JP5255213B2 - Ultraviolet absorbing resin composition and laminate using the ultraviolet absorbing resin composition - Google Patents

Description

  The present invention is capable of effectively preventing yellowing of a plastic substrate due to ultraviolet rays, and an ultraviolet-absorbing resin composition for forming an ultraviolet-absorbing layer excellent in stain resistance, and the ultraviolet-absorbing resin composition The present invention relates to a laminate in which an ultraviolet absorbing layer obtained from a product is formed on the surface of a plastic substrate.

  Plastic substrates used for various applications are generally weak against ultraviolet rays, and there is a problem that the polymer main chain is broken and the strength as a substrate is lowered when exposed to sunlight. In particular, polyester films represented by polyethylene terephthalate (hereinafter sometimes referred to as “PET”) are widely used in optical applications because of their excellent dimensional stability, heat resistance, transparency, strength, and the like. However, since polyester films are usually made from aromatic dicarboxylic acids, polyester films contain an aromatic ring in the skeleton, and this aromatic ring is deteriorated and colored (yellowed) by ultraviolet rays. There's a problem.

  Therefore, a method of protecting a plastic substrate from ultraviolet rays by providing a layer that absorbs ultraviolet rays (hereinafter sometimes simply referred to as “ultraviolet absorption layer”) on the surface of the plastic substrate has been conventionally performed ( For example, see Patent Documents 1 to 3). The present inventor has also disclosed an ultraviolet-absorbing polymer for forming an ultraviolet-absorbing layer provided on the surface of a plastic substrate so far (see, for example, Patent Document 4), and has a single structure having a predetermined structure. It has been found that an ultraviolet absorbing polymer obtained by polymerizing a monomer composition is useful.

  By the way, in recent years, when such an ultraviolet absorbing layer is used for plastic substrates used outdoors such as agricultural greenhouses, and plastic substrates used for electronic devices such as thin displays and mobile phones, light resistance is improved. In addition to weather resistance such as anti-yellowing and yellowing resistance, characteristics relating to stain resistance such as fingerprint resistance and raindrop resistance are required.

Here, as one of methods for imparting stain resistance to the ultraviolet absorbing layer, there may be mentioned a method of mixing a surfactant with the ultraviolet absorbing polymer. However, although various types of surfactants have been developed so far (see, for example, Non-Patent Document 1), these surfactants impair the transparency of the ultraviolet absorbing layer or are sufficient for the ultraviolet absorbing layer. High contamination resistance could not be imparted.
JP-A-11-40833 JP 2003-107690 A JP 2004-126345 A JP 11-348199 A “Kao Surfactant”, Kao Corporation Chemicals Division, August 2005, p1-20

  The present invention has been made in view of the above problems, and as a result of intensive studies by the present inventors, a surfactant having a specific structure is effective for an ultraviolet absorbing layer without deteriorating the transparency of the ultraviolet absorbing layer. It has been found that stain resistance can be imparted. That is, an object of the present invention is to provide an ultraviolet absorbing layer having excellent transparency, weather resistance and stain resistance, and an ultraviolet absorbing resin composition capable of forming the ultraviolet absorbing layer.

  The ultraviolet-absorbing resin composition of the present invention has the following formula (1)

[Wherein, R ¹ represents an alkyl group having 8 to 18 carbon atoms, and X ¹ represents a sulfonate or phosphate whose counter ion is an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or an amine ion. Represents. n represents an integer of 0 to 12. ] The ultraviolet absorptivity which superposed | polymerized the monomer type composition containing at least 1 type chosen from the solvent type surfactant represented by these, and the ultraviolet absorptive monomer represented by following formula (2) to (5) And a polymer.

[Wherein R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³ represents an alkylene group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, and X ² represents hydrogen. An atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a nitro group is represented. ]

Wherein, R ⁵ and R ^2, R ⁶ has the same meaning as R ^4, R ⁷ represents a hydrogen atom or a hydroxyl group, R ⁸ represents a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, R ⁹ represents an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having 1 to 10 carbon atoms, and X ³ represents an ester bond, an amide bond, an ether bond, or a urethane bond. m represents 0 or 1; ]

[Wherein, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 2 to 2 carbon atoms. 10 represents an alkenyl group or an alkoxy group having 1 to 10 carbon atoms, X ⁴ represents a hydrogen atom or a methyl group, and A represents — (CH ₂ CH ₂ O) _p —, —CH ₂ CH (OH). _{-CH 2 O -, - (CH} 2) p -O -, - CH 2 CH (CH 2 oR 18) -O -, - CH 2 CH (R 18) -O-, or, -CH ₂ (CH _{2 Q} represents COO—B—O—, R ¹⁸ represents an alkyl group having 1 to 10 carbon atoms, B represents a methylene group, an ethylene group, or —CH ₂ CH (OH) CH ₂ —, and p represents The integer of 1-20 is represented, q represents 0 or 1. ]

[Wherein R ¹⁹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and R ²⁰ represents an element capable of forming a hydrogen bond. R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. ]

The ultraviolet absorbing polymer constituting the present invention is a solvent system, and the surfactant constituting the present invention is also a solvent system, whereby the compatibility between the ultraviolet absorbing polymer and the surfactant is excellent. Thus, it is possible to prevent the solution of the ultraviolet absorbing resin composition obtained by mixing these from being separated into layers or clouded. Also, the surfactant is by having an alkyl chain of appropriate length as R ^1, such R ¹ is serves as an anchor, the surfactant is easily held in the UV absorbing polymer. Furthermore, by using the surfactant as an additive to the ultraviolet absorbing polymer, it becomes easy to dispose the surfactant on the surface of the ultraviolet absorbing layer obtained from the ultraviolet absorbing resin composition.

  In the present specification, the “solvent-based surfactant” is used when synthesizing an ultraviolet absorbing polymer from the ultraviolet absorbing monomer represented by (2) to (5) used in the present invention. When an organic solvent solution of 5% by mass of a surfactant is prepared at 25 ° C. using an organic solvent that can be used or an organic solvent that can be used (details of these organic solvents will be described later). Refers to a surfactant capable of forming a transparent solution.

  In the ultraviolet absorbing resin composition of the present invention, the monomer composition may further include at least one selected from monomers represented by the following formulas (6) and (7). .

[Wherein R ²³ represents a hydrogen atom or a cyano group, R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a methyl group, and R ²⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or carbon. It represents the number 1-6 alkoxy group, X ⁵ represents an oxygen atom or an imino group. ]

[Wherein, R ²⁷ represents a hydrogen atom or a methyl group, and X ⁶ represents a hydrocarbon group having 1 or more carbon atoms. ]
By constituting the monomer composition further including the monomer represented by the above formula (6), the resulting UV-absorbing polymer has not only UV-absorbing performance but also UV-stabilizing performance. It becomes. Moreover, the ultraviolet-absorbing polymer excellent in a weather resistance is compoundable by further comprising the monomer represented by the said Formula (7) to comprise the said monomer composition.

  The ultraviolet-absorbing resin composition of the present invention is a preferred embodiment in which the surfactant has a number average molecular weight (Mn) of 350 to 2,000.

  With this configuration, the surfactant used in the present invention has excellent compatibility with the ultraviolet absorbing polymer.

  In the ultraviolet absorbing resin composition of the present invention, it is preferable that the content of the surfactant is 0.8 to 5 parts by mass with respect to 100 parts by mass of the ultraviolet absorbing polymer.

