JPH078959B2 - Laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a laminate having a colored intermediate layer having particularly excellent weather resistance.

(Prior Art) As a laminate having a conventional colored intermediate layer, as a dye-containing layer, for example, a compound obtained by dispersing a compound having the following structures [A] to [C] in a polymer compound or forming a film, or [ There is a laminate in which a polymer compound layer containing a compound of A] to [C] is applied on a film and sandwiched between substrates to form a laminate.

(Problems to be Solved by the Invention) However, such a conventional dye-containing laminate has a problem in weather resistance such as deterioration of the dye such as fading and discoloration.

(Means for Solving the Problems) As a result of various studies to solve the above problems associated with a laminate containing a dye, the present inventors have found that the dye layer contains a nitroxy free radical, whereby a colored laminate is obtained. They have found that the weather resistance of the body can be improved, and have completed the present invention.

That is, in the present invention, at least one is a transparent body 2
The gist is a laminate having a dye-containing intermediate layer between a plurality of supports and having a colored intermediate layer containing a nitroxy free radical as a stabilizer in the intermediate layer.

Hereinafter, the present invention will be described in detail.

What is a nitroxy free radical? The nitroxy free radical used in the intermediate layer of the laminate of the present invention is a stable radical that can be isolated.

Specific examples of such nitroxy free radicals include the following general formula [I] And those represented by the formula [I] above.
Examples of R ¹ and R ² include a substituted or unsubstituted aryl group and a carbon atom adjacent to a nitrogen atom which is a third carbon atom or a fourth carbon atom, and only ^one of R ^{1 and} R ² And the carbon atom adjacent to the nitrogen atom has a double bond and the carbon atom has a substituent such as sec-alkyl group and tert-alkyl group. Furthermore,
R ¹ and R ² may be bonded to each other to form a ring, and the ring may have a substituent. These synthetic methods are described in "New Experimental Chemistry Course" (Maruzen Co., Ltd., edited by The Chemical Society of Japan, Volume 14, P1594 to P159).
It is performed according to the method described in “8”.

In addition, the bicyclo nitroxy radical that stops at the stage of the nitroxy radical without being oxidized to the nitrone according to the Brett rule Is also included.

As other nitroxy free radicals, for example,
Those listed in Table 7.66 of the above-mentioned document P1597 can be used.

The nitroxy free radical preferably used in the present invention, from the viewpoint of heat resistance and activity persistence, for example, Etc. are preferred.

Further, an antioxidant, an ultraviolet absorber or the like may be added together with the nitroxy free radical.

As the antioxidant, for example, a hindered phenol type compound represented by the following structural formula [D] is preferable.

As the ultraviolet absorber, for example, benzotriazole compounds represented by the following structural formulas [E] or [F] are preferable.

As the pigment, any pigment may be used as long as it does not show a coloration phenomenon due to light, for example, azo dye, anthraquinone dye, indigoid dye, phthalocyanine dye, carbonium dye, quinoneimine dye, methine dye, quinoline dye, nitro dye, nitroso dye. , Benzoquinone and naphthoquinone dyes, naphthalimide dyes, perinone dyes and the like, and azo dyes and anthraquinone dyes are preferably used.

As the polymer substance forming the intermediate layer, the dye used,
Any substance that has good compatibility with nitroxy free radicals and that is optically transparent and has excellent film-forming ability, such as polymethacrylic acid ester, polyacrylic acid ester, polystyrene, polyvinyl acetate, polyvinyl acetal, etc. , Polyvinyl chloride, polyvinylidene chloride and vinyl chloride-vinyl acetate, ethylene-vinyl acetate and other copolymers, polypropylene, polyethylene, polyacrylonitrile, urethane resin, epoxy resin, phenoxy resin, polyester, cellulose ester and the like. Preferably, polyvinyl butyral is used.
If necessary, it may contain a plasticizer or may be crosslinked. Any plasticizer may be used as long as it imparts plasticity to the polymer substance, and examples thereof include phthalate systems such as dibutyl phthalate and dioctyl phthalate, adipate systems such as dioctyl adipate, and tricresyl phosphate. Phosphate-based, ethylene glycol diester-based such as triethylene glycol hexanoate and mixtures thereof.

The laminate of the present invention in which the dye layer contains nitroxy free radicals is produced, for example, as follows. First, a dye, a polymer substance, a nitroxy free radical, and an additive that is added as necessary are dissolved in a suitable solvent. Any solvent may be used as long as it dissolves the polymer substance and the nitroxy free radical. This solution is coated on a suitable transparent substrate using a casting or spinner, and another substrate is placed on the coating layer to form a laminate by vacuum pressure bonding, or this solution is prepared by a suitable method. It can be obtained by a method in which a transparent film is coated by screen printing or the like, and the film having the coating layer is sandwiched between two appropriate transparent substrates and vacuum-pressed to form a laminate. .

Examples of the substrate include polyethylene terephthalate, cellulose acetate, polymethylmethacrylate, polycarbonate, glass and the like, and at least one of them may be transparent.

Further, various polymer films are used as the film, and among them, a film of polyvinyl butyral which is generally used as an intermediate film of laminated glass or the like is preferable. The thickness of the dye layer is 0.5 μm to 1 mm, preferably 10 to
Use at 250 μm.

