JP2010188686A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent resin material laminate excellent in scratch resistance and weathering resistance and also in productivity. <P>SOLUTION: A laminate includes at least first and second layers on a transparent resin substrate material, and is formed by laminating a first layer (containing a compound having a UV-ray absorption function and an acrylic resin) and a second layer (containing a UV-ray curable resin) in this order. The laminated part of the first and the second layers has an absorbance of light having a wavelength of 290-300 nm higher than 1. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminate. Specifically, it relates to a transparent plastic substrate laminate.

  Attempts have been widely made to use a transparent plastic material as a substitute for glass by taking advantage of its impact resistance, light weight, easy processing, and the like. However, since the transparent plastic material does not have sufficient scratch resistance, there has been a problem that scratches are easily generated when wiping off dirt. In addition, since the weather resistance is insufficient, there is a problem that the appearance and physical properties are impaired when the transparent plastic material is decomposed and deteriorated during long-term outdoor use.

  In order to improve these problems, several techniques have been disclosed in which a protective layer is provided on the surface of a transparent plastic substrate made of a transparent plastic material to impart scratch resistance and weather resistance of the transparent plastic substrate. . They are particularly prominent when a polycarbonate resin, which is excellent in transparency and impact resistance and has many demands for improving weather resistance, is used as a transparent plastic substrate.

  In a laminate in which an acrylic resin primer layer (undercoat layer) and a siloxane-based thermosetting resin layer are sequentially provided on a polycarbonate resin as a transparent plastic substrate, weather resistance is improved by incorporating an ultraviolet absorber in the primer layer. Techniques are disclosed in Patent Documents 1-6.

  In addition, since the wavelength of light that easily deteriorates the polycarbonate resin is around 290 nm, a technique for mixing an ultraviolet absorber having excellent light absorption ability at a wavelength of around 290 nm into the primer layer is disclosed in Patent Documents 7 and 8, for example. It is disclosed. In addition, attention is paid to the fact that light having a wavelength of 300 nm or less in the sunlight spectrum is hardly irradiated by the ozone layer when actually exposed to the outdoors, and the technology for making the light absorption capacity of the wavelength 300 nm in the laminate more than a certain level. Is disclosed in Patent Document 9.

  Further, for example, in Patent Document 10, as a polycarbonate resin laminate excellent in actual weather resistance, an acrylic resin having a specific ultraviolet absorbing ability and thickness in a primer layer, and a colloidal silica as a thermosetting resin in a scratch resistant layer. The laminated body by which the composition hardening layer containing containing organosiloxane resin was laminated | stacked one by one is disclosed. Further, Patent Document 11 discloses a coating member containing a UV absorber in a primer layer and / or a scratch-resistant layer, and a coating composition comprising a silicon-containing polymer is cured as the scratch-resistant layer. Disclosed is a film comprising silicon oxide formed.

  Similarly, Patent Documents 12 to 15 disclose techniques for imparting weather resistance and scratch resistance to a laminate in which a primer layer and an ultraviolet curable resin layer are sequentially laminated on a polycarbonate resin that is a transparent plastic substrate. Yes.

  Attempts have also been made to ensure weather resistance by curing a photocurable resin composition containing an ultraviolet absorber, and such techniques are disclosed in Patent Documents 16 to 18. However, since light having a wavelength necessary for curing the photo-curing resin is also absorbed by the ultraviolet absorber as an additive, there has been a problem that enormous energy is required for curing the coating film. Thus, for example, Patent Document 19 discloses a method of curing an ultraviolet curable resin containing an ultraviolet absorber having an absorption region at 300 nm to 400 nm by a specific irradiation method. As another method, Patent Document 20 discloses a method using an initiator that absorbs light having a wavelength different from that of an ultraviolet absorber as an additive to initiate a photocuring reaction.

Japanese Patent No. 3106696 JP-A-2-16048 Japanese Patent Laid-Open No. 2-16129 JP-A-4-106161 JP 2000-318106 A JP 2001-47574 A JP-A-9-176476 JP-A-9-313334 JP 2004-25726 A JP 2004-25726 A JP 2006-240294 A JP-A-63-83117 JP-A-1-96266 Japanese Patent Laid-Open No. 3-56514 JP-A-9-117998 JP-A-2-163134 JP-A-6-142611 Japanese Patent Laid-Open No. 10-60307 JP 2005-125208 A JP 2006-89697 A

  As described above, many techniques for incorporating a compound having ultraviolet absorbing ability into a primer layer have been disclosed. However, although they are excellent in weather resistance, since thermosetting resin is used for the scratch-resistant layer, it takes time to cure the thermosetting resin, and there is a problem that productivity may not be good. Was.

  Furthermore, in the techniques disclosed in Patent Documents 12 to 15, the weather resistance is not sufficient, and a thick layer may have to be provided on the surface of the primer layer in order to sufficiently impart ultraviolet absorbing ability, and there still remains a problem. Had.

  Further, in the technique disclosed in Patent Document 19, there are cases where it is necessary to irradiate ultraviolet rays twice, and further, it is necessary to cure using a special ultraviolet light source that exhibits high output on the long wavelength side. There was also a problem that sometimes.

  In the technique disclosed in Patent Document 20, there is a problem that the coating film may be colored yellow because an initiator having a light absorption band on the wavelength side significantly longer than the ultraviolet absorber is used. Was.

  This invention is made | formed in view of said subject, Comprising: The objective of this invention is providing the transparent plastic substrate laminated body excellent in productivity while being excellent in abrasion resistance and a weather resistance.

  As a result of intensive studies to solve the above problems, the present inventors have found that a first layer (primer layer) containing a specific resin and a second layer (cured product of an ultraviolet curable resin) on a transparent plastic substrate. Layer) in this order, and by making the absorbance of light with a wavelength of 290 nm or more and 300 nm or less in the laminated portion of the first layer and the second layer into a specific range, it has excellent scratch resistance and weather resistance, The present inventors have found that a transparent plastic substrate laminate excellent in productivity can be provided and completed the present invention.

That is, the gist of the present invention is a laminate in which at least a first layer and a second layer are provided in this order on a transparent plastic substrate, and the first layer comprises a compound and an acrylic resin having ultraviolet absorbing ability. And the second layer contains an ultraviolet curable resin, and the light absorbency of light having a wavelength of 290 nm or more and 300 nm or less is greater than 1 in the laminated portion of the first layer and the second layer. Claim 1).
At this time, in the first layer formed with a thickness of 1 μm, the absorbance of light having a wavelength of 290 nm to 300 nm is larger than 0.1, and further has the ultraviolet absorbing ability for light having a wavelength of 290 nm to 300 nm. It is preferable that the extinction coefficient ε of the compound is larger than 10,000 mL / (g · cm).
Further, the first layer has a compound having a UV-absorbing ability greater than 10000 mL / (g · cm) for light having a wavelength of 290 nm or more and 300 nm or less and having a group polymerizable with another monomer. It is preferable to include an acrylic resin obtained by copolymerizing the other monomer.

Furthermore, the second layer is a layer formed of a composition containing at least the resin mixture (A) not containing the ultraviolet polymerization initiator and the ultraviolet polymerization initiator (B), and is formed to a thickness of 2 μm. In addition, in the resin mixture (A), the absorbance of light having a wavelength of 290 nm to 300 nm is greater than 0.2, the absorbance of light having a wavelength of 254 nm is 0.4 or less, and the ultraviolet polymerization with respect to light having a wavelength of 254 nm The extinction coefficient ε of the initiator (B) is preferably 30000 mL / (g · cm) or more (Claim 4).
The second layer is a layer formed of a composition containing at least the resin mixture (A) containing no ultraviolet polymerization initiator and the ultraviolet polymerization initiator (B), and has a thickness of 2 μm. Further, in the resin mixture (A), the absorbance of light having a wavelength of 290 nm to 300 nm is greater than 0.2, the absorbance of light having a wavelength of 365 nm is 0.4 or less, and the ultraviolet polymerization for light having a wavelength of 365 nm. The extinction coefficient ε of the initiator (B) is preferably 400 mL / (g · cm) or more (Claim 5).

The transparent plastic substrate is preferably a polycarbonate resin, an acrylic resin, a polyester resin, a cellulose acylate resin, or a cycloolefin polymer resin.
And it is preferable that this laminated body is a window material for automobiles, or a sunroof (Claim 7).
Moreover, it is preferable that this laminated body is a building material sheet (Claim 8).

