. Can be mentioned. That is, a structure in which one heat-resistant layer is sandwiched between two weather-resistant layers can be mentioned. Thereby, the further improvement of the weather resistance and heat resistance of the base material 1 is achieved.

  Examples of the first weather resistant layer and the second weather resistant layer include those composed of a material containing a polycarbonate resin, an ultraviolet absorber, and a plasticizer, for example. Examples of the heat-resistant layer include those composed of a material containing a polycarbonate-based resin, a heat ray absorbent, and a plasticizer. In addition, when importance is attached to the weather resistance, the addition of the UV absorber and / or the plasticizer to the first and second weather resistance layers can be omitted. Addition of a heat ray absorbent and / or a plasticizer can be omitted.

  As an ultraviolet absorber, the same thing as having demonstrated as an ultraviolet absorber contained in the coating layer 2 is mentioned.

  Examples of the heat ray absorbent include carbon black, carbon powder, tin oxide, indium oxide, zinc oxide, ITO, ATO, and the like, and one or more of these can be used in combination. .

  Furthermore, examples of the plasticizer include polyethylene glycol, polyamide oligomer, ethylene bisstearoamide, phthalate ester, polystyrene oligomer, polyethylene wax, silicone oil, and the like, and one or more of these are combined. Can be used.

  The coating layer 2 composed of a cured product of the resin composition as described above is adhered by the cross-cut method defined in JIS K 5600-5-6 after being irradiated with ultraviolet rays for 3000 hours using a sunshine weatherometer. The property may be 90% or more, but is preferably 100%. Thereby, it can be said that the transparency of the windshield 100 is appropriately suppressed or prevented from being reduced by impacts such as sand dust and stepping stones.

  Further, in the windshield 100, the yellowing degree of the base material 1 measured according to JIS K 7105 after the coating layer 2 is irradiated with ultraviolet rays for 3000 hours using a sunshine weatherometer is 6.0. [ΔYI] or less is preferable, 3.0 [ΔYI] or less is more preferable, and 2.0 [ΔYI] or less is more preferable. Thereby, it can be said that the windshield 100 is provided with more excellent weather resistance, and as a result, the windshield 100 can be more appropriately suppressed or prevented from deterioration in appearance.

<Manufacturing method of windshield>
The windshield 100 configured as described above can be obtained by, for example, the following manufacturing method.

  The manufacturing method of the windshield 100 has a coating layer formation process which forms a coating layer by apply | coating a resin composition on the upper surface of the base material 1, and a flat plate formation process which dries a coating layer and forms a flat plate.

Hereinafter, each step will be described.
(Coating layer forming process)
First, the base material 1 and the resin composition are prepared in advance, and then the resin composition is applied to the upper surface of the base material 1 to form a coating layer.

  The method for applying the resin composition is not particularly limited, and examples thereof include known methods such as a roll coating method, a flow coating method, a spray coating method, a curtain coating method, a dip coating method, a die coating method, and a bar coating method. By using these alone or in combination, the resin composition can be applied to the upper surface of the substrate 1. In addition, by using these coating methods, the resin composition is applied to the base material 1 arranged in a direction orthogonal to the vertical direction. The coating layer 2 obtained by drying the coating layer can be formed with a more uniform film thickness.

  In addition, before supplying a resin composition to the base material 1, you may perform the surface treatment as mentioned above to the base material 1 beforehand as needed.

(Flat plate forming process)
Then, the coating layer 2 is formed by drying and hardening the resin composition which comprises the apply | coated application layer.

  For example, in the case where the resin composition contains a solvent (diluting solvent), the coating layer is formed by sufficiently heating the base material 1 and the atmosphere and heating to sufficiently dry the solvent to form a dry coating film. 2 is obtained.

  In addition, when an isocyanate is contained in the resin composition, a cross-linked structure (network structure) is formed by the chemical bond formed between the silicon-modified (meth) acrylic resin and the isocyanate by this heating. The coat layer 2 is formed by thermally curing the dried coating film.

  The method for heating the coating layer is not particularly limited, and examples thereof include a method of heating using an oven or the like.

