JP2008133486A - Resin composition for forming ultraviolet shielding layer and ultraviolet shielding laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which can form a coat having excellent properties as an ultraviolet shielding layer (coat) by finding out a polymer capable of maintaining ultraviolet shielding ability for a long time, in the synthesis of a polymer for forming the ultraviolet shielding layer by using a monomer having a benzotriazole ring or a benzophenone skeleton. <P>SOLUTION: The resin composition forming an ultraviolet shielding layer comprises a polymer synthesized from a monomer mixture comprising a benzotriazole-based ultraviolet absorbing monomer or a benzophenone-based ultraviolet absorbing monomer each having a specific substituent on a specific site and a monomer having a ≥4C alkyl group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition obtained from an ultraviolet-absorbing monomer, for example, by coating an ultraviolet-degradable resin base material such as plastic, and absorbing ultraviolet rays such as sunlight to block the penetration of ultraviolet rays. The present invention relates to a resin composition for forming an ultraviolet shielding layer that prevents coloring, fading, deterioration and the like of a substrate.

  Recently, for example, resin films such as polycarbonate, resin sheets, and resin molded members such as resin plates are excellent in transparency, heat resistance, flame retardancy, etc., so automobile parts, road building materials, building materials, etc. It is widely used in the future, and its use is expected to expand further in the future. However, these resins generally have insufficient weather resistance, and there is a problem that the surface is deteriorated or discolored particularly when exposed to ultraviolet rays.

  In order to solve the above problems, many methods have been proposed in which an ultraviolet absorber is contained in a surface layer such as a primer layer or a surface hardened layer, and ultraviolet rays are absorbed by the surface layer. According to these methods, the deterioration of the base material due to ultraviolet rays can be suppressed to some extent, but low molecular weight ultraviolet absorbers bleed out to the surface of the surface layer and are washed away by rain, etc. There was a problem that Noh could not be expected.

  For these reasons, recently, attempts have been made to synthesize a polymer having ultraviolet absorbing ability using a monomer having an ultraviolet absorbing group, thereby forming an ultraviolet shielding layer. Since the ultraviolet absorbing group is incorporated in the side chain of the high molecular weight polymer, the problem of bleed out as in the case of a low molecular weight ultraviolet absorber does not occur. However, when a benzotriazole ring or a benzophenone skeleton is introduced into a polymer as an ultraviolet absorbing group, a new problem has arisen in that the ultraviolet shielding ability gradually decreases.

  Therefore, in the present invention, in synthesizing a polymer for forming an ultraviolet shielding layer using a monomer having a benzotriazole ring or a benzophenone skeleton, a polymer capable of maintaining the ultraviolet shielding ability over a long period of time has been found. An object of the present invention is to provide a resin composition capable of forming a coating film excellent in performance as a shielding layer (coating film), that is, substrate adhesion, water resistance, alkali resistance, bending resistance, and the like.

  A first type of the resin composition for forming an ultraviolet shielding layer of the present invention is a monomer that essentially includes a benzotriazole-based ultraviolet absorbing monomer represented by the following formula (1) and a monomer having an alkyl group having 4 or more carbon atoms. It has a gist in that it contains a polymer synthesized from a mixture.

［式中、Ｒ¹は水素原子、ハロゲン原子、炭素数１〜８のアルキル基、炭素数１〜４のアルコキシ基、シアノ基またはニトロ基を表し、Ｗ１は炭素数３〜１２のアルキル基または下式（２）で表される基を示し、

[Wherein, R ¹ 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 W1 represents an alkyl group having 3 to 12 carbon atoms or A group represented by the following formula (2):

（Ｒ²は水素結合を形成し得る基を有する結合であり、Ｒ³は水素原子またはメチル基を表す。）
Ｗ１が炭素数３〜１２のアルキル基の場合には、Ｘ１は上記式（２）で表される基を表し、Ｗ１が上記式（２）で表される基の場合には、Ｘ１は水素原子または炭素数１〜８の炭化水素基を表す。］

(R ² is a bond having a group capable of forming a hydrogen bond, and R ³ represents a hydrogen atom or a methyl group.)
When W1 is an alkyl group having 3 to 12 carbon atoms, X1 represents a group represented by the above formula (2), and when W1 is a group represented by the above formula (2), X1 is hydrogen. Represents an atom or a hydrocarbon group having 1 to 8 carbon atoms. ]

  By synthesizing a polymer using a benzotriazole-based monomer having a specific substituent at a specific position represented by the above formula (1) and a monomer having 4 or more carbon atoms that enhances the hydrophobicity of the coating film, the ultraviolet shielding ability is improved. Maintenance over a long period of time has become possible.

  It is a particularly preferred embodiment of the present invention that the monomer having an alkyl group having 4 or more carbon atoms is a (meth) acrylate represented by the following formula (5). It is excellent in copolymerizability with the benzotriazole-based monomer and can improve the physical properties of the coating film.

（式中、Ｒ⁸は水素原子またはメチル基を表し、Ｙは炭素数が４以上のアルキル基を表す。）

(In the formula, R ⁸ represents a hydrogen atom or a methyl group, and Y represents an alkyl group having 4 or more carbon atoms.)

  In synthesizing the polymer, it is also preferable that the monomer mixture (I) further contains a monomer having a UV-stable group, and a higher UV-blocking ability can be obtained.

  The present invention also includes an ultraviolet shielding laminate in which an ultraviolet shielding layer formed from the ultraviolet shielding layer-forming resin composition of the present invention is laminated on an ultraviolet-degradable resin substrate.

  In the present invention, by using a UV-absorbing monomer having a specific substituent at a specific position and a monomer having an alkyl group having 4 or more carbon atoms to enhance the water resistance of the coating film, We succeeded in suppressing the decomposition of UV-absorbing groups by light and water.

  For this reason, since the ultraviolet shielding layer formed from the resin composition for forming an ultraviolet shielding layer of the present invention exhibits the ultraviolet shielding ability over a long period of time, the ultraviolet shielding can be achieved by applying it to a base material that deteriorates due to ultraviolet rays. Can be manufactured.