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in abrasion resistance and a weather resistance, the transparent plastic base material laminated body excellent in productivity can be provided. In particular, the second layer also has the ability to absorb ultraviolet light by setting the absorbance of light having a wavelength of 290 nm to 300 nm in the second layer to a value within a certain range. Further, scratch resistance can be obtained by setting the absorbance of the resin at a wavelength at which the polymerization initiator acts efficiently so as not to inhibit the curing reaction of the ultraviolet curable resin.

4 is a graph showing an absorption spectrum of light in a laminated portion of a first layer and a second layer in the laminated body manufactured in Example 1. It is a graph showing the absorption spectrum of light when a 1st layer is formed so that the thickness after drying may be set to 1 micrometer on a quartz plate. It is a graph showing the absorption spectrum of the light of the film | membrane when the compounding liquid 2 is apply | coated to a quartz plate so that it may become a thickness of 2 micrometers, and a film | membrane is formed. It is a graph showing the extinction coefficient (epsilon) of tinuvin 213. 4 is a graph showing an absorption spectrum of light in a stacked portion of a first layer and a second layer in the stacked body manufactured in Example 2. It is a graph showing the light absorption spectrum when apply | coating on a quartz plate so that thickness may be set to 1 micrometer and forming a film | membrane. 2 is a graph showing an extinction coefficient ε of 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole. It is a graph showing the absorption spectrum of the light of the laminated part of the 1st layer in the laminated body manufactured in the laminated body manufactured in Example 3, and the 2nd layer. It is a graph showing the light absorption spectrum of the film | membrane formed so that it might become a thickness of 2 micrometers on a quartz plate using the liquid mixture 4. FIG. It is a graph showing the light absorption spectrum of the said 1st layer by forming a 1st layer so that the thickness after drying may be set to 1 micrometer on the quartz board using the comparison liquid mixture 1. FIG. 5 is a graph showing an absorption spectrum of light in a stacked portion of a first layer and a second layer in a stacked body manufactured in Comparative Example 2.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist thereof.

  In the present specification, when a compound bearing “(meth)” is described, for example, “(meth) acrylic acid” indicates “at least one selected from the group consisting of acrylic acid and methacrylic acid”. The same shall apply to other compounds.

[1. Laminate]
The laminate of the present invention is a laminate in which at least a first layer and a second layer are provided in this order on a transparent plastic substrate, and the first layer includes a compound having an ultraviolet absorbing ability and an acrylic resin. The second layer contains an ultraviolet curable resin, and the absorbance of light having a wavelength of 290 nm to 300 nm in the laminated portion of the first layer and the second layer is greater than 1.

[1-1. Transparent plastic substrate]
The transparent plastic base material is a plastic base material in which transmitted light mainly consists of regular transmission and has high regular transmittance in the visible region as defined in JIS K7361-1, but the effect of the present invention is remarkably improved. Any one can be used as long as it is not impaired.

Specific examples of the transparent plastic substrate include polycarbonate resin, acrylic resin, polyester resin, cellulose acylate resin, cycloolefin polymer resin, polyethylene resin, polypropylene resin, polystyrene resin, and polyvinyl chloride resin. Among these, the transparent plastic substrate is preferably a polycarbonate resin, an acrylic resin, a polyester resin, a cellulose acylate resin, or a cycloolefin polymer resin, and among these, a polycarbonate resin is more preferable.
A transparent plastic base material may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.

The number average molecular weight of the transparent plastic substrate is usually 5 × 10 ³ or more, preferably 1 × 10 ⁴ or more, and the upper limit is usually 1 × 10 ⁷ or less, preferably 1 × 10 ⁶ or less. If the number average molecular weight is too small, it may be brittle and may not be used as a base material. If it is too large, the viscosity at the time of melting may be too high and molding may be difficult. The number average molecular weight can be measured, for example, by preparing a tetrahydrofuran solution of a transparent plastic substrate and using a Tosoh TSKgel GMHXL-L column, an RI detector, or the like.

  The thickness of the transparent plastic substrate is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.05 mm or more, preferably 0.5 mm or more, and the upper limit is usually 20 mm or less, preferably 10 mm or less. It is. If the thickness is too thin, the strength of the substrate may be insufficient, and if it is too thick, it may be uneconomical, such as being too heavy or making movement inconvenient.

  The form of the transparent plastic substrate is arbitrary as long as the effects of the present invention are not significantly impaired, and may be any form such as a sheet form, a film form, and a molded body.

The method for producing the transparent plastic substrate is arbitrary as long as the effects of the present invention are not significantly impaired.
Especially, as a monomer (monomer) at the time of manufacturing a transparent plastic base material, it is preferable to manufacture using the dihydric alcohol which gives monomer units, such as a polyester resin, a polyarylate resin, a polycarbonate resin, for example.

Specifically, hydroquinone, resorcinol, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene Bifunctional phenolic compounds such as 2,7-dihydroxynaphthalene;
4,4′-biphenol, 3,3′-dimethyl-4,4′-dihydroxy-1,1′-biphenyl, 3,3′-di (t-butyl) -4,4′-dihydroxy-1,1 '-Biphenyl, 3,3', 5,5'-tetramethyl-4,4'-dihydroxy-1,1'-biphenyl, 3,3 ', 5,5'-tetra (t-butyl) -4, 4′-dihydroxy-1,1′-biphenyl, 2,2 ′, 3,3 ′, 5,5′-hexamethyl-4,4′-dihydroxy-1,1′-biphenyl, 2,4′-biphenol, 3,3′-dimethyl-2,4′-dihydroxy-1,1′-biphenyl, 3,3′-di (t-butyl) -2,4′-dihydroxy-1,1′-biphenyl, 2,2 '-Biphenol, 3,3'-dimethyl-2,2'-dihydroxy-1,1'-biphenyl, 3,3'-di (t-butyl) -2, '- biphenol compounds such as dihydroxy-1,1'-biphenyl;
Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 1, 1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) hexane, 2,2-bis (4- Hydroxyphenyl) hexane, 3,3-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) bisphenol compounds having no substituents on the aromatic rings such as cyclohexane;
Bis (3-phenyl-4-hydroxyphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) ethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2 A bisphenol compound having an aryl group as a substituent on an aromatic ring such as bis (3-phenyl-4-hydroxyphenyl) propane;
Bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) propane, 2,2 -Bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, bis (4-hydroxy-3-ethylphenyl) methane, 1,1-bis ( 4-hydroxy-3-ethylphenyl) ethane, 1,1-bis (4-hydroxy-3-ethylphenyl) propane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 1,1-bis (4-hydroxy-3-ethylphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis 4-hydroxy-3- (sec-butyl) phenyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane, 2 , 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, bis (4-hydroxy-3,6-dimethylphenyl) Methane, 1,1-bis (4-hydroxy-3,6-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,6-dimethylphenyl) propane, bis (4-hydroxy-2,3, 5-trimethylphenyl) methane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) ethane, 2,2-bis (4-hydroxy-) , 3,5-trimethylphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphenyl) phenylmethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) phenylethane, A bisphenol compound having an alkyl group as a substituent on an aromatic ring such as 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) cyclohexane;
Bis (4-hydroxyphenyl) (phenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylpropane, bis (4- A bisphenol compound in which a divalent group connecting aromatic rings such as hydroxyphenyl) (diphenyl) methane and bis (4-hydroxyphenyl) (dibenzyl) methane has an aryl group as a substituent;
Bisphenol compounds in which aromatic rings such as 4,4′-dihydroxydiphenyl ether and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl ether are connected by an ether bond; 4,4′-dihydroxydiphenyl sulfone Bisphenol compounds in which aromatic rings such as 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylsulfone are connected by sulfone bonds; 4,4′-dihydroxydiphenyl sulfide, 3,3 ′, A bisphenol compound in which aromatic rings such as 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide are linked by a sulfide bond;
Bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, phenolphthalein;
Etc.
One of these may be used alone, or two or more thereof may be used in any ratio and combination.

  Among these, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxy-3-methylphenyl) Methane and 2,2-bis (4-hydroxy-3-methylphenyl) propane are preferred, and 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are more preferred.

[1-2. First layer]
The 1st layer in the layered product of the present invention is formed on the above-mentioned transparent plastic substrate, and the 1st layer contains the compound which has ultraviolet absorption ability, and an acrylic resin.

(Compound with UV absorbing ability)
Any compound having ultraviolet absorbing ability can be used as long as the effects of the present invention are not significantly impaired. However, in the laminate of the present invention, a compound having an ultraviolet absorbing ability is selected so that the absorbance of light having a wavelength of 290 nm to 300 nm is greater than 1 in the laminated portion of the first layer and the second layer described later. It is preferable to do.

