JP2011202144A - Adhesive composition, adhesive tape or film using the same, surface protective film, laminated glass and solar cell module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition keeping long wave ultraviolet shielding effects for a long term and exhibiting excellent light resistance, in long-term time lapse.SOLUTION: There is provided the adhesive composition usable for an adhesive layer composing laminates and comprising the adhesive and an ultraviolet absorber represented by formula (1). In the formula, R, R, R, Rand Rrepresent each independently hydrogen or a monovalent substituent except OH, at least one of substituents represents a substituent having a positive σp value of Hammett's rule. The substituents may bind each other to form a ring. R, R, R, R, Rand Rrepresent each independently hydrogen or a monovalent substituent. The substituents may bind each other to form a ring. Rand Reach independently represent hydrogen, a halogen atom or a monovalent substituent connected with S, C or N.

Description

  The present invention relates to a pressure-sensitive adhesive composition containing a triazine compound and a pressure-sensitive adhesive, and a pressure-sensitive adhesive tape or film, a surface protective film, a laminated glass or a solar cell module using the same.

Conventionally, ultraviolet absorbing properties are imparted by using an ultraviolet absorber in common with various resin compositions. An inorganic ultraviolet absorber and an organic ultraviolet absorber may be used as the ultraviolet absorber. Inorganic ultraviolet absorbers (see, for example, Patent Documents 1 to 3, etc.) are excellent in durability such as light resistance and heat resistance, but are free to be selected because the absorption wavelength is determined by the band gap of the compound. There is nothing that can absorb the long-wave ultraviolet (UV-A) region near 400 nm, and the one that absorbs the long-wave ultraviolet has absorption up to the visible region and is colored.
On the other hand, since the organic ultraviolet absorber has a high degree of freedom in the structural design of the absorbent, it is possible to obtain various absorption wavelengths by devising the structure of the absorbent.

So far, a system using various organic ultraviolet absorbers has been studied, and Patent Document 4 discloses a triazole ultraviolet absorber. Patent Document 5 describes a trisaryl-s-triazine having an alkoxy group and a hydroxy group at a specific position. However, those having a maximum absorption wavelength in the long wave ultraviolet region have poor light resistance, and the ultraviolet shielding effect decreases with time.
Furthermore, materials applied to solar cells, etc. that have been developed in recent years need to be exposed to sunlight outdoors for a long time, and it is inevitable that their properties will deteriorate due to exposure to ultraviolet rays over time. It was. For this reason, there is a need for a compound that can be used as an ultraviolet absorber that exhibits a shielding effect up to the UV-A region and has an excellent light resistance.
In addition, solar control films, films and transparent glass, UV absorbing glass and glass coatings, windscreens, retroreflective sheets, solar reflectors, etc. are known as products exposed to the sun and other ultraviolet sources. These products are often laminated products in which a resin film or glass forms a layer. Usually, these laminates have a structure in which each base material layer is bonded with a pressure-sensitive adhesive layer or a structure in which a pressure-sensitive adhesive layer is formed on the base material layer, but these products were exposed to ultraviolet rays over time. Sometimes, when the pressure-sensitive adhesive layer is decomposed or destroyed, the useful life of the product is shortened. Therefore, protecting the pressure-sensitive adhesive layer itself from ultraviolet rays is also a very important issue.

  On the other hand, benzophenone-based and benzotriazole-based UV absorbers have relatively good light resistance, and can be cut relatively clearly up to a long wavelength region by increasing the concentration and film thickness (see, for example, Patent Documents 6 and 7). . However, when these ultraviolet absorbers are usually mixed and applied in a resin composition such as an adhesive, the film thickness is limited to about several tens of μm. When cutting to a long wavelength region with this film thickness, it is necessary to add an ultraviolet absorber at a considerably high concentration. However, there has been a problem that simply adding to a high concentration causes precipitation of ultraviolet absorbers and bleeding out due to long-term use. When added to a high concentration, there may be a problem in terms of odor. Further, many benzophenone-based and benzotriazole-based UV absorbers have low solubility, and it has been difficult to apply them mixed with a resin composition such as an adhesive at a high concentration.

JP-A-5-339033 JP-A-5-345639 JP-A-6-56466 Special Table 2002-524442 Japanese Patent No. 3965631 JP-A-6-145387 JP 2003-177235 A

  An object of the present invention is to provide a pressure-sensitive adhesive composition that maintains a long-wave ultraviolet shielding effect for a long period of time and exhibits excellent light resistance. Moreover, the objective of this invention is providing the adhesive tape or film which has an adhesive layer formed using this adhesive composition, a surface protection film, a laminated glass, or a solar cell module.

As a result of examining the above problems in detail, the present inventors have found a novel triazine-based compound that exhibits a shielding effect up to the UV-A region and has an unprecedented light resistance, and includes this in a pressure-sensitive adhesive composition. Thus, the present invention has been completed.
That is, the subject of this invention was achieved by the following means.

[1]
A pressure-sensitive adhesive composition comprising a pressure-sensitive adhesive and an ultraviolet absorber represented by the following general formula (1).

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or OH, and at least one of the substituents has a Hammett's σp value Represents a substituent which is positive. Moreover, you may combine with substituents and may form a ring. R ^1g , R ¹ⁱ , R ^1j , R ^1k , R ^1m and R ^1p each independently represent a hydrogen atom or a monovalent substituent. Moreover, you may combine with substituents and may form a ring. R ^1h and R ¹ⁿ each independently represent a hydrogen atom, a halogen atom, or a monovalent substituent linked by S, C, or N. ]
[2]
The monovalent substituent is a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, substituted or Unsubstituted alkylcarbonyl group, nitro group, substituted or unsubstituted amino group, hydroxy group, alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group, substituted or unsubstituted sulfamoyl group, thiocyanate group, Or a substituted or unsubstituted alkylsulfonyl group, and when the monovalent substituent has a substituent, the substituent is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, an alkoxycarbonyl group, Carbamoyl group, alkylcarbonyl group, nitro group, amino group, hydroxy group, alkoxy group having 1 to 20 carbon atoms Aryloxy group, a sulfamoyl group, a pressure-sensitive adhesive composition according to characterized in that it is a thiocyanate group or an alkylsulfonyl group (1).
[3]
The pressure-sensitive adhesive composition according to [1] or [2], wherein at least one of R ^1b , R ^1c, and R ^1d is a substituent having a positive Hammett σp value.
[4]
The substituent having a positive Hammett's σp value is a group selected from COOR ^r , CONR ^s ₂ , CN, CF ₃ , a halogen atom, NO ₂ and SO ₃ M [1] To [3], the pressure-sensitive adhesive composition [R ^r , R ^s each independently represents a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal. ].
[5]
The pressure-sensitive adhesive composition according to any one of [1] to [4], wherein the substituent having a positive Hammett σp value is COOR ^r or CN [R ^r is a hydrogen atom Or represents a monovalent substituent. ].
[6]
The pressure-sensitive adhesive composition according to any one of [1] to [5], wherein R ^1h or R ¹ⁿ is a hydrogen atom.
[7]
The R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p are hydrogen atoms, [1] to [6] Adhesive composition.
[8]
The pressure-sensitive adhesive composition according to any one of [1] to [7], comprising 0.01 to 30% by mass of the compound represented by the general formula (1) in the pressure-sensitive adhesive composition.
[9]
The pressure-sensitive adhesive composition according to [8], wherein the pressure-sensitive adhesive contains polyvinyl butyral or an ethylene-vinyl acetate copolymer.
[10]
Further, it contains at least one additive selected from the group consisting of antioxidants, other ultraviolet absorbers, sterically hindered amines, and 0.01 to 10 mass of the additive with respect to the adhesive. The pressure-sensitive adhesive composition according to any one of [1] to [9], comprising:
[11]
It is used for the adhesive layer which comprises a laminated body, The adhesive composition of any one of [1]-[10] characterized by the above-mentioned.
[12]
The adhesive tape or film containing the base material and the adhesive layer which consists of an adhesive composition in any one of [1]-[10].
[13]
The surface protection film containing the adhesive layer which consists of a base material and the adhesive composition in any one of [1]-[10].
[14]
A laminated glass comprising a base material and a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition according to any one of [1] to [10].
[15]
The solar cell module containing the adhesive layer which consists of a base material and the adhesive composition in any one of [1] to [10].

  The pressure-sensitive adhesive composition of the present invention contains a compound represented by the general formula (1) having high solubility in an organic solvent and an ultraviolet shielding effect even in a long wavelength region, and having light resistance. The shielding effect is maintained for a long time, and deterioration such as decomposition and hue change over time is suppressed. Moreover, deterioration was suppressed in laminated bodies, such as a tape and a film which have an adhesive layer formed using this, The long-term continuation of adhesive force and the long-term protection of the content were attained. Furthermore, although it is preferable that an ultraviolet absorber composition is odorless depending on a use, the ultraviolet absorber composition of this invention is odorless even if it uses it in high concentration, and is excellent also in the point of odor.

FIG. 1 is a schematic view showing an example of the solar cell module of the present invention.

Hereinafter, the present invention will be described in detail.
The pressure-sensitive adhesive composition of the present invention contains a pressure-sensitive adhesive and an ultraviolet absorber represented by the following general formula (1). It is preferable that the adhesive composition of this invention is used for the adhesive layer which comprises a laminated body.
The compound represented by the general formula (1) is highly soluble in an organic solvent, exhibits an ultraviolet shielding effect even in a long wavelength region, and has light resistance. Therefore, when added to an adhesive as an ultraviolet absorber, there is no precipitation or bleed-out, long-wave ultraviolet absorption ability can be maintained for a long period of time, and degradation such as decomposition of the adhesive and change in hue can be suppressed.
First, the compound represented by the following general formula (1) will be described.

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or OH, and at least one of the substituents has a Hammett's σp value Represents a substituent which is positive. Moreover, you may combine with substituents and may form a ring. R ^1g , R ¹ⁱ , R ^1j , R ^1k , R ^1m and R ^1p each independently represent a hydrogen atom or a monovalent substituent. Moreover, you may combine with substituents and may form a ring. R ^1h and R ¹ⁿ each independently represent a hydrogen atom, a halogen atom, or a monovalent substituent linked by S, C, or N. ]

R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or OH, and at least one of the substituents has a Hammett's rule σp value Represents a substituent that is positive.
Among the substituents represented by R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e , it is preferable that 1 to 3 represent a substituent having a positive Hammett's σp value, and 1 to 2 represent a Hammett rule. More preferably, it represents a substituent having a positive σp value.

Examples of the monovalent substituent (hereinafter referred to as A) in the general formula (1) include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group having 1 to 20 carbon atoms (for example, Methyl, ethyl), an aryl group having 6 to 20 carbon atoms (eg, phenyl, naphthyl), cyano group, carboxyl group, alkoxycarbonyl group (eg, methoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), substituted or unsubstituted Carbamoyl groups (eg carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl groups (eg acetyl), arylcarbonyl groups (eg benzoyl), nitro groups, substituted or unsubstituted amino groups (eg amino, dimethyl) Amino, anilino, substituted sulfoamino groups , Acylamino groups (eg acetamide, ethoxycarbonylamino), sulfonamido groups (eg methanesulfonamide), imide groups (eg succinimide, phthalimide), imino groups (eg benzylideneamino), hydroxy groups, alkoxy groups having 1 to 20 carbon atoms (Eg methoxy), aryloxy groups (eg phenoxy), acyloxy groups (eg acetoxy), alkylsulfonyloxy groups (eg methanesulfonyloxy), arylsulfonyloxy groups (eg benzenesulfonyloxy), sulfo groups, substituted or unsubstituted Sulfamoyl group (for example, sulfamoyl, N-phenylsulfamoyl), alkylthio group (for example, methylthio), arylthio group (for example, phenylthio), thiocyanate group, alkylsulfonyl (Eg methanesulfonyl), an arylsulfonyl group (e.g., benzenesulfonyl), and the like Hajime Tamaki having 6 to 20 carbon atoms (e.g. pyridyl, morpholino).
Further, the substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. In that case, the above-mentioned monovalent substituent A can be mentioned as an example of a substituent. Moreover, you may combine with substituents and may form a ring.

  Rings formed by bonding between substituents include benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, oxadiazole And a ring, a thiazole ring, a thiadiazole ring, a furan ring, a thiophene ring, a selenophene ring, a silole ring, a gelmol ring, and a phosphole ring.