  The present inventors examined why the ultraviolet shielding effect of a polymer using a benzotriazole monomer deteriorates with time. In a benzotriazole-based compound, a hydrogen atom of the hydroxyl group at the 2-position of the benzene ring linked to the benzotriazole ring and a nitrogen atom of the benzotriazole ring form a kind of ring, and this ring portion is It is believed that the ability to absorb ultraviolet light is exhibited by absorbing light energy and converting it into heat energy. However, if the formation of an intramolecular hydrogen bond between the hydrogen atom of the hydroxyl group at the 2-position of the benzene ring and the nitrogen atom of the benzotriazole ring is hindered for some reason, the ultraviolet absorbing ability is not exhibited.

  As a hydrogen bond inhibiting factor, for example, a hydroxyl group such as a polyisocyanate curing agent (crosslinking agent) having a reactivity with a hydroxyl group is contained in the resin composition, so that the hydroxyl group at the 2-position of the benzene ring is consumed. It has been considered that this hydroxyl group may form a complex in the presence of a metal ion. Furthermore, it has been found that the benzotriazole ring itself is decomposed by the action of light and water.

  Also in the case of a benzophenone-based monomer, at least one benzene ring connected by a carbonyl group has a hydroxyl group at the 2-position, and forms a hydrogen bond with a carbonyl oxygen atom to form a ring. Therefore, it was considered that the mechanism for demonstrating the ultraviolet absorbing ability and the mechanism for decreasing the ultraviolet absorbing ability over time due to consumption of hydroxyl groups are the same as in the case of the benzotriazole monomer. It was also found that the benzophenone skeleton was decomposed by light and water, resulting in a decrease in ultraviolet absorption ability.

  Therefore, the present inventors combined the effects of consumption of the hydroxyl group at the 2-position and decomposition of the UV-absorbing group with light and water, and the UV-absorbing ability of the benzotriazole-based and benzophenone-based monomers decreased with time. As a result of conclusion and diligent study, the present invention has been conceived.

  That is, the present invention synthesizes a polymer having ultraviolet shielding ability from a monomer mixture (I) that essentially contains a benzotriazole monomer having a specific substituent at a specific position and a monomer having an alkyl group having 4 or more carbon atoms. Or a resin composition for forming an ultraviolet shielding layer containing this (first type), or a benzophenone-based monomer having a specific substituent at a specific position and a monomer having an alkyl group having 4 or more carbon atoms. A polymer having ultraviolet ray shielding ability is synthesized from the monomer mixture (II) containing the resin composition for forming an ultraviolet ray shielding layer containing the polymer (second type).

  A benzotriazole monomer and a benzophenone monomer having a specific substituent at a specific position are compounds having a bulky substituent having a high steric hindrance such as W1 or W2 at the 3-position adjacent to the hydroxyl group at the 2-position of the benzene ring. is there. The presence of W1 or W2 at the 3-position prevents the hydroxyl group at the 2-position from binding to a compound or metal ion that is reactive with the hydroxyl group, so that the hydroxyl group may be consumed. As a result, ring formation between the hydrogen atom of the hydroxyl group at the 2-position and the nitrogen atom in the benzotriazole ring, or ring formation between the hydrogen atom of the hydroxyl group at the 2-position and the oxygen atom of the carbonyl group of the benzophenone skeleton The ultraviolet absorptivity by this was maintained over a long period of time. Furthermore, coloring and the like when immersed in an alkaline solution could be prevented.

  In addition, a monomer having an alkyl group having 4 or more carbon atoms can suppress the decomposition of the benzotriazole ring and the benzophenone skeleton, which are considered to be decomposed by light and water, in order to increase the water resistance of the coating film. It was. Hereinafter, the present invention will be described in more detail.

(i) Benzotriazole-based UV-absorbing monomer (hereinafter referred to as (A1))
The benzotriazole-based ultraviolet absorbing monomer (A1) used in the present invention is represented by the following formula (1).

（式中、Ｒ¹、Ｗ１、Ｘ１は前記と同じ意味である。）

(In the formula, R ¹ , W 1 and X ¹ have the same meaning as described above.)

  W1 is an alkyl group having 3 to 12 carbon atoms or a group represented by the following formula (2).

（式中、Ｒ²、Ｒ³は前記と同じ意味である。）

(In the formula, R ² and R ³ have the same meaning as described above.)

  As described above, W1 functions as a steric hindrance group that prevents consumption of the hydroxyl group at the 2-position of the benzene ring linked to the benzotriazole ring. For this reason, it must be located in the third place. Moreover, if it is an alkyl group, the one where carbon number is more and the one where it branched is preferable. The group represented by the above formula (2) is a part having a group capable of forming a hydrogen bond with a (meth) acryloyl group having a radically polymerizable unsaturated double bond, and introduces a benzotriazole ring into the polymer. This is an essential group for this purpose, but it is sufficiently bulky, so when W1 is this group, there may be no further steric hindrance group, and X1 may be a hydrogen atom. Of course, there may be another alkyl group having 3 to 12 carbon atoms at positions other than the 3rd position.

  Specific examples of the alkyl group having 3 to 12 carbon atoms include propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, heptyl group, octyl group. Is a alicyclic alkyl group such as a straight chain or branched alkyl group or a cyclohexyl group such as a group, a tert-octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group or a dodecyl group. In particular, the tert-octyl group represented by the following formula is very bulky and most preferable.

R ² in the case where W 1 is a group represented by the formula (2) must be a bond having a group capable of forming a hydrogen bond. This R ² has a function of forming hydrogen bonds between the polymer molecules after synthesis and improving the physical properties (flexibility, water resistance, etc.) of the coating film. Specific examples of R ² 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. When a crosslinking agent (curing agent) that is reactive with an amino group or a hydroxyl group is added to the resin composition, the amino group or hydroxyl group in R ² reacts with the crosslinking agent and chemically bonds, Although intermolecular hydrogen bonds may not be formed, the effect of improving the physical properties of the coating film is the same as that of forming intermolecular hydrogen bonds as a result of chemical bonding. is not. Among R ² , —NH— and —CH ₂ NH— containing a nitrogen atom having active hydrogen are particularly preferable.