  Among them, in the first layer formed with a thickness of 1 μm, the absorbance of light having a wavelength of 290 nm to 300 nm is usually larger than 0.1, preferably 0.2 or more. Further, a compound having an ultraviolet absorption ability for light having a wavelength of 290 nm or more and 300 nm or less is usually larger than 10000 mL / (g · cm), preferably 15000 mL / (g · cm) or more. When the absorbance is too small, the amount of ultraviolet rays absorbed in the second layer increases, and the amount of ultraviolet rays reaching the transparent plastic substrate may increase.

Absorbance is the product of extinction coefficient ε, content concentration, and thickness. Under conditions where the thickness is limited, if an absorption coefficient lower than this is used, a compound having ultraviolet absorption ability must be mixed in a large amount. In some cases, the acrylic resin content may decrease. Since the adhesiveness of the first layer is usually affected by the content of the acrylic resin, the adhesiveness may be lowered by containing a large amount of a compound having an ultraviolet absorbing ability.
The absorbance can be measured according to JIS K0115 “Abstract spectrophotometric analysis”. The extinction coefficient ε is expressed as mL / (g · cm) in the present invention because it is difficult to express the concentration in terms of mole, but otherwise it conforms to the above JIS K0115.

  The compound having an ultraviolet absorbing ability may be an organic compound or an inorganic compound, but it is preferable to use an organic compound because it is easy to ensure the affinity with the acrylic resin forming the layer, and thus it can be easily dispersed uniformly.

  Specific examples of the compound having ultraviolet absorbing ability include benzotriazole compounds, hydroxyphenyltriazine compounds, hydroxybenzophenone compounds, cyanoacrylate compounds, and the like. The compound which has an ultraviolet absorptivity may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.

  More specific examples of the benzotriazole compounds include 2- (2′-hydroxy-3′-methyl-5′-hexylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl- 5'-hexylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t -Octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-dodecylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t-dodecylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) ) -5-t-butyl-4-hydroxyphenyl) propionate and the like, and as the hydroxyphenyltriazine-based compound, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxy Phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyl) Oxyphenyl) -s-triazine and the like. Examples of hydroxybenzophenone compounds include 2,2′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of cyanoacrylate compounds include ethyl 2-cyano-3,3-diphene. Le acrylate, 2'-ethylhexyl 2-cyano-3,3-diphenyl acrylate.

  Among these, 2- (2′-hydroxy-3′-t-butyl-5′-hexylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- [ 4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,2 ′, 4,4′-tetrahydroxybenzophenone is preferred.

(acrylic resin)
In the laminated body of the present invention, the first layer is formed from the viewpoint of ensuring a certain degree of ultraviolet absorbing ability while improving the adhesion and scratch resistance between the transparent plastic substrate and the second layer (described later). A compound having an ultraviolet absorbing ability and an acrylic resin.

The molecular weight of the acrylic resin is preferably 2 × 10 ⁴ or more and more preferably 5 × 10 ⁴ or more in terms of number average molecular weight from the viewpoint of adhesion and strength as a layer. Moreover, from a viewpoint that it can manufacture easily and can apply | coat, 1 * 10 < ⁷ > or less is preferable and 1 * 10 < ⁶ > or less is more preferable. If the molecular weight is too small, it is brittle and the strength cannot be maintained, and it may become unsuitable as a substrate. If it is too large, it may be difficult to form a uniform layer due to high viscosity. The number average molecular weight can be measured, for example, by preparing a tetrahydrofuran solution of an acrylic resin and using a Tosoh TSKgel GMHXL-L column and an RI detector.

  The acrylic resin is usually a resin obtained by polymerizing at least one compound selected from a compound group having an acryloyl group and / or a methacryloyl group (hereinafter referred to as “(meth) acryloyl group” as appropriate). Accordingly, since the acrylic resin is produced by polymerization by a carbon-carbon double bond existing at the end of the compound, it is preferable to use a compound having a (meth) acryloyl group as a monomer.

  Especially, in order to adjust the physical property of an acrylic resin, it is more preferable that an acrylic resin is a copolymer by the compound which has multiple types of (meth) acryloyl group. However, if the molecular weight of the compound having a (meth) acryloyl group is too large, it may be difficult to produce an acrylic resin. Therefore, the compound preferably has 50 or less carbon atoms, more preferably 40 or less, particularly preferably. Is 35 or less.

上記式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又は有機基を表す。 As the compound having a (meth) acryloyl group that forms an acrylic resin, a compound represented by the following formula (1) is usually used.

In said formula (1), R < ¹ > and R < ² > represents a hydrogen atom or an organic group each independently.

R ¹ is optional as long as it is a hydrogen atom or an organic group. When R ¹ is an organic group, R ¹ is preferably a methyl group or an ethyl group from the viewpoint of availability.

On the other hand, R ^{2 is} also arbitrary as long as it is a hydrogen atom or an organic group. When R ² is an organic group, R ² may be chain or cyclic. Furthermore, the organic group may be linear or branched.

From the above viewpoint, the following compound having a (meth) acryloyl group having R ¹ and R ² (hereinafter referred to as “unsaturated monomer (a-1)” as appropriate) is preferable.

  Specific examples of the unsaturated monomer (a-1) include 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl. (Meth) acrylate, cetyl (meth) acrylate, behenyl (meth) acrylate, etc. can be mentioned. One of these may be used alone, or two or more thereof may be used in any ratio and combination.

In addition, from the viewpoint of improving the weather resistance of the laminate, it is preferable that the absorbance of light having a wavelength of 290 nm to 300 nm with respect to a film having a thickness of 1 μm is larger than 0.1, but the transmittance of light in the wavelength range is adjusted. For this purpose, a compound having a group that absorbs or blocks light having a wavelength of 290 nm to 300 nm in R ² can be used. More specifically, the compound, as a monomer for forming an acrylic resin, has an ultraviolet absorption capacity greater than 10,000 mL / (g · cm) for light having a wavelength of 290 nm to 300 nm, and other A compound having a group polymerizable with a monomer, for example, a compound having a (meth) acryloyl group having a so-called ultraviolet absorbing group derived from a compound used as an ultraviolet absorber (hereinafter referred to as “unsaturated single” (Referred to as “mer (a-2)”). When an acrylic resin obtained by copolymerizing the compound with the other monomer is used as the first layer, UV absorption ability can be imparted more uniformly in the layer, and severe conditions such as weather resistance tests can be provided. Even underneath, it is preferable because the phenomenon that only the ultraviolet absorber bleeds can be prevented. That is, the first layer has an ultraviolet absorption ability greater than 10000 mL / (g · cm) for light having a wavelength of 290 nm to 300 nm, and a compound having a group polymerizable with another monomer; It is preferable to include an acrylic resin obtained by copolymerizing the other monomer. Under the present circumstances, the 1st layer may contain the compound which has said ultraviolet absorptivity.

  Here, examples of the “group polymerizable with other monomer” include a (meth) acryloyl group and a vinyl group, and among them, a (meth) acryloyl group is particularly preferable. These may have 1 type independently and may have 2 or more types by arbitrary ratios and combinations.

Examples of the ultraviolet absorbing group as R ² for adjusting the transmittance of light having a wavelength of 290 nm to 300 nm include a group having a benzophenone skeleton such as 2,4-dihydroxybenzophenone, a group having a triazine skeleton, and 2- (5 A group having a benzotriazole skeleton such as'-methyl-2'-hydroxyphenyl) benzotriazole, a group having a cyanoacrylate skeleton such as ethyl-2-cyano-3,3'-diphenylacrylate, and a salicylate skeleton such as phenyl salicylate. And a group having a benzylidene malonate skeleton such as diethyl-p-methoxybenzylidene malonate are preferably used.

  Among them, a group having a benzophenone skeleton, a group having a triazine skeleton, and a group having a benzotriazole skeleton are preferable, and a group having a benzotriazole skeleton is particularly preferably used.

More specifically, as the unsaturated monomer (a-2), for example, a compound having a benzotriazole skeleton represented by the formula (3), a benzophenone skeleton represented by the formula (4) And a compound having a triazine skeleton as represented by the formula (5).

In formula (3), X represents a hydrogen atom or a chlorine atom, and R ⁶ represents a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 8 carbon atoms. R ⁷ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and R ⁸ represents a hydrogen atom or a methyl group. n represents 0 or 1.