Examples of the monovalent substituent in the general formula (1) include a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted. Substituted carbamoyl group, substituted or unsubstituted alkylcarbonyl group, nitro group, substituted or unsubstituted amino group, hydroxy group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group , A substituted or unsubstituted sulfamoyl group, a thiocyanate group, or a substituted or unsubstituted alkylsulfonyl group is preferable, and OR ^U (R ^u represents a hydrogen atom or a monovalent substituent), an alkyl group, or an amide group. More preferably, OR ^u and an alkyl group are still more preferable.
R ^u represents a hydrogen atom or a monovalent substituent, and examples of the monovalent substituent include the substituent A. Among them, it is preferable to represent a linear or branched alkyl group having 1 to 20 carbon atoms. A linear or branched alkyl group having 1 to 6 carbon atoms is more preferable, and examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i -Butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-octyl, t-octyl, i-octyl Methyl or ethyl is preferred, and methyl is particularly preferred.

As a preferred first embodiment of the present invention, an embodiment in which at least one of R ^1a , R ^1c and R ^1e represents a substituent having a positive Hammett's σp value can be mentioned. More preferably, R ^1c represents a substituent having a positive Hammett's σp value.
More preferably, R ^1c is a substituent having a positive Hammett's σp value, and R ^1a , R ^1b , R ^1d , and R ^1e represent a hydrogen atom.
When R ^1c represents a substituent having a positive Hammett's σp value, LUMO is stabilized by the electron-attracting group, which is preferable because the excitation lifetime is shortened and the light resistance is improved.

Further, as a preferred second embodiment, at least one of R ^1b , R ^1c and R ^1d can include a substituent having a positive Hammett's σp value, preferably R ^1a , R ^1c and R ^1e represents a hydrogen atom, R ^1b and R ^1d each independently represent a hydrogen atom or a substituent having a positive Hammett's σp value, and at least one has a positive Hammett's σp value. The embodiment which is a substituent which is can be mentioned. As a result, the compound represented by the general formula (1) is particularly excellent in solvent solubility because of its excellent solvent solubility, and the resin composition containing the compound is difficult to precipitate or bleed out. It has the effect.
Solvent solubility means solubility in an organic solvent such as ethyl acetate, methyl ethyl ketone, and toluene, and is preferably 10% by mass or more based on the solvent used in terms of compatibility with the resin. It is more preferable to dissolve by mass% or more.

<Preferred first embodiment>
In a first aspect, the substituent σp value is a positive Hammett equation in formula (1), preferably, sigma electron withdrawing group _p value of 0.1 to 1.2. Specific examples of the electron withdrawing group having a σ _p value of 0.1 or more include COOR ^r (R ^r represents a hydrogen atom or a monovalent substituent, and includes a hydrogen atom and an alkyl group, preferably hydrogen CONR ^s ₂ (R ^s represents a hydrogen atom or a monovalent substituent), CN, halogen atom, NO ₂ , SO ₃ M (M represents a hydrogen atom or an alkali metal). ), Acyl group, formyl group, acyloxy group, acylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, dialkylphosphono group, diarylphosphono group, dialkylphosphinyl group, diarylphosphinyl group, phosphoryl group, alkyl Substituted with sulfinyl group, arylsulfinyl group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, imino group, N atom Imino group, a carboxy group (or a salt thereof), alkyl group (e.g. CF ₃₎ which is substituted by at least two halogen atoms, at least two or more alkoxy groups substituted with a halogen atom, at least two An aryloxy group substituted with a halogen atom, an acylamino group, an alkylamino group substituted with at least two halogen atoms, an alkylthio group substituted with at least two halogen atoms, and a σ _p value of 0.2 or more And aryl groups, heterocyclic groups, halogen atoms, azo groups, and selenocyanate groups substituted with other electron-withdrawing groups. For Hammett σp values, see Hansch, C .; Leo, A .; Taft, R .; W. Chem. Rev. 1991, 91, 165-195.

The substituent having a positive Hammett's σp value in the general formula (1) is more preferably COOR ^r , CONR ^s ₂ , CN, CF ₃ , a halogen atom, NO ₂ , or SO ₃ M [R ^r , R ^s each independently represents a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal]. Among these, COOR ^r or CN is more preferable, and COOR ^r is more preferable. This is because it has excellent light resistance and solubility.

R ^r and R ^s represent a hydrogen atom or a monovalent substituent, and examples of the monovalent substituent include the substituent A. Of these, a linear or branched alkyl group having 1 to 20 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i- Examples include pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-octyl, t-octyl and i-octyl, preferably methyl or ethyl, and particularly preferably methyl.

In the compound represented by the general formula (1), R ^1c is preferably any one of COOR ^r , CONR ^s ₂ , CN, CF ₃ , a halogen atom, NO ₂ , SO ₃ M, and COOR ^r or CN CN is more preferable.

In the present invention, when R ^1g , R ¹ⁱ , R ^1j , R ^1k , R ^1m and R ^1p represent a monovalent substituent, R ^1g , R ¹ⁱ , R ^1j , R ^1k , R ^1m and R More preferably, at least one of ^1p represents a substituent having a positive Hammett's σp value, and at least one of R ^1g , R ¹ⁱ and R ^1j has a positive Hammett's σp value (preferably Is more preferably 0.1 to 1.2). It is particularly preferable that R ^1c represents a substituent having a positive (preferably 0.1 to 1.2) σp value according to the Hammett rule. This is because it has excellent light resistance.
In the present invention, R ^1h or R ¹ⁿ is preferably each independently a hydrogen atom, COOR ^r , CONR ^s ₂ , CN, CF ₃ , halogen atom, NO ₂ , or SO ₃ M [R ^r , R ^s independently represents a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal], R ^1h or R ¹ⁿ is more preferably a hydrogen atom, R ^1h and R ¹ⁿ are more preferably a hydrogen atom, and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p particularly preferably represent a hydrogen atom. It is for showing the outstanding light resistance. Of course, the monovalent substituent connected by S, C or N does not include an OH group and an OR group (R is a monovalent substituent).

In the compound represented by the general formula (1), R ^1c is a substituent having a positive Hammett's σp value (preferably 0.1 to 1.2), and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p preferably represent a hydrogen atom, and R ^1c is any of COOR ^r , CONR ^s ₂ , CN, CF ₃ , a halogen atom, NO ₂ , SO ₃ M More preferably, R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p are hydrogen atoms. It is for showing the outstanding light resistance.

  The compound represented by the general formula (1) preferably has a pKa in the range of -5.0 to -7.0. Further, it is more preferably in the range of -5.2 to -6.5, particularly preferably in the range of -5.4 to -6.0.

<Preferred second embodiment>
In a preferred second embodiment, R ^1a , R ^1c and R ^1e represent a hydrogen atom, and R ^1b and R ^1d each independently represent a hydrogen atom or a substituent having a positive Hammett's σp value. , At least one of the embodiments may be a substituent having a positive Hammett's σp value.
R ^1a , R ^1c and R ^1e represent a hydrogen atom, R ^1b and R ^1d each independently represent a hydrogen atom or a substituent having a positive Hammett's σp value, and at least one is a Hammett In the second aspect in which the σp value of the rule is positive, the substituent having a positive Hammett's σp value in the general formula (1) is more preferably COOR ^r , CONR ^s ₂ , CN, CF ₃ , halogen atom, NO ₂ , or SO ₃ M [R ^r and R ^s each independently represent a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal]. ^{Examples of} the monovalent substituent for R ^r and R ^s include the substituent A as described above.
The substituent having a positive Hammett's σp value in the general formula (1) is more preferably a COOR ^r or cyano group, and further preferably COOR ^r . This is because when the substituent having a positive Hammett's σp value is a cyano group, excellent light resistance is exhibited. Further, when the substituent having a positive Hammett's σp value is COOR ^r , excellent solubility is exhibited.
R ^r preferably represents a hydrogen atom or an alkyl group, more preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and still more preferably a linear or branched alkyl group having 1 to 15 carbon atoms.

R ^r is more preferably a branched alkyl group having 5 to 15 carbon atoms from the viewpoint of solubility in a solvent.
The branched alkyl group has a secondary carbon atom or a tertiary carbon atom, preferably contains 1 to 5 secondary carbon atoms or tertiary carbon atoms, preferably contains 1 to 3, preferably 1 or 2 It is preferable to contain it, and it is more preferable to contain 1 or 2 secondary carbon atoms and tertiary carbon atoms. Moreover, it is preferable that 1-3 asymmetric carbons are included.
R ^r is a branched alkyl group having 5 to 15 carbon atoms containing 1 or 2 secondary carbon atoms and tertiary carbon atoms and 1 or 2 asymmetric carbons from the viewpoint of solubility in a solvent. It is particularly preferred. This is because the symmetry of the compound structure is broken and the solubility is improved.

On the other hand, from the viewpoint of ultraviolet absorbing ability, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable.
Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i- Examples include pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-octyl, t-octyl and i-octyl, preferably methyl or ethyl, and particularly preferably methyl.

In the present invention, when R ^1g , R ¹ⁱ , R ^1j , R ^1k , R ^1m and R ^1p represent a monovalent substituent, R ^1g , R ¹ⁱ , R ^1j , R ^1k , R ^1m and R More preferably, at least one of ^1p represents a substituent having a positive Hammett's σp value, and at least one of R ^1g , R ¹ⁱ and R ^1j has a positive Hammett's σp value (preferably Is more preferably 0.1 to 1.2). It is particularly preferable that R ^1b or R ^1d represents a substituent having a positive (preferably 0.1 to 1.2) σp value according to the Hammett rule. This is because it has excellent light resistance.
In the present invention, R ^1h or R ¹ⁿ is preferably each independently a hydrogen atom, COOR ^r , CONR ^s ₂ , a cyano group, CF ₃ , a halogen atom, a nitro group, or SO ₃ M, and R ^1h or R ¹ⁿ is more preferably a hydrogen atom, R ^1h and R ¹ⁿ are more preferably hydrogen atoms, and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p Particularly preferably represents a hydrogen atom. It is for showing the outstanding light resistance. Of course, the monovalent substituent connected by C or N does not include an OH group and an OR group (R is a monovalent substituent).

In the compound represented by the general formula (1), R ^1b or R ^1d is a substituent having a positive Hammett's σp value (preferably 0.1 to 1.2), and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p preferably represent a hydrogen atom, and R ^1b or R ^1d is COOR ^r , CONR ^s ₂ , a cyano group, CF ₃ , a halogen atom , nitro group, in any one of _{^{SO 3 M, R 1g, R}} 1h, R 1i, R 1j, R 1k, R 1m, R 1n and ^{R 1p} is more preferably a hydrogen atom. It is for showing the outstanding light resistance.

  The compound represented by the general formula (1) preferably has a pKa in the range of -5.0 to -7.0. Further, it is more preferably in the range of -5.2 to -6.5, particularly preferably in the range of -5.4 to -6.0.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.
In the following specific examples, Me represents a methyl group, Ph represents a phenyl group, and —C ₆ H ₁₃ represents n-hexyl.

  The compound represented by the general formula (1) can take a tautomer depending on the structure and the environment in which the compound is placed. Although the present invention is described in one of the representative forms, tautomers different from those described in the present invention are also included in the compounds of the present invention.

The compound represented by the general formula (1) may contain an isotope (for example, ² H, ³ H, ¹³ C, ¹⁵ N, ¹⁷ O, ¹⁸ O, etc.).

The compound represented by the general formula (1) can be synthesized by any method.
For example, known patent documents and non-patent documents, for example, 325 of JP-A-7-188190, JP-A-11-315072, JP-A-2001-220385, “Dye and Drug” Vol. 40 No. 12 (1995) It can be synthesized with reference to page 339. Specifically, exemplary compound (16) can be synthesized by reacting salicylamide, 3,5-bis (trifluoromethyl) benzoyl chloride and 2-hydroxybenzamidine hydrochloride. It can also be synthesized by reacting salicylamide, salicylic acid and 3,5-bis (trifluoromethyl) benzamidine hydrochloride.

The compound represented by the general formula (1) according to the present invention is characterized by excellent solubility in an organic solvent. In addition, since it has a substituent having a positive Hammett's σp value at a specific position, LUMO is stabilized by an electron-attracting group, so that the excitation life is shortened and it has excellent light resistance. Have. Even when used as a UV absorber, known triazine compounds have adverse effects such as precipitation and bleeding out due to long-term use, decomposition and yellowing when used at high concentrations. On the other hand, since the compound represented by the general formula (1) according to the present invention has excellent solubility and light resistance, it does not precipitate or bleed out even when used at a high concentration, and is decomposed even when used for a long time. The effect of not yellowing is obtained.
In the pressure-sensitive adhesive composition of the present invention, the compound represented by the general formula (1) may be used alone or in combination of two or more having different structures.