  The present invention includes a laminate in which an ultraviolet absorbing layer obtained from the above ultraviolet absorbing resin composition is provided on the surface of a plastic substrate.

  According to the present invention, since the solution (resin liquid) of the UV-absorbing resin composition does not cause layer separation or white turbidity, by using such a resin liquid, weather resistance (yellowing resistance, etc.) It was possible to obtain an ultraviolet-absorbing layer excellent not only in stain resistance (such as fingerprint resistance and raindrop stain resistance) but also in transparency and coating film appearance (such as coating film smoothness and gloss). Specifically, an ultraviolet absorbing layer excellent in transparency having a haze of less than 1% could be obtained.

  Further, the surfactant represented by the formula (1) is easily retained in the ultraviolet absorbing polymer obtained by using the ultraviolet absorbing monomer represented by the formulas (2) to (5). The ultraviolet absorbing layer of the present invention was able to exhibit the above effects over a long period of time.

  The ultraviolet-absorbing resin composition of the present invention has the following formula (1)

[Wherein, R ¹ , X ¹ and n have the same meaning as described above. ] The ultraviolet absorptivity which superposed | polymerized the monomer type composition containing at least 1 type chosen from the solvent type surfactant represented by these, and the ultraviolet absorptive monomer represented by following formula (2) to (5) And a polymer.

[Wherein R ² , R ³ , R ⁴ , and X ² have the same meaning as described above. ]

[Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X ³ , and m have the same meaning as described above. ]

[Wherein, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , X ⁴ , and A have the same meaning as described above. ]

[Wherein, R ¹⁹ , R ²⁰ , R ²¹ , R ²² have the same meaning as described above. ]
Hereinafter, the ultraviolet ray absorbing resin composition of the present invention will be described.

<Surfactant>
The surfactant used in the present invention is not particularly limited as long as it is represented by the above formula (1), and these surfactants may be used alone or in combination of two or more. It must be a solvent-based surfactant. When the surfactant used in the present invention is not solvent-based, the ultraviolet-absorbing polymer obtained from the ultraviolet-absorbing monomer represented by the formulas (2) to (5) used in the present invention is a solvent-based (organic Even if a solution of the UV-absorbing resin composition (resin liquid) is obtained by mixing the surfactant and the UV-absorbing polymer, both components are not compatible with each other and the layers are separated. Will become cloudy. For this reason, even if this resin liquid is applied to the surface of a plastic substrate and dried, an ultraviolet absorbing layer having excellent transparency and coating film appearance may not be obtained.

In the above formula (1), R ¹ is an alkyl group having 8 to 18 carbon atoms. When R ¹ is an alkyl group having 7 or less carbon atoms, it is difficult to retain the surfactant by the ultraviolet absorbing polymer, and therefore, an ultraviolet absorbing resin composition obtained by mixing them is used. In some cases, the surfactant tends to bleed out from the ultraviolet absorbing layer, resulting in poor blocking resistance, or the ultraviolet absorbing layer cannot exhibit excellent stain resistance over a long period of time. In addition, when R ¹ is an alkyl group having 19 or more carbon atoms, the compatibility between the surfactant and the ultraviolet absorbing polymer is lowered due to the hydroxyl group contained in the ultraviolet absorbing polymer. Therefore, the solution (resin liquid) of the ultraviolet absorbing resin composition may become cloudy. As a result, there is a possibility that the transparency and the coating film appearance of the ultraviolet absorbing layer formed using this resin liquid may be deteriorated. Moreover, since the surfactant is likely to bleed out and the surface of the ultraviolet absorbing layer is tacky, the blocking resistance may deteriorate. Furthermore, the ultraviolet absorbing layer may not exhibit excellent contamination resistance over a long period of time.

In the above formula (1), examples of the alkyl group having 8 to 18 carbon atoms represented by R ¹ include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group and the like.

Surfactants include anionic surfactants, cationic surfactants, and nonionic surfactants. In order to improve the stain resistance and weather resistance of the UV absorbing layer, the surfactant used in the present invention is used. The agent is required to be an anionic surfactant. Among these, X ¹ in the above formula (1) is preferably a sulfonate or phosphate whose counter ion is an ammonium ion or an amine ion. In particular, sulfonates whose counter ions are ammonium ions or amine ions are particularly preferred. With this configuration, the stain resistance and weather resistance of the ultraviolet absorbing layer obtained using the ultraviolet absorbing resin composition of the present invention can be further improved.

In said formula (1), it is preferable that n is an integer of 0-12, and it is more preferable that it is 0-10. When n is an integer of 13 or more, the compatibility between the ultraviolet absorbing polymer and the surfactant may be lowered. The surfactant used in the present invention may be composed of a uniform product in which n in the above formula (1) is single (for example, n is 4), or n may be composed of a mixture of 0 to 12. Good.

  The number average molecular weight (Mn) of the surfactant used in the present invention is preferably 350 or more, preferably 2000 or less, more preferably 1500 or less, and further preferably 1000 or less. When Mn of the surfactant is less than 350, it is difficult for the ultraviolet absorbing polymer to hold the surfactant. Moreover, when Mn of surfactant exceeds 2000, the compatibility of an ultraviolet-absorbing polymer and surfactant falls.

  In addition, the number average molecular weight (Mn) of surfactant can be calculated | required by the molecular weight of polystyrene conversion similarly to the calculation method of the weight average molecular weight (Mw) of the ultraviolet-absorbing polymer mentioned later.

  The content of the surfactant used in the present invention is preferably 0.8 parts by mass or more, more preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of the ultraviolet absorbing polymer. Is more preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass or less. When the content of the surfactant is less than 0.8 parts by mass, it is difficult for the ultraviolet absorbing layer to exhibit the stain resistance derived from the surfactant. Further, such stain resistance cannot be exhibited for a long time. Moreover, when content of surfactant exceeds 5 mass parts, the compatibility of a ultraviolet absorptive polymer and surfactant may fall. Further, since the surfactant is likely to bleed out from the ultraviolet absorbing layer and the surface of the ultraviolet absorbing layer is tacky, blocking resistance and coating film appearance may be deteriorated.

<Ultraviolet absorbing monomer>
The ultraviolet absorbing monomer used in the present invention is represented by the above formulas (2) to (5). These ultraviolet absorbing monomers may be used alone or in combination of two or more. Hereinafter, formulas (2) to (5) will be described in detail.

In the above formula (2), examples of the alkyl group having 1 to 8 carbon atoms represented by R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, and pentyl. Group, hexyl group, heptyl group, octyl group and other chain alkyl groups; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and other alicyclic alkyl groups; phenyl group, tolyl group, xylyl group , Aromatic alkyl groups such as benzyl group and phenethyl group;

In said formula (2), as a C1-C6 alkylene group represented by R < ³ >, linear alkylene groups, such as a methylene group, ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, are mentioned, for example. And branched chain alkylene groups such as an isopropylene group, an isobutylene group, a sec-butylene group, a t-butylene group, an isopentylene group, and a neopentylene group.