Nitroxy free radical is 0.1 to 5 for polymer
It is used at 0% by weight, preferably 0.5-20% by weight.

If the nitroxy free radical is less than 0.1% by weight, no effect is obtained, and if the amount is more than 50% by weight, the effect is constant and the cost becomes high, which is not preferable.

(Example) The present invention will be described by the following examples and comparative examples, but the present invention is not limited to the following examples. In each of the examples, the weather resistance was evaluated by the decrease in absorption intensity (Abs) by a spectrophotometer, and expressed as the time required to reach 50% or less of the initial absorption intensity. A xenon fade meter manufactured by Suga Test Instruments Co., Ltd. was used as the deterioration promoting device.

Example 1 Yellow dye [A] having the following structure: 0.1% by weight 0.1% by weight of nitroxy free radical having the following structure (t-C ₄ H _{9 2} NO · and 10% by weight of polyvinyl butyral containing triethylene glycol di-2-ethylbutyrate as a plasticizer)
Was dissolved in a solvent (toluene: ethanol = 6: 4).
The obtained solution was coated on a glass substrate by casting. This coating layer was dried in a vacuum drier at 70 ° C. under reduced pressure for 6 hours, and then sandwiched between two sheets of clear glass having a thickness of 2 mm and vacuum-pressed to obtain a laminate of Example 1.

As Comparative Example 1, a laminate of Comparative Example 1 was produced under the same conditions as in this Example except that the nitroxy free radical was not used.

In order to evaluate the weather resistance of these samples, the initial absorption intensity (Abs) was measured with a spectrophotometer, and then light irradiation was performed in a xenon fade meter to measure the change with time in the decrease of the absorption intensity.

As a result, the laminate of this example showed a coloring performance of 50% or more of the initial value even after irradiation for 2000 hours, whereas the photosensitive sample of Comparative Example was within 400 hours and 50% or less of the initial value. It became the absorption intensity (Abs) of.

Example 2 Dye [B] having the structure shown on the left: 1% by weight, nitroxy free radical having the following structure: 1% by weight, polyvinyl butyral resin: 10% by weight as a solvent (ethanol: toluene: n
-Butanol = 50: 45: 5) (t-C ₄ H _{9 2} NO.) The resulting solution was screened on a polyvinyl butyral interlayer film (material: Tetron, mesh size: 10).
0) was used for printing so that the film thickness was 20 μm. The printed interlayer film was air dried for one day and then dried in an oven at 60 ° C. for 1 to 2 minutes.

The interlayer film obtained here was sandwiched between two 2 mm glass substrates and vacuum-pressed to prepare a laminate having a dye between the substrates.

Next, the weather resistance was evaluated in the same manner as in Example 1, and it was found that the initial value was 50 even after irradiation for 2000 hours in a xenon fade meter.
It showed an absorption intensity (Abs) of not less than%.

Comparative Example-2 Example 2 except that the nitroxy radical was not used.
A laminated body of Comparative Example 2 was produced under the same conditions as in.

Next, when the weather resistance was evaluated in the same manner as in Example 1,
Initial value of 50 within 400 hours in xenon fade meter
The absorption intensity (Abs) was less than%.

Examples 3 to 36, Comparative Example 3 Dye [A] having the following structure in the same manner as in Example 2,
Using [B] and [C], in combination with various nitroxy radicals as shown in Table 1, laminates of Examples 3 to 36 and Comparative Example 3 were prepared, and weather resistance test was conducted on each sample. The results are shown in Table 1 together with the results of Examples 1 and 2 and Comparative Examples 1 and 2. Although the effect of three kinds of dyes was shown in this example, it goes without saying that the effect is not limited to these.

Example 37 Example 37 was prepared under the same conditions as in Example 13 except that 0.1% by weight of the hindered phenylol antioxidant [D] was added in addition to the nitroxy free radical shown in Example 13, and the weather resistance was improved. Tests were conducted and the results are shown in Table-1.

Example 38 Example 38 was prepared under the same conditions as in Example 13, except that 0.1% by weight of the benzotriazole-based ultraviolet absorber [F] was added in addition to the nitroxy free radical shown in Example 13.
A weather resistance test was conducted, and the results are shown in Table 1.

Example 39 Example 13 except that 0.1% by weight of each of the hindered phenol antioxidant [D] and the benzotriazole ultraviolet absorber [E] was added in addition to the nitroxy free radical shown in Example 13. Example 39 was prepared under the same conditions as in Example 1, and the results are shown in Table 1.

(Effect of the Invention) As described above, according to the present invention, since the structure is a laminate having a dye layer in which a triplet quencher, for example, a nitroxy free radical, is mixed with a dye, a reduction in the color retention is caused. Can be prevented.

Therefore, the laminated body containing the dye of the present invention has greatly improved weather resistance as compared with the conventional one, and thus it is suitably used for various light-shielding materials, display materials, and ornaments outdoors under severe operating environments.

Claims (1)

[Claims] 1. A laminate having a dye-containing intermediate layer between two supports, at least one of which is a transparent body, wherein the intermediate layer contains a nitroxy free radical as a stabilizer. A laminate having an intermediate layer.