Wherein (4), R ⁸ represents the same as R ⁸ in formula (3), R ⁹ represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ¹⁰ represents a hydrogen atom or a hydroxyl group, and R ¹¹ represents a hydrogen atom, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

Wherein (5), ^{R 8} represents the same as ^{R 8} in formula ^{(3), R 12} is a direct _bond, -CH 2 _CH 2 O- or _-CH 2 CH (OH) a _-CH 2 O- M represents an integer of 1 to 5. R ¹³ each independently represents a hydrogen atom, an alkyl group or an alkenyl group having 1 to 10 carbon atoms, o represents an integer of 0 to 4, and p and q each independently represent 0 or more. Represents an integer of 5 or less.

In addition to the above compounds, a compound having an ultraviolet absorption capacity greater than 10000 mL / (g · cm) for light having a wavelength of 290 nm to 300 nm and having a group polymerizable with other monomers Specific examples of (that is, a component that provides a structural unit having ultraviolet absorbing ability; an unsaturated monomer (a-2)) include benzotriazole-based compounds such as 2- (2′-hydroxy-5′-methacryloxyethyl). Phenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-acryloxyethylphenyl) -2H-benzotriazole, and the like. As the benzophenone-based compound, 2-hydroxy-4- (2- And methacryloxyethyl) oxybenzophenone.
One of these may be used alone, or two or more thereof may be used in any ratio and combination.

  In the case of producing an acrylic resin having a structural unit having ultraviolet absorbing ability by copolymerizing the unsaturated monomer (a-2) and another monomer, the amount of the unsaturated monomer (a-2) used Is usually 0.05 mol times or more, preferably 0.1 mol times or more, and the upper limit thereof is usually 2.3 mol times or less, preferably 0.7 mol, relative to a total of 1 mol of other monomers. Is less than double. If the amount used is too small, the desired ultraviolet absorbing ability may not be obtained, so that the weather resistance may not be exhibited. If the amount used is too large, the layer may be fragile.

  The acrylic resin is usually a resin obtained by polymerizing a compound having a (meth) acryloyl group, but the acrylic resin may be a copolymer using a compound having a plurality of types of (meth) acryloyl groups.

  The other monomer that can react with the unsaturated monomer (a-2) is optional as long as the effects of the present invention are not significantly impaired. From the viewpoint of ease of copolymerization, for example, the unsaturated monomer ( a-1), other alkyl methacrylates, monomers other than the unsaturated monomer (a-1) and the unsaturated monomer (a-2) (hereinafter referred to as “unsaturated monomer (a-3) Among them, alkyl methacrylates and vinyl esters are preferable, and other monomers may be used alone or in combination of two or more in any ratio and combination. Good.

  Examples of the unsaturated monomer (a-3) that can be copolymerized with the unsaturated monomer (a-1) and / or the unsaturated monomer (a-2) include (meth) acrylic An acid, (meth) acrylonitrile, (meth) acrylamide, alkyl vinyl ether, vinyl ester, or derivatives thereof can be mentioned. An unsaturated monomer (a-3) may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.

  Specific examples of (meth) acrylic acid and derivatives thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth). C1-C20 alkyl methacrylate such as acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethoxyethyl (meth) Acrylate, ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, cyanoethyl (meth) ) Acrylate, methoxypolyethylene glycol (meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate such as methoxypolypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate glycidyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3- Phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, (meth) acrylic acid, 2-acryloyloxy Tyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloylpropyl phthalate, (meth) acryloyloxyethyl succinate, 2-isocyanatoethyl (meth) acrylate, 3- (meth) acryloyloxypropyl Methyldimethoxysilane, 3- (meth) acryloyloxypropylmethyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyltriethoxysilane, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, 3-methacryloxypropyltrimethoxysilane Etc.

  Specific examples of (meth) acrylonitrile and derivatives thereof include α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, and vinylidene cyanide.

  Specific examples of (meth) acrylamide and derivatives thereof include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N, N-ethyl (meth) acrylamide. , N-methoxy (meth) acrylamide, N, N-dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-ethoxy (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide N- (2-hydroxyethyl) (meth) acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N- (2-dimethylamino) ethyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, N, N-ethylenebis (meta) Or the like can be mentioned acrylamide.

  Specific examples of the alkyl vinyl ether and derivatives thereof include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and the like.

  Specific examples of vinyl esters and derivatives thereof include vinyl formate, vinyl acetate, vinyl propionate, vinyl acrylate, vinyl butyrate, vinyl caproate, and vinyl stearate.

  Among them, the unit derived from the unsaturated monomer (a-1) is usually 5% by mass to 95% by mass, and the unit derived from the unsaturated monomer (a-2) is usually 5% by mass or more. Unsaturated monomer (a-3) which is 70% by mass or less and can be copolymerized with unsaturated monomer (a-1) and / or unsaturated monomer (a-2) An acrylic resin (A) containing usually 30% by mass or less of a unit derived from is preferred.

The reaction conditions for producing the acrylic resin contained in the first layer using the above raw materials are arbitrary as long as the effects of the present invention are not significantly impaired.
For example, what is necessary is just to set the usage-amount of each component similarly to the quantity of the structural unit contained in an acrylic resin. Further, a solvent may be used to facilitate reaction control. The reaction temperature at the time of polymerization varies depending on the type of monomer used, the type of solvent, and the type of polymerization initiator, but is usually 30 ° C. or higher, preferably 50 ° C. or higher, and the upper limit is usually 150 ° C. or lower, preferably 100 It is below ℃. The reaction time is usually 1 hour or longer, preferably 2 hours or longer, and the upper limit is usually 24 hours or shorter, preferably 12 hours or shorter. If the reaction time is too short, it may be difficult to control the reaction, and if it is too long, it may be uneconomical.

(Other ingredients)
The 1st layer in the layered product of the present invention may contain other ingredients other than the compound and acrylic resin which have the above-mentioned ultraviolet absorption ability. Specific examples of other components that may be mixed may include a light stabilizer, an antioxidant, and the like.

  Examples of light stabilizers that can be included include hindered amine compounds and organonickel compounds. Examples of hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, methyl (1,2,2,6,6-pentamethyl-4 -Piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate and the like, and examples of the organic nickel compound include [2,2′-thiobis (4-t-octylphenolate)]-n-butylamine nickel salt, dibutyldithiocarbamate nitric acid It can be mentioned Le salts, and the like.

Examples of antioxidants that can be included include hindered phenolic compounds and phosphorus compounds. Examples of hindered phenolic compounds include 2,6-di-t-butyl-4-methylphenol, 2,4-diphenol. Examples include -t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and examples of phosphorus compounds include triisopropyl phosphite and triisodecyl phosphite.
In addition, a light stabilizer and antioxidant may be used individually independently, respectively, and 2 or more types may be used in arbitrary ratios and combinations.

(Physical properties of the first layer)
In the first layer, the absorbance of light having a wavelength of 290 nm to 300 nm is usually larger than 0.1, preferably 0.2 or more. If the absorbance is too small, the amount of ultraviolet rays absorbed in the second layer may increase, and the amount of ultraviolet rays reaching the transparent plastic substrate may increase. If it is too large, the content of the compound having ultraviolet absorbing ability is high. Adhesion with the second layer may be reduced. The absorbance of the first layer can be determined by forming a first layer having a thickness of 1 μm on quartz and measuring the absorbance of light with respect to the first layer.

  The content of the compound having ultraviolet absorbing ability in the first layer is arbitrary as long as the effect of the present invention is not significantly impaired, but is preferably less than 50% by mass, more preferably less than 40% by mass. When there is too much content of the compound which has an ultraviolet absorptivity, adhesiveness with a 2nd layer may fall.

  Further, the content of the acrylic resin in the first layer is arbitrary as long as the effects of the present invention are not significantly impaired, but usually 70% by mass or more, preferably 80% by mass or more, and the upper limit is usually 98% by mass. % Or less, preferably 96% by mass or less. When the content of the acrylic resin is too small, the effect of ultraviolet shielding may not be obtained, and when it is too large, the adhesion with the second layer may be lowered.

  Moreover, it is also preferable that a 1st layer contains the acrylic resin which has an ultraviolet absorptivity as mentioned above. When the 1st layer contains the acrylic resin which has ultraviolet absorption ability, the usage-amount of the acrylic resin which does not have ultraviolet absorption ability for the purpose of maintaining layer strength can be reduced thereby.