In the above formula (2), examples of the halogen atom represented by X ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 8 carbon atoms represented by X ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, and a heptyl group. Chain alkyl groups such as octyl group: cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and other alicyclic alkyl groups; phenyl group, tolyl group, xylyl group, benzyl group, phenethyl group, etc. An aromatic alkyl group of The alkoxy group having 1 to 6 carbon atoms represented by X ^2, for example, can be exemplified methoxy group, an ethoxy group, a propoxy group, a butoxy group, pentyloxy group, and hexyloxy group.

  Although it does not specifically limit as an ultraviolet absorptive monomer represented by the said Formula (2), For example, 2- [2'-hydroxy-5 '-(methacryloyloxymethyl) phenyl] -2H- Benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(methacryloyloxyethyl) Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5′-tert-butyl-3 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5′- (Methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5 ′ Etc. (methacryloyloxyethyl) phenyl] -5-methoxy -2H- benzotriazole and the like. These monomers may be used alone or in combination of two or more.

In the above formula (3), examples of the alkoxy group having 1 to 6 carbon atoms represented by R ⁸ include the substituents listed above as the alkoxy group having 1 to 6 carbon atoms represented by X ^2. be able to.

In the above formula (3), examples of the alkylene group having 1 to 10 carbon atoms represented by R ⁹ include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, An octamethylene group, a decamethylene group, etc. can be mentioned. Preferably, a C1-C6 alkylene group can be mentioned. Examples of the alkylene group having 1 to 6 carbon atoms include the substituents listed above as the alkylene group having 1 to 6 carbon atoms represented by R ³ . Moreover, as a C1-C10 oxyalkylene group represented by R < ⁹ >, an oxymethylene group, an oxyethylene group, an oxypropylene group etc. can be mentioned, for example.

  The ultraviolet absorbing monomer represented by the above formula (3) is not particularly limited, and examples thereof include 2-hydroxy-4- (meth) acryloyloxybenzophenone and 2-hydroxy-4- [ 2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] butoxybenzophenone, 2,2′-dihydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxy-4 '-(2-hydroxyethoxy) benzophenone, 2-hydroxy-3-tert-butyl-4- [2- (meth) acryloyloxy] ethoxy Benzophenone, 2-hydroxy-3-tert-butyl-4- [2- (meth) acryloyloxy] butoxybenzophenone, etc. It can gel. These monomers may be used alone or in combination of two or more.

In the above formula (4), examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ or R ¹⁷ include a methyl group, Ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, 2,2-dimethylpropyl group, n-heptyl group, n- Linear or branched alkyl groups such as octyl group, n-nonyl group, n-decyl group, 1,1,3,3 -tetramethylbutyl group and 2-ethylhexyl group; alicyclic alkyl such as cyclohexyl group Group; and the like. Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ or R ¹⁷ include a vinyl group, an allyl group, and a 1-propenyl group. , Isopropenyl group, 1-butenyl group, 2-butenyl group, 2-pentenyl group, 3-pentenyl group, 4-hexenyl group, 5-heptenyl group, 4-methyl-3-pentenyl group, 2,4-dimethyl- A 3-pentenyl group, 6-methyl-5-heptenyl group, 2,6-dimethyl-5-heptenyl group and the like can be mentioned. Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ or R ¹⁷ include methoxy group, ethoxy group, propoxy group, butoxy Group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group and the like.

In the above formula (4), examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹⁸ in A include R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ^16. Or the said substituents enumerated as a C1-C10 alkyl group represented by R < ¹⁷ > can be mentioned.

  Although it does not specifically limit as an ultraviolet absorptive monomer represented by the said Formula (4), For example, 2,4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxy) Phenyl] -1,3,5-triazine, 2,4-bis (2-methylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- ( 2-A Liloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-diphenyl-6- [2-hydroxy-4- (2-methacryloyloxyethoxy) phenyl] -1,3,5-triazine, 2 , 4-Bis (2-methylphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2-methoxyphenyl)- 6- [2-hydroxy-4- (2-methacryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2 -Methacryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2-methacryloyl) Oxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2,4-dimethoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3 , 5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4- Bis (2,4-diethoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2,4-diethylphenyl) ) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2- [2-hydroxy-4- (11-acryloyloxy-un) Decyloxy) phenyl] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (11-methacryloyloxy-undecyloxy) phenyl] -4,6-diphenyl-1,3 , 5-triazine, 2- [2-hydroxy-4- (2-methacryloyloxyethoxy) phenyl] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (11- Acryloyloxy-undecyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2 -Hydroxy-4- (11-methacryloyloxyundecyloxy) phenyl] -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2 Such as hydroxy-4- (2-methacryloyloxy) phenyl] -1,3,5-triazine and the like. These monomers may be used alone or in combination of two or more. Of these monomers, the formula (4-1)

A monomer represented by formula (4-2)

A monomer represented by formula (4-3)

A monomer represented by is preferable.

In the above formula (5), examples of the halogen atom represented by R ¹⁹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹⁹ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n -Linear or branched such as -pentyl group, isopentyl group, 2,2-dimethylpropyl group, n-heptyl group, n-octyl group, 1,1,3,3 -tetramethylbutyl group, 2-ethylhexyl group An alicyclic alkyl group such as a cyclohexyl group; and the like. The alkoxy group having 1 to 4 carbon atoms represented by R ^19, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group.

In the above formula (5), examples of the group having an element capable of forming a hydrogen bond represented by R ²⁰ include —NH—, —CH ₂ NH—, —OCH ₂ CH (OH) CH ₂ O—. , —CH ₂ CH ₂ COOCH ₂ CH (OH) CH ₂ O—, and the like. Among these groups, in that they contain a nitrogen atom having an active hydrogen, -NH -, - CH ₂ NH- are preferred, -CH ₂ NH- is particularly preferred.

In the above formula (5), as the alkyl group having 1 to 12 carbon atoms represented by R ²² , for example, in addition to the above-described substituents listed as the alkyl group having 1 to 8 carbon atoms represented by R ¹⁹ Linear or branched alkyl groups such as nonyl group, decyl group, undecyl group and dodecyl group; aromatic alkyl groups such as phenyl group, tolyl group, xylyl group, benzyl group and phenethyl group; it can. Of these substituents, a linear or branched alkyl group having 4 to 12 carbon atoms is preferable, and a bulky branched alkyl group such as 1,1,3,3-tetramethylbutyl group (or the like). Particularly preferred are groups having

Although it does not specifically limit as an ultraviolet absorptive monomer represented by the said Formula (5), For example, 2- [2'-hydroxy-3 '-(meth) acryloylaminophenyl] -2H- Benzotriazole, 2- [2′-hydroxy-3 ′-(meth) acryloylaminomethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′-(meth) acryloylamino-5 ′-(1 , 1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′-(meth) acryloylaminomethyl-5 ′-(1,1,3,3-tetra Methylbutyl) phenyl] -2H-benzotriazole and the like. These monomers may be used alone or in combination of two or more. Of these monomers, 2- [2′-hydroxy-3 ′-(meth) acryloylamino-5 ′-(1,1,1), which has a bulky substituent R ²² bonded to the 5-position. 3,3-tetramethylbutyl) phenyl] -2H-benzotriazole and 2- [2′-hydroxy-3 ′-(meth) acryloylaminomethyl-5 ′-(1,1,3,3-tetramethyl) Butyl) phenyl] -2H-benzotriazole is preferred.