  Furthermore, when at least 1 sort (s) of urethane (meth) acrylate and (meth) acrylate monomer is contained in a resin composition, it is preferable to irradiate electron beams, such as an ultraviolet-ray, after formation of a dry coating film. Thereby, a crosslinked structure (network structure) is formed by forming a chemical bond between the silicon-modified (meth) acrylic resin and at least one of urethane (meth) acrylate and (meth) acrylate monomers, Thereby, the coat layer 2 is formed by photocuring a dry coating film.

  Examples of the method of irradiating with ultraviolet rays include a method of using a general electroded or electrodeless high-pressure mercury lamp or metal halide lamp. Also, a low voltage electron beam irradiation apparatus of about 100 KeV can be used. In addition, when hardening with an electron beam, addition to the resin composition of the photoinitiator mentioned above is unnecessary.

Furthermore, you may make it heat the dry coating film which finished irradiating an electron beam as needed. Thereby, thermosetting of the coat layer 2 can be advanced more reliably.
By passing through the above processes, the windshield 100 which makes flat form can be obtained.

(Molding process)
In addition, when a part or all of the flat windshield 100 is formed into a curved shape, a molding step of forming a part or all of the flat plate into a curved shape after the flat plate forming step. To implement.

  As a method for forming a part or all of the windshield plate 100 into a curved shape, for example, a method of heating the flat windshield plate 100 and pressing it against a mold immediately after the resin is softened to form a curved shape. Can be mentioned.

  The method for heating the resin is not particularly limited, and examples thereof include known methods such as an infrared drying furnace, a gas hot air drying furnace, and a hot air circulation drying furnace. Moreover, as a method of thermoforming, methods, such as vacuum forming, pressure forming, press molding, free blow molding, are mentioned, for example.

  The curved surface shape is a shape having a curved surface, and includes, for example, a shape in which the cross-sectional shape of the molded body is an arc shape.

  As described above, the windshield 100 in which a part or all of the flat plate is formed into a curved shape is formed.

Second Embodiment
Next, a second embodiment of the windshield will be described.
FIG. 2 is a longitudinal sectional view showing a second embodiment of the windshield of the present invention.

  Hereinafter, the windshield 100 according to the second embodiment will be described with a focus on differences from the windshield 100 according to the first embodiment, and description of similar matters will be omitted.

  As shown in FIG. 2, the windshield 100 of the present embodiment has the coating layer 2 provided on both the upper surface side and the lower surface side of the base material 1, and the windshield plate of the first embodiment. 100.

  That is, in the windshield 100 according to the second embodiment, the coat layer 2 is provided by being laminated on both the upper surface side and the lower surface side of the base material 1. The laminate is composed of two coat layers 2 that hold the material 1.

  When the windshield 100 is formed of such a laminate, the coat layer 2 is formed on both surfaces of the base material 1. Therefore, when the windshield 100 is applied to a vehicle windshield, the vehicle is used. The windshield 100 can be arranged without considering the position of the person and / or the object, that is, without considering the back surface and the surface of the windshield 100.

  In the windshield 100 having such a configuration, the base material 1 can have the same configuration as the base material 1 included in the windshield board 100 of the first embodiment, and the two coat layers 2 can be used in the first embodiment. It can be set as the thing of the structure similar to the coat layer 2 with which the windshield 100 of a form is provided.

  The two coat layers 2 may be composed of the same constituent material, or may be composed of different constituent materials.

  The same effect as that of the first embodiment can be obtained by the windshield 100 of the second embodiment.

  The windshield plate and the vehicle according to the present invention have been described above. However, the present invention is not limited to this, and each part constituting the windshield plate is replaced with an arbitrary structure that can exhibit the same function. be able to. Moreover, arbitrary components may be added.

  In addition, when the windshield plate is configured to include two coat layers that hold the base material, a bonding layer (adhesive layer) or the like may be interposed between the base material and the coat layer. .

  Hereinafter, based on an Example, this invention is demonstrated more concretely. In addition, this invention is not limited at all by these Examples.