  Although the thickness of the 1st layer after drying is arbitrary unless the effect of this invention is impaired remarkably, 1 micrometer or more is preferable and 30 micrometers or less are preferable especially. If the thickness is too thin, the adhesion may be poor, and the ultraviolet absorbing ability of the first layer may be reduced. On the other hand, if it is too thick, it is difficult to volatilize the solvent at the time of coating for layer formation, and as a result, the solvent remaining in the first layer may impair the appearance, weather resistance, etc. of the first layer. .

(Formation method of the first layer)
The first layer is usually formed by applying and drying a solution containing the above-mentioned compound having ultraviolet absorbing ability and an acrylic resin, and, if necessary, an acrylic resin having ultraviolet absorbing ability on a transparent plastic substrate. At this time, an appropriate solvent may be included for the purpose of improving the convenience when synthesizing the acrylic resin and the coating property when the coating forming method is adopted when forming the first layer. As the coating method, methods such as bar coating, dip coating, flow coating, spray coating, and roll coating can be appropriately selected according to the shape of the transparent plastic substrate, the properties of the solution, and the like. After application to the transparent plastic substrate, the solvent is usually dried and removed under conditions of room temperature to a temperature lower than the thermal deformation temperature of the substrate.

  Specific examples of the solvent are not limited as long as the transparent plastic base material is whitened or reacts to impair the performance. For example, methanol, ethanol, Alcohols such as 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-ethoxyethanol, 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, Examples thereof include esters such as propyl acetate and butyl acetate, and hydrocarbons such as hexane, heptane, toluene and xylene. A solvent may be used individually by 1 type and may be used 2 or more types by arbitrary ratios and combinations.

  In addition, the first layer may be provided by the above method, but may be formed of, for example, a resin that is thermoset or UV-cured. In that case, it is preferable that a crosslinkable reactive group such as a vinyl group or an isocyanate group is introduced into the acrylic resin and the crosslinkable reactive group reacts.

[1-3. Second layer]
(UV curable resin)
The second layer in the laminate of the present invention contains an ultraviolet curable resin from the viewpoint of obtaining a scratch-resistant layer (that is, a scratch-resistant layer) with high productivity. The ultraviolet curable resin, for example, emits light having a wavelength at which the ultraviolet polymerization initiator (B) can effectively work against a composition comprising a resin mixture (A) and an ultraviolet polymerization initiator (B) that do not contain an ultraviolet polymerization initiator. By irradiation, active species such as radicals are generated and cured. Here, the “wavelength that can work effectively” represents a region where the absorption coefficient ε of the ultraviolet polymerization initiator (B) shows a large value, but is usually the ultraviolet region, and particularly the absorption of the resin mixture (A). The wavelength is preferably small.

In order to prevent light having a wavelength of 290 nm to 300 nm from reaching the transparent plastic substrate, which may affect the transparent plastic substrate (particularly polycarbonate substrate) of the laminate, the first layer also has a wavelength of 290 nm or more. While absorbing light of 300 nm or less, it is preferable that the second layer also absorbs light of this wavelength. However, when a large amount of the ultraviolet polymerization initiator (B) is used and a large amount of the ultraviolet curable resin is contained in the second layer and a larger amount of ultraviolet light is absorbed, a large amount of the unreacted product of the ultraviolet polymerization initiator after curing. Tends to remain, which may reduce the weather resistance of the laminate.
Therefore, in the present invention, the high-pressure mercury lamp that is usually used for curing using ultraviolet rays is strongly radiated, and is slightly separated from the wavelength range of 290 to 300 nm, that is, at least one of 254 nm and 365 nm. It is preferable to use an ultraviolet curable resin that is cured by light having a wavelength.

  More specifically, the second layer in the laminate of the present invention is formed by ultraviolet curing a composition containing at least a resin mixture (A) not containing an ultraviolet polymerization initiator and an ultraviolet polymerization initiator (B). In the resin mixture (A) formed with a thickness of 2 μm, from the viewpoint of improving the weather resistance of the laminate, the absorbance of light having a wavelength of 290 nm to 300 nm is usually larger than 0.2, preferably The absorbance of light having a wavelength of 0.3 or more and a wavelength of 254 nm is usually 0.4 or less, preferably 0.3 or less, and the absorption coefficient ε of the ultraviolet polymerization initiator (B) with respect to light having a wavelength of 254 nm is usually 30000 mL. / (G · cm) or more is preferable.

  The second layer in the laminate of the present invention is a layer formed of a composition containing at least a resin mixture (A) not containing an ultraviolet polymerization initiator and an ultraviolet polymerization initiator (B), and having a thickness of 2 μm. In the resin mixture (A) formed with a thickness, from the viewpoint of improving the weather resistance of the laminate, the absorbance of light having a wavelength of 290 nm to 300 nm is usually larger than 0.2, preferably 0.3 or more, and the wavelength The absorbance of 365 nm light is usually 0.4 or less, preferably 0.3 or less, and the absorption coefficient ε of the ultraviolet polymerization initiator (B) with respect to light having a wavelength of 365 nm is usually 400 mL / (g · cm) or more, It is preferably 800 mL / (g · cm) or more.

  In both cases of wavelengths 254 nm and 365 nm, if the absorbance of light with a wavelength of 290 nm to 300 nm is too small, the amount of ultraviolet rays to be absorbed by the first layer may increase, making it difficult to design the first layer. is there.

  In addition, when the absorbance of light having a wavelength of 290 nm to 300 nm is too large, in order for the ultraviolet polymerization initiator (B) to work efficiently, a large amount of ultraviolet rays must be irradiated, which may be inefficient. Furthermore, there is a possibility that heat is accumulated in the transparent plastic laminate during the irradiation to cause deformation.

  The absorbance and extinction coefficient can be measured as in the case of the first layer. Specifically, for example, the resin mixture (A) is applied and dried on a quartz plate so that the thickness after drying is 2 μm, and the absorbance and extinction coefficient of the formed layer can be measured. it can.

(Resin mixture (A))
The ultraviolet curable resin contained in the resin mixture (A) is usually a mixture of an oligomer and a reactive diluent. As the oligomer, for example, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, and the like can be used. These may be used individually by 1 type and may be used 2 or more types by arbitrary ratios and combinations.

Moreover, you may add the copolymer which copolymerized the compound which has the ultraviolet-absorbing ability which the group which can superpose | polymerize couple | bonded with the other monomer to the resin mixture (A). As the compound having ultraviolet absorbing ability, for example, it has a polymerizable group such as an acryl group and a vinyl group, and has an absorption coefficient ε at a wavelength of 290 nm to 300 nm which is larger than 10,000 mL / (g · cm). Specifically, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-acryloxyethylphenyl) -2H-benzotriazole and the like.
Other monomers include, for example, short-chain alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate; long-chain alkyls such as lauryl methacrylate and stearyl methacrylate from the viewpoint of ease of production of the copolymer. Methacrylate; vinyl esters are preferred. Moreover, vinyl esters such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, 3-methacryloxypropyltrimethoxysilane, vinyl acetate, and vinyl butyrate can also be exemplified. One of these may be used alone, or two or more thereof may be used in any ratio and combination.

  Furthermore, you may contain the compound which has an ultraviolet absorptivity with a wavelength of 290 to 300 nm. Examples of such compounds are 2- (2′-hydroxy-3′-methyl-5′-hexylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-hexylphenyl). ) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-methyl-5′-t-octylphenyl) benzo Triazole, 2- (2′-hydroxy-5′-t-dodecylphenyl) benzotriazole, 2- (2′-hydroxy-3′-methyl-5′-t-dodecylphenyl) benzotriazole, 2- (2 ′ -Hydroxy-5'-t-butylphenyl) benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4 Hydroxyphenyl) propionate, and the like. These may be used individually by 1 type and may be used 2 or more types by arbitrary ratios and combinations.

The reactive diluent is a low molecular weight component capable of reacting with the above monomer or oligomer. Specific examples thereof include ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and tetrahydrofurfuryl (meth). Monofunctional (meth) acrylates such as acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Examples thereof include polyfunctional (meth) acrylates such as acrylate and dipentaerythritol hexa (meth) acrylate. One of these may be used alone, or two or more thereof may be used in any ratio and combination.
For example, fine resinous inorganic fillers such as alumina and silica, those in which they are dispersed in a colloidal form, or their surfaces are coated with alkoxysilane and / or a reaction product thereof to the resin. Those having improved affinity may be mixed.