  The benzotriazole-based monomer represented by the above formula (2) or (5) is, for example, (meth) acrylic acid chloride, N-methylol acrylamide or its benzotriazole (commercially available as an ultraviolet absorber). It can be synthesized by a method such as reacting an alkyl ether. For example, 2- [2′-hydroxy-3′-methacryloylamino-5 ′-(1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole is 2- [2′-hydroxy-3 It can be obtained by reacting '-amino-5'-(1,1,3,3-tetramethylbutyl) phenyl] -benzotriazole with methacrylic acid chloride. Further, 2- [2′-hydroxy-3′-methacryloylaminomethyl-5 ′-(1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole is 2- [2′-hydroxy- 5 ′-(1,1,3,3-tetramethylbutyl) phenyl] -benzotriazole (for example, CYASORB (registered trademark) UV-5411, manufactured by CYTEC) and N-methylolacrylamide (for example, Nitto Chemical Industries, Ltd.) Etc.) can be obtained by reaction.

<Ultraviolet absorbing polymer>
The ultraviolet absorbing polymer used in the present invention can be obtained by polymerizing a monomer composition containing at least one selected from the above ultraviolet absorbing monomers. Other monomers that can be included in the monomer composition will be described later.

In synthesizing the ultraviolet absorbing polymer used in the present invention, the content of the ultraviolet absorbing monomer is preferably 5% by mass or more, more preferably 7% by mass or more in 100% by mass of the monomer composition, 10 mass% or more is further more preferable, 60 mass% or less is preferable, 50 mass% or less is more preferable, and 40 mass% or less is further more preferable. If it is this range, the ultraviolet absorption ability of an ultraviolet absorption layer will become enough, and the yellowing of a plastic base material, especially a polyester-type film can be suppressed over a long period of time. When the content of the ultraviolet absorbing monomer is less than 5% by mass, sufficient weather resistance may not be imparted to the ultraviolet absorbing layer. Further, the amount of the phenolic hydroxyl group derived from the ultraviolet absorbing monomer in the ultraviolet absorbing polymer is decreased, and the phenolic hydroxyl group and — (CH ₂ CH ₂ in the surfactant represented by the formula (1) are reduced. Since the interaction with O)-is reduced, the compatibility between the surfactant represented by formula (1) and the surfactant having a specific structure and the UV-absorbing polymer is reduced, and the UV-absorbing layer Transparency and coating film appearance may deteriorate. Further, when the content of the ultraviolet absorbing monomer exceeds 60% by mass, the amount of phenolic hydroxyl group derived from the ultraviolet absorbing monomer in the ultraviolet absorbing polymer is excessively increased, and the phenolic hydroxyl group is increased. And R ¹ in the surfactant represented by the formula (1), the interaction between the UV-absorbing polymer and the surfactant represented by the formula (1) becomes small, and the formula ( Among the surfactants represented by 1), the compatibility between the surfactant having a specific structure and the UV-absorbing polymer may be decreased, and the transparency and coating film appearance of the UV-absorbing layer may be decreased. . In addition, since the surfactant represented by the formula (1) is likely to bleed out, the contamination resistance of the ultraviolet absorbing layer may not be maintained for a long time.

  There is no particular limitation on the polymerization method for synthesizing the ultraviolet absorbing polymer, and a known polymerization method such as a solution polymerization method, a bulk polymerization method, an aqueous solution polymerization method, a suspension polymerization method, or an emulsion polymerization method is used. be able to. In particular, the solution polymerization method is preferable because it can be used as the ultraviolet-absorbing resin composition of the present invention as it is or simply by diluting the obtained reaction product.

  Examples of the organic solvent used in the solution polymerization include toluene, xylene, and other aromatic solvents; alcohol solvents such as n-butyl alcohol, propylene glycol methyl ether, diacetone alcohol, and ethyl cellosolve; butyl acetate, ethyl acetate, Ester solvents such as cellosolve acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; dimethylformamide and the like can be used. The kind of organic solvent to be used is not limited to these. These organic solvents may use only 1 type and may use 2 or more types as a mixed solvent. The amount of the organic solvent used may be appropriately determined in consideration of the monomer concentration, the desired molecular weight of the polymer, or the polymer solution concentration.

  Examples of polymerization initiators that can be used for solution polymerization include 2,2′-azobis- (2-methylbutyronitrile), tert-butylperoxy-2-ethylhexanoate, and 2,2′-azo. Known radical polymerization initiators such as bisisobutyronitrile, benzoyl peroxide, and di-tert-butyl peroxide can be exemplified. The amount of the polymerization initiator used is not particularly limited, but is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and preferably 30 parts by mass or less with respect to 100 parts by mass of the total monomer composition. 10 parts by mass or less is more preferable. If necessary, one or more chain transfer agents such as n-dodecyl mercaptan may be added to adjust the molecular weight of the ultraviolet absorbing polymer.

  The temperature of the polymerization reaction is not particularly limited, but is preferably room temperature or higher, more preferably 40 ° C or higher, preferably 200 ° C or lower, and more preferably 140 ° C or lower. In addition, what is necessary is just to set reaction time suitably so that a polymerization reaction can be completed efficiently according to the composition of the monomer composition to be used, the kind of polymerization initiator, etc.

  The molecular weight of the ultraviolet absorbing polymer is preferably 10,000 or more, more preferably 50,000 or more, preferably 400,000 or less, and more preferably 200,000 or less in terms of weight average molecular weight (Mw). When the Mw of the ultraviolet absorbing polymer is less than 10,000, the substrate adhesion of the ultraviolet absorbing layer may be insufficient. Further, when the Mw of the UV-absorbing polymer exceeds 400,000, the compatibility with the surfactant represented by the formula (1) is lowered, and the UV-absorbing resin composition when a cross-linking agent described later is blended. The stability of the product solution may be reduced.

<Monomer composition>
The ultraviolet absorbing polymer used in the present invention may be synthesized by copolymerizing a monomer composition containing other monomers listed below in addition to the above ultraviolet absorbing monomer. . By selecting the type and amount of other monomers contained in the monomer composition of the present invention, the characteristics of the ultraviolet absorbing polymer of the present invention can be variously changed.

(Monomer having UV-stable group)
The monomer composition used in the present invention may contain a monomer having a UV-stable group (hereinafter sometimes simply referred to as “UV-stable monomer”). In particular, when UV-absorbing monomers and UV-stable monomers are used in combination, the resulting polymer has UV stability in addition to UV-absorbing properties, so that the weather resistance of the UV-absorbing layer lasts for a long time. Will be. The ultraviolet-stable monomer is not particularly limited as long as it has a polymerizable double bond and an ultraviolet-stable group in the molecule, and among them, the ultraviolet-stable monomer represented by the following formula (6) Is preferred.

[Wherein R ²³ represents a hydrogen atom or a cyano group, R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a methyl group, and R ²⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or carbon. It represents the number 1-6 alkoxy group, X ⁵ represents an oxygen atom or an imino group. ]

In the above formula (6), the alkyl group having 1 to 18 carbon atoms represented by R ²⁶ is, for example, in addition to the above-described substituents listed as the alkyl group having 1 to 8 carbon atoms represented by R ^2. And chain alkyl groups such as nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. The alkoxy group having 1 to 6 carbon atoms represented by R ^26, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group.