In the pressure-sensitive adhesive composition of the present invention, the compound represented by the general formula (1) may be used alone or in combination of two or more.
The compounds according to the invention are particularly suitable for stabilizing organic materials against damage by light, oxygen or heat. Among them, the compound represented by the general formula (1) can be suitably used as a light stabilizer, particularly an ultraviolet absorber.

Since the compound represented by the general formula (1) has a substituent having a positive Hammett's σp value at a specific position, LUMO is stabilized by an electron-attracting group, so that an excitation lifetime is shortened. It has the feature of having excellent light resistance. Even when it is used as an ultraviolet absorber, when a known triazine compound is used, it has an adverse effect such as decomposition and yellowing when used for a long time.
On the other hand, since the compound represented by the general formula (1) has excellent light resistance, the effect of not decomposing and yellowing even when used for a long time can be obtained.

Although the maximum absorption wavelength of the compound represented by the general formula (1) is not particularly limited, it is preferably 250 to 400 nm, more preferably 280 to 380 nm. The full width at half maximum is preferably 20 to 100 nm, more preferably 40 to 80 nm.
The molecular weight of the compound represented by the general formula (1) is preferably 1,000 or less.

  Those skilled in the art can easily measure the maximum absorption wavelength and the half-value width defined in the present invention. The measurement method is described in, for example, “The Fourth Edition Experimental Chemistry Course 7 Spectroscopy II” (Maruzen, 1992), pages 180-186, edited by the Chemical Society of Japan. Specifically, the sample is dissolved in a suitable solvent, and measurement is performed by a spectrophotometer using a cell made of quartz or glass and using two cells for sample and control. The solvent to be used is required to have no absorption in the measurement wavelength region, have a small interaction with the solute molecule, and have a very low volatility in addition to the solubility of the sample. Any solvent that satisfies the above conditions can be selected. In the present invention, measurement is performed using ethyl acetate (EtOAc) as a solvent.

In the present invention, the maximum absorption wavelength and the half-value width of the compound were measured using a quartz cell having an optical path length of 10 mm by preparing a solution having a concentration of about 5 × 10 ⁻⁵ mol · dm ^{−3 using} ethyl acetate as a solvent. Use the value.

  The half width of the spectrum is described in, for example, “The Fourth Edition Experimental Chemistry Course 3 Basic Operation III” (Maruzen, 1991), page 154, edited by the Chemical Society of Japan. In the above-mentioned book, the half-value width is explained with an example in which the horizontal axis is taken on the wave number scale, but the half-value width in the present invention is the value when the axis is taken on the wavelength scale, The unit is nm. Specifically, it represents the width of the absorption band that is half the absorbance at the maximum absorption wavelength, and is used as a value that represents the shape of the absorption spectrum. A spectrum with a small half-value width is a sharp spectrum, and a spectrum with a large half-value width is a broad spectrum. The UV-absorbing compound that gives a broad spectrum has absorption in a wide region from the maximum absorption wavelength to the long wave side. Therefore, in order to effectively block the long wave UV region without yellowing, a spectrum with a small half-value width is used. The ultraviolet absorbing compound having is preferable.

  As described in Sumida Tokita "Chemistry Seminar 9 Color Chemistry" (Maruzen, 1982), pages 154-155, the intensity of light absorption, that is, the oscillator strength, is proportional to the integral of the molar extinction coefficient, and the absorption spectrum. When the symmetry is good, the oscillator strength is proportional to the product of the absorbance at the maximum absorption wavelength and the full width at half maximum (however, the full width at half maximum is a value obtained by taking an axis on the wavelength scale). This means that when the transition moment values are the same, a compound having a spectrum with a small half width has a large absorbance at the maximum absorption wavelength. Such UV-absorbing compounds have the advantage of being able to effectively shield the area around the maximum absorption wavelength with a small amount of use, but since the absorbance decreases sharply when the wavelength is slightly away from the maximum absorption wavelength, a wide range of areas can be used. It cannot be shielded.

  The compound represented by the general formula (1) preferably has a molar extinction coefficient at the maximum absorption wavelength of 20000 or more, more preferably 30000 or more, and particularly preferably 50000 or more. If it is 20000 or more, the absorption efficiency per mass of the compound represented by the general formula (1) can be sufficiently obtained, so that the compound represented by the general formula (1) for completely absorbing the ultraviolet region can be obtained. The amount used can be reduced. This is preferable from the viewpoint of preventing skin irritation and accumulation in a living body and from the point that bleeding out hardly occurs. The molar extinction coefficient is based on the definition described in, for example, “New Edition Experimental Chemistry Lecture 9 Analytical Chemistry [II]” (Maruzen, 1977), page 244, edited by the Chemical Society of Japan. It can be determined together with the absorption wavelength and the half width.

  The pressure-sensitive adhesive composition of the present invention can contain the compound represented by the general formula (1) in any amount necessary for imparting desired performance. These differ depending on the compound used and the pressure-sensitive adhesive, but the content can be appropriately determined. As content, it is preferable that it is 0.01-30 mass% in an adhesive composition, it is more preferable that it is 0.1-15.0 mass%, and it is 1.0-4.0 mass%. Is more preferable. If the content is in the above range, an ultraviolet shielding effect can be obtained, and precipitation and bleed out can be more effectively suppressed, which is preferable.

Next, the pressure-sensitive adhesive composition of the present invention will be described.
As the pressure-sensitive adhesive composition of the present invention, any type of organic solvent-based, water-based (emulsion-based), hot-melt-based pressure-sensitive adhesive, etc. can be used. A hot melt adhesive is preferred.
As the resin component of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive composition of the present invention, any resin used as the resin component of the pressure-sensitive adhesive can be used. Polyvinyl alcohol resin, ethylene-vinyl acetate copolymer, styrene -It is preferable to use 1 or more types of resin selected from the group which consists of a diene copolymer, a urethane type resin, and an acrylic resin. It is more preferred to use polyvinyl butyral and / or ethylene-vinyl acetate copolymer.
The content of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive composition of the present invention is preferably 70 to 99.99% by mass, more preferably 85 to 99.9% by mass, and 96. More preferably, it is -99 mass%. If content is said range, since sufficient adhesive effect is acquired, it is preferable.
Each resin will be described below.

(Polyvinyl alcohol resin)
As the polyvinyl alcohol resin, polyvinyl alcohol, modified polyvinyl alcohol and the like can be used, and the saponification degree thereof is preferably 70 to 100%, more preferably 80 to 100%, and particularly preferably 95 to 100%. The polymerization degree of polyvinyl alcohol is preferably 100 to 5,000.
Modified polyvinyl alcohol is obtained by introducing a modifying group into polyvinyl alcohol by copolymerization modification, chain transfer modification or block polymerization modification. In the copolymerization modification, COONa, Si (OH) ₃ , N (CH ₃ ) ₃ .Cl, C ₉ H ₁₉ COO, SO ₃ Na, C ₁₂ H ₂₅ can be introduced as a modifying group. In chain transfer modification, COONa, SH, or SC ₁₂ H ₂₅ can be introduced as a modifying group.
The degree of polymerization of the modified polyvinyl alcohol is preferably 100 to 3,000. The modified polyvinyl alcohol is described in JP-A-8-338913, JP-A-9-152509, and JP-A-9-316127.
Further, unmodified polyvinyl alcohol having a saponification degree of 85 to 95% and alkylthio-modified polyvinyl alcohol are particularly preferable. Furthermore, two or more kinds of polyvinyl alcohol and modified polyvinyl alcohol may be used in combination.

(Ethylene-vinyl acetate copolymer)
Examples of the ethylene-vinyl acetate copolymer adhesive include a hot melt type and an emulsion type. The emulsion type is obtained by copolymerizing at least vinyl acetate and ethylene in the presence of an emulsifier such as polyvinyl alcohol and a surfactant. Commercially available products can also be used, for example, S450HQ (manufactured by Sumika Chemtex Co., Ltd., Tg 0 ° C., nonvolatile content 55%, product name), S205HQ (manufactured by Sumika Chemtex Co., Ltd., Tg-20 ° C., nonvolatile content 55%, Product name), # 59 (manufactured by Denki Kagaku Kogyo Co., Ltd., Tg-18 ° C., nonvolatile content 56%), # 90 (manufactured by Denki Kagaku Kogyo Co., Ltd., Tg 1 ° C., 55% nonvolatile content, 70% toluene insolubles, product Name). The hot melt type is, for example, an ethylene vinyl acetate copolymer resin having a vinyl acetate content of 20 to 30%, a melt index of 2 to 5 g / 10 minutes, and a softening point of 150 to 190 ° C., for example, Evaflex 360 [Mitsui -The thing based on DuPont polychemical Co., Ltd.] can be mentioned.

(Styrene-diene copolymer)
The diene of the styrene-diene copolymer is not particularly limited, such as a diolefin having a carbon-carbon double bond or an cycloaliphatic cyclopentane. Specifically, 1,3-butadiene, isoprene, 2,3-dimethyl -1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like are preferable examples. For example, in the case of a styrene-butadiene copolymer which is a polymer containing styrene and butadiene in the polymer molecular chain, the content of styrene and butadiene in the polymer is not particularly limited, but styrene is 20 to 70% by mass, butadiene is 20 to 20%. When expressed in a molar ratio of about 75% by mass, styrene: butadiene is preferably in the range of 99: 1 to 40:60. The molecular weight is preferably in the range of 2,000 to 1,000,000, more preferably 5,000 to 500,000. The styrene-butadiene copolymer is usually a random copolymer but may be a block copolymer. Further, it may be a linear polymer, and may be branched or crosslinked. Commercially available products can also be used, for example, LACSTAR 5215A, DS-6137310KDN-703 (Dainippon Ink Chemical Co., Ltd.), Nipol Lx426, 432A, 435 (Nihon Zeon Co., Ltd.), L1151, 1260 , 1876 (manufactured by Asahi Kasei Kogyo Co., Ltd.).

(Polyvinyl butyral)
Polyvinyl butyral is a kind of polyvinyl alcohol. The polyvinyl butyral is not particularly limited as long as it is a polymer having a vinyl butyral group in the molecule, but a polymer having a weight average molecular weight of 10,000 to 500,000 in which polyvinyl butyral, polyvinyl acetate and polyvinyl alcohol are randomly polymerized in the molecule. Preferably there is. Specific examples of the polyvinyl butyral resin include those manufactured by Denki Kagaku Kogyo Co., Ltd., trade names: electrified butyral 3000-1, 3000-K, 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical ( Co., Ltd., ESREC BH series, BX series, KS series, BL series, BM series, Kuraray Co., Ltd., product name: Mobital series, Solutia, Butvar series Etc.

(Urethane resin or acrylic resin)
In addition to those mentioned above, general-purpose urethane resins and acrylic resins can also be used for the pressure-sensitive adhesive composition of the present invention.
Examples include Takelac / Takenate manufactured by Mitsui Chemicals Polyurethane Co., Ltd., Seika Bond / Seikadyne manufactured by Dainichi Seika Kogyo Co., Ltd., Adcoat / Tomoflex manufactured by Toyo Morton Co., Ltd., Adlock manufactured by Rock Paint, and Dick Dry manufactured by Dainippon Ink Chemical Co. Acrylic copolymers can also be used. Specific examples thereof include a copolymer of 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate.

  As described above, the pressure-sensitive adhesive composition of the present invention may contain two or more compounds represented by the general formula (1) having different structures as the ultraviolet absorber. Moreover, you may use together the compound represented with the said General formula (1), and 1 or more types of ultraviolet absorbers which have another structure. When two types (preferably three types) of ultraviolet absorbers having different basic skeleton structures are used in combination, ultraviolet rays in a wide wavelength region can be absorbed. Further, when two or more kinds of ultraviolet absorbers are used in combination, the dispersion state of the ultraviolet absorber is also stabilized. Any ultraviolet absorber having a structure other than the general formula (1) can be used. Triazine, benzotriazole, benzophenone, merocyanine, cyanine, dibenzoylmethane, cinnamic acid, cyano Examples include acrylate-based and benzoate-based compounds. For example, Fine Chemical, May 2004 issue, pages 28-38, published by Toray Research Center, Research Division, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999), pages 96-140, Junichi Okachi Examples include ultraviolet absorbers described in the supervision of “Development of polymer additives and environmental measures” (CMC Publishing Co., Ltd., 2003), pages 54 to 64.