  The fine powdery inorganic filler preferably has a particle size of 5 nm or more, and preferably 100 nm or less from the viewpoint of maintaining the stability of the coating liquid while ensuring the transparency of the coating film. From the viewpoint of ease of use, alumina sol, silica sol, etc. dispersed in water or an organic solvent in a colloidal form are more preferable, and these surfaces are coated with alkoxysilane or a reaction product thereof to improve the affinity to the resin. Is more preferable.

  Further, a solvent for dissolving the ultraviolet curable resin may be mixed. Specific examples of the solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-ethoxyethanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl. Examples include ketones such as ketone and cyclohexanone, esters such as ethyl acetate, propyl acetate, and butyl acetate, and hydrocarbons such as hexane, heptane, toluene, and xylene. One of these may be used alone, or two or more thereof may be used in any ratio and combination.

  The content of the compound having ultraviolet absorbing ability in the resin mixture (A) is usually 1% by mass or more, preferably 2% by mass or more, and the upper limit is usually 30% by mass or less, preferably 10% by mass. It is as follows. If the content is too small, the ability to block light with a wavelength of 290 nm or more and 300 nm or less may be poor. If the content is too large, the scratch resistance of the second layer is inferior and the scratch resistance of the entire laminate is insufficient. Or the adhesion with the first layer may be insufficient.

(UV polymerization initiator (B))
As the ultraviolet polymerization initiator (B), it is preferable that the curing reaction is initiated by efficiently absorbing at least one of the lights having a wavelength of 254 nm or 365 nm.
For example, the light irradiated from the high-pressure mercury lamp has a relatively large light energy, so that the surface curability of the surface of the second layer containing the ultraviolet curable resin is improved. Therefore, it is preferably used in a cured product requiring surface hardness. However, since the radiation intensity at a wavelength of 365 nm is very strong, the absorption coefficient of an ultraviolet polymerization initiator that initiates polymerization at the wavelength is slightly low. However, when light of 254 nm is to be used, since the radiation intensity is low, it is preferable to use an ultraviolet polymerization initiator (B) having a high extinction coefficient ε at 254 nm.
Specifically, the absorption coefficient ε of the ultraviolet polymerization initiator (B) with respect to light having a wavelength of 254 nm is 30000 mL / (g · cm) or more, or the extinction coefficient of the ultraviolet polymerization initiator (B) with respect to light having a wavelength of 365 nm. It is preferable that ε is 400 mL / (g · cm) or more. Which wavelength is used is preferably determined in consideration of the composition of the resin mixture (A), the compound having ultraviolet absorption ability, the absorption wavelength region of the ultraviolet polymerization initiator (B), the amount used, and the like.

  Examples of the ultraviolet polymerization initiator (B) include any one as long as the effects of the present invention are not significantly impaired. Examples of the photopolymerization initiator include α-hydroxyacetophenones, benzylmethyl ketals, α-amino. Examples include acetophenones. As the ultraviolet polymerization initiator (B), one type may be used alone, or two or more types may be used in optional ratio and combination.

Examples of α-hydroxyacetophenones include 1-hydroxycyclohexyl phenyl ketone (absorption coefficient 254 at 254 nm ε = 33200, ε = 88.6 at 365 nm (unit: mL / (g · cm), and so on). )), 2-hydroxy-2-methyl-1-phenylpropan-1-one (ε = 40600 at 254 nm = ε = 73.9 at 365 nm), and the like.
Examples of benzylmethyl ketals include 2,2-dimethoxy-1,2-diphenylethane-1-one (ε = 47100 at 254 nm = ε = 361 at 365 nm) and the like.
Examples of α-aminoacetophenones include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (ε = 3940 at 254 nm = ε = 467 at 365 nm), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butan-1-one (ε = 7470 at 254 nm, ε = 7860 at 365 nm) and the like.

  The ratio of the amount used of the monomer or oligomer of the ultraviolet curable resin and the ultraviolet polymerization initiator (B) is arbitrary as long as the effect of the present invention is not significantly impaired, but the usage amount of the ultraviolet polymerization initiator (B) is as follows: Usually, it is 0.1 mass% or more with respect to the resin total mass, Preferably it is 0.5 mass% or more, and an upper limit is 10 mass% or less normally, Preferably it is 5 mass% or less. When the content is less than 0.1% by mass, curing may be remarkably slow, or desired scratch resistance may not be obtained even when sufficiently irradiated with ultraviolet rays. In addition, when it exceeds 10% by mass, most of it remains in the layer without making a substantial contribution to the curing reaction, so it is not uneconomical and bleeds in weather resistance tests, etc., adversely affecting the appearance and adhesion May affect

(Other ingredients)
In addition, the second layer may contain components other than the above-described ultraviolet curable resin and the above-described resin mixture (A) and ultraviolet polymerization initiator (B) used as necessary. Examples of the component that may be included include a light stabilizer and an antioxidant.

Specific examples of the light stabilizer include hindered amine compounds and organic nickel compounds. Examples of hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, methyl (1,2,2,6,6-pentamethyl-4 -Piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate and the like.
Examples of the organic nickel compound include [2,2′-thiobis (4-t-octylphenolate)]-n-butylamine nickel salt, nickel salt of dibutyldithiocarbamate, and the like.
In addition, a light stabilizer may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.

Specific examples of the antioxidant include hindered phenol compounds and phosphorus compounds. Examples of the hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2, Examples include 4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and examples of the phosphorus compound include triisopropyl phosphite and triisodecyl phosphite. .
In addition, an antioxidant may be used individually by 1 type and may be used 2 or more types by arbitrary ratios and combinations.

(Thickness of the second layer)
The thickness of the second layer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 2 μm or more, preferably 5 μm or more, and the upper limit is usually 20 μm or less, preferably 15 μm or less. If the thickness is too thin, sufficient scratch resistance may not be exhibited. If it is too thick, cracks may occur in the coat layer (ie, the first layer) due to stress generated during curing. There is a possibility that the adhesion between the coating layer and the transparent plastic substrate may be lowered.

(Method for forming second layer)
The second layer is usually formed on the first layer, and after that, if necessary, the solvent is removed by drying and then cured by irradiation with ultraviolet rays. The coating method is arbitrary as long as the effects of the present invention are not significantly impaired, but a method such as bar coating, dip coating, flow coating, spray coating, roll coating, etc. is appropriately selected according to the shape of the transparent plastic substrate and the properties of the solution. You can choose. These may be performed alone or in any combination of two or more.
As the ultraviolet lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, or the like can be used. An ultraviolet lamp may also be used individually by 1 type, and may be used in arbitrary combination of 2 or more types.

Also, the amount of ultraviolet irradiation is arbitrary as long as the effects of the present invention are not significantly impaired, and depending on the amount of the ultraviolet polymerization initiator added, the radiation intensity is usually strong in a high-pressure mercury lamp, and most measuring instruments in 365nm it is in measurable, is usually 0.1 J / cm ² or more 10J / cm ² or less.

[1-4. Other layers]
If necessary, an additional layer may be provided in addition to the first layer and the second layer. Specifically, a layer for enhancing scratch resistance or providing an additional function may be provided. As a method of forming the additional layer, in addition to a method of applying and curing an ultraviolet curable resin, a thermosetting resin or the like, it can be provided by sputtering, vapor deposition, or the like.

[2. Physical properties of laminates]
(Absorbance)
In the laminate of the present invention, the absorbance of light having a wavelength of 290 nm to 300 nm in the laminated portion of the first layer and the second layer is greater than 1, preferably 1.5 or more. When the absorbance is larger than 1, harmful ultraviolet rays reaching the surface of the transparent plastic substrate can be blocked, and productivity is improved by forming a cured product of the ultraviolet curable resin contained in the second layer. Can be achieved.
In addition, the light absorbency in the lamination | stacking part of a 1st layer and a 2nd layer can be measured according to the method of JISK0115.

(thickness)
The total thickness of the first layer and the second layer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 5 μm or more, preferably 10 μm or more, and the upper limit is usually 50 μm or less, preferably 30 μm or less. If the thickness is too thin, the scratch resistance may be insufficient even if the second layer is provided within the above preferred range. On the other hand, if it is too thick, cracks are likely to occur in the first layer and / or the second layer, adhesion may be poor, and the degree of improvement in scratch resistance is reduced, which is uneconomical. there is a possibility.