  Specific examples of the monomer represented by the formula (6) are not particularly limited, but 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine (for example, Asahi) “Adekastab (registered trademark) LA87” manufactured by Denka Kogyo Co., Ltd.), 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6 6-pentamethylpiperidine (for example, “Adekastab LA-82” manufactured by Asahi Denka Kogyo Co., Ltd.), 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- ( (Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2, , And the like 6-tetramethylpiperidine. These ultraviolet stable monomers may be used alone or in combination of two or more as necessary.

  The content of the UV-stable monomer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, preferably 20% by mass or less, and preferably 10% by mass or less in 100% by mass of the monomer composition. Is more preferable.

  Next, monomers other than the above-described UV-absorbing monomer and UV-stable monomer that can be used in the synthesis of the UV-absorbing polymer used in the present invention will be described. The content of the monomer is the balance of the UV-absorbing monomer and the UV-stable monomer in 100% by mass of the monomer composition.

((Meth) acrylates)
The monomer composition used in the present invention may contain (meth) acrylates represented by the following formula (7). Such (meth) acrylates can synthesize UV-absorbing polymers having good copolymerization with the UV-absorbing monomer and excellent weather resistance.

[Wherein, R ²⁷ represents a hydrogen atom or a methyl group, and X ⁶ represents a hydrocarbon group having 1 or more carbon atoms. ]

In the formula (7), examples of the hydrocarbon group having 1 or more carbon atoms represented by X ⁶ include an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkylene group, and an aromatic ring. Can do.

  Specific examples of the monomer represented by the above formula (7) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl acrylate, n-butyl (meth) acrylate, and isobutyl. (Meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (Meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, 2-acetoacetoxyethyl (meth) Examples thereof include acrylates (for example, “Eastman AAEM” manufactured by Eastman) and phenoxyethyl (meth) acrylate. These (meth) acrylates may be used alone or in combination of two or more as necessary.

  In this specification, (meth) acrylate may be either methacrylate or acrylate.

(Hydroxyl group-containing monomer)
The monomer composition used in the present invention may contain a hydroxyl group-containing monomer in order to introduce a crosslinking point with a crosslinking agent to be described later into the ultraviolet absorbing polymer.

  Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, And ε-caprolactone adducts of 2-hydroxyethyl (meth) acrylate (for example, “Placcel (registered trademark) FM1D” or “Placcel FM2D” manufactured by Daicel Chemical Industries, Ltd.). These hydroxyl group-containing monomers may be used alone or in combination of two or more as necessary.

(Other)
The monomer composition used in the present invention may further contain the following various monomers.

  Vinyl acetate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl pivalate, vinyl octylate, vinyl monochloroacetate Vinyl esters such as divinyl adipate, vinyl methacrylate, vinyl crotonic acid, vinyl sorbate, vinyl benzoate and vinyl cinnamate.

  Silicon-containing monomers such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, trimethylsiloxyethyl (meth) acrylate .

  Trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadodecafluorodecyl (meth) acrylate, Halogen-containing compounds such as β- (perfluorooctyl) ethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, ethylene oxide addition (meth) acrylate of tribromophenol, and tribromophenyl (meth) acrylate Mers.

  (Meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acryloyloxyethyltrimethylammonium chloride, dimethylaminoethyl (meth) acrylate sulfate, ethylene oxide addition (meth) acrylate of morpholine, N -Vinylpyridine, N-vinylimidazole, N-vinylpyrrole, N-vinylpyrrolidone, N-vinyloxazolidone, N-vinylsuccinimide, N-vinylmethylcarbamate, N, N-methylvinylacetamide, 2-isopropenyl-2 -Nitrogen-containing monomers such as oxazolines.

  Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol-propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-1,3-di ( (Meth) acryloxypropane di (meth) acrylate, 2,2-bis [4- (meth) acryloxydiethoxyphenyl] propanedi (meth) acrylate, 2,2-bis [4- (methacryloxy) Polyethoxy) phenyl] propanedioic (meth) acrylate, polyfunctional monomers such as ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate.

  Vinyl methyl ether, vinyl ethyl ether, vinyl isopropyl ether, vinyl n-propyl ether, vinyl isobutyl ether, vinyl n-butyl ether, vinyl n-amyl ether, vinyl isoamyl ether, vinyl-2-ethylhexyl ether, vinyl-n -Vinyl ethers such as octadecyl ether, cyanomethyl vinyl ether, 2,2-dimethylaminoethyl vinyl ether, 2-chloroethyl vinyl ether, β-difluoromethyl vinyl ether, benzyl vinyl ether, phenyl vinyl ether, divinyl ether and divinyl acetal.

  Glycidyl (meth) acrylate, α-methylglycidyl acrylate, α-methylglycidyl methacrylate (for example, “MGMA” manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, “Cyclocycle manufactured by Daicel Chemical Industries, Ltd.” Mer (registered trademark) A400 ") and 3,4-epoxycyclohexylmethyl methacrylate (for example," Cyclomer M100 "manufactured by Daicel Chemical Industries, Ltd.).

  Acid functional group-containing monomers such as sulfoethyl (meth) acrylate, 4-sulfo (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, and salts thereof.

<Ultraviolet absorbing resin composition>
The aspect of the ultraviolet absorbent resin composition of the present invention is particularly limited as long as it contains the solvent-based surfactant represented by the above formula (1) and the ultraviolet absorbent polymer. In addition, it may be configured to contain a crosslinking agent, a solvent, an additive, and other resins as necessary.

(Crosslinking agent)
The crosslinking agent contained in the ultraviolet absorbing resin composition of the present invention is not particularly limited, but is preferably a polyisocyanate-based crosslinking agent. The polyisocyanate-based cross-linking agent causes the weather resistance and strength of the UV absorbing layer formed by using the UV absorbing resin composition and chemical resistance by causing a crosslinking reaction with the hydroxyl group introduced into the UV absorbing polymer. Can increase the sex. It should be noted that other crosslinking agents such as melamine resin are not preferable because a high temperature and / or a long time are required until the crosslinking reaction is completed, and the ultraviolet absorbing layer is easily yellowed.

  The polyisocyanate-based crosslinking agent is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule. Tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), etc. Known diisocyanate compounds; Buret polyisocyanate compounds such as “Sumijour (registered trademark) N”; “Desmodur (registered trademark) IL”, “Desmodur HL” (both manufactured by Sumika Bayer Urethane Co., Ltd.), “Coronate” Polyisocyanate compounds having an isocyanurate ring known as “(registered trademark) EH” (manufactured by Nippon Polyurethane Industry Co., Ltd.); Adduct polyisocyanate compounds such as “Sumijour L” (manufactured by Sumika Bayer Urethane Co., Ltd.); “Coronate L” And "Coronate L-55E" Both Nippon Polyurethane Co., Ltd.) adduct polyisocyanate compounds, such as and the like "Takenate (registered trademark) D110N" (manufactured by Mitsui Takeda Chemicals, Inc.) Polyisocyanate compound having an aromatic ring such as. These can be used alone or in combination of two or more. In addition, so-called blocked isocyanates in which the isocyanate groups of these compounds are inactivated by reacting with a masking agent having active hydrogen can also be used.