  Preferable specific examples of the benzotriazole monomer (A1) include 2- [2′-hydroxy-3 ′-(meth) acryloylaminophenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′-( (Meth) acryloylaminomethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′-(meth) acryloylamino-5′-tert-octylphenyl] -2H-benzotriazole, 2- [2′- Hydroxy-3 '-(meth) acryloylaminomethyl-5'-tert-octylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-octyl-5'-(meth) acryloylaminophenyl ] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-octyl-5 ' (Meth) acryloylaminomethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(3- (meth) acryloyloxy-2-hydroxypropoxy) -3′-tert-butylphenyl] -2H -A benzotriazole etc. are mentioned, Monomer mixture (I) can contain these 1 type (s) or 2 or more types.

  These monomers (A1) can be synthesized, for example, by a method of reacting a corresponding benzotriazole (commercially available as an ultraviolet absorber) with (meth) acrylic acid chloride.

(ii) Benzophenone-based ultraviolet absorbing monomer (hereinafter referred to as (A2))
The benzophenone monomer (A2) used in the present invention is represented by the following formula (3).

［式中、Ｒ^４は水素原子または水酸基を表し、Ｒ^５は水素原子または炭素数１〜６のアルコキシ基を表し、Ｗ２は炭素数３〜１２のアルキル基または下式（４）で表される基を示し、

[Wherein R ⁴ represents a hydrogen atom or a hydroxyl group, R ⁵ represents a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, and W2 is represented by an alkyl group having 3 to 12 carbon atoms or the following formula (4): Group

(R ⁶ is a bond having a group capable of forming a hydrogen bond, and R ⁷ represents a hydrogen atom or a methyl group.)
When W2 is an alkyl group having 3 to 12 carbon atoms, X2 represents a group represented by the above formula (4), and when W2 is a group represented by the above formula (4), X2 is hydrogen. Represents an atom or a hydrocarbon group having 1 to 8 carbon atoms. ]

The meanings and preferred groups of W2, R ⁶ , R ⁷ and X2 are the same as the meanings and preferred groups of W1, R ² , R ³ and X1 in the benzotriazole monomer (A1), respectively. Preferable specific examples of the benzophenone monomer (A2) include 2-hydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] -3-propylbenzophenone, 2-hydroxy-4- [3- (meta ) Acryloyloxy-2-hydroxypropoxy] -3-tert-butylbenzophenone and the like, and the monomer mixture (II) may contain one or more of these.

  These monomers (A2) can be synthesized, for example, by a method such as reacting glycidyl (meth) acrylate with a corresponding benzophenone (commercially available as an ultraviolet absorber).

(iii) Monomer having an alkyl group having 4 or more carbon atoms (hereinafter referred to as (B))
Specifically, the monomer (B) is preferably a (meth) acrylate represented by the following general formula (5).

（式中、Ｒ⁸、Ｙは前記と同じ意味である）。

(Wherein R ⁸ and Y have the same meaning as described above).

  The monomer (B) has an effect of increasing the hydrophobicity of the obtained polymer and suppressing the decomposition of the benzotriazole ring and the benzophenone skeleton by the action of water and light. The water resistance of the coating film is also improved. Therefore, the alkyl group linked to the ester bond of (meth) acrylate must be highly hydrophobic, and Y must be an alkyl group having 4 or more carbon atoms. Furthermore, (meth) acrylates are preferable because they are originally excellent in weather resistance and excellent in copolymerizability with the benzotriazole monomers and benzophenone monomers.

  Specific examples of the substituent represented by Y in the above formula are alicyclic hydrocarbon groups having 4 or more carbon atoms such as cyclohexyl group, methylcyclohexyl group, and cyclododecyl group; butyl group, isobutyl group, tert-butyl group A linear or branched alkyl group having 4 or more carbon atoms such as 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, pentadecyl group and octadecyl group; And a polycyclic hydrocarbon group having 4 or more carbon atoms such as an isobornyl group. A larger carbon number is preferred because hydrophobicity increases, and among these, an alicyclic hydrocarbon group, a branched alkyl group, and a linear alkyl group having 6 or more carbon atoms are particularly preferred.

  More specific examples of the monomer represented by the general formula (5) include, for example, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. One or two or more of these can be used as components of the monomer mixture (I) or (II).

  The monomer mixture (I) used in the first type of the present invention includes the monomer (A1) and the monomer (B), and the monomer mixture (II) used in the second type includes the monomer (A2). And the monomer (B) are essential, but the monomer (B) used in the monomer mixture (I) and the monomer mixture (II) may be the same or different compounds. Further, the monomer (A2) may be used in combination in the monomer mixture (I), and conversely, the monomer (A1) may be used in combination in the monomer mixture (II). Furthermore, you may use the following monomers together as needed.

(iv) Monomer having an ultraviolet-stable group (hereinafter referred to as (C))
When the monomer (C) having a UV-stable group is copolymerized, UV stability is imparted to the coating film. In addition, the effect of suppressing the photodecomposition of the UV-absorbing groups of the monomers (A1) and (A2) is further enhanced, and the UV shielding performance is maintained for a long period. The monomer (C) having a UV-stable group is not particularly limited as long as it has a polymerizable double bond and a UV-stable group in the molecule at the same time. It is a monomer represented by (C-1) or (C-2).

（式中、Ｒ⁹は水素原子またはシアノ基を表し、Ｒ¹⁰、Ｒ¹¹はそれぞれ独立して水素原子またはメチル基を表し、Ｒ¹²は水素原子または炭化水素基を表し、Ｚ１は酸素原子またはイミノ基を表す。）

(Wherein R ⁹ represents a hydrogen atom or a cyano group, R ¹⁰ and R ¹¹ each independently represents a hydrogen atom or a methyl group, R ¹² represents a hydrogen atom or a hydrocarbon group, and Z 1 represents an oxygen atom or Represents an imino group.)

（式中、Ｒ¹³は水素原子またはシアノ基を表し、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷はそれぞれ独立して水素原子またはメチル基を表し、Ｚ２は酸素原子またはイミノ基を表す。）

(In the formula, R ¹³ represents a hydrogen atom or a cyano group, R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a methyl group, and Z 2 represents an oxygen atom or an imino group.)

  Specific examples of the monomer (C-1) include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetra. Methylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 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-2,2,6 , 6-Tetramethylpiperidine and the like are mentioned without limitation, and these may be used alone or in combination of two or more as necessary.