1. Windshield formation (Example 1)
[1] First, a resin composition was prepared for forming a coating layer.

Specifically, a mixture of a silicon-modified (meth) acrylic resin and an acrylate monomer (trade name “MFG Coat SD-101”, silicon-modified (meth) acrylic resin: 16 parts by mass, acrylate monomer: 5.5 parts by mass, DIC Corporation): 21.5 parts by mass and bifunctional urethane acrylate as urethane (meth) acrylate (weight average molecular weight 1.3 × 10 ³ , viscosity 17000 mPa · s [60 ° C.], trade name “EBECRYL8804”, Daicel Orne 26 parts by mass, tetrafunctional acrylate monomer (trade name “NK Ester A-TMMT”, manufactured by Shin-Nakamura Chemical Co., Ltd.): 14.7 parts by mass, bifunctional acrylate monomer (trade name “NK Ester A- BPE-4 ", manufactured by Shin-Nakamura Chemical Co., Ltd.): 21.8 parts by mass, isocyanate As a trifunctional polyisocyanate (trade name “Bernock DN-992S”, manufactured by DIC Corporation): 16 parts by mass were prepared to obtain a mixture (main component).

  Furthermore, with respect to 100 parts by mass of the obtained mixture, as an additive, an ultraviolet absorber 1 (hydroxyphenyltriazine derivative, trade name “Tinuvin 400”, manufactured by BASF): 6.5 parts by mass and a surface conditioner (product) Name “Granol 450” (manufactured by Kyoeisha Chemical Co., Ltd.): 0.04 parts by mass is added, butyl acetate as a solvent is added and stirred so that the non-volatile content is 30%, all components are dissolved, and the resin composition Got.

  [2] Next, the obtained resin composition was applied to a multilayer body having a thickness of 4 mm as a base material so that the thickness after drying (the thickness of the coat layer) was 11 μm with a bar coater. Thus, a coating layer was obtained. The multilayer body has a structure in which a main layer containing polycarbonate (thickness: 3.8 mm) is covered with two coating layers (thickness: 0.1 mm) containing polycarbonate and an ultraviolet absorber on both the upper and lower surfaces. It is a base material which has. The polycarbonate contained in the main layer is the trade name “Iupilon E-2000-N” (manufactured by Mitsubishi Gas Chemical Industries, Ltd.), and the polycarbonate contained in the coating layer is the trade name “Caliver 200-3” (Sumika). The ultraviolet absorber contained in the coating layer is a trade name “ADK STAB LA-31” (benzotriazole derivative, manufactured by Adeka).

And after drying the base material with which the coating layer was apply | coated for 10 minutes in a 65 degreeC hot-air oven, using the electrodeless UV lamp made from FUSION Systems, irradiation distance 90mm, conveyor speed 2.6mm / min, irradiation intensity 200mW The coating layer was photocured by irradiating ultraviolet rays under the conditions of / cm ² and an integrated light quantity of 700 mJ / cm ² . After this irradiation, the coating layer was further thermally cured by heating in a hot air oven at 60 ° C. for 48 hours.
This obtained the windshield board of Example 1 which consists of a flat plate in which the coating layer was formed on the base material.

(Examples 2 to 17, Comparative Example 1)
A windshield made of a flat plate was produced in the same manner as in Example 1 except that the type, content and molecular weight of the material constituting the resin composition were changed as shown in Table 1.

  In addition, when using the thing different from Example 1 as a material and base material which comprise the resin composition contained in a coat layer, the windshield board was produced using the raw material shown below.

Specific raw materials used are shown below.
Unless otherwise specified, the amount of each component is part by mass.

(Urethane (meth) acrylate 2)
As urethane (meth) acrylate 2 used in Examples 4, 5, and 8 to 10, bifunctional urethane acrylate (weight average molecular weight 1.5 × 10 ³ , viscosity 3000 mPa · s [60 ° C.], trade name “EBECRYL270”, Daicel Ornex made).

(Urethane (meth) acrylate 3)
As urethane (meth) acrylate 3 used in Example 6, bifunctional urethane acrylate (weight average molecular weight 2.7 × 10 ³ , viscosity 60000 mPa · s [40 ° C.], trade name “U-200PA”, manufactured by Shin-Nakamura Chemical Co., Ltd. ) Was prepared.