  The blending amount of the polyisocyanate-based crosslinking agent is preferably 0.1 parts by mass (dry) or more, preferably 30 parts by mass (dry) or less, and 20 parts by mass (dry) or less with respect to 100 parts by mass of the ultraviolet absorbing polymer. Is more preferable. When the amount of the crosslinking agent is less than 0.1 parts by mass, the substrate adhesion of the ultraviolet absorbing layer may be lowered. Moreover, when the compounding quantity of a crosslinking agent exceeds 30 mass parts, stability of the ultraviolet-absorbing resin composition solution (resin liquid) after a crosslinking agent mix | blends may fall.

(solvent)
The ultraviolet absorbing resin composition of the present invention may further be mixed with a solvent as appropriate.

  As a solvent, the solvent illustrated at the time of the synthesis | combination of an ultraviolet absorptive polymer, or the solvent illustrated as a solvent which can be used can be mentioned.

(Additive)
The ultraviolet absorbent resin composition of the present invention may further contain the following additives.

  Additives include organic ultraviolet absorbers such as benzotriazole, benzophenone, triazine, and indole, and inorganic ultraviolet absorbers such as zinc oxide; sterically hindered piperidine compounds (for example, manufactured by Ciba Specialty Chemicals) Additive UV stabilizers such as “Tinuvin (registered trademark) 123”, “Tinuvin 144”, “Tinuvin 765”, etc .; Leveling agents, antioxidants, fillers such as talc, rust preventives, fluorescent whitening Agents, antioxidants, surfactant-based, lithium-based, organoboron-based antistatic agents, pigments, dyes, thickeners, colloidal silica, alumina sol and other inorganic particles, and polymethyl methacrylate-based acrylic particles Additives common in the paint field. When these additives are used, the content of the ultraviolet absorbing polymer in the ultraviolet absorbing resin composition of the present invention is 50% by mass or more (more preferably 80% by mass or more, more preferably 90% by mass or more). It is desirable to use so that it becomes.

(Other resins)
The ultraviolet absorbing resin composition of the present invention may contain other resins as long as the object of the present invention is not impaired. Examples of other resins include thermoplastic resins and thermosetting resins that are crosslinked and cured by the action of the resin itself or by a curing agent. More specifically, thermoplastic resins such as vinyl chloride resins, polyester resins, acrylic resins, silicone resins; urethane resins, aminoplast resins, silicone resins, epoxy resins, acrylic resins, etc. Examples thereof include single-curing heat / ultraviolet / electron beam curable resins; thermosetting resins that are cured by a curing agent such as polyester resin, acrylic resin, and epoxy resin. The type and amount of these other resins may be appropriately determined according to the use and required characteristics of the ultraviolet absorbing layer formed from the ultraviolet absorbing resin composition of the present invention.

  In particular, by blending the saturated polyester resin with the ultraviolet absorbing resin composition of the present invention, excellent adhesion between the ultraviolet absorbing layer and the plastic substrate can be ensured. Moreover, if a single-curing ultraviolet / electron beam curable resin is blended with the ultraviolet-absorbing resin composition of the present invention, a high-hardness ultraviolet-absorbing layer can be formed.

  As described above, the ultraviolet absorbing resin composition of the present invention has been described. However, a laminated body formed by forming an ultraviolet absorbing layer formed using such an ultraviolet absorbing resin composition on the surface of a plastic substrate will be described below. To do.

<Laminated body>
In the laminate of the present invention, the solution (resin liquid) of the ultraviolet absorbing resin composition is dipped, sprayed, brushed, curtain flow coated, gravure coated, roll coated, spin coated, bar coated onto the surface of a plastic substrate. It can be manufactured by coating by a known coating method such as coating or electrostatic coating, and then drying to form an ultraviolet absorbing layer. The drying may be performed at a temperature suitable for the solvent contained in the resin liquid.

  The thickness of the UV-absorbing layer depends on the amount of UV-absorbing groups introduced into the polymer according to Lambert-Beer's law, that is, the amount of UV-absorbing monomer used during polymerization. Therefore, the thickness of the ultraviolet absorbing layer may be determined in consideration of the amount of the ultraviolet absorbing group in the polymer and the weather resistance required for the ultraviolet absorbing layer, and is usually in the range of 0.5 to 15 μm. It is. When the thickness exceeds 15 μm, it takes time to dry the coating film, and the curl resistance is also lowered. On the other hand, when the thickness is less than 0.5 μm, it is difficult to uniformly coat the base material, and the ultraviolet absorption performance may be insufficient. A more preferable lower limit of the thickness is 1.0 μm, and a more preferable upper limit of the thickness is 10 μm.

  The plastic substrate used in the present invention is mainly a polyester film. This polyester film is a film obtained using a polyester having an aromatic ring in its skeleton as a cause of yellowing. For example, in addition to homopolyester films such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate, other saturated polyester resin films are also included. The plastic substrate constituting the laminate of the present invention may be a uniaxially stretched or biaxially stretched film. As the biaxially stretched PET film, for example, “O-PET” manufactured by Kanebo Corporation is available.

  In addition, polyester films can be used as the plastic substrate of the laminate of the present invention. For example, polyethylene, polypropylene, triacetyl cellulose, polyacrylate, polymethyl methacrylate, polystyrene, polycarbonate, polyethersulfone, cellophane, aromatic polyamide, polyvinyl alcohol, ABS, polyacetal, polyphenylene ether, polyphenylene sulfide, polyimide, polyamideimide, poly Examples thereof include plastic substrate films such as fluororesin films such as ether imide, polyether ether ketone, and polytetrafluoroethylene. Optical resin films such as “ARTON (registered trademark)” (manufactured by JSR), “ZEONEX (registered trademark)” (manufactured by Nippon Zeon), and “OPTREZ (registered trademark)” (manufactured by Hitachi Chemical Co., Ltd.) can also be used. is there. Further, the following formula (8)

[Wherein, R ²⁸ , R ²⁹ and R ³⁰ each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom. ]
The polymer film which has a lactone structure shown by these may be sufficient. As said organic residue, a C1-C20 alkyl group, an alkenyl group, a cycloalkylene group, an aromatic ring etc. can be mentioned. Conventionally known additives may be added to these substrate films (including plate-like films).

  The surface of the plastic substrate constituting the laminate of the present invention is preferably subjected to an easy adhesion treatment. Examples of the easy adhesion treatment include corona discharge treatment, plasma treatment, treatment with an alkali metal compound solution, high frequency sputter etching treatment, and formation of an easy adhesive layer (undercoat layer).

The present invention will be described below by experimental examples in more detail, the present invention is not limited thereto, and can be implemented appropriately changed within the scope adaptable to the purposes described above and below, They are all included in the technical scope of the present invention. In the following experimental examples , “parts” and “%” represent parts by mass or mass%.

<Evaluation method>
First, the evaluation method of the laminate created by experimental examples will be described below.

