JP2951641B1 - Weather resistant styrenic resin laminate - Google Patents

Abstract

A styrene-based resin laminate having both excellent mechanical strength and weather resistance is provided. SOLUTION: The styrenic resin laminate of the present invention has a general formula (1): [In the formula (1), A represents an alkylene group having 1 to 6 carbon atoms,
¹ and R ³ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
R ² and R ⁴ each represent the group (2). A film comprising a polycarbonate-based resin composition containing 1 to 50% by weight of a bisbenzotriazole-based compound represented by the following formula:
It is characterized by being laminated on at least one surface of a styrene resin base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a styrene resin laminate excellent in mechanical strength and weather resistance.

[0002]

2. Description of the Related Art Styrene resins such as polystyrene, styrene-acrylonitrile resin and ABS resin (acrylonitrile-butadiene-styrene) are excellent in impact resistance, workability, etc., and are used in automobile parts. Widely used for electrical product parts, sundries and the like. However, it is significantly inferior in the weather resistance as compared with the acrylic resin, so that various restrictions are imposed on the field of use, particularly in the field of outdoor use.

Therefore, a method of adding an ultraviolet absorber to a styrene-based resin is widely used. However, conventionally known addition-type ultraviolet absorbers are mostly low molecular compounds and have high vapor pressures, and therefore, are difficult to mold. There is a problem that the ultraviolet absorbent evaporates during processing. Further, there is also a problem that the ultraviolet absorbent bleeds out from the surface of the molded article with time, and especially when used outdoors, the ultraviolet absorbent flows out due to rain, water containing detergent, or the like. For this reason, it has been difficult for conventional additive-type ultraviolet absorbers to provide sufficient weather resistance for a long period of time.

[0004] Among the conventional additive-type UV absorbers, benzotriazole-based UV absorbers, in particular, are compounds having excellent ultraviolet absorbing ability, but have high crystallinity and low compatibility with resins. When added, there is a problem that the mechanical strength of the resin is significantly reduced.

On the other hand, there has been proposed a method of laminating an acrylic resin having excellent weather resistance on a styrene resin base material. However, in this case, even if the styrene-based resin is subjected to a stretching treatment to improve the impact resistance, the effect is impaired. In addition, when the peripheral portion of the laminate, particularly the sheet-like laminate, is recycled, problems such as delamination due to low compatibility between the styrene resin and the acrylic resin and further reduction in impact resistance are caused. Occurs.

Further, Japanese Patent Application Laid-Open No. Hei 7-232412 discloses a method for solving the above problem by using a polystyrene-polycarbonate laminated film using an ultraviolet absorbent having a molecular weight of 380 or more. However, since the ultraviolet absorber disclosed in the above publication has a low ultraviolet absorption capacity per unit weight, the amount of addition increases when trying to obtain a sufficient ultraviolet absorption capacity, or the cost increases,
Moldability is reduced. Further, there is a variety of problems such as a low compatibility between the ultraviolet absorber and the resin, which easily causes phase separation, and a decrease in mechanical strength of the obtained film.

Accordingly, an object of the present invention is to solve the above problems and to provide a styrene resin laminate having both excellent mechanical strength and weather resistance.

[0008]

Means for Solving the Problems The present inventor has conducted intensive studies to solve the above-mentioned problems, and as a result, general formula (1):

[0009]

Embedded image [Wherein, A is a direct bond or an alkylene group having 1 to 6 carbon atoms, a group: -O-, a group: -NH-, a group: -S-, a group:-
SO— or a group: —SO ₂ —. R ¹ and R ³ are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. R ² and R ⁴ are the same or different and have the following groups:

[0010]

Embedded image (Wherein, R ⁵ is a direct bond or a linear or branched alkylene group having 1 to 12 carbon atoms. R ⁶ and R ⁷
Are the same or different and are each a hydrogen atom or a carbon number of 1 to 10
Represents an alkyl group. m represents an integer of 1 to 20, and n represents an integer of 1 to 10. ). When a polycarbonate-based film containing a bisbenzotriazole-based compound represented by the following is laminated on a styrene-based resin substrate, excellent properties such as excellent mechanical strength inherent in the styrene-based resin are not impaired. The present inventors have found a completely new fact that weather resistance can be obtained, and have completed the present invention.

That is, the weatherable styrene-based resin laminate of the present invention comprises a film made of a polycarbonate-based resin composition containing 1 to 50% by weight of a bisbenzotriazole-based compound represented by the above general formula (1). It is characterized by being laminated on at least one surface of a base resin substrate.