  Specific examples of the monomer (C-2) include 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano. Non-limiting examples include -4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like. These may be used alone or in combination of two or more as necessary.

(v) Other monomer (hereinafter referred to as (D))
In the present invention, in both the first and second types, the monomer (B) having an alkyl group having 4 or more carbon atoms is an essential component, but in order to change the design of the physical properties of the coating film depending on the application, A monomer having an alkyl group having 3 or less carbon atoms can be used in combination. Specific examples include methyl (meth) acrylate and ethyl (meth) acrylate. These (meth) acrylates are excellent in copolymerization with the monomers (A1), (A2), (B) and (C) described above, and are hard and form a shielding layer excellent in water resistance and mechanical strength. It is easy to use because it is inexpensive and plays a role. Among them, when using a polycarbonate resin, an acrylic resin, or a polyester resin as a base material when forming an ultraviolet shielding laminate, a coating film excellent in adhesion with the base material is formed. Methyl methacrylate is particularly preferred. However, since methyl methacrylate has a slightly low hydrophobicity, if it is used in a large amount, the effect of preventing the ultraviolet absorbing monomer from being decomposed by water and light is hardly exhibited. Therefore, the ultraviolet absorbing monomer (A1) or (A2) and the carbon number The total amount (mass) with the monomer (B) having 4 or more alkyl groups is preferably used in the same amount or less.

  Further, for the purpose of adjusting the physical properties of the coating film, the ultraviolet shielding layer may be crosslinked by synthesizing a polymer using a monomer having a crosslinkable functional group and blending a curing agent (crosslinking agent) separately. Specific examples of the monomer having a crosslinkable functional group include monomers having a carboxyl group such as (meth) acrylic acid, itaconic acid and maleic anhydride; acidic phosphate esters such as 2- (meth) acryloyloxyethyl acid phosphate Monomer: Epoxy group-containing (meta) such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, alicyclic epoxy group-containing (meth) acrylate (for example, manufactured by Daicel Chemical Industries, Ltd .; trade name “CYCLOMER M-100”) ) Acrylate; activity of 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyl-terminated flexible (meth) acrylate (for example, manufactured by Daicel Chemical Industries, Ltd .; trade name “Placcel FM”) Mono having a hydrogen (hydroxyl) group Chromatography and the like can be used.

  Among these, it is preferable to use a hydroxyl group-containing monomer and to contain a polyisocyanate as a curing agent in the resin composition for an ultraviolet shielding layer and to crosslink the ultraviolet shielding layer by a reaction between the hydroxyl group and the isocyanate group. In the present invention, since the ultraviolet absorbing monomer (A1) or (A2) having a steric hindrance group at a specific position is used as described above, the ultraviolet absorbing ability is lowered even if a crosslinking agent capable of reacting with a hydroxyl group is used. Such inconvenience does not occur.

  Furthermore, for the purpose of adjusting film properties, nitrogen-containing monomers such as (meth) acrylamide, imide (meth) acrylate and N-methylol (meth) acrylamide; two polymerizable doubles such as ethylene glycol di (meth) acrylate Monomer having a bond; Halogen-containing monomer such as vinyl chloride; Aromatic monomer such as styrene and α-methylstyrene; Vinyl ether; Triazine-based UV-absorbing monomer; Reaction of 3- (meth) acryloyloxypropyltrimethoxysilane Monomers such as reactive silyl group-containing monomers can also be used.

  The above is the monomer that can be used as the monomer mixture (I) used in the first type of the present invention and the monomer mixture (II) used in the second type.

  Preferred amounts of each monomer that can be used in the monomer mixture (I) or (II) are as follows. In addition, the following amount range is a standard of the preferable usage amount of each monomer when selecting so that the total amount of the monomer to be used may be 100 mass%.

  The benzotriazole-based ultraviolet absorbing monomer (A1) and the benzophenone-based ultraviolet absorbing monomer (A2) are both 0.1% by mass or more (more preferably 5% by mass or more) and 70% by mass or less (more preferably 50%). Mass% or less) is preferred. If the amount is too small, the ultraviolet shielding ability is insufficient. Further, when the amount of the monomer (A1) or (A2) is too small and the amount of the monomer (B) having an alkyl group having 4 or more carbon atoms is increased, it is preferable because the coating film becomes hard and flexibility is lowered. Absent. On the contrary, when the amount of the monomer (A1) or (A2) is too large, the monomer (B) for improving the water resistance is relatively decreased, and the water resistance is lowered, which is not preferable.

  The monomer (B) having an alkyl group having 4 or more carbon atoms is preferably 3% by mass or more (more preferably 5% by mass or more) and 80% by mass or less (more preferably 60% by mass or less). If the amount is too small, the effect of addition will not be exhibited, and the water resistance and weather resistance will be insufficient.

  The monomer (C) having a UV-stable group is preferably 0.1% by mass or more (more preferably 0.5% by mass or more) and 20% by mass or less (more preferably 10% by mass or less). If the amount is too small, the effect of improving the weather resistance is not exhibited. If the amount is too large, the monomer (B) for improving the water resistance is relatively decreased, which is not preferable because the water resistance is lowered.

  The amount of other monomer (D) to be used may be appropriately adjusted according to the type of the product and the application / required characteristics of the product.

  By polymerizing the monomer mixture (I) described so far, an essential polymer is synthesized in the first type resin composition, and by polymerizing the monomer mixture (II), the second type resin composition is synthesized. The essential polymer is synthesized.

  The polymerization method is not particularly limited, and known polymerization methods such as solution polymerization method, dispersion polymerization method, suspension polymerization method, emulsion polymerization method and the like can be used. The solution polymerization method is a preferable polymerization method because the resin composition of the present invention can be obtained by directly or diluting the obtained reaction product. Solvents used for solution polymerization include toluene, xylene, and other aromatic solvents; alcohol solvents such as n-butyl alcohol, propylene glycol methyl ether, diacetone alcohol, ethyl cellosolve; butyl acetate, ethyl acetate, cellosolve Ester solvents such as acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; dimethylformamide and the like can be used. The kind of solvent to be used is not limited to these. These solvents may be used alone, or two or more may be used as a mixed solvent. The amount of solvent used is determined in consideration of the monomer concentration, the desired molecular weight of the polymer, the polymer solution concentration, and the like. What is necessary is just to determine suitably.