(Transparency of initial UV absorbing layer (haze))
In accordance with JIS K7105, the transparency of the plastic substrate and the laminate is measured using a turbidimeter “NDH300A” manufactured by Nippon Denshoku Industries Co., Ltd. The transparency (haze) of the ultraviolet absorbing layer at the initial stage (that is, before the weather resistance test) was evaluated according to the following criteria.
○: Haze less than 1% Δ; Haze 1% or more and less than 2% ×; Haze 2% or more

(Blocking resistance)
Five sheets of gauze are stacked on the UV absorbing layer surface of the laminate after drying at 100 ° C. for 2 minutes, a weight is placed so as to be a pressure of 250 g / cm ² , and left at 50 ° C. for 24 hours, and after 48 hours. The state of the ultraviolet absorbing layer was observed and evaluated according to the following criteria.
○: No gauze traces △;

(Fingerprint resistance)
The actual fingerprints are attached to the initial laminate (ie, left at 50 ° C. and 90% RH for 48 hours) and the laminate after left at 50 ° C. and 90% RH for 48 hours, and the fingerprints of each laminate are attached. The degree was evaluated according to the following criteria.
○: Almost not adhered or not visible Δ; Slightly adhered or visually visible level ×;

(Rain dripping resistance)
The laminate was installed in an outdoor raindrop test apparatus for 3 months and 6 months in Suita City, Osaka Prefecture, and evaluated according to the following criteria. The raindrop test apparatus arranges the laminated body in a substantially vertical direction with respect to the ground based on the exposure A method described in the outdoor exposure test method (JSTM J7601-1992) for contamination of building exterior wall materials. A plastic corrugated plate with an inclination angle of 10 ° with respect to the ground is provided above the laminated body so that the rain water directly drops from the end of the plastic corrugated plate onto the ultraviolet absorbing layer surface of the laminated body. I went.
○: Almost no raindrop pollution △; Slightly raindrop pollution ×: Clearly raindrop pollution

(Weatherability)
Using an ultraviolet deterioration accelerating tester (“I-Super UV Tester UV-W131”; manufactured by Iwasaki Electric Co., Ltd.) in an atmosphere of 70 ° C. and 60% RH (relative humidity), 80 mW /% from the ultraviolet absorbing layer side of the laminate. Irradiation with ultraviolet rays of cm ² was conducted for 240 hours, and b values before and after irradiation and transparency (haze) of the ultraviolet absorbing layer were measured and evaluated according to the following criteria.

The b value is measured with a spectroscopic color difference meter (“SE-2000”; manufactured by Nippon Denshoku Kogyo Co., Ltd.) according to JIS K 7105 (2004 edition), and the difference in b value before and after irradiation is yellowed. The degree was Δb. Moreover, the transparency (haze) of the ultraviolet absorbing layer was measured by the same method as described above.
Yellowing resistance ○: Δb is less than 2 Δ; Δb is 2 or more and less than 4 ×; Δb is 4 or more Transparency of the ultraviolet absorbing layer after the weather resistance test (haze)
○: Haze less than 1% Δ; Haze 1% or more and less than 2% ×; Haze 2% or more

<Synthesis Example 1 of UV Absorbing Polymer>
In a 500 ml flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, 2- [2′-hydroxy-5′- represented by the formula (2) is used as an ultraviolet absorbing monomer. (Methacryloyloxyethyl) phenyl] -2H-benzotriazole (trade name “RUVA93”: manufactured by Otsuka Chemical Co., Ltd .: UVA1), 25 parts of methyl methacrylate (MMA) represented by the formula (7) as another monomer ) 54 parts, 11 parts of n-butyl acrylate (BA), 10 parts of 2-hydroxyethyl methacrylate (HEMA) as a hydroxyl group-containing monomer, 120 parts of ethyl acetate as a solvent, refluxed while flowing nitrogen gas and stirring The temperature was raised to temperature. On the other hand, a mixture of 10 parts of ethyl acetate and 1 part of 2,2′-azobis- (2-methylbutyronitrile) as a polymerization initiator was charged into a dropping tank and dropped over 2 hours. After completion of the dropping, the reflux reaction was continued, and after 6 hours from the start of dropping, the mixture was cooled and diluted with ethyl acetate so that the nonvolatile content became a 40% solution to obtain a solution of the UV-absorbing polymer 1.

  The weight average molecular weight (Mw) of the obtained UV-absorbing polymer 1 is GPC (“HLC8120” manufactured by Tosoh Corporation), and “TSK-GEL GMHXL-L” (manufactured by Tosoh Corporation) is used as a column. It calculated | required as molecular weight of conversion.

  Table 1 shows the amount of the monomer composition used and the weight average molecular weight Mw of the synthesized UV-absorbing polymer 1.

<Synthesis Examples 2 to 5 of UV Absorbing Polymer>
Ultraviolet absorbing polymers 2 to 5 were synthesized in the same manner as in Synthesis Example 1 except that the monomer composition and the nonvolatile content were changed as shown in Table 1.

  Table 1 shows the amount of the monomer composition used and the weight average molecular weight Mw of the synthesized UV-absorbing polymers 2 to 5.

In Table 1, UVA2 represents 2- [2′-hydroxy-3′-methacryloylaminomethyl-5 ′-(1,1,3,3-tetramethylbutyl) phenyl]-represented by the formula (5). 2H-benzotriazole,
UVA3 is 2- [2-hydroxy-4- (11-methacryloyloxy-undecyloxy) phenyl] -4,6-diphenyl-1,3,5-triazine represented by the formula (4).
“HALS” means 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine (trade name “ADK STAB LA82”: manufactured by Asahi Denka Kogyo Co., Ltd.) represented by the formula (6).

<Creation of laminate>
Experimental example 1
100 parts of the solution of the UV-absorbing polymer 1 obtained in Synthesis Example 1, 6 parts of a polyisocyanate-based crosslinking agent (“Desmodule (registered trademark) N3200”; manufactured by Sumika Bayer Urethane Co., Ltd.), and a surfactant C ₁₂ Add 1 part each of H ₂₅ O (CH ₂ CH ₂ O) _n SO ₃ NH (CH ₂ CH ₂ OH) ₃ (n is a mixture of 0 to 8) to a container, and further with methyl ethyl ketone until the nonvolatile content reaches 20%. The solution (resin liquid) of the ultraviolet-absorbing resin composition was prepared by diluting.

  The above resin solution was applied to a 188 μm-thick PET film (“A-4100” manufactured by Toyobo Co., Ltd.) having a single-sided easy-adhesion treatment as a base material, and dried at 100 ° C. for 2 minutes. Then, an ultraviolet absorption layer having a thickness of 5 μm after drying was formed, and a laminate in which the ultraviolet absorption layer was arranged on the PET film was obtained.

  About this laminated body, transparency (haze), blocking resistance, fingerprint resistance, raindrop stain resistance, and weather resistance of the ultraviolet absorbing layer were evaluated by the above-described methods. Each evaluation result is shown in Table 2.

Experimental Examples 2-16
Except having changed the composition as shown in Table 2, it was carried out similarly to Experimental Example 1, and obtained the laminated body which has arrange | positioned the ultraviolet absorption layer on PET film.

  About the obtained laminated body, the transparency (haze), blocking resistance, fingerprint resistance, raindrop stain resistance, and weather resistance of the ultraviolet absorbing layer were evaluated by the methods described above. Each evaluation result is shown in Table 2. In addition, when the transparency of the ultraviolet absorbing layer before the weather resistance test was poor (that is, the evaluation was x), the evaluation was stopped for other characteristics such as blocking resistance.