(Urethane (meth) acrylate 4)
As the urethane (meth) acrylate 4 used in Example 7, a bifunctional urethane acrylate (weight average molecular weight 8.0 × 10 ² , viscosity 7000 mPa · s [60 ° C.], trade name “EBECRYL5129”, manufactured by Daicel Ornex) is prepared. did.

(Urethane (meth) acrylate 5)
As urethane (meth) acrylate 5 used in Examples 11 and 12 and Comparative Example 1, bifunctional urethane acrylate (weight average molecular weight 1.2 × 10 ³ , viscosity 23000 mPa · s [25 ° C.], trade name “EBECRYL285”, Daicel Ornex made).

(Urethane (meth) acrylate 6)
As the urethane (meth) acrylate 6 used in Example 16, a bifunctional urethane acrylate (weight average molecular weight 5.0 × 10 ³ , viscosity 40000 mPa · s [60 ° C.], trade name “EBECRYL230”, manufactured by Daicel Ornex) is prepared. did.

(Urethane (meth) acrylate 7)
As the urethane (meth) acrylate 7 used in Example 17, a bifunctional urethane acrylate (weight average molecular weight 1.0 × 10 ⁴ , viscosity 7000 mPa · s [60 ° C.], trade name “EBECRYL 8807”, manufactured by Daicel Ornex) is prepared. did.

(UV absorber 2)
As the ultraviolet absorber 2 used in Example 14, an ultraviolet absorber (benzotriazole derivative, trade name “TinuvinPS”, manufactured by BASF) was prepared.

(Single layer)
As a base material used in Example 15, a 4 mm thick single layer body including polycarbonate was prepared. In addition, the polycarbonate contained is a brand name "Iupilon E-2000-N" (made by Mitsubishi Gas Chemical Industries, Ltd.).

2. Evaluation The windshields of the examples and comparative examples were evaluated by the following methods.

<1> Adhesion Evaluation Regarding windshields of each of the examples and comparative examples, first, using a cut out sample (60 mm × 60 mm), first promoted to carry out ultraviolet irradiation for 3000 hours with a carbon arc sunshine weatherometer. After the test, in accordance with the cross-cut method defined in JIS K 5600-5-6, the windshield was coated with a right-angled grid pattern (25 squares) at intervals of 2 mm using a single blade. A cut was made. Subsequently, a tape having an adhesion strength of 10 ± 1 N per 25 mm width was applied to a 25 square grid (coat layer 2), and the adhesive was applied at an angle close to 60 ° within 5 minutes. The tape was pulled away in 0.0 seconds. The number of lattices where the coat layer was peeled along the edge of the cut and / or at the intersection was measured, and the ratio of the lattice (coat layer 2) adhering to the substrate 1 was calculated. And it evaluated as follows based on the ratio of the obtained lattice to adhere.

A: The ratio of the adhering lattice is 100%.
B: The ratio of the attached lattice is 90% or more and less than 100%.
C: The ratio of the attached lattice is 50% or more and less than 90%.
D: The ratio of the attached lattice is less than 50%.

<2> Weather resistance evaluation Each windshield of each example and comparative example was subjected to an acceleration test using a carbon arc type sunshine weatherometer, and in accordance with JIS K 5600, the appearance after 3000 hours of ultraviolet irradiation, yellowing The degree (ΔYI) was evaluated as follows.

A: ΔYI is 2.0 or less and no change in appearance.
B: Appearance change is slightly observed when ΔYI is more than 2.0 and 3.0 or less.
C: Appearance change is slightly observed when ΔYI is more than 3.0 and less than 6.0.
D: Appearance change is noticeable when ΔYI exceeds 6.0.

<3> Thermoformability evaluation About the windshield plate of each Example and Comparative Example, each sample (width 60 mm, length 120 mm, thickness 3 mm) was heated and softened in a hot air circulation oven set at 170 ° C. for 10 minutes, Immediately after taking out, the surface of the paint film is placed outside, and it is attached to a wooden cylinder of each radius via a flannel cloth, and the sample is left as it is until it is cooled to near room temperature. And evaluated as follows.