  The ultraviolet absorber having a structure other than the general formula (1) is preferably a benzotriazole compound, a benzophenone compound, a salicylic acid compound, a benzoxazinone compound, a cyanoacrylate compound, a benzoxazole compound, or a merocyanine compound. , A triazine compound. More preferred are benzoxazinone compounds, benzotriazole compounds, benzophenone compounds, and triazine compounds. Particularly preferred are benzoxazinone compounds. The ultraviolet absorber having a structure other than the general formula (1) is described in detail in paragraphs [0117] to [0121] of Japanese Patent Application No. 2008-273950, and the material described in the publication is the present invention. It can also be applied.

  As described above, the pressure-sensitive adhesive composition of the present invention preferably contains a combination of the compound represented by the general formula (1) and a benzoxazinone compound. Since the compound represented by the general formula (1) has excellent light resistance even in the long wavelength region, it has the effect of preventing deterioration of the benzoxazinone that can be shielded to a longer wavelength region, together with the benzoxazinone-based compound. Use is preferable because the shielding effect can be sustained for a long time up to a longer wavelength region.

  The pressure-sensitive adhesive composition of the present invention preferably further contains an additive. As described above, other ultraviolet absorbers (ultraviolet absorbers having a structure other than the compound represented by the general formula (1)), Antioxidants, sterically hindered amines, phosphites or phosphonites, hydroxylamines, nitrones, benzofuran-2-ones, thiosynergists, polyamide stabilizers, metal stearates, nucleating agents, fillers, reinforcing agents, lubricants, emulsifiers , Dyes, pigments, fluorescent brighteners, flame retardants, antistatic agents, plasticizers, foaming agents, and other optional additives. These additives preferably contain 0.01 to 10% by mass of the additive with respect to the pressure-sensitive adhesive.

  The pressure-sensitive adhesive composition of the present invention can practically provide a sufficient ultraviolet shielding effect only by using the compound represented by the general formula (1) as an ultraviolet absorber, but requires more strictness. May be used in combination with a white pigment having a strong hiding power, such as titanium oxide. In addition, when the appearance and color tone become problems, or a small amount (0.05% by mass or less) of a colorant can be used in combination depending on the preference. For applications where transparency or white color is important, a fluorescent brightening agent may be used in combination. Examples of the fluorescent whitening agent include commercially available products, general formula [1] described in JP-A-2002-53824, and specific compound examples 1 to 35.

  As the antioxidant, it is preferable that the pressure-sensitive adhesive composition of the present invention further contains a phosphorus-based stabilizer from the viewpoint that the thermal stability can be improved. Phosphorous stabilizers include phosphorous acid, phosphoric acid, phosphite esters, phosphate esters, etc. Among them, phosphites, phosphonites and the like are included because they contain trivalent phosphorus and easily exhibit a discoloration suppressing effect. Phosphites are preferred.

  Examples of the phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (tridecyl) phosphite. Phyto, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, water Bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butyl) Ruphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4'-isopropylidene diphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilaurylpentaerythritol diphosphite Phosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

  Examples of phosphonites include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6- -Tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, and tetrakis (2,6-di-) tert-butylphenyl) -3,3′-biphenylenediphosphonite and the like.

  Examples of the acid phosphate include methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, and lauryl phosphate. Phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid Sulfate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phenyl Acid phosphate, bisnonylphenyl acid phosphate, etc. are mentioned.

Although the phosphorus stabilizer used for this invention can mix and contain 2 or more types, the total content rate of a phosphorus stabilizer is 0.0005-0. The amount is preferably 3 parts by mass, and more preferably 0.001 to 0.1 parts by mass. If it is said range, the effect as a stabilizer is enough, and the fall of the molecular weight at the time of shaping | molding and a hue deterioration do not occur easily.
In particular, in the present invention, the amount of the compound represented by the general formula (1) is 0.05 to 3 parts by mass and the phosphorus stabilizer is 0.0005 to 0.3 parts by mass with respect to 100 parts by mass of the resin composition. preferable.

As an antioxidant, the pressure-sensitive adhesive composition of the present invention further contains a hindered phenol stabilizer, which stabilizes the compound represented by the general formula (1) and improves the light stability of the resin composition. It is preferable in that it can be increased.
Examples of the hindered phenol stabilizer include, for example, a substituent other than at least one hydrogen atom at the ortho position of the phenolic hydroxyl group (for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, And compounds having an aryloxy group, a substituted amino group, etc.).
The hindered phenol-based stabilizer is a compound known as an antioxidant and may be a commercially available one. For example, 2,6-di-t-butyl-4-methylphenol or 2,6-di- -Tert-butyl-p-cresol (BHT), an antioxidant manufactured by Ciba Specialty Chemicals Co., Ltd., and the like.
The hindered phenol-based stabilizer used in the present invention can be mixed and contained in two or more types, but the total content of the hindered phenol-based stabilizer is 0. It is preferable that it is 0001-1 mass part, and it is more preferable that it is 0.001-0.1 mass part.

  Examples of sterically hindered amines (hindered amines) include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, n- Butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester, 1- (2-hydroxyethyl) -2,2 , 6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensation product, N, N ′-(2,2,6,6-tetramethylpiperidyl) hexamethylenediamine and 4-tert-octylamino-2 , 6-dichloro-s-triazine condensation product, tris (2,2,6,6-tetramethylpiperidyl) nitrilotriacetate, tetrakis (2,2,6,6) Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 ′-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the like can be mentioned.

  Examples of hydroxylamine include N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N derived from hydrogenated tallow amine -Dialkylhydroxylamine etc. are mentioned.

  Examples of nitrones include N-benzyl-α-phenyl-nitrone, N-ethyl-α-methyl-nitrone, N-octyl-α-heptyl-nitrone, N-lauryl-α-undecyl-nitrone, and N-tetradecyl-α. -Tridecyl-nitrone, N-hexadecyl-α-pentadecyl-nitrone, N-octadecyl-α-heptadecyl-nitrone, N-hexadecyl-α-heptadecyl-nitrone, N-octadecyl-α-pentadecyl-nitrone, N-heptadecyl-α -Heptadecyl-nitrone, N-octadecyl-α-hexadecyl-nitrone, nitrone derived from N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

  Examples of benzofuran-2-one include 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one and 5,7-di-tert-butyl-3. -[4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3′-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran -2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di -Tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one, and the like.

  Examples of the thiosynergist include dilauryl thiodipropionate or distearyl thiodipropionate. Examples of the polyamide stabilizer include a copper salt combined with an iodide and / or a phosphorus compound, and a divalent manganese salt. Examples of the metal stearate include calcium stearate, zinc stearate, magnesium stearate and the like. Examples of the nucleating agent include 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid and the like. Examples of the filler and reinforcing agent include calcium carbonate, silicate, glass fiber, asbestos, talc, kaolin, mica, barium sulfate, metal oxide and metal hydroxide, carbon black, and graphite.

There is no restriction | limiting in particular about the method of mixing the compound represented with the said General formula (1), and an adhesive, and preparing the adhesive composition of this invention.
When the compound represented by the general formula (1) is compatible with the pressure-sensitive adhesive, the compound represented by the general formula (1) can be directly added to the pressure-sensitive adhesive.
The compound represented by the general formula (1) may be dissolved in an auxiliary solvent having compatibility with the adhesive, and the solution may be added to the adhesive. For example, the compound represented by the general formula (1) may be dissolved in a plasticizer, and the plasticizer solution and the pressure-sensitive adhesive may be kneaded. Further, the compound represented by the general formula (1) may be dispersed in a high-boiling organic solvent or polymer, and the dispersion may be added to the pressure-sensitive adhesive.

  Examples of the plasticizer include glycol ester. For example, triethylene glycol-diethylene butyrate triethylene glycol di-2-ethylhexoate, triethylene glycol dicaprylate, triethylene glycol di-n-octate, triethylene glycol di-n-heptate, tetraethylene glycol di N-heptate, 1,3-propylene glycol di-2-ethylbutyrate, 1,4-propylene glycol di-2-ethylbutyrate, 1,4-butylene glycol di-2-ethylbutyrate, 1,2- Butylene glycol di-2-ethylene butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethylhexoate, dipropylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethylpe Toeto, tetraethylene glycol di-2-ethyl butyrate, and the like diethylene dicaprylate benzoate.

  Examples of the high boiling point organic solvent include phosphate ester, phosphonate ester, benzoate ester, phthalate ester, fatty acid ester, carbonate ester, amide, ether, halogenated hydrocarbon, alcohol and paraffin. Phosphate esters, phosphonate esters, phthalate esters, benzoate esters and fatty acid esters are preferred.

  The pressure-sensitive adhesive composition of the present invention can be used for all applications in which the pressure-sensitive adhesive is used, but can be particularly suitably used for applications that may be exposed to light including sunlight or ultraviolet rays. Specific examples include, for example, films, laminated glass, glass substitutes and their surface coating materials, window glass for housing, facilities, transportation equipment, coating materials for daylighting glass and light source protection glass, housing, facilities, transportation equipment, etc. Window film, fluorescent light, mercury lamp and other light source materials, precision machinery, electronic and electrical equipment materials, electromagnetic wave shielding materials from various displays, food, chemicals, chemical containers and packaging materials, bottles , Boxes, blisters, cups, special packaging, compact disc coats, agricultural or industrial sheets or film materials, protective films for polymer supports (eg for plastic parts such as machinery and automotive parts), printed overcoats, Laminated matte, optical light film, safety glass / windshield interlayer, electro Romic / photochromic applications, overlaminate films, surface protection films, solar heat control films, sports textiles, textile products for clothing such as hats, home interiors such as textiles, curtains, carpets, wallpaper, medical instruments, optical filters, Examples include backlight display films, prisms, mirrors, optical materials such as photographic materials, mold films, transfer stickers, anti-graffiti films, tapes, adhesive tapes, marking plates, marking devices, and their surface coating materials. .

(Laminate)
It is preferable that the adhesive composition of this invention is used for the adhesive layer which comprises a laminated body.
The laminate has at least a substrate and an adhesive layer, and examples of the substrate include glass and resin. Examples of the resin include polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, Polyolefin film such as ethylene / ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer, polyester film such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyacrylate film, polystyrene film, nylon 6, nylon 6,6, Examples thereof include polyamide films such as partially aromatic polyamides, polyvinyl chloride films, polyvinylidene chloride films, polycarbonate films, and fluororesin films. Of these, polyethylene and polypropylene are preferable. These resins may be used alone or in combination of two or more.
As a laminated body, what has a laminated structure is mentioned among the uses mentioned above, Especially, an adhesive tape, a film, a film for surface protection, a laminated glass etc. can be mentioned.

(Adhesive tape or film, surface protection film)
The pressure-sensitive adhesive tape or film of the present invention and the film for surface protection have a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition of the present invention on one surface of a film substrate. The film substrate may be a single layer or a plurality of layers. In the case of a single layer, the thickness of the film substrate is usually 30 to 200 μm, preferably about 50 to 150 μm. When a plurality of layers are laminated, the thickness of one layer of the base material layer is usually about 0.5 to 80 μm, preferably about 1 to 40 μm. Moreover, the thickness of the whole film base material is about 20-300 micrometers normally, Preferably it is about 20-250 micrometers, More preferably, it is about 40-200 micrometers. If the base material layer is less than 20 μm, the base material may be torn or torn during peeling, and if it exceeds 300 μm, the stiffness of the base material becomes large, and floating or the like tends to occur after sticking. The film substrate and the pressure-sensitive adhesive layer can be integrally formed, for example, by coextrusion molding. Further, the surface of the film substrate may be subjected to easy attachment treatment such as corona treatment or plasma treatment.

The constituent component (polymer) of the film base is not particularly limited as long as it is a resin that can be formed into a sheet or film, and has heat resistance and solvent resistance and has flexibility. preferable. When the base material layer has flexibility, it can be wound into a roll and various processes can be appropriately performed.
Specifically, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, ethylene -Polyolefin film such as ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer, polyester film such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyacrylate film, polystyrene film, nylon 6, nylon 6, 6, part Examples thereof include polyamide films such as aromatic polyamide, polyvinyl chloride films, polyvinylidene chloride films, and polycarbonate films. Of these, polyethylene and polypropylene are preferable. These polymers may be used alone or in combination of two or more.