  When the monomer mixture (I) or (II) is polymerized, a polymerization initiator is usually used. Examples of the polymerization initiator include 2,2′-azobis- (2-methylbutyronitrile), tert-butylperoxy-2-ethylhexanoate, 2,2′-azobisisobutyronitrile, benzoyl Known radical polymerization initiators such as peroxide and di-tert-butyl peroxide can be used. The amount of the polymerization initiator to be used should be appropriately determined according to the required properties of the polymer and is not particularly limited, but is 0.01% by mass or more, 50% with respect to the total amount of the monomer mixture (I) or (II). It is preferably at most mass%, more preferably at least 0.05 mass% and at most 20 mass%. If necessary, for example, one or more chain transfer agents such as n-dodecyl mercaptan may be added to adjust the molecular weight of the polymer.

  The temperature of the polymerization reaction is not particularly limited, but is preferably in the range of room temperature to 200 ° C, more preferably 40 to 140 ° C. 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 mixture to be used, the kind of polymerization initiator, etc.

  The molecular weight of the polymer is not particularly limited, but is preferably 2,000 to 1,000,000 in terms of weight average molecular weight (Mw). A more preferable lower limit of Mw is 5,000, and a more preferable lower limit is 10,000. A more preferable upper limit of Mw is 800,000, and a more preferable upper limit is 500,000. A weight average molecular weight here means the value calculated | required on the basis of standard polystyrene using GPC.

  The first type of resin composition contains a polymer obtained from the monomer mixture (I), and the second type of resin composition contains a polymer obtained from the monomer mixture (II). However, in any case, from the viewpoint of workability during coating, a solution state in which a polymer is dissolved in a solvent is preferable. As the solvent, any of the solvents exemplified in the solution polymerization can be used. When the polymer is synthesized by a method other than solution polymerization, after polymerization, the polymer may be collected and dissolved in a solvent.

  Various additives may be included in the resin composition of the present invention (in the following description, the first and second types of resin compositions are simply represented by the resin composition). Hereinafter, compounds that can be suitably used as additives will be described.

Curing agent When the polymer is obtained from the monomer mixture (I) or (II) containing a monomer having a crosslinkable functional group among the other monomers (D) described above, the functional group capable of reacting with the functional group of the monomer. It is preferable to add a curing agent having a group (crosslinking agent) to the resin composition to cause a crosslinking reaction in forming a coating film, thereby improving various characteristics of the ultraviolet shielding layer. Various known curing agents can be used depending on the functional group of the monomer used. The amount of these curing agents used is not particularly limited, and may be appropriately increased or decreased depending on the amount of monomers used (the amount of functional groups in the polymer).

  When a hydroxyl group-containing monomer is used as the monomer having a crosslinkable functional group, a rapid crosslinking and curing reaction can be achieved by using a polyisocyanate compound having two or more isocyanate groups or a modified product thereof or an aminoplast resin as a curing agent. Is the preferred embodiment.

  Specific examples of the polyisocyanate compound include known diisocyanate compounds such as tolylene diisocyanate (TDI) and 4,4′-diphenylmethane diisocyanate (MDI); bullet polyisocyanates such as “Sumijour N” (manufactured by Sumitomo Bayer Urethane Co., Ltd.) Compound: Polyisocyanate compound having an isocyanurate ring known as “Desmodur IL”, “Desmodur HL” (all manufactured by Bayer AG), “Coronate EH” (manufactured by Nippon Polyurethane Industry), etc .; Adduct polyisocyanate compounds such as “Sumijour L” (manufactured by Sumitomo Bayer Urethane Co., Ltd.); adduct polyisocyanate compounds such as “Coronate L” and “Coronate L-55E” (both manufactured by Nippon Polyurethane Co., Ltd.), and the like. 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.

  Examples of aminoplast resins include methyl etherified melamine resins, butyl etherified melamine resins, butyl etherified benzoguanamine resins, butyl etherified cyclohexyl benzoguanamine resins, and water-soluble products thereof.

Ultraviolet stabilizer When a polymer is synthesized without using the monomer (C) having the above-described ultraviolet stabilizer group, an additive type ultraviolet stabilizer can also be used. Preferred addition type UV stabilizers are sterically hindered piperidine compounds. For example, commercially available products such as “Tinuvin 123”, “Tinuvin 144”, “Tinuvin 765” (all manufactured by Ciba Specialty Chemicals), etc. Is mentioned. In addition, since these relatively low molecular weight UV stabilizers may bleed out, a polymer type UV stabilizer is separately synthesized from the monomer (C) having the UV stabilizing group and added. May be.

  A preferable blending amount of the ultraviolet stabilizer is in a range of 0.1 to 20% by mass with respect to 100% by mass of the polymer. If it is less than 0.1% by mass, the ultraviolet shielding ability may not be maintained for a long time, but if it exceeds 20% by mass, it is not preferable because it tends to bleed out or reduce water resistance.

Other resins Other resin may coexist in the resin composition as long as the object of the present invention is not impaired. Examples thereof include a thermosetting resin that is crosslinked and cured by the action of a thermoplastic resin or the resin itself or a curing agent (crosslinking agent). What is necessary is just to determine suitably the kind and usage-amount of these other resin according to the use, required characteristic, etc. of a ultraviolet-ray shielding resin laminated body. Specific examples of other resins include thermoplastic resins such as vinyl chloride resins, polyester resins, acrylic resins, and silicone resins; urethane resins, aminoplast resins, silicone resins, epoxy resins, and acrylic resins. Examples thereof include single-curing heat / ultraviolet / electron beam curable resins such as resins; thermosetting resins that are cured by a curing agent such as polyester resins, acrylic resins, and epoxy resins.

Other additives Leveling agents, antioxidants, fillers such as talc, rust inhibitors, fluorescent whitening agents, antioxidants, antistatic agents, pigments, etc. Inorganic fine particles such as dyes, thickeners, colloidal silica, and alumina sol, or polymethyl methacrylate acrylic fine particles may be added. Further, composite inorganic fine particles in which an organic polymer is fixed to the surface of the inorganic fine particles as described in JP-A-7-178335 and 9-302257 can also be added. Furthermore, as long as the object of the present invention is not inhibited, a part of organic ultraviolet absorbers such as benzotriazole, benzophenone, triazine, and indole, and inorganic ultraviolet absorbers such as zinc oxide may be included. Absent.