A: Thermoformed with a wooden mold having a radius of 25 mm, and there is no occurrence of cracks or coating film peeling and no change in appearance.
B: Thermoformed with a wooden mold having a radius of 30 mm, and there is no occurrence of cracks or peeling of the coating film and no change in appearance.
C: Thermoformed with a wooden mold having a radius of 40 mm, and there is no occurrence of cracks or peeling of the coating film and no change in appearance.
D: Thermoforming with a wooden mold with a radius of 50 mm, appearance changes such as generation of cracks and peeling of the coating film, white turbidity, and rough skin.

<4> Durability Evaluation About the windshields of each Example and Comparative Example, each sample (size: 100 mm square) was left in a constant temperature and humidity chamber at a temperature of 60 ° C. and a humidity of 95% or more. Observed and evaluated as follows.

A: No change in appearance such as peeling, cracking or yellowing of the coating film was observed after a standing time of 500 hours.
B: No change in appearance such as peeling, cracking or yellowing of the coating film was observed after a standing time of 250 hours.
C: No change in appearance such as peeling, cracking or yellowing of the coating film was observed at a standing time of 125 hours.
D: Appearance changes such as peeling, cracking, and yellowing of the coating film are observed at a standing time of 73 hours.

  The evaluation results in the windshields of the examples and comparative examples obtained as described above are shown in Table 1 below.

  As shown in Table 1, the windshield plate in each example has a coat layer formed using a resin composition containing a silicon-modified (meth) acrylic resin, so that ultraviolet rays can be emitted using a sunshine weatherometer. After irradiation for 3000 hours, the following requirement A can be satisfied, and it has superior durability against ultraviolet rays compared to the comparative example, thereby maintaining the scratch resistance against impact over a long period of time. Results were obtained indicating that

  Requirement A: The windshield has an adhesion of 90% or more to the base material of the coating layer cut in a lattice shape by the cross-cut method defined in JIS K 5600-5-6.

100 windshield 1 base material 2 coat layer

Claims (11)

A base material formed using a material containing a thermoplastic resin, and a coating layer provided on at least one surface side of the base material and formed using a resin composition containing a silicon-modified (meth) acrylic resin; Have
A windshield board that satisfies the following requirement A after the coating layer is irradiated with ultraviolet rays for 3000 hours using a sunshine weatherometer.
Requirement A: The windshield has an adhesion of 90% or more to the base material of the coating layer cut in a lattice shape by the cross-cut method defined in JIS K 5600-5-6.   2. The windshield according to claim 1, wherein the base material has a yellowing degree measured in accordance with JIS K 7105 of 6.0 [ΔYI] or less after the coating layer is irradiated with the ultraviolet rays for 3000 hours. .   The windshield plate according to claim 1 or 2, wherein the resin composition further contains urethane (meth) acrylate.   The windshield plate according to claim 3, wherein the content of the urethane (meth) acrylate is 10 parts by mass or more and 75 parts by mass or less in 100 parts by mass of the resin composition.   The windshield plate according to any one of claims 1 to 4, wherein the resin composition contains a (meth) acrylate monomer.   6. The windshield according to claim 5, wherein the content of the (meth) acrylate monomer is 15 parts by mass or more and 55 parts by mass or less in 100 parts by mass of the resin composition.   The windshield plate according to any one of claims 1 to 6, wherein the resin composition contains isocyanate.   The windshield plate according to claim 7, wherein the content of the isocyanate is 3 parts by mass or more and 40 parts by mass or less in 100 parts by mass of the resin composition.   The windshield plate according to any one of claims 1 to 8, wherein a content of the silicon-modified (meth) acrylic resin is 5 parts by mass or more and 45 parts by mass or less in 100 parts by mass of the resin composition.   The windshield plate according to any one of claims 1 to 9, wherein a part or all of the windshield plate is formed into a curved surface shape.   A vehicle comprising the windshield according to any one of claims 1 to 10.

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