The bisbenzotriazole-based compound represented by the general formula (1) has an extremely high ultraviolet absorbing ability per unit weight, and is superior to the conventional additive type ultraviolet absorbing agent. In addition, due to the high melting point, high transpiration resistance,
Furthermore, since it has high compatibility with the resin, it does not evaporate during the molding process or bleed out from the surface of the molded body. Furthermore, it has excellent metal ion resistance. Therefore, the weather-resistant styrene-based resin laminate of the present invention in which a film made of the polycarbonate-based resin composition containing the bisbenzotriazole-based compound (1) is laminated has excellent styrene-based resin excellent mechanical strength and the like. Excellent weather resistance can be exhibited without impairing the properties.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the weather-resistant styrene resin laminate of the present invention will be described in detail.

[Polycarbonate Resin] The polycarbonate resin used in the present invention is a phosgene method for reacting various dihydroxydiaryl compounds with phosgene, or an ester for reacting a dihydroxydiaryl compound with a carbonate ester such as diphenyl carbonate. It is a polymer obtained by an exchange method, and a typical example is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A).

Examples of the dihydroxydiaryl compound include, in addition to bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3)
-Methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-
Bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-
Bis (hydroxyaryl) alkanes such as 3,5-dichlorophenyl) propane; bis (hydroxyaryl) such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane Cycloalkanes; 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,
Dihydroxy diaryl ethers such as 3'-dimethyl diphenyl ether; dihydroxy diaryl sulfides such as 4,4'-dihydroxy diphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide; 4,4'-dihydroxy diphenyl Dihydroxydiarylsulfoxides such as sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide; and 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone. And dihydroxydiaryl sulfones.

These are used singly or as a mixture of two or more kinds. In addition, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like may be used in combination.

Further, a phenol compound having a valency of 3 or more may be used in combination with the above dihydroxyaryl compound. Examples of trivalent or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri-
(4-hydroxyphenyl) -heptene-2,4,6-
Dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -Ethane and 2,2-bis-
[4,4- (4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

The viscosity-average molecular weight of the polycarbonate resin is usually 10,000 to 100,000, preferably 1,000
0 to 40,000. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst and the like can be used as required.

[Bisbenzotriazole compound] The bisbenzotriazole compound represented by the general formula (1) used in the present invention has an extremely low vapor pressure and a decomposition temperature of 35.
Since the temperature is 0 ° C. or higher, which is significantly higher than that of the conventional additive type ultraviolet absorber, there is no possibility of causing evaporation, decomposition, and the like at the time of blending with a polycarbonate resin and molding.

In addition, bisbenzotriazole compounds
In the molecule of (1), one benzotriazolylphenol becomes a bulky substituent for the phenolic hydroxyl group of the other benzotriazolylphenol, and thus protects the phenolic hydroxyl group. As a result, there is no problem such as discoloration due to contact with metal ions, and excellent metal ion resistance is provided.

Furthermore, since it has a plurality of long-chain polyester groups in the molecule, it exhibits extremely high compatibility with general-purpose resins. Therefore, after blending with polycarbonate resin,
The problem of bleeding out is extremely low. Further, when processed by extrusion or the like after being blended with the polycarbonate resin, the transesterification reaction causes the group (2) in the bisbenzotriazole compound (1)
May react with the main chain or side chain of the polycarbonate resin, and in this case, the problem of bleed-out does not occur.

In the bisbenzotriazole compound represented by the general formula (1), examples of the alkylene group having 1 to 6 carbon atoms represented by A include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, Ethylidene, propylene, propylidene, isopropylidene, ethylethylene, 2-butylidene, 1-
Methyltrimethylene, 2-methyltrimethylene, 2,2
Straight-chain or branched groups such as -dimethyltrimethylene.

A in the general formula (1) represents, in addition to the above alkylene group, an oxy group (—O—) and an amino group (—NH
-), Thio group (-S-), sulfinyl group (-SO-)
Or a group such as a sulfonyl group (—SO ₂ —) or a single bond. When A represents a single bond, benzotriazolylphenol on both sides of A is represented by the following general formula (17)
Direct coupling as shown in

In the general formula (1), examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
sec-butyl, tert-butyl and the like. Examples of the aryl group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group and a naphthyl group which may have a halogen atom or the like on a phenyl ring. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (1), the compound having 1 to ⁵ carbon atoms represented by R ⁵
Examples of the 12 straight-chain or branched alkylene groups include, in addition to the above-mentioned alkylene groups having 1 to 6 carbon atoms, straight-chains such as heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene and the like. And a branched or branched alkylene group having 7 to 12 carbon atoms. In the present invention, among the above alkylene groups, those having 2 to 4 carbon atoms are particularly preferred.

In the general formula (1), as the alkyl group having 1 to 10 carbon atoms represented by R ⁶ and R ⁷ ,
In addition to the alkyl group of 4, groups such as pentyl, hexyl, heptyl, octyl, nonyl, and decyl are exemplified.

Further, by arbitrarily changing the number m of the repeating units of the chain polyester, the properties of the compound can be adjusted to a crystalline, waxy or oily state.