  The resin composition of the present invention is used for forming an ultraviolet shielding layer by forming an ultraviolet shielding layer on the surface side of a substrate. At this time, it is formed on the surface of the substrate directly or as necessary via an adhesion improving layer (primer layer, etc.), a printing layer, a heat ray shielding layer, an adhesive layer, a gas barrier layer such as a (semi) transparent inorganic vapor deposition film, etc. can do. The amount of the above various additives is regulated so that the polymer according to the present invention in 100% by mass of the dried coating film (ultraviolet shielding layer) obtained from the resin composition is contained by 50% by mass or more, preferably 80% by mass or more. It is desirable. If it is less than 50% by mass, the weather resistance of the coating film may be insufficient.

Hereinafter, the ultraviolet shielding laminate formed by using the resin composition of the present invention will be described. The most suitable substrate is a resin that is easily deteriorated by ultraviolet rays, and such a resin substrate requires the ultraviolet shielding layer of the present invention. Degradation due to ultraviolet rays means that the chemical structure such as the formation of a gel due to cross-linking, resulting in a decrease in mechanical strength and transparency, or yellowing, as a result of changes in molecular weight, such as the formation of gels by crosslinking. It means that the physical properties are lowered. Examples of such resins include polycarbonate resins, polyarylate resins, acrylic resins, polyolefin resins, polyester resins, ABS resins, polystyrene resins, vinyl chloride resins, and the like. Among these, polycarbonate resins, polyester resins, and acrylic resins that are inexpensive, light, durable, and excellent in transparency are preferable.

  The shape and manufacturing method of the resin base material may be anything, and there is no particular limitation, but highly versatile ones are plate-like, curved-plate-like, corrugated-plate-like, or film-like ones. . Moreover, it is also possible to use the resin base material with the design which gave printing, such as wood grain printing. Furthermore, for the purpose of protecting contents such as a container made of an inorganic transparent substrate such as glass from ultraviolet rays, an ultraviolet shielding layer can be provided on the front side of the inorganic transparent substrate.

  As a method for applying the UV shielding layer forming resin composition to the substrate, known coating methods such as dipping, spraying, brush coating, curtain flow coating, gravure coating, roll coating, spin coating, bar coating, electrostatic coating, etc. Any method can be adopted.

  The thickness of the ultraviolet shielding layer depends on the amount of the ultraviolet absorbing group introduced into the polymer, that is, the amount of the ultraviolet absorbing monomer (A1) or (A2) used in the polymerization, according to Lambert-Beer's law. . Therefore, the thickness of the layer may be determined in consideration of the amount of the ultraviolet absorbing group in the polymer and the weather resistance and ultraviolet shielding performance required for the ultraviolet shielding laminate. Usually, it exists in the range of 0.5-500 micrometers. When the thickness exceeds 500 μm, the ultraviolet absorption performance is saturated, which is wasteful in cost. On the other hand, when the thickness is less than 0.5 μm, it is difficult to uniformly coat the substrate, and the ultraviolet shielding ability may be insufficient. A more preferable thickness range is 1 to 300 μm, and more preferably 2 to 50 μm.

  The drying temperature when the resin composition of the present invention is applied to a substrate in a thin film to form an ultraviolet shielding layer can be appropriately changed depending on whether or not a curing agent (crosslinking agent) is blended in the resin composition. In general, it is generally preferable to dry at room temperature to 200 ° C.

  Even if the laminate of the present invention has a laminated structure of a substrate and an ultraviolet shielding layer (other layers described above may be present between the substrate and the ultraviolet shielding layer), the ultraviolet shielding layer is water resistant. Since it is excellent in various properties such as property, strength, and weather resistance, it can be utilized for various applications as it is. However, for use in applications such as window glass, a structure having a hard coat layer on the surface layer (the side opposite to the substrate) of the ultraviolet shielding layer is preferable in order to further increase the scratch resistance and surface hardness. The hard coat layer is preferably formed using a resin capable of forming a coating film having high hardness and excellent scratch resistance, and is not particularly limited as long as it is such a resin, but JP-A-2000-177070. Silicone curable resins and organic curable resins as disclosed in the publication can be preferably used.

  The laminate of the present invention may be provided with a heat ray shielding layer in the laminate structure or on the outermost layer of the laminate together with or without using the hard coat layer. When used as a window material for automobiles or buildings, it is effective in reducing the heating and cooling costs by preventing the deterioration of ultraviolet rays in the interior and interior of the vehicle and preventing the temperature increase in the interior and interior of the vehicle. It is also effective to form a photocatalytic functional layer for improving contamination resistance; a gas barrier layer; a conductive layer, a magnetic layer, etc .; an antifogging layer, etc., in the laminate structure or on the outermost layer of the laminate. Furthermore, the ultraviolet shielding layer of the present invention is formed as an intermediate layer between two substrates such as an organic substrate and an inorganic substrate, and can be used as a laminated glass.

  In order to form the heat ray shielding layer, for example, a method in which a heat ray shielding substance is dispersed inside the substrate, or a coating material containing the heat ray shielding substance is applied to one side or both sides of the substrate can be employed. Moreover, you may add the heat ray shielding substance in the resin composition of this invention, and may form the layer which can shield an ultraviolet-ray and a heat ray simultaneously.

  The heat ray shielding material is not particularly limited as long as it is a material having absorption in the infrared region, but depending on the application, it is desirable to have a small color in the visible light region (400 to 700 nm) and a large molar extinction coefficient. One kind or a combination of two or more kinds of known organic and inorganic heat ray shielding substances can be used. Further, depending on the application, a substance having absorption in the visible light region may be used in combination in order to perform color matching in the visible light region or to color the target color.