(Abrasion resistance)
The abrasion resistance to be exhibited by the laminate having the first layer and the second layer described above varies depending on the purpose of use of the laminate. For example, the abrasion resistance described in JIS K6735 (plastic-polycarbonate plate-size and characteristics) With regard to the plate, as a wear resistance item, when using a Taber type wear tester specified in JIS K7204 and rotating 100 times with a wear wheel of CS-10F and a load of 4.90 N, fogging before and after the wear test It is stipulated that the difference in value must be 15% or less, and the laminate of the present invention preferably satisfies this condition. Since the conditions (that is, the range) relating to the scratch resistance are the same as the ranges to be satisfied by the wear-resistant plate in JIS K6735, there are uses where both scratch resistance and weather resistance are required, for example, It can be suitably used for materials such as organic glass of safety glass for automobiles of JIS R3211, and can also be suitably used for automobile window materials such as sunroofs, panoramic roofs, and rear windows. Furthermore, since the laminated body which cannot be easily damaged when wiping off the attached dust can be manufactured and also has weather resistance, the laminated body of the present invention can be suitably used as a building material sheet.

(Weatherability)
Moreover, the laminated body of this invention has the advantage that it is excellent in a weather resistance. Specifically, even after a test under the following measurement conditions, there is an advantage that yellowing, cracking, peeling, and the like do not occur in the laminate. As a measurement condition, a xenon arc lamp type weather resistance tester based on JIS B7754 can be used and the following operating conditions can be used.
(1) Light source used Xenon arc light source (2) Lamp operation mode Continuous irradiation, filter system Daylight, irradiation intensity 180 W / m ²
(3) Service thermometer Black panel temperature 63 ± 3 ℃
(4) Relative humidity 50 ± 5%
(5) Water spray, no spray for 102 minutes + spray for 18 minutes is one cycle. After 250 hours and 500 hours, the test piece is taken out and visually observed, and the weather resistance can be evaluated according to the evaluation items of the weather resistant plate of JIS K6735.

  Hereinafter, the present invention will be described in more detail with reference to production examples, examples and comparative examples. In addition, the following examples are shown in order to explain the present invention in detail, and the present invention is not limited to the following examples unless departing from the gist thereof.

<Method of conducting weather resistance test>
Using a xenon arc lamp type weather resistance tester in accordance with JIS B7754, the following operating conditions were used.
(1) Light source used Xenon arc light source (2) Lamp operation mode Continuous irradiation, filter system Daylight, irradiation intensity 180 W / m ²
(3) Service thermometer Black panel temperature 63 ± 3 ℃
(4) Relative humidity 50 ± 5%
(5) Water spray, no spray for 102 minutes + spray for 18 minutes is one cycle. After 250 hours and 500 hours, the test piece was taken out and visually observed, and yellowing, cracking and peeling were evaluated according to the evaluation items of the weather resistant plate of JIS K6735.

<Measurement method of coating thickness>
The thickness of the coating film formed on the substrate was measured with a non-contact surface / layer cross-section measurement system VertScan (registered trademark) (model R3300H Lite) of Ryoka System.

<UV lamp>
The ultraviolet irradiation was performed by passing a coating film through a position 15 cm under a light source in an air atmosphere using a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd. having an output density of 120 W / cm. At this time, to measure the radiation dose per under 1 passes lamp illumination and a light source in Eye Graphics Co. EYE UVmeter UVPF-A1, 254nm, in each lamp illuminance at the ^{365nm 1300mW / cm 2, 550mW /} cm 2, the irradiation amount of the lower per pass light 254 nm, was adjusted so that each becomes ^{1200mJ / cm 2, 500mJ / cm} 2 at 365 nm.

<Method of conducting scratch resistance test>
Using a Taber type wear tester specified in JIS K7204, CS-10F wear wheel was rotated 100 times with a load of 4.90 N, and the difference in fog value before and after rotation was evaluated according to JIS K-7136.

<Measurement method of molecular weight>
A tetrahydrofuran solution of the polymer was prepared and measured using a Tosoh TSKgel GMHXL-L column and an RI detector, and obtained as a molecular weight in terms of standard polystyrene.

[Reference Example 1]
500 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Biscoat 300, manufactured by Osaka Organic Chemical Industry Co., Ltd., hydroxyl value 130 mgKOH / g) and 25 g of 3-isocyanatopropyltriethoxysilane were stirred, cooled and thermometer Was added, and 0.26 g of 4-methoxyphenol and 0.26 g of dioctyltin dilaurate were added and reacted at 70 ° C. for 2 hours. When this reaction mixture was analyzed by an infrared absorption spectrum, absorption at 2250 cm ⁻¹ derived from an isocyanate group was not observed. Into this reaction mixture, 1167 g of silica sol (IPA-ST, manufactured by Nissan Chemical Industries, Ltd., solid content 30%) having a dispersion medium of 2-propanol, 0.26 g of 4-methoxyphenol, 0.34 g of acetylacetone aluminum and water 1. 69 g was added and reacted at 70 ° C. for 4 hours. Then, 2-propanol was added and it adjusted so that solid content might be 50 mass%, and the organic inorganic composite 1 was obtained.

[Reference Example 2]
In a 1 L flask equipped with a stirrer, a cooler, and a thermometer, 40 g of methyl methacrylate, 25 g of dimethylacrylamide, and 2- (2′-hydroxy) as a compound having ultraviolet absorbing ability (that is, a component giving a structural unit having ultraviolet absorbing ability) -5'-methacryloxyethylphenyl) -2H-benzotriazole (RUVA-93 manufactured by Otsuka Chemical Co., Ltd.) 30 g, 1-methoxy-2-propanol 225 g and cyclohexanone 75 g were added, and the temperature was raised to 55 ° C. after nitrogen substitution. did. Add 5 g of mercapto-modified silicone oil (X-22-167B manufactured by Shin-Etsu Chemical Co., Ltd.) and 1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) The temperature was raised to 65 ° C. over 30 minutes and reacted for 3 hours. Then, an additional 1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted for another 3 hours, and then 100 ° C. For 30 minutes to prepare a polymer solution having ultraviolet absorbing ability.
The extinction coefficients of 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole at 290 nm and 300 nm are 35800 mL / (g · cm) and 43700 mL / (g · cm), respectively. In other words, the extinction coefficient ε for light having a wavelength of 290 nm to 300 nm was greater than 10000 mL / (g · cm).

[Reference Example 3]
In a 1 L flask equipped with a stirrer, a condenser and a thermometer, 150 g of methyl methacrylate, 40 g of stearyl methacrylate, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole (RUVA manufactured by Otsuka Chemical Co., Ltd.) -93) 10 g and 1-methoxy-2-propanol 300 g were added, and the atmosphere was replaced with nitrogen, followed by heating to 55 ° C. 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the temperature was raised to 65 ° C. over 30 minutes, followed by reaction for 3 hours. , 2′-azobis (2,4-dimethylvaleronitrile) was added in an amount of 2 g, and the mixture was further reacted for 3 hours, and then reacted at 100 ° C. for 30 minutes to prepare a polymer solution having an ultraviolet absorbing ability.

  The weight average molecular weight and number average molecular weight in terms of standard polystyrene of the polymer having ultraviolet absorbing ability were 68000 and 29000, respectively, in the tetrahydrofuran solution.

[Example 1]
First, 10 parts by weight of Parapet HR-G (manufactured by Kuraray Co., Ltd.) as an acrylic resin, and Tinuvin 213 (methyl 3- (3- (2H-benzotriazol-2-yl) -5-t-) as a compound having ultraviolet absorption ability (Butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 0.5 parts by weight, manufactured by Ciba Japan Ltd., Tinuvin 765 (bis (1,2,2,6,6-pentamethyl-) as a light stabilizer 4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, manufactured by Ciba Japan Ltd.) 0.15 parts by weight, 1-methoxy-2-propanol 146 parts by weight Were mixed to prepare Formulation Solution 1.

Next, 48 parts by weight of the organic-inorganic composite 1 prepared in Reference Example 1, 6 parts by weight of a mixture of polyfunctional acrylate isocyanuric acid EO-modified di- and triacrylate (M313 manufactured by Toagosei Co., Ltd.), Reference Example 2 12 parts by weight of the polymer solution having ultraviolet absorbing ability prepared in the above, 0.15 parts by weight of tinuvin 765 as a light stabilizer, and 18.5 parts by weight of cyclohexanone were mixed to prepare a mixed solution 2.
And 78.7 parts by weight of Formulation 2 and Irgacure 184 (1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Japan Co., Ltd., extinction coefficient ε = 33200 mL / (g · cm) at 254 nm) as an ultraviolet polymerization initiator 0.83 part by weight was mixed to prepare a compounded liquid (ie, composition) 3.