The bisbenzotriazole-based compound of the present invention represented by the general formula (1) is specifically exemplified by the general formulas (11) to (17)
It is represented by

[0029]

Embedded image

[0030]

Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as described above. (CH ₂ ) _x represents a linear or branched alkylene group having 1 to 6 carbon atoms.) Bisbenzotriazole compound used
Specific compound names of (1) are shown below. .2,2′-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (glycoloyloxyethyl) phenol], 2,2'-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (3-hydroxypropanoyloxyethyl) phenol], 2,2′-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (4-hydroxybutanoyloxyethyl) phenol], 2,2′-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (5-hydroxyheptanoyloxyethyl) phenol], 2,2′-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (6-hydroxyhexanoyloxyethyl) phenol], 2,2′-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (16-hydroxy-4,11-dioxo-3,10-dioxahexadecyl) phenol], 2,2′-methylenebis [6- (2H-1,2,2 3-
Benzotriazol-2-yl) -4- (24-hydroxy-4,11,18-trioxo-3,10,17-
Trioxatricosyl) phenol], 2,2'-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (31-hydroxy-4,11,18,25-tetraoxo-3,1
0,17,24-tetraoxahexadecyl) phenol], 2,2'-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (37-hydroxy-4,11,18,25,32-heptaoxo-
3,10,24,31-Heptaoxaheptatriacontyl) phenol] The above-mentioned bisbenzotriazole-based compound (1) is usually used alone, but two or more of them can be used in combination. It can also be used in combination with commercially available general-purpose ultraviolet absorbers, hindered amine light stabilizers, and other polymer additives.

Further, bisbenzotriazole compounds
(1) is contained in the polycarbonate resin constituting the film at a ratio of 1 to 50% by weight. If the content of the bisbenzotriazole compound (1) is less than 1% by weight, the weather resistance is poor, and if it exceeds 50% by weight, film processing becomes difficult. The content ratio of the bisbenzotriazole compound (1) is preferably from 1 to 30% by weight in the above range, from the viewpoints of weather resistance and film processability.
More preferably, it is 3 to 15% by weight.

The method for producing the polycarbonate resin composition is not particularly limited, and it can be obtained by mixing the above-mentioned bisbenzotriazole compound (1) with the polycarbonate resin during or after polymerization.
In mixing, a known mixer such as a Banbury mixer, an extruder, and a roll can be used.

If necessary, other additives such as a colorant, an antioxidant, a heat stabilizer, an antistatic agent, a lubricant, and a flame retardant are appropriately added to the polycarbonate resin composition to be a film. You can also.

There is no particular limitation on the method of forming a film using the above-mentioned polycarbonate resin composition, and the film can be formed by a known film extruder such as a T-die film cast extruder or an inflation film device.

The thickness of the film made of the polycarbonate-based resin composition containing the bisbenzotriazole-based compound (1) is not particularly limited, but is usually preferably set in the range of 5 to 500 μm. If the thickness of the film is less than 5 μm, sufficient weather resistance may not be provided to the laminate. Also, it is difficult to produce a film having a thickness of less than 5 μm. Conversely, if the thickness exceeds 500 μm, it may be difficult to bond the film to the styrene-based resin substrate, or the recyclability of the weatherable styrene-based resin laminate may be reduced.

When a film made of a polycarbonate-based resin composition is prepared and then wound up and placed on a styrene-based resin base material until lamination resistance is obtained, one or both sides of the film may be used. It is preferable to improve the film winding property by subjecting the resin composition to a graining treatment or adding a film lubricant such as silicon oxide to the resin composition.

[Styrene resin base material] A styrene resin is a styrene monomer alone or a monomer copolymerizable with another styrene monomer in the presence or absence of a rubbery polymer. And a resin obtained by polymerizing

Examples of the rubbery polymer that can constitute the styrene resin include polybutadiene, polyisoprene, butadiene-styrene copolymer, and isoprene-
Diene rubbers such as styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-isoprene-styrene copolymer, and polychloroprene; ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene (ethylidene norbornene, dicyclothione) Ethylene-propylene rubber such as pentadiene) copolymer; and acrylic rubber such as polybutyl acrylate. These can be used alone or in combination of two or more.

Examples of the styrene monomer include styrene, α-methylstyrene, paramethylstyrene and the like, and these can be used alone or in combination of two or more. Among the above examples, it is particularly preferable to use styrene and α-methylstyrene.

Other copolymerizable monomers that can be used together with the styrene monomer include, for example, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; and (meth) compounds such as methyl methacrylate and methyl acrylate. Acrylic acid ester compounds; maleimide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide; unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, itaconic acid and fumaric acid, each of which is used alone or in combination of two or more be able to.