  The resin composition for forming an ultraviolet shielding layer of the present invention can also be used as a transfer sheet for forming an ultraviolet shielding layer on the surface of a molded product. For example, a transfer sheet having a structure in which a layer (ultraviolet shielding layer) made of the resin composition for forming an ultraviolet shielding layer of the present invention is formed on one side of a base film and an adhesive layer is further laminated thereon. After the transfer sheet is brought into close contact with the surface of the molded product and heat-bonded, if the base film is peeled off to cure the ultraviolet shielding layer, an ultraviolet shielding layer that also functions as a surface protective layer is formed on the molded product surface. The Between the ultraviolet shielding layer and the adhesive layer, a decorative layer on which a pattern, a character, or the like is printed may be provided as necessary.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples, and may be implemented with appropriate modifications within a range that can meet the purpose described above and below. All of these are possible within the scope of the present invention. In the following examples and comparative examples, “parts” and “%” represent parts by mass or mass%.

Synthesis example 1
In a flask equipped with a stirrer, a dripping port, a thermometer, a condenser tube and a nitrogen gas inlet tube, 20 parts of ethyl acetate and 2- (2′-hydroxy-5′-methacryloylaminomethyl-3′-tert-octylphenyl) 10 parts of -2H-benzotriazole (referred to as UVA (i)) was charged, nitrogen gas was introduced, and the mixture was heated to reflux temperature with stirring. Separately, 30 parts of cyclohexyl methacrylate (CHMA), 10 parts of 2-ethylhexyl acrylate (2EHA), 20 parts of methyl methacrylate (MMA), 10 parts of butyl acrylate (BA), 15 parts of 2-hydroxyethyl methacrylate (HEMA) and the UVA ( i) A mixture was prepared by dissolving 5 parts and 3 parts of 2,2′-azobis- (2-methylbutyronitrile) as an initiator in 80 parts of ethyl acetate, and the resulting mixture was stirred for 1 hour. It was dripped over. After the addition, the mixture was further heated for 6 hours, diluted with 50 parts of ethyl acetate, and polymer solution No. 4 having a nonvolatile content concentration of 40.0%. 1 was obtained. The weight average molecular weight (Mw) of this polymer was 17,000. In each synthesis example, the non-volatile content concentration is a value measured by weighing 1 g of a polymer solution and heating and drying at 200 ° C. for 15 minutes, and the weight average molecular weight is a value obtained using GPC as a standard polystyrene. is there. Table 1 summarizes the types of monomers and the charge / mixing amount.

Polymer synthesis examples 2 to 10
As shown in Table 1, the polymer solution No. was changed in the same manner as in the above Polymer Synthesis Example 1 except that the monomer type and the charged amount were changed. 2 to 10 were produced, and their characteristics are shown in Table 1.

In addition, the abbreviation in Table 1 has the following meaning.
UVA (i): 2- (2′-hydroxy-5′-methacryloylaminomethyl-3′-tert-octylphenyl) -2H-benzotriazole UVA (ii): 2- (2′-hydroxy-3′-methacryloyl) Aminomethyl-5′-tert-octylphenyl) -2H-benzotriazole UVA (iii): 2- (2′-hydroxy-3′-methacryloylaminomethylphenyl) -2H-benzotriazole UVA (iv): 2- ( 2'-hydroxy-3'-methacryloylamino-5'-tert-octylphenyl) -2H-benzotriazole UVA (v): 2- (2'-hydroxy-5'-methacryloylaminomethylphenyl) -2H-benzotriazole UVA (vi): 2-hydroxy-4- (3-methacryloyloxyethoxy-2-hydroxypropoxy) -3- ert-Butylbenzophenone UVA (vii): 2-hydroxy-4- (2-acryloyloxyethoxy) benzophenone CHMA: cyclohexyl methacrylate 2EHA: 2-ethylhexyl acrylate t-BMA: tert-butyl methacrylate BA: butyl acrylate HALS: 2, 2 , 6,6-pentamethyl-4-piperidyl methacrylate (made by Asahi Denka Kogyo Co., Ltd .; trade name “ADK STAB LA87”)
MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate

Experimental Examples 1-7 and Comparative Experimental Examples 1-3
Polymer solution Nos. Obtained in Polymer Synthesis Examples 1 to 5 and 7 to 10 were used. 1 to 5 and 7 to 10 are blended with an isocyanate curing agent (“N3200”; manufactured by Sumitomo Bayer Urethane Co., Ltd.) such that the isocyanate group is 1 equivalent with respect to 1 equivalent of the hydroxyl group in the polymer. Dilute to a final non-volatile content of 20%. Polymer solution No. obtained in Polymer Synthesis Example 6 No. 6 was diluted with toluene until the nonvolatile content concentration became 20% without blending the curing agent. The obtained solution was applied to a polyethylene terephthalate (PET) film (“E5101”; manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm so that the dry thickness was 5 μm (No. 5 was 20 μm, No. 6 was 2 μm). And dried at 80 ° C. for 2 hours. A laminated film test piece on which a cured coating film (ultraviolet shielding layer) was formed was obtained. The following items were evaluated in each experimental example, and the results are shown in Table 2.

(1) Adhesion 100 grids (1 mm ² ) are engraved on the cured coating of the laminated film test piece, the cellophane tape is adhered to the grid part, and then the adhered cellophane tape is peeled away from the test piece. The test piece was peeled off by hand so as to form a right angle, and the appearance of the test piece was evaluated according to the following criteria while taking into account the number of peeled grids.
○: No abnormality, Δ: Grids slightly peeled, X: All grids peeled.

(2) Water resistance After the laminated film specimen was immersed in warm water at 80 ° C. for 30 days, it was taken out and the appearance of the cured coating film was evaluated according to the following criteria, and the adhesion was also evaluated according to the criteria (water resistance adhesion) ).
○: No abnormality, △: Slightly glossy or whitened, ×: Overall glossy / whitened

(3) Alkali resistance The laminated film test piece was immersed in a 0.1N NaOH aqueous solution at 40 ° C., and the coating film appearance and adhesion after 10 days and 20 days were evaluated according to the following criteria.
○: No abnormality, Δ: Slightly colored, ×: Whole colored

(4) Flexibility The laminated film test piece was bent 180 degrees, and the appearance of the bent portion was visually evaluated according to the following criteria. In addition, the bending resistance was also evaluated after 8 cycles of exposure under the conditions described below.
○: No abnormality, △: Slight whitening, ×: Whitening of the entire bent part

(5) Weather resistance 1 (Retention rate of tensile strength and elongation)
Using a temperature variable tension tester (“Shimadzu Autograph AGS-100D”; manufactured by Shimadzu Corporation), a laminated film specimen cut to a width of 10 mm was subjected to conditions of 23 ° C., a distance between chucks of 40 mm, and a tensile speed of 200 mm / min. The tensile strength and elongation rate until pulling to break were determined. As for the uncoated PET film, the tensile strength and the elongation rate were similarly determined. As a result, the tensile strength (17.8 kN / cm ² ) and the elongation rate (17.8 kN / cm ² ) between the laminated film test piece after coating and the base material before coating ( 168%) confirmed no difference.