(Laminated glass)
The laminated glass of this invention has the adhesive layer which consists of an adhesive composition of this invention in the single side | surface of a glass base material, It is characterized by the above-mentioned. In a preferred embodiment, this pressure-sensitive adhesive layer is prepared in advance from the pressure-sensitive adhesive composition of the present invention as an intermediate film. Laminated glass is obtained by pre-pressing and pressurizing a glass sheet having the intermediate film sandwiched between two glass substrates.
As the glass substrate, inorganic ones are preferable, in addition to raw glass, those subjected to tempering processing such as peripheral tempering processing, full tempering processing, etc. Various things, such as what was given, can be used. The thickness of the laminated glass is not particularly limited. For example, in the case of an automobile window glass, it is usually about 1.0 to 5.0 mm, and in the case of an architectural window glass, it may exceed 10.0. It can be selected as appropriate.

  The adhesive tape or film of the present invention, the film for surface protection, in order to effectively utilize the long wave ultraviolet shielding effect, in particular, a solar cell backsheet, a window pasting film, a food / medical packaging film, an agricultural film, It is suitably used for optical film and fiber applications.

  The pressure-sensitive adhesive tape or film, the surface protecting film, and the laminated glass of the present invention can be used for various building materials. For example, exterior building materials, wooden structures for building materials, roofing materials for building materials, antibacterial building materials, base materials for building materials, antifouling building materials, flame retardant materials, ceramic building materials, decorative building materials, painted articles for building materials, makeup Materials, nets for building materials, moisture permeable waterproof sheets for building materials, mesh sheets for building work, film for covering materials for building materials, coating materials for building materials, adhesive compositions for building materials, civil engineering and building structures, pedestrian coating materials, Examples thereof include a sheet-like photocurable resin, wood protective coating, a cover for a push button switch, a bonding sheet agent, a base material for building material, wallpaper, a polyester film for covering, a polyester film for covering a molded member, and a flooring.

  The pressure-sensitive adhesive tape or film, the surface protecting film, and the laminated glass of the present invention can be used for various image display devices. For example, an image display device using the described electrochromic element, an image display device called so-called electronic paper, a plasma display, an image display device using an organic EL element, and the like can be given.

  The pressure-sensitive adhesive tape or film of the present invention, the surface protecting film, the glass containing laminated glass, and the glass film will be described. Applications include, for example, heat ray-shielding glass window glass, colored glass, ultraviolet sharp-cut glass for high-intensity light sources such as mercury lamps and metal halide lamps, frit glass, automotive UV-shielding glass, colored heat ray-absorbing glass, and fluorescent enhancement White agent UV absorbing heat insulating glass, automotive UV heat blocking glass, exterior stained glass, water repellent UV infrared absorbing glass, glass for vehicle head-up display device, light control and heat insulation multi-layer window, UV infrared cut glass, UV cut Glass, UV-infrared absorbing glass for windows, UV-blocking antifouling films for windows, translucent panels for cultivation rooms, UV-infrared absorbing and low-transmitting glass, low reflectance and low-transmitting glass, edgelight devices, rough surface forming plate glass, and displays Laminated glass, glass with conductive film, anti-glare glass, absorbing ultraviolet and infrared light Over glass, window glass for privacy protection, glass for anti-fogging vehicle, glass for pavement material, glass plate with water droplet adhesion preventing property and heat ray blocking property, ultraviolet infrared absorption bronze glass, laminated glass, glass with ID identification function , PDP optical filters, skylights, and the like.

  Other use examples include light source covers for lighting devices, sports goggles, deflecting lenses, window covering films, high-definition antiglare hard coat films, antistatic hard coat films, transparent hard coat films, and resin film sheet bonding. Sealant, light guide, agricultural coating, prism sheet, special protective layer transfer sheet, floor sheet, light-shielding printing label, oil cup, low temperature heat shrinkable film for labels, fishing equipment, thin film, heat shrinkable Film, label for in-mold molding, projection screen, decorative sheet, wood surface protection, light control material, light control film, light control glass, flashlight, touch panel, resin film sheet bonding sealant, polycarbonate film coating, optical fiber For example, tape.

(Protective sheet for solar cell)
The pressure-sensitive adhesive composition of the present invention can be used for a solar cell protective sheet.
The solar cell applied to the present invention may be a solar cell composed of any type of element such as a crystalline silicon solar cell, an amorphous silicon solar cell, and a dye-sensitized solar cell. In crystalline silicon solar cells and amorphous silicon solar cells, a cover material is used as a protective member for imparting antifouling, impact resistance, and durability as described in JP-A-2000-174296. In dye-sensitized solar cells, as described in JP-A-2006-282970, a metal oxide semiconductor that is activated by light (especially ultraviolet rays) and becomes active is used as an electrode material. There is a problem that the adsorbed dye deteriorates and the photovoltaic power generation efficiency gradually decreases, and it is proposed to provide an ultraviolet absorbing layer. In this case, since the protective sheet for solar cells containing the pressure-sensitive adhesive composition of the present invention can maintain the long-wave ultraviolet shielding effect for a long time, it has an effect of exhibiting excellent light resistance.

  The protective sheet for solar cells using the pressure-sensitive adhesive composition of the present invention may further contain other components as necessary. Examples of the other components include a crosslinking agent, a crosslinking aid, an antioxidant, a flame retardant, a light stabilizer, a heat stabilizer, and a fluorescent brightening agent.

(Method for producing protective sheet for solar cell)
The solar cell protective sheet using the pressure-sensitive adhesive composition of the present invention may have any shape. Films and sheets described in JP-A-2000-91610 and JP-A-11-261085, for example, laminated films described in JP-A-11-40833, cover glass structures described in JP-A-11-214736, etc. Is mentioned. In addition, from the viewpoint of versatility, a sheet shape is preferable. When the solar cell protective sheet is in the form of a sheet or film, the thickness can be arbitrarily determined according to the standard used. Although it does not restrict | limit, Preferably it is the range of 30-300 micrometers, More preferably, it is 50-200 micrometers. A thickness within the above range is preferable because rigidity and mechanical strength can be obtained. The sheet-like protective sheet for solar cell can be used for both a solar cell front sheet and a solar cell back sheet.

The production of a solar cell protective sheet using the pressure-sensitive adhesive composition of the present invention will be described. A pressure-sensitive adhesive is applied so as to have an adhesive layer made of the pressure-sensitive adhesive composition of the present invention on one surface of the film substrate. At this time, the antiglare treatment layer may be laminated on the surface of the film base material to which the adhesive is not applied, and the antireflection layer may be laminated further outside the antiglare treatment layer. Next, the adhesive layer is sandwiched using another film base material. You may provide the resin layer for adhere | attaching on a solar cell module in the surface which is not in contact with the contact bonding layer of this film base material. From the viewpoint of barrier properties, a metal layer may be provided in the middle of the adhesive layer.
The film substrate is not particularly limited as long as it is a resin that can be formed into a sheet shape or a film shape, and any of the specific examples described in the section of a laminate, an adhesive tape or film, and a surface protective film. May be used.
The formation of the antiglare treatment layer includes a lamination treatment by an antiglare treatment using an acrylic binder and a silica filler. The thickness of the antiglare treatment layer is preferably 0.1 to 100 μm, more preferably 0.5 to 10 μm. Moreover, in order to form the said antireflection layer, for example, an antireflection treatment HEA coating may be performed. The thickness of the antireflection layer is preferably 1 to 1000 nm, more preferably 10 to 500 nm. Examples of the resin layer for adhering to the solar cell module include a release coat layer made of silicone resin and an acrylic resin layer. The thickness of the resin layer is preferably 5 to 500 μm, more preferably 10 to 200 μm. The acrylic resin can be mixed with titanium oxide having a strong hiding power. As the metal layer included in the middle of the adhesive layer, a transparent thin film of metal oxide such as gold, silver, copper, aluminum, nickel, or an alloy, tin oxide, indium tin oxide, and antimony oxide can be provided. As a method of providing these coat layers, a vacuum deposition method, a sputtering method, or the like can be used. The thickness of such a coat layer is usually about 1-1000 nm.

(Solar cell module)
The solar cell module of this invention contains the adhesion layer containing a base material and the adhesive composition of this invention. The solar cell module of the present invention preferably includes a protective sheet for solar cells using the pressure-sensitive adhesive composition of the present invention. In general, a solar cell module has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a protective sheet for solar cell or protective glass, and light is taken in from the opposite side of the support substrate. However, a transparent material such as tempered glass may be used for the support substrate, and a cell may be formed on the support substrate so that light is taken in from the transparent support substrate side. Specifically, a module structure called a super straight type, a substrate type, or a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known, and these module structures can be appropriately selected. Specifically, the structure and aspect described in Japanese Patent Application No. 11-8457 are preferable.

(Method for manufacturing solar cell module)
In the solar cell module of the present invention, the solar cell protective sheet using the pressure-sensitive adhesive composition of the present invention can be used without any particular limitation as long as the solar cell is sealed.
The protective sheet for solar cells using the pressure-sensitive adhesive composition of the present invention can be incorporated into a known solar cell module. For example, a protective sheet for a solar cell in which a module is assembled by the method described in JP-A-2007-128943, JP-A-2006-10057, JP-A-2002-134767, JP-A-2010-27714 and the pressure-sensitive adhesive composition of the present invention is used for this. Can be used.
For example, when a solar cell protective sheet is fixed on a cell, the solar cell protective sheet can seal the solar cell by a method such as heat adhesion after roll pressurization or heat adhesion after vacuum pressurization. is there.
When the periphery of the solar cell is surrounded by a frame and the space between the frame and the outer periphery of the solar cell is sealed with a sealing resin, the solar cell protective sheet can be used as the frame.

  FIG. 1 is a schematic view showing an example of the solar cell module of the present invention. In FIG. 1, 31 is a tempered glass, 32 is a resin layer, 33 is a solar cell sealing material of the present invention, 34 is a solar cell (cell), 35 is a frame, 36 is a sealing resin, 37 is a wiring, and 38 is an adhesive layer. Respectively. In the solar cell module of FIG. 1, light enters from the surface.

Next, the manufacturing method of the said solar cell module is demonstrated with reference to FIG.
(1) An EVA (ethylene vinyl acetate copolymer) sheet 32 is placed on a clean tempered glass 31, and a solar cell (cell) 34 is placed thereon.
(2) The solar cell encapsulant 33 of the present invention is placed on top of it and heated in this state for about 1 hour to crosslink the EVA layer.
(3) Cut excess EVA and back surface sealing material (back sheet) along the tempered glass.
(4) The produced member is pushed into the frame 35 from the tempered glass 31 side (becomes a front surface on which sunlight is incident).
(5) The EVA layer 32 and the solar cell sealing material 33 of the present invention are partially cut, and the wiring 37 is soldered to the terminal portion of the solar cell.
(6) The cut portion is coated with silicone resin or silicone rubber, and the terminal portion is sealed with the sealing resin 36.
(7) Provide a terminal box and perform wiring if necessary.

  Since the solar cell module of the present invention uses the pressure-sensitive adhesive composition of the present invention, the solar cell module has high light resistance and is excellent in adhesion due to improved heat and moisture resistance, and is included in the solar cell encapsulant. The deterioration of the resin can be suppressed, and the production is easy.

Next, a method for evaluating the light resistance of the polymer material will be described. As a method for evaluating the light resistance of a polymer material, “Polymer Light Stabilization Technology” (CMC Co., Ltd., 2000), pages 85 to 107, “Basic and Physical Properties of High-Functional Paint” (CMC Co., Ltd.) , 2003) pages 314 to 359, "Durability of polymer materials and composite products" (CMC Corporation, 2005), "Extension of polymer material life and environmental measures" (CMC Corporation, 2000), H.C. Zweifel edition “Plastics Additives Handbook 5th Edition” (Hanser Publishers) 238-244, Katsura Tadahiko “Basic Science 2 Science of Plastic Packaging Containers” (Japan Packaging Society, 2003) Chapter 8 it can.
The evaluation for each application can be achieved by the following known evaluation method. The deterioration of the polymer material due to light is determined according to JIS-K7105: 1981, JIS-K7101: 1981, JIS-K7102: 1981, JIS-K7219: 1998, JIS-K7350-1: 1995, JIS-K7350-2: 1995, JIS. It can be evaluated by the method of -K7350-3: 1996, JIS-K7350-4: 1996 and a method referring to this.