  Using a polycarbonate plate with a thickness of 3 mm as a transparent plastic substrate (NF2000U manufactured by Mitsubishi Engineering Plastics), apply a mixture solution 1 containing an acrylic resin thereon with a bar coater so that the thickness after drying is 3 μm. A first layer was formed by drying.

On the first layer, the mixture 3 was applied with a bar coater so that the thickness after drying was 8 μm (thickness of only the second layer) and dried, and then the irradiation dose at a wavelength of 365 nm was 1 J / cm. Ultraviolet rays were irradiated so as to be ² and cured to form a second layer, thereby producing a laminate.

  At this time, the absorption spectrum of light in the laminated portion (thickness: 11 μm) of the first layer and the second layer is shown in FIG. The absorbance of light having a wavelength of 290 nm to 300 nm was 1.84 to 2.204. Further, the difference in haze before and after the scratch resistance test was 3.2%.

  When the weather resistance test of this laminated body was carried out, there was no discoloration, a crack, and peeling in the laminated body until 500 hours.

  Here, FIG. 2 shows an absorption spectrum of light when the first layer is formed on the quartz plate so that the thickness after drying becomes 1 μm on the quartz plate by using the above-described mixed solution 1. From FIG. 2, the absorbance of light having a wavelength of 290 nm to 300 nm was greater than 0.1.

  Moreover, the light absorption spectrum of the film | membrane when the compounding liquid 2 is apply | coated so that it may become a thickness of 2 micrometers on a quartz plate and a film | membrane is formed is shown in FIG. The absorbance of light having a wavelength of 290 nm to 300 nm was greater than 0.2, and the absorbance at 254 nm was 0.288.

  In addition, the graph of the extinction coefficient (epsilon) of the tinubin 213 contained in the liquid mixture 1 is shown in FIG. From FIG. 2, the extinction coefficient at a wavelength of 290 nm to 300 nm was greater than 10,000 mL / (g · cm).

[Example 2] (The first layer has an ultraviolet absorption capacity greater than 10000 mL / (g · cm) for light having a wavelength of 290 nm to 300 nm and has a group capable of being polymerized with other monomers. Example including an acrylic resin obtained by copolymerizing a compound and the other monomer)
A laminate was produced in the same manner as in Example 1 except that the polymer solution having the ultraviolet absorbing ability prepared in Reference Example 3 was used instead of Compounding Solution 1.

  FIG. 5 shows the light absorption spectrum of the laminated portion (thickness 11 μm) of the first layer and the second layer in the manufactured laminate. From FIG. 5, the absorbance of light having a wavelength of 290 nm to 300 nm was 1.469 to 1.603, which was larger than 1. Further, the difference in haze before and after the scratch resistance test was 2.8%. Furthermore, when this laminated body was subjected to a weather resistance test, the laminated body was not discolored, cracked or peeled up to 500 hours.

  FIG. 6 shows an absorption spectrum of light when a film is formed by coating on a quartz plate so as to have a thickness of 1 μm. The absorbances at wavelengths of 290 nm and 300 nm were 0.149 and 0.163, respectively, and were larger than 0.1.

  In addition, FIG. 7 shows the extinction coefficient ε of 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, which is a compound having ultraviolet absorbing ability used in Reference Example 3. It was larger than 10000 mL / (g · cm) at a wavelength of 290 nm to 300 nm.

[Example 3]
78.7 parts by weight of the above blended liquid 2 and an ultraviolet polymerization initiator (Irgacure 369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, Ciba Japan Co., Ltd. The compounding liquid (namely, composition) 4 was produced by mixing 0.83 parts by weight of an absorption coefficient ε = 7860 mL / (g · cm)) manufactured by company.

  A laminate was produced in the same manner as in Example 2 except that the second layer was formed by using the above-described blending liquid 4 instead of the blending liquid 2.

  FIG. 8 shows the light absorption spectrum of the laminated portion (thickness 11 μm) of the first layer and the second layer in the produced laminate. The absorbance of light having a wavelength of 290 nm to 300 nm was 1.885 to 2.206, which was larger than 1. Further, the difference in haze before and after the scratch resistance test was 2.8%. And when this laminated body was subjected to a weather resistance test, the laminated body was not discolored, cracked or peeled up to 500 hours.

  Further, a film was formed on the quartz plate to a thickness of 2 μm using the blending solution 4. The light absorption spectrum of the film is shown in FIG. The absorbance of light having a wavelength of 290 nm to 300 nm was greater than 0.2, and the absorbance of light having a wavelength of 365 nm was 0.237.

[Comparative Example 1]
First, Comparative Compound 1 was prepared by dissolving 10 parts by weight of Parapet HR-G and 0.15 parts by weight of Tinuvin 765 in 146 parts by weight of 1-methoxy-2-propanol.

  A laminate was produced in the same manner as in Example 1 except that the first layer was formed using the mixed liquid comparison 1 instead of the mixed liquid 1. When this layered product was subjected to a weather resistance test, the layered product turned yellow in 250 hours.

  The first layer is formed on the quartz plate using the comparative blending solution 1 so that the thickness after drying becomes 1 μm, and the light absorption spectrum of the first layer is shown in FIG. Absorbances at wavelengths of 290 nm and 300 nm were 0.001 and 0.002, respectively.

[Comparative Example 2]
A laminate was manufactured in the same manner as in Example 1 except that the thickness of the first layer was 1 μm and the thickness of the second layer was 4 μm. At this time, an absorption spectrum of light in a laminated portion of the first layer and the second layer is shown in FIG. The absorbance of light having a wavelength of 290 nm to 300 nm was 0.849 to 0.975. Furthermore, the difference in haze before and after the scratch resistance test was 5.2%. Moreover, when the weather resistance test of this laminated body was carried out, yellowing and a crack were recognized 500 hours afterward.

  Although the laminated body of this invention can be used for well-known arbitrary uses, it can be used suitably for a window material for motor vehicles, a sunroof, a building material sheet | seat, etc. especially.

Claims (8)

A laminate in which at least a first layer and a second layer are provided in this order on a transparent plastic substrate,
The first layer includes a compound having an ultraviolet absorbing ability and an acrylic resin,
While the second layer contains an ultraviolet curable resin,
The laminated body characterized by the light absorbency of light with a wavelength of 290 nm or more and 300 nm or less being larger than 1 in the laminated portion of the first layer and the second layer. In the first layer formed with a thickness of 1 μm,
The absorbance of light having a wavelength of 290 nm to 300 nm is greater than 0.1,
Furthermore, the layered product according to claim 1, wherein an absorption coefficient ε of the compound having ultraviolet absorbing ability with respect to light having a wavelength of 290 nm to 300 nm is larger than 10,000 mL / (g · cm). The first layer is
A compound having an ultraviolet absorption capacity greater than 10000 mL / (g · cm) for light having a wavelength of 290 nm or more and 300 nm or less, and having a group polymerizable with another monomer;
The other monomer,
The laminate according to claim 1, comprising an acrylic resin obtained by copolymerization of The second layer is a layer formed by UV-curing a composition containing at least the resin mixture (A) not containing the UV polymerization initiator and the UV polymerization initiator (B),
In the resin mixture (A) formed with a thickness of 2 μm,
The absorbance of light having a wavelength of 290 nm to 300 nm is greater than 0.2,
And the absorbance of light with a wavelength of 254 nm is 0.4 or less,
The laminate according to any one of claims 1 to 3, wherein an absorption coefficient ε of the ultraviolet polymerization initiator (B) with respect to light having a wavelength of 254 nm is 30000 mL / (g · cm) or more. The second layer is a layer formed by UV-curing a composition containing at least the resin mixture (A) not containing the UV polymerization initiator and the UV polymerization initiator (B),
In the resin mixture (A) formed with a thickness of 2 μm,
The absorbance of light having a wavelength of 290 nm to 300 nm is greater than 0.2,
And the absorbance of light with a wavelength of 365 nm is 0.4 or less,
The laminate according to any one of claims 1 to 3, wherein an absorption coefficient ε of the ultraviolet polymerization initiator (B) with respect to light having a wavelength of 365 nm is 400 mL / (g · cm) or more. The laminate according to any one of claims 1 to 5, wherein the transparent plastic substrate is a polycarbonate resin, an acrylic resin, a polyester resin, a cellulose acylate resin, or a cycloolefin polymer resin. The laminate according to any one of claims 1 to 6, wherein the laminate is an automobile window material or a sunroof. The laminate according to any one of claims 1 to 6, wherein the laminate is a building material sheet.

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