The laminated film test piece is used as a fixed metal halide lamp type accelerated weathering tester, SUGA TESTING MACHINE's super energy irradiation tester "UE-IDEC type" (using quartz as inner filter and # 275 as outer filter) The ultraviolet light incident side was set to be an ultraviolet shielding layer. [Irradiated with 100 mW / cm ² ultraviolet ray in an environment of 70 ° C. and 70% RH for 6 hours] → [Leave for 6 hours in an environment of 80 ° C. and 90% RH] was set as one cycle, and 12 cycles of exposure were performed.

For the laminated film specimen after exposure, the tensile strength and elongation were measured under the above conditions, and the ratio to the tensile strength before exposure (the tensile strength after exposure divided by the tensile strength before exposure of 17.8 kN / cm ^2). , 100) was taken as the tensile strength retention rate (%), and the elongation retention rate (%) was similarly determined. If the substrate deteriorates due to exposure, these retention rates will decrease.

(6) Weather resistance 2 (retention rate of UV cut rate)
The laminated film test piece was repeatedly exposed for 12 cycles in the same manner as in the case of weather resistance 1. Using a spectrophotometer ("UV-3100") manufactured by Shimadzu Corporation, the UV transmittance (%) of only the base material of each laminate as a blank was measured, and UV transmission at 360 nm before and after the weather resistance test The rate (%) was measured, and the UV cut rate [(100−UV transmittance) (%)] before the test (initial) was determined. Further, assuming that the initial UV cut rate is X and the UV cut rate after exposure is Y, the value obtained by [(X−Y) / X] × 100 (%) is the UV cut rate retention rate ( %).

  UVA (i) to (iv) which are benzotriazole monomers (A1) having a sterically hindering group at the 3-position of the benzene ring according to the present invention, and monomers having an alkyl group having 4 or more carbon atoms ( In Examples 1 to 6 in which a polymer was synthesized using B), excellent coating film properties were exhibited, and good bending resistance, weather resistance, and ultraviolet shielding properties were exhibited over a long period of time.

  In Comparative Experimental Example 1 using the benzotriazole-based monomer UVA (v) having no steric hindrance group for suppressing consumption of hydroxyl groups, coloring was observed when immersed in an alkaline solution. Further, the retention rate of the UV cut rate was also reduced, and it was confirmed that the ultraviolet absorbing group was decomposed. Moreover, in Comparative Experimental Example 2 in which the monomer (B) having an alkyl group having 4 or more carbon atoms that enhances the water resistance of the coating film was not used, all of the properties other than the initial flex resistance were inferior.

  Even in the case of the benzophenone-based monomer (A2), such a sterically hindered group is compared with Experimental Example 7 using UVA (vi) having a sterically hindered group capable of forming a hydrogen bond at the 3-position. It was confirmed that Comparative Experimental Example 3 using UVA (vii) having no water resistance was inferior in water resistance, alkali resistance, flex resistance, and weather resistance.

  In the present invention, by using a UV-absorbing monomer having a specific substituent at a specific position and a monomer having an alkyl group having 4 or more carbon atoms to enhance the water resistance of the coating film, We succeeded in suppressing the decomposition of UV-absorbing groups by light and water.

  For this reason, since the ultraviolet shielding layer formed from the resin composition for forming an ultraviolet shielding layer of the present invention exhibits the ultraviolet shielding ability over a long period of time, the ultraviolet shielding can be achieved by applying it to a base material that deteriorates due to ultraviolet rays. Can be manufactured.

  Accordingly, the ultraviolet-shielding laminate of the present invention is, for example, for content protection or surface protection (various food packaging materials, solar cells, etc.), insulation (insulation film, display element, etc.), optical (lens, reflection) Prevention films, light diffusion films, etc.), building materials (soundproof walls, etc.), antifouling sheets and tents, marking films, outdoor extension (agricultural houses, etc.), indoor and outdoor overlays (display materials, electrical signs) Etc.) and for windows (vehicles, construction, daylighting materials, etc.), etc.

Claims (4)

An ultraviolet ray comprising a polymer synthesized from a monomer mixture (I) essentially comprising a benzotriazole-based ultraviolet absorbing monomer represented by the following formula (1) and a monomer having an alkyl group having 4 or more carbon atoms: A resin composition for forming a shielding layer.

[Wherein, R ¹ 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 W1 represents an alkyl group having 3 to 12 carbon atoms or A group represented by the following formula (2):

(R ² is a bond having a group capable of forming a hydrogen bond, and R ³ represents a hydrogen atom or a methyl group.)
When W1 is an alkyl group having 3 to 12 carbon atoms, X1 represents a group represented by the above formula (2), and when W1 is a group represented by the above formula (2), X1 is hydrogen. Represents an atom or a hydrocarbon group having 1 to 8 carbon atoms. ] The resin composition for forming an ultraviolet shielding layer according to claim 1, wherein the monomer having an alkyl group having 4 or more carbon atoms is a (meth) acrylate represented by the following formula (5).

(In the formula, R ⁸ represents a hydrogen atom or a methyl group, and Y represents an alkyl group having 4 or more carbon atoms.)   The resin composition for forming an ultraviolet shielding layer according to claim 1 or 2, wherein the monomer mixture (I) further contains a monomer having an ultraviolet stable group.   An ultraviolet shielding layered product, wherein an ultraviolet shielding layer formed from the resin composition for forming an ultraviolet shielding layer according to any one of claims 1 to 3 is laminated on an ultraviolet-degradable resin substrate. .