The light resistance when used as a packaging / container application can be evaluated by the method of JIS-K7105 and a method referring to this. Specific examples include light transmittance of bottle body, transparency evaluation, sensory test evaluation of bottle contents after UV exposure using xenon light source, haze value evaluation after xenon lamp irradiation, haze value evaluation as halogen lamp light source , Yellowing evaluation using a blue wool scale after exposure to mercury lamp, haze value evaluation using a sunshine weather meter, visual evaluation of coloring, UV transmittance evaluation, UV blocking rate evaluation, light transmittance evaluation, ink in ink container Viscosity evaluation, light transmittance evaluation, sample in container after sun exposure, color difference ΔE evaluation, ultraviolet transmittance evaluation after white fluorescent light irradiation, light transmittance evaluation, color difference evaluation, light transmittance evaluation, haze value evaluation, Color tone evaluation, yellowness evaluation, light-shielding evaluation, L ^* a ^* b ^* whiteness evaluation using the color system color difference formula, post-exposure support for each wavelength after spectral separation of xenon light Color difference ΔEa ^* b ^* in samples, after UV exposure, UV absorption rate evaluation, film tensile elongation after exposure using a sunshine weather meter, antibacterial evaluation after xenon weather meter exposure, after fluorescent light irradiation Evaluation of discoloration of packaging contents, peroxide value evaluation of oil after exposure to fluorescent lamps for bottles filled with salad oil, color evaluation, evaluation of absorbance difference after chemical lamp irradiation, surface gloss retention after exposure using sunshine weather meter Appearance evaluation, color difference after exposure using a sunshine weatherometer, bending strength evaluation, light shielding ratio evaluation, peroxide production amount evaluation in kerosene, and the like.

The long-term durability when used for paints and coatings is JIS-K5400, JIS-K5600-7-5: 1999, JIS-K5600-7-6: 2002, JIS-K5600-7-7: 1999, JIS. -K5600-7-8: It can be evaluated by the method of 1999, JIS-K8741 and a method referring to this. Color difference ΔEa ^* b ^* in the color density and CIE ^L * ^a * ^{b *} color coordinates after exposure by a xenon light resistance test machine and UVCON device and specific examples thereof include evaluation using residual gloss, xenon arc light for quartz slides on the film Absorbance evaluation after exposure using a test machine, evaluation using a fluorescent light in wax, color density after exposure to UV lamp and color difference ΔEa ^* b ^* in CIE L ^* a ^* b ^* color coordinates, metal weather light resistance tester Hue evaluation after exposure using a glass, gloss retention evaluation after an exposure test using a metal hydride lamp, evaluation using a color difference ΔEa ^* b ^* , evaluation of glossiness after exposure using a sunshine carbon arc light source, metal weather evaluation using lightfastness tester color difference ΔEa ^* b ^* after exposure using, gloss retention, appearance evaluation, sunshine weatherometer Gloss retention evaluation after exposure using Ta, evaluation using color difference after exposure using QUV lightfastness tester ΔEa ^* b ^*, gloss retention evaluation, post exposure gloss retention using a sunshine weatherometer Evaluation, Appearance evaluation after exposure using sunshine weatherometer on coated plate Gloss retention after exposure using sunshine weatherometer, Evaluation of change in lightness value, Evaluation of coating deterioration after exposure to Ducycle WOM for coating Appearance evaluation, evaluation of UV transmittance of coating film, evaluation of UV blocking rate of coating film, evaluation of time comparison to achieve gloss retention of 80% using sunshine weatherometer, exposure using dew panel light control weather meter color difference after after rust evaluation the strength of the concrete evaluation of painted formwork after weathering, outdoor weathering ΔEa ^* b ^* Evaluation Using crosscut adhesion evaluation, the surface appearance evaluation, gloss retention evaluation after weathering, yellowing after exposure using a carbon arc light source (.DELTA.YI) Evaluation, and the like.

The light resistance when used as an ink application can be evaluated by the method of JIS-K5701-1: 2000, JIS-K7360-2, ISO105-B02 and a method referring to this. Specifically, evaluation by measurement of color density and CIE L ^* a ^* b ^* color coordinates after exposure using an office fluorescent lamp, a fading tester, evaluation of electrophoresis after exposure to ultraviolet rays using a xenon arc light source, Density evaluation of printed matter using a xenon fade meter, evaluation of ink removal using a 100 W chemical lamp, evaluation of dye remaining rate of an image forming site using a weather meter, evaluation of choking of printed matter using an eye super UV tester, and discoloration evaluation, xenon fade For the printed matter after exposure to the meter, evaluation using the color difference ΔEa ^* b ^* in the CIE L ^* a ^* b ^* color coordinates, evaluation of the reflectance after exposure using a carbon arc light source, and the like can be given.

  The light resistance of the solar cell module can be evaluated by the method of JIS-C8917: 1998, JIS-C8938: 1995 and a method referring to this. Specifically, IV measurement after exposure with a light source equipped with a correction filter for solar simulation on a xenon lamp, photovoltaic power generation efficiency evaluation, sunshine weather meter, faded gray scale rating evaluation using a fade meter, Examples include color and appearance adhesion evaluation.

The light resistance of the fibers and fiber products is JIS-L1096: 1999, JIS-A5905: 2003, JIS-L0842, JIS-K6730, JIS-K7107, DIN75.202, SAEJ1885, SN-ISO-105-B02, AS / NZS4399. This method can be evaluated by the above method and a method referring to this method. Evaluation of UV transmittance, evaluation of discoloration of blue scale after exposure using xenon light source, carbon arc light source, evaluation of UV cut rate described, evaluation of UV blocking property, change of blue scale after exposure using carbon arc light source after dry cleaning Fading evaluation, lightness index after exposure using a fadeometer, color difference ΔE ^* evaluation based on chromaticness index, tensile strength evaluation after exposure using a UV tester, sunshine weather meter, total transmittance evaluation, strength retention evaluation , UVF (UPF) evaluation, discoloration gray scale evaluation after exposure using a high-temperature fade meter, appearance evaluation after outdoor exposure, yellowness (YI) after yellow exposure, yellowness (ΔYI) evaluation, regulations For example, reflectivity evaluation.

The light resistance of building materials can be evaluated by the method of JIS-A1415: 1999 and a method referring to this. Specifically, surface color evaluation after exposure using a sunshine weatherometer, appearance evaluation after exposure using a carbon arc light source, appearance evaluation after exposure using an eye super UV tester, absorbance evaluation after exposure, Chromaticity after exposure, color difference evaluation, evaluation using CIE L ^* a ^* b ^* color difference after exposure using a metal hydride light source, evaluation using color difference ΔEa ^* b ^* in color coordinates, evaluation of gloss retention, Japanese Patent Laid-Open No. 10-44352 Gazette, Japanese Patent Application Laid-Open No. 2003-111538, evaluation of haze value change after exposure using sunshine weather meter, evaluation of elongation retention using tensile tester after exposure, evaluation of ultraviolet transmittance after immersion in solvent, eye super Appearance visual evaluation after exposure using UV tester, gloss rate change evaluation after QUV test, gloss retention after exposure using sunshine weatherometer Value, evaluation using black light blue fluorescent color difference after ultraviolet exposure using a lamp ΔEa ^* b ^*, adhesion retention evaluation after exposure using Kobukon accelerated tester, ultraviolet screening assessment, especially outdoor exposure (JIS- A1410) Appearance evaluation, total light transmittance evaluation, haze change evaluation, tensile shear bond strength evaluation, total light transmittance evaluation after exposure using a xenon weather meter, haze evaluation, yellowing degree evaluation, sunshine weathering The yellowing degree (ΔYI) after exposure using a meter, the evaluation of the residual ratio of the ultraviolet absorber, and the like can be mentioned.

The light resistance when used as a recording medium can be evaluated by the method of JIS-K7350 and a method referring to this. Specifically, the background color difference change evaluation in the printed part after the fluorescent lamp irradiation, the image density residual rate evaluation by the exposure using the xenon weather meter, the optical reflection density change evaluation by the exposure using the xenon weather meter, the Suntest CPS light L ^* a ^* b ^* post-exposure yellowing evaluation using an amber tester, fading evaluation after exposure using a fade meter, visual discoloration evaluation after exposure using a xenon fade meter, indoor sunlight Evaluation of color density retention after exposure, evaluation of color density retention after exposure using a xenon weather meter, evaluation of C / N after exposure using a fade meter, evaluation of fog density after exposure to fluorescent light, use fluorescent light There optical reflection density evaluation after exposure, erasability evaluation, color difference Delta] E ^* evaluation after exposure using Atlas fade meter, a carbon arc fade menu Fading visually after exposure using a coater evaluation, the organic EL element color conversion characteristic retention evaluation, the organic EL display luminance measurement evaluation after exposure by a xenon discoloration tester and the like.

  As other evaluation methods, it can be evaluated by the method of JIS-K7103 and ISO / DIS9050 and a method referring to this. Specifically, appearance evaluation of polycarbonate coated film after exposure with UV tester, evaluation of blue scale after exposure to ultraviolet rays in artificial hair, evaluation of treated fabric contact angle for evaluation after exposure using an accelerated light resistance tester, Visual evaluation of images projected on a projection screen after exposure using the weathering tester described in Japanese Unexamined Patent Publication No. 2005-55615, surface deterioration of the specimen after exposure using a sunshine weather meter, metal weather meter, visual inspection of changes in design Evaluation, visual visual evaluation after exposure to lighting using a metal lamp reflector Evaluation of light transmittance of bottle labels, evaluation of deterioration of polypropylene after exposure using a xenon weather meter, hard coat using a sunshine weatherometer Film degradation assessment, substrate degradation assessment, hydrophilicity assessment, scratch resistance assessment Grayscale color difference evaluation of artificial leather after exposure using a xenon lamp light source, evaluation of liquid crystal device characteristics after exposure using a mercury lamp, adhesion evaluation after exposure using a sunshine weatherometer, evaluation of the degree of purpura on the turf, xenon Post-exposure UV transmittance evaluation using an arc light source, tensile strength evaluation, concrete adhesion rate evaluation, post-exposure appearance evaluation using a sunshine weatherometer, coating film adhesion evaluation, yellow after exposure using a carbon arc light source Degree of change, adhesion evaluation, adhesion performance evaluation using an ultraviolet fade meter, insect flying suppression evaluation during lighting, yellowing degree (ΔYI) evaluation of laminated glass using an eye super UV tester, QUV irradiation, moisture resistance test Surface appearance evaluation, gloss retention evaluation, dew panel light control weather meter Color difference evaluation over time, glossiness (DI), yellowness index (YI) evaluation in the coated state of a wood substrate after exposure using a xenon weatherometer, ultraviolet ray irradiation, ultraviolet absorption evaluation after repeated darkness, ultraviolet light And dye fading color difference ΔE evaluation after exposure.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

(Synthesis example)
Synthesis example 1
(Preparation of exemplary compound (2))

(Synthesis of X-2)
A three-necked flask was charged with 39.5 g (1.1 molar equivalent) of acetoxime, 600 mL of DMF (N, N-dimethylformamide), 60.6 g (1.1 molar equivalent) of potassium tert-butoxide at room temperature. Stir for minutes. Thereafter, the internal temperature was set to 0 ° C., and 60 g (1.0 molar equivalent) of the compound (X-1) was slowly added dropwise thereto. After the dropwise addition, the internal temperature was raised to 25 ° C. and stirred at that temperature for 1 hour.
The reaction mixture was extracted and separated with an aqueous ammonium chloride solution and ethyl acetate, and the resulting organic phase was washed with saturated brine and separated. The organic phase thus obtained was concentrated by a rotary evaporator to obtain a residue obtained as a crude product of compound (X-2).

(Synthesis of X-3)
The whole composition of the compound (X-2) obtained above is put into a three-necked flask, 700 mL of ethanol and 500 mL of 1M hydrochloric acid water are added, and the reaction mixture is heated to an internal temperature of 80 ° C. For 3 hours.
The reaction mixture was cooled to an internal temperature of 25 ° C., extracted and separated with a saturated aqueous sodium hydrogen carbonate solution and ethyl acetate, and saturated brine was added to the obtained organic phase to wash and separate the layers. The organic phase thus obtained was concentrated by a rotary evaporator to obtain a residue obtained as a crude product of compound (X-3).