In Table 2, surfactant 2 is C _X H _{X + 1} O (CH ₂ CH ₂ O) ₃ SO ₃ Na (X is a mixture of 12 to 16),
Surfactant 3 is a polyoxyethylene alkyl ether phosphate ester amine salt (trade name “phosphanol (registered trademark) RS-710M” manufactured by Toho Chemical Industry Co., Ltd.),
Surfactant 4 is polyoxyethylene alkyl ether phosphate Na salt (trade name “Phosphanol GB-520”: manufactured by Toho Chemical Industry Co., Ltd.),
Surfactant 5 is an aliphatic alkyl quaternary ammonium salt (trade name “Katiogen (registered trademark) ES-L-9” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.),
Surfactant 6 is sorbitan monooleate (trade name “Solgen 40V” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.),
Surfactant 7 is a polymer of p-styrenesulfonic acid sodium salt (40%) / polyethylene glycol monomethacrylate (60%) (number average molecular weight (Mn) is 3000, and polyethylene glycol monomethacrylate has 4 to 4 alkylene oxide units. 5 chains are used),
Surfactant 8 is sodium butyl phosphate.

Based on Table 2, when the surfactant contained in the UV-absorbing resin composition is represented by the formula (1) as in Experimental Examples 1 to 8 (specifically, the surfactant is an anionic surfactant) ), The obtained laminate is excellent in weather resistance and stain resistance. On the other hand, when it is a cationic surfactant or a nonionic surfactant as in Experimental Examples 11 and 12 , yellowing resistance It was found that the contamination resistance was poor. In addition, among Experimental Examples 1 to 8, particularly for X ¹ in the formula (1), when the counter ion is a sulfonate salt which is an amine ion ( Experimental Example 1), the weather resistance and contamination resistance of the laminated body It was found that the properties were the best.

Further, from the results of Experimental Example 13 , when a polymer having an alkylene oxide and a sodium sulfonate group in the side chain was used as the surfactant (additive), the transparency (haze) of the initial ultraviolet absorbing layer was determined. ) Was found to be bad. From the results of Experimental Example 14 , when a low molecular weight surfactant having a number average molecular weight (Mn) of 195 is used, the transparency (haze) of the initial ultraviolet absorbing layer is excellent, but blocking resistance is improved. It was found that the weather resistance and contamination resistance were poor.

From the results of Experimental Examples 1 to 8 and Experimental Examples 9 and 10 , the content of the surfactant contained in the ultraviolet absorbing resin composition is 0.8 to 5 parts by mass with respect to 100 parts by mass of the ultraviolet absorbing polymer. In this case, the resulting laminate is excellent in weather resistance and stain resistance, whereas when it is less than 0.8 part by mass (0.5 part by mass) ( Experimental Example 9 ), the stain resistance is excellent. It turned out that when the amount exceeds 5 parts by mass (6 parts by mass) ( Experimental Example 10 ), the transparency (haze) of the initial ultraviolet absorbing layer is poor.

From the results of Experimental Examples 4 and 5 and Experimental Examples 15 and 16 , when the content of the ultraviolet absorbing monomer (UVA) in 100% by mass of the monomer composition is 5 to 60% by mass, The resulting laminate is excellent in weather resistance and stain resistance, whereas when it is less than 5% by mass (3% by mass) ( Experimental Example 15 ), the transparency (haze) and resistance of the initial ultraviolet absorbing layer are excellent. It was found that the yellowing property was poor, and when it exceeded 60% by mass (70% by mass) ( Experimental Example 16 ), the transparency (haze) of the initial ultraviolet absorbing layer was poor.

  The UV-absorbing resin composition of the present invention is used for deterioration protection for protecting the contents and the substrate from UV rays, for example, a coating for forming an UV-absorbing layer on a material such as a medicine or food packaging material or a glass bottle. It can be used as an agent. In addition, as a coating agent for preventing discoloration of pigments such as dyes, as a pressure-sensitive adhesive or adhesive when laminating plastic substrates such as fluororesin films, or as a primer for silicone or acrylic hard coat layers Can also be used. Further, it can also be used as a weather-resistant recording liquid, a fiber treatment agent, an insulating coating agent for insulating elements and display elements.

The laminate of the present invention (including the laminate expressed as “film”) is a recording material (for reversible heat sensitive, melt transfer, sublimation transfer, ink jet, heat sensitive, IC card, IC tag, etc.), Packaging materials for chemicals and food, back sheets for solar cells, marking films, photosensitive resin plates, adhesive sheets, dye-sensitized solar cells, polymer solid electrolytes, ultraviolet absorbing insulating films, various optical films (polarizing plate protective films) , Light diffusion film, etc.), film for building materials (glass scattering prevention film, decorative sheet, film for window), indoor / outdoor overlay film (display material, electric signboard), shrink film, etc.

Claims (5)

Following formula (1)
[Wherein, R ¹ represents an alkyl group having 8 to 18 carbon atoms, and X ¹ represents a sulfonate or phosphate whose counter ion is an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or an amine ion. Represents. n represents an integer of 0 to 12. A solvent-based surfactant represented by the formula:
An ultraviolet-absorbing polymer obtained by polymerizing a monomer composition containing 5 to 60% by mass of at least one selected from ultraviolet-absorbing monomers represented by the following formulas (2) to (5), an organic solvent,
The ultraviolet-absorbing resin composition characterized by containing 0.8-5 mass parts with respect to 100 mass parts of ultraviolet-absorbing polymers .
[Wherein R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³ represents an alkylene group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, and X ² represents hydrogen. An atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a nitro group is represented. ]
Wherein, R ⁵ and R ^2, R ⁶ has the same meaning as R ^4, R ⁷ represents a hydrogen atom or a hydroxyl group, R ⁸ represents a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, R ⁹ represents an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having 1 to 10 carbon atoms, and X ³ represents an ester bond, an amide bond, an ether bond, or a urethane bond. m represents 0 or 1; ]
[Wherein, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 2 to 2 carbon atoms. 10 represents an alkenyl group or an alkoxy group having 1 to 10 carbon atoms, X ⁴ represents a hydrogen atom or a methyl group, and A represents — (CH ₂ CH ₂ O) _p —, —CH ₂ CH (OH). _{-CH 2 O -, - (CH} 2) p -O -, - CH 2 CH (CH 2 oR 18) -O -, - CH 2 CH (R 18) -O-, or, -CH ₂ (CH _{2 Q} represents COO—B—O—, R ¹⁸ represents an alkyl group having 1 to 10 carbon atoms, B represents a methylene group, an ethylene group, or —CH ₂ CH (OH) CH ₂ —, and p represents The integer of 1-20 is represented, q represents 0 or 1. ]
[Wherein R ¹⁹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and R ²⁰ represents an element capable of forming a hydrogen bond. R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. ] The ultraviolet-absorbing resin composition according to claim 1, wherein the monomer composition further comprises at least one selected from monomers represented by the following formulas (6) and (7).
[Wherein R ²³ represents a hydrogen atom or a cyano group, R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a methyl group, and R ²⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or carbon. It represents the number 1-6 alkoxy group, X ⁵ represents an oxygen atom or an imino group. ]
[Wherein, R ²⁷ represents a hydrogen atom or a methyl group, and X ⁶ represents a hydrocarbon group having 1 or more carbon atoms. ]   The ultraviolet-absorbing resin composition according to claim 1 or 2, wherein the surfactant has a number average molecular weight (Mn) of 350 to 2,000. The ultraviolet ray absorbing resin composition according to any one of claims 1 to 3 , wherein the ultraviolet ray absorbing polymer is obtained by solution polymerization. The laminated body provided with the ultraviolet absorption layer obtained from the ultraviolet absorptive resin composition of any one of Claim 1 to 4 in the surface of the plastic base material.