(Synthesis of X-4)
After filling the flask with nitrogen gas, 6.5 g of 10% Pd-C (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the three-necked flask, and ethanol (2,000 mL) was added to the compound (X- The whole composition of 3) was added and heated and refluxed. Thereto was slowly added 55 mL (3 molar equivalents) of formic acid, and the mixture was stirred at this temperature for 5 hours. Thereafter, the reaction mixture was cooled to an internal temperature of 25 ° C., 105 g of 1,5-naphthalenedisulfonic acid was added to the mother liquor filtered through celite and separated by furnace, the internal temperature was raised to 70 ° C., and the mixture was stirred for 30 minutes. Then, it cooled gradually to room temperature, the crystal | crystallization was separated by filtration, and 100g of compounds (X-4) were obtained. The yield was 72% starting from compound (X-1). The obtained crystal was light brown. ¹ H NMR (deuterated DMSO): δ 6.95-6.98 (1H), δ 7.02-7.04 (1H), δ 7.40-7.51 (3H), δ 7.90-7.95 (1H ), Δ 8.75 (1H), δ 8.85-8.88 (2H), δ 9.03 (2H), δ 10.89 (1H)

  To 160.0 g of salicylamide, 600 mL of acetonitrile and 355.2 g of DBU were added and dissolved. To this solution, 193.2 g of 4-cyanobenzoyl chloride was added and stirred at room temperature for 24 hours. To this reaction solution, 1200 mL of water and 150 mL of hydrochloric acid were added, and the resulting solid was filtered and washed with water to obtain 292.8 g of synthetic intermediate C (yield 94%).

  To 200.0 g of the synthetic intermediate C, 1200 mL of acetonitrile and 110.5 g of sulfuric acid were added and stirred at 90 ° C. for 4 hours. To this reaction solution, 600 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 177.2 g of synthetic intermediate D (yield 95%).

50 mL of methanol and 4.3 g of 28% sodium methoxide methanol solution were added to 6.2 g of compound (X-4). Synthetic intermediate D5.0g was added to this solution, and it stirred at 60 degreeC for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 7.1 g of Compound (2) (yield 96%). MS: m / z 367 (M +) ¹ H NMR (CDCl ₃ ): δ 7.01-7.13 (4H), δ 7.56-7.59 (2H), δ 7.91-7.93 (2H), δ 8.52-8.54 (2H), δ 8.58-8.60 (2H), δ 12.77 (2H) λmax = 355 nm (EtOAc)

Synthesis example 2
(Preparation of exemplary compound (m-2))
To 160.0 g of salicylamide, 600 mL of acetonitrile and 355.2 g of DBU were added and dissolved. To this solution, 193.2 g of 3-cyanobenzoyl chloride was added and stirred at room temperature for 24 hours. 1200 mL of water and 150 mL of hydrochloric acid were added to the reaction solution, and the resulting solid was filtered and washed with water to obtain 296.0 g of synthetic intermediate M (yield 95%).

  Acetonitrile 1200mL and sulfuric acid 110.5g were added to the synthetic intermediate M200.0g, and it stirred at 90 degreeC for 4 hours. To this reaction solution, 600 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 177.3 g of synthetic intermediate N (yield 95%).

  50 mL of methanol and 4.3 g of 28% sodium methoxide methanol solution were added to 6.2 g of compound (X-4). The synthetic intermediate N5.0g was added to this solution, and it stirred at 60 degreeC for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.9 g of exemplary compound (m-2) (yield 93%). MS: m / z 367 (M +)

  The compounds used in the examples were prepared using the same method as described above.

<Measurement method of pKa>
Exemplified compound (1) was dissolved in acetonitrile so that the absorbance was 1, and 70% perchloric acid (acetic acid solvent) was added dropwise to this solution to change the pH. The solution absorption spectrum at that time was measured, and the ratio between the triazine free form and the proton adduct at each pH was calculated from the absorbance at λmax. The pKa value was determined from the point at which the values became equal. Here, the triazine-free form represents the exemplified compound (1) itself, and the proton adduct represents a compound in which a proton is added to the nitrogen atom of the triazine ring of the exemplified compound (1). Similarly, exemplary compounds (2), (20), (23), (84), (m-2), (m-3), (m-4), (m-21), (m-31) , (M-20), (m-1), and comparative compounds (Example A1) and (Example A2), the pKa value was determined. The absorption spectrum was measured using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation. The pH was measured using a pH meter meter HM60G (trade name) manufactured by Toa Denpa Kogyo. The absorbance is a value measured at the maximum absorption wavelength of each compound. The results are shown in Table 1.

As an example of the pressure-sensitive adhesive composition, an interlayer film was prepared and evaluated as a laminated glass.
[Examples 1 to 7] Use for laminated glass [Example 1]
≪Preparation of interlayer film≫
The materials shown in Table 2 were supplied to a roll mill and melt kneaded at 95 ° C. to prepare an adhesive composition. The addition amount of the ultraviolet absorber is mass% with respect to the resin.
The obtained composition was sandwiched between two polyethylene terephthalate films and press molded at 120 ° C. for 5 minutes. After standing to cool, the obtained intermediate film was peeled off from the film, and the thickness was 0.8 mm. A membrane was obtained.
≪Production of laminated glass≫
The intermediate film is sandwiched between two 3 mm thick float glass plates that have been washed and dried in advance, put in a rubber bag, vacuum degassed, and pre-pressed at a temperature of about 80 ° C. Next, this pre-pressed glass was put in an autoclave and subjected to a pressure treatment for 30 minutes under conditions of a pressure of 5 kg / cm ² and 150 ° C.
As described above, the laminated glass of Example 1 obtained was less colored and less optically distorted.

[Example 2]
≪Preparation of interlayer film≫
40 parts by mass of triethylene glycol-di-ethylene butyrate, 0.2 parts by mass of 2,6-di-tert-butyl-P-cresol (BHT) (Sumirider BHT manufactured by Sumitomo Chemical Co., Ltd.) as an antioxidant, and As a UV absorber, 4.0 parts by mass of the compound (23) was stirred and mixed until a uniform transparent solution was prepared to prepare a plasticizer solution.
After adding 44.2 parts by mass of the plasticizer solution to 100 parts by mass of the resin 2, this was sufficiently kneaded with a mixing roll, and then press-molded at 150 ° C. for 30 minutes using a press molding machine. An interlayer film having a thickness of 0.76 mm was obtained.
≪Manufacture of laminated glass≫
The obtained intermediate film was sandwiched by transparent float glass of 30 cm × 30 cm × thickness 2.5 mm from both ends, put in a rubber bag, deaerated at a vacuum degree of 2660 Pa for 20 minutes, and then deaerated. It was transferred to an oven as it was, and further vacuum-pressed while being kept at 90 ° C. for 30 minutes. The laminated glass preliminarily pressure-bonded in this manner was pressure-bonded for 20 minutes in an autoclave at 135 ° C. and a pressure of 118 N / cm ² to obtain a laminated glass.
As described above, the laminated glass of Example 2 obtained was less colored and less optically distorted.

[Example 3] to [Example 7]
For Examples 3 to 7, the components listed in Table 2 were used, and when Resin 1 was used, the same as Example 1, and when Resin 2 was used, the same as Example 2. In addition, a laminated glass was manufactured.

[Comparative Example 1]
Similarly to Example 1, laminated glass was prepared using the materials shown in Table 2.

[Comparative Example 2]
Similarly to Example 2, laminated glass was prepared using the materials shown in Table 2.

≪Evaluation≫
[Light resistance]
Each of the prepared laminated glasses was irradiated with light with a metal halide lamp (in the presence of a cut filter of about 350 nm or less) (trade name: iSuper UV Tester, manufactured by Iwasaki Electric Co., Ltd.) at an illuminance of 90 mW / cm ² , a temperature of 63 ° C., and a humidity of 50%. did.
The evaluation was judged as follows and shown in the table. Each laminated glass was evaluated for the time taken for the shielding rate to reach 5% after light irradiation at a wavelength where the shielding rate before light irradiation was 1%. When the time taken for testing Comparative Example 1 was 1 (reference), the light resistance was evaluated using the following criteria.
A: 4 or more for Comparative Example 1 ○: 2 or more and less than 4 for Comparative Example 1 Δ: 1 or more and less than 2 for Comparative Example 1 ×: 0 for Comparative Example 1 1 to less than 1

[Image distortion]
Before making the laminated glass, each resin composition (intermediate film) is irradiated with a metal halide lamp (in the presence of a cut filter of about 350 nm or less) (trade name: iSuper UV Tester, manufactured by Iwasaki Electric Co., Ltd.) with an illuminance of 90 mW / cm ² and a temperature of 63 ° C. And light irradiation under the condition of humidity 50%.
The evaluation was made as follows and shown in Table 2.
Whether or not image distortion occurred after light irradiation was evaluated based on an image viewed through the film before light irradiation in each resin composition. Comparison Example 1 was compared with the image distortion produced when tested and evaluated according to the following criteria.
○: When image distortion is smaller than that of Comparative Example 1 Δ: When image distortion equivalent to that of Comparative Example 1 occurs ×: When image distortion is larger than that of Comparative Example 1

The materials described in Table 2 will be described.
Resin 1: Ethylene / vinyl acetate copolymer (“UE750R” manufactured by Tosoh Corporation), melting temperature (Tm) 66 ° C., vinyl acetate content 32%, melt flow rate (MFR): 30 g / 10 min

Resin 2: Polyvinyl butyral resin synthesized as follows To 2890 g of pure water, 275 g of polyvinyl alcohol having an average polymerization degree of 1700 and a saponification degree of 99.2 mol% was added and dissolved by heating. The temperature of this solution was adjusted to 15 ° C., 201 g of hydrochloric acid having a concentration of 35 mass% and 157 g of n-butyraldehyde were added, and the reaction product was precipitated while maintaining 15 ° C. Next, the reaction system was held at 60 ° C. for 3 hours to complete the reaction, and then washed with excess water to wash away unreacted n-butyraldehyde, and the hydrochloric acid catalyst was used as a general-purpose neutralizing agent, sodium hydroxide. The mixture was neutralized with an aqueous solution, further washed with excess water for 2 hours, and dried to obtain a white powdery polyvinyl butyral resin. The average degree of butyralization of this polyvinyl butyral resin was 68.5 mol%.

Additive 1: 2,6-di-tert-butyl-P-cresol (BHT) as an antioxidant (Sumitomo Chemical Co., Sumirider BHT)
Additive 2: LA-94 manufactured by ADEKA as a hindered amine light stabilizer

  UV absorber used in comparative example:

  The above-mentioned compound is commercially available, Example A1 is Tinuvin 1577FF manufactured by Ciba, and Example A2 is CYASORB UV-1164 manufactured by CYTEC.

[Examples 8 to 12] Use in Solar Cell Modules The present invention will be described in more detail with reference to Examples 8 to 12, but the layer structure, layer thickness, and the like that can be used in the present invention are not limited thereto.

[Production Example 1]
≪Preparation of solar cell front sheet≫
A biaxially stretched polyethylene terephthalate film (manufactured by Toray Industries Inc., Lumirror S56) having a thickness of 50 μm was used as the transparent resin sheet. An antiglare treatment layer comprising 100 parts by mass of an acrylic binder (NIPOL Lx811, manufactured by Nippon Zeon Co., Ltd.) and 5 parts by mass of silica filler (trade name Snowtex ZL manufactured by Nissan Chemical Co., Ltd.) is provided on one side of the transparent resin sheet. (Coat thickness: about 2 μm).
A pressure-sensitive adhesive (2-ethylhexyl acrylate-2-hydroxyethyl acrylate copolymer (2-ethylhexyl acrylate copolymer) is used so that the dry film thickness is 20 μm as a transparent adhesive on the untreated side of the sheet. 92% by mass of an acrylic copolymer (weight average molecular weight = 400,000) prepared by copolymerizing 80 parts by weight and 20 parts by weight of hydroxyethyl acrylate and 8% by mass of the compound (m-21) as an ultraviolet absorber ) And a polyethylene terephthalate film (SPPET 3811, manufactured by Lintec Co., Ltd., having a thickness of 38 μm was produced as a laminated solar cell front sheet. The solar cell front sheet thus produced should be used by adhering to a solar cell module. Can do.
From the outside, a solar cell front sheet of antiglare treatment layer / PET / adhesive layer (2-ethylhexyl acrylate-2-hydroxyethyl acrylate copolymer + UV absorber (m-21)) / PET was prepared.

[Production Example 2]
≪Preparation of solar cell front sheet≫
40 parts by mass of triethylene glycol-di-ethylene butyrate, 0.2 parts by mass of 2,6-di-tert-butyl-P-cresol (BHT) (Sumirider BHT manufactured by Sumitomo Chemical Co., Ltd.) as an antioxidant, and As a UV absorber, 2.9 parts by mass of (m-21) was stirred and mixed until a uniform transparent solution was obtained, thereby preparing a plasticizer solution.
The composition obtained by adding 40 parts by mass of the plasticizer solution to 100 parts by mass of the resin 2 and sufficiently kneading the mixture with a mixing roll was used to prepare two polyethylene terephthalate films (Lintec Corp. SPPET 3811, thickness 38 μm). The film was press-molded at 150 ° C. for 30 minutes using a press molding machine, and a film having an average film thickness of 0.76 mm was obtained.
On one side of the polyethylene terephthalate film, an antiglare treatment layer comprising 100 parts by mass of an acrylic binder (NIPOL Lx811, manufactured by Nippon Zeon Co., Ltd.) and 5 parts by mass of silica filler (trade name Snowtex ZL manufactured by Nissan Chemical Co., Ltd.) A provided solar cell front sheet (coat thickness: about 2 μm) was prepared.
A front sheet for solar cell of antiglare treatment layer / PET / adhesive layer (resin 2+ ultraviolet absorber (m-21)) / PET was prepared from the outside.

[Production Example 3]
≪Preparation of solar cell backsheet≫
Application in which 5% by mass of compound (84) as a two-component curable urethane adhesive (AD76P1 / CAT10 manufactured by Toyo Morton Co., Ltd.) and a UV absorber is mixed with 25 μm of a fluororesin film (PVF Tedlar manufactured by DuPont). The liquid was applied so that the solid content was 4 g / m ^2, and 250 μm of PET film (Lumirror S10 manufactured by Toray Industries, Inc.) was laminated by the dry laminating method. Next, a rutile type is further added to a coating solution in which an acrylic resin (Serken Chemical Co., Ltd. Thermolac) with an introduced polyester skeleton and an acrylic resin (Act Flow manufactured by Soken Chemical Industry Co., Ltd.) are blended in a ratio of 70:30. Titanium oxide (CR-90 manufactured by Ishihara Sangyo Co., Ltd.) was added and mixed in an amount of 10% by mass based on the resin solid content to obtain a white coating solution. This coating solution is applied to one side of the PET film surface of the laminate by a gravure coating method, and an adhesive coating layer (thickness 2 μm) of 4 g / m ² is provided as a solid content coating amount. A back sheet for solar cell on the inner surface side was prepared. The back sheet for a solar cell thus produced can be used by being bonded to a solar cell module.
A solar cell backsheet of fluororesin film layer / adhesive layer (urethane resin + ultraviolet absorber (84)) / PET / acrylic resin + titanium oxide layer was prepared from the outside.

[Production Example 4]
≪Preparation of solar cell front sheet≫
100 parts by mass of Resin 1 and 2.3 parts by mass of an ultraviolet absorber (84) were supplied to a roll mill and melt-kneaded at 95 ° C. to prepare an adhesive composition.
The obtained composition was sandwiched between two polyethylene terephthalate films (SPPET 3811 manufactured by Lintec Co., Ltd., thickness 38 μm) and press-molded at 150 ° C. for 30 minutes to obtain a film having a thickness of 142 μm. An anti-glare treatment layer consisting of 100 parts by mass of an acrylic binder (NIPOL Lx811, manufactured by Nippon Zeon Co., Ltd.) and 5 parts by mass of silica filler (trade name Snowtex ZL manufactured by Nissan Chemical Co., Ltd.) is provided on one side of the polyethylene terephthalate film. (Coat thickness: about 2 μm).
A solar cell front sheet was prepared. The solar cell front sheet thus produced can be used by being bonded to a solar cell module.
From the outside, a solar cell front sheet of antiglare treatment layer / PET / adhesive layer (resin 1 + ultraviolet absorber (84)) / PET / was prepared.

[Production Example 5]
≪Preparation of solar cell backsheet≫
On one side of a 150 μm thick polyethylene terephthalate (PET) resin film (raw material PET: Diafoil Hoechst, Diafoil T-600 (registered trademark)) manufactured by an extrusion method as a base plastic film Using a dry laminating machine, the compound (20) as an ultraviolet absorber is added to a polyurethane adhesive (main agent Takelac A515 / curing agent Takenate A50 = 10/1 solution) manufactured by Mitsui Chemicals Polyurethane Co., Ltd. having a solid content of 30% by mass. The coating liquid added so that it might become the mass% was apply | coated so that the application quantity in a dry state might be 4.0 g / m < ² >. An aluminum foil having a thickness of 25 μm was bonded as a metal foil thereon to provide a metal layer. Furthermore, on one side of the aluminum foil side of the laminate, a dry laminating machine was used to apply a polyurethane adhesive (main agent Takelac A515 / curing agent Takenate A50 = 10/1 solution) having a solid content of 30% by mass to Mitsui Chemical Polyurethanes. A coating solution in which the compound (20) is added in an amount of 2.0% by mass as an ultraviolet absorber is applied so that the coating amount in a dry state is 4.0 g / m ^2, and is extruded as a plastic film. A polyethylene terephthalate (PET) resin film (raw material PET: manufactured by Diafoil Hoechst Co., Ltd., Diafoil T-600 (registered trademark)) produced by the above method was bonded to prepare a solar battery back sheet.
A back sheet for solar cell of PET / adhesive layer (urethane resin + ultraviolet absorber (20)) / metal layer / adhesive layer (urethane resin + ultraviolet absorber (20)) / PET was prepared from the outside.

[Examples 8 to 12]
≪Production of solar cell module≫
Using the solar cell front sheet and back sheet produced in Production Examples 1 to 5, solar cell modules of Examples 8 to 12 were produced.

<Creation of solar cell module>
3 mm thick tempered glass, EVA sheet [SC50B manufactured by Mitsui Chemicals Fabro Co., Ltd.], crystalline solar cell, EVA sheet [SC50B manufactured by Mitsui Chemicals Fabro Co., Ltd.], and sheet prepared in Example Were laminated in this order, and hot-pressed using a vacuum laminator [Nisshinbo Co., Ltd., vacuum laminating machine] to adhere to EVA. EVA bonding conditions are as follows.
Using a vacuum laminator, evacuation was performed at 128 ° C. for 3 minutes, and then pressure was applied for 2 minutes to temporarily bond. Thereafter, the main adhesion treatment was performed in a dry oven at 150 ° C. for 30 minutes.
In this way, a crystalline solar cell module was produced. When the generated solar cell module was used for power generation operation, it showed good power generation performance as a solar cell.

Production of Comparative Examples 3 to 7 For Comparative Examples 3 to 7, solar cell modules were produced in the same manner as in Examples 8 to 12 except that Example A1 was substituted as the ultraviolet absorber.

≪Evaluation of film adhesion durability≫
In Examples 8 to 12, the metal halide lamp (in the presence of a cut filter of about 350 nm or less) (trade name: iSuper UV Tester, manufactured by Iwasaki Electric Co., Ltd.), illuminance of 90 mW / cm ² , temperature of 63 ° C., humidity of 50 from the outside direction. % Was irradiated with light. The peeling of the film (checking the bubbles between the adhesive layer and the substrate) was visually confirmed, and evaluation and comparison were performed. Evaluation and comparison were performed on Examples 8 to 12 using Comparative Examples 3 to 7 containing the same amount of (Example A1) in place of the respective ultraviolet absorbers. The evaluation was judged as follows and is shown in Table 3.
A: Time required for confirming film peeling is 5 times or more than that for each comparative example. O: Time required for confirming film peeling is more than 1 time and less than 5 times for each comparative example. : Time required for confirming film peeling is 1 time as compared with each comparative example ×: Time required for confirming film peeling is less than 1 time compared with each comparative example

≪Evaluation of power generation efficiency of solar cell module≫
Evaluation was performed by comparing the power generation efficiency of Examples 8 to 12 with Comparative Examples 3 to 7 including the same amount of (Example A1) instead of each ultraviolet absorber as the respective standards. The evaluation was judged as follows and is shown in Table 3.
◎: The power generation efficiency is 1.5 times or more than when the protective sheet of each comparative example is used. ○: The power generation efficiency is more than 1 time and less than 1.5 times than when the protective sheet of each comparative example is used. When the protective sheet of the comparative example is used and the power generation efficiency is 1 time ×: The power generation efficiency is less than 1 time than when the protective sheet of each comparative example is used

  The power generation efficiency was measured using the solar cell modules of Examples 8-12. The power generation efficiency of the solar cell module of the present invention was found to be higher than that of a conventional solar cell module using an ultraviolet absorber.

DESCRIPTION OF SYMBOLS 10 ... Solar cell module 31 ... Tempered glass 32 ... Resin layer 33 ... Solar cell sealing material 34 ... Solar cell (cell)
35 ... Frame 36 ... Sealing resin 37 ... Wiring 38 ... Adhesive layer

Claims (15)

A pressure-sensitive adhesive composition comprising a pressure-sensitive adhesive and an ultraviolet absorber represented by the following general formula (1).

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or OH, and at least one of the substituents has a Hammett's σp value Represents a substituent which is positive. Moreover, you may combine with substituents and may form a ring. R ^1g , R ¹ⁱ , R ^1j , R ^1k , R ^1m and R ^1p each independently represent a hydrogen atom or a monovalent substituent. Moreover, you may combine with substituents and may form a ring. R ^1h and R ¹ⁿ each independently represent a hydrogen atom, a halogen atom, or a monovalent substituent linked by S, C, or N. ]   The monovalent substituent is a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, substituted or Unsubstituted alkylcarbonyl group, nitro group, substituted or unsubstituted amino group, hydroxy group, alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group, substituted or unsubstituted sulfamoyl group, thiocyanate group, Or a substituted or unsubstituted alkylsulfonyl group, and when the monovalent substituent has a substituent, the substituent is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, an alkoxycarbonyl group, Carbamoyl group, alkylcarbonyl group, nitro group, amino group, hydroxy group, alkoxy group having 1 to 20 carbon atoms Aryloxy group, a sulfamoyl group, a pressure-sensitive adhesive composition according to claim 1, characterized in that a thiocyanate group or an alkylsulfonyl group. The pressure-sensitive adhesive composition according to claim 1 or 2, wherein at least one of R ^1b , R ^1c and R ^1d is a substituent having a positive Hammett's σp value. The substituent having a positive Hammett's σp value is a group selected from COOR ^r , CONR ^s ₂ , CN, CF ₃ , a halogen atom, NO _2, and SO ₃ M. the pressure-sensitive adhesive composition according to any one of ~3 [R ^r, R ^s independently of one another, represent a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal. ]. The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the substituent having a positive Hammett's σp value is COOR ^r or CN [R ^r is a hydrogen atom or a monovalent Represents a substituent. ]. The pressure-sensitive adhesive composition according to claim 1, wherein R ^1h or R ¹ⁿ is a hydrogen atom. The pressure-sensitive adhesive composition according to claim ¹ , wherein R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p are hydrogen atoms. .   The pressure-sensitive adhesive composition according to claim 1, comprising 0.01 to 30% by mass of the compound represented by the general formula (1) in the pressure-sensitive adhesive composition.   The pressure-sensitive adhesive composition according to claim 8, wherein the pressure-sensitive adhesive comprises polyvinyl butyral or ethylene-vinyl acetate copolymer.   Further, it contains at least one additive selected from the group consisting of antioxidants, other ultraviolet absorbers, sterically hindered amines, and 0.01 to 10 mass of the additive with respect to the adhesive. The pressure-sensitive adhesive composition according to claim 1, comprising:   It is used for the adhesive layer which comprises a laminated body, The adhesive composition as described in any one of Claims 1-10 characterized by the above-mentioned.   The adhesive tape or film containing the adhesive layer containing a base material and the adhesive composition as described in any one of Claims 1-10.   The surface protection film containing the adhesive layer containing a base material and the adhesive composition as described in any one of Claims 1-10.   The laminated glass containing the adhesive layer containing a base material and the adhesive composition as described in any one of Claims 1-10.   The solar cell module containing the adhesive layer containing a base material and the adhesive composition as described in any one of Claims 1-10.

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