Specific examples of the styrene resin used for the styrene resin substrate in the present invention include polystyrene (PS) and styrene-acrylonitrile copolymer (A
S), α-methylstyrene-acrylonitrile copolymer (αMS-ACN), methyl methacrylate-styrene copolymer (MS), methyl methacrylate-acrylonitrile-styrene copolymer (MAS), styrene-N-phenylmaleimide Copolymer (S-NPMI), styrene-
So-called "rubber non-reinforced" styrene resins such as N-phenylmaleimide-acrylonitrile copolymer (SA-NPMI); acrylonitrile-butadiene rubber-styrene polymer (ABS), acrylonitrile-ethylene propylene rubber-styrene So-called "rubber-reinforced" styrene-based resins such as polymer (AES), acrylonitrile-acrylate rubber-styrene polymer (AAS), butadiene rubber-styrene copolymer (HIPS); An arbitrary "mixture" composed of a styrene resin and a rubber-reinforced styrene resin is exemplified.

From the viewpoint of balance of physical properties of the final composition, ABS,
It is particularly preferable to use a rubber-reinforced styrene resin such as AES or AAS, or a mixture of a rubber-unreinforced styrene resin and a rubber-reinforced styrene resin.

Known additives such as a coloring agent, an antioxidant, a heat stabilizer, an antistatic agent, a lubricant, and a flame retardant are also added to a styrene resin as a base material by using a Banbury mixer, an extruder,
It can be compounded using a known mixer such as a roll.
Of course, various ultraviolet absorbers can be blended, but from the viewpoint of cost, the amount is preferably smaller than the amount (% by weight) blended in the polycarbonate resin composition film.

The thickness of the styrenic resin base material is not particularly limited, but may be 0.1 to 30 m in view of impact resistance, weather resistance and the like.
m, particularly preferably 0.5 to 15 mm.

[Method for Producing a Weather-Resistant Styrene-Based Resin Laminate] The method for producing the laminate of the present invention is not limited at all, and includes a method for bonding a polycarbonate-based film to a styrene-based resin base via an adhesive, A method of laminating and supplying a polycarbonate film simultaneously with the extrusion molding of a styrene resin substrate, a method of simultaneously extruding a styrene resin substrate and a polycarbonate resin composition, and mounting the polycarbonate film in a mold. A method of laminating a styrene-based resin base material by injection molding is exemplified.

The film made of the polycarbonate-based resin composition only needs to be laminated on at least one surface of the styrene-based resin base material. Properties can be imparted. However, a film may be laminated on both surfaces of the styrene-based resin substrate as long as excellent properties such as mechanical strength of the styrene-based resin substrate itself are not impaired.

[0047]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

[Production of Bisbenzotriazole Compound] Synthesis Example 1 2,4′-methylenebis [6- (2H-) was placed in a four-necked flask equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirrer.
1,2,3-benzotriazol-2-yl) -4-
(2-hydroxyethyl) phenol] (trade name "RU
VA-100 ", 129.3 g, manufactured by Otsuka Chemical Co., Ltd. and 1-caprolactone (manufactured by Daicel Chemical Industries, Ltd.) 1
70.3 g, and a mono-n-butyltin fatty acid salt (trade name “SCAT-24”, manufactured by Sankyoki Gosei Co., Ltd.)
Was added at a rate of 50 ppm.

Next, the reaction was carried out for 6 hours while maintaining the reaction temperature at 150 ° C. to obtain 2,2′-methylenebis [6- (2H-1,2,3-benzotriazole-
2-yl) -4- (2,3-hydroxy-4,11,1
8-trioxo-3,10,17-trioxatricosyl) phenol] (yield 98%).

The target compound is a viscous oil having an acid value (mg KOH / g) of 1.8 and a viscosity of 2645 cP.
(60 ° C.), number average molecular weight (Mn) 1391, weight average molecular weight (Mw) 1688 and Mw / Mn = 1.213
Met.

Synthesis Example 2 The amount of “RUVA-100” was 93.7 g, and ε-
Except that the amount of caprolactone was 206.3 g,
The reaction was carried out in the same manner as in Synthesis Example 1, and the target compound, 2,2′-methylenebis [6- (2H-1,2,3-benzotriazol-2-yl) -4- (37-hydroxy-4, 11, 18, 25, 32-heptaoxo-3,
10,24,31-heptaoxaheptatriacontyl) phenol] (yield 98%).

The target compound is a waxy solid,
Acid value (mgKOH / g) 2.5, viscosity 987 cP (60
° C), Mn = 2017, Mw = 2465 and Mw / M
n = 1.222.

[Production of Weatherable Styrenic Resin Laminate] Example 1 Polycarbonate resin 1 having a viscosity average molecular weight of 23,000
After blending 10 parts by weight of the bisbenzotriazole-based compound obtained in Synthesis Example 1 with respect to 00 parts by weight,
At 280 ° C., a film having a width of 400 mm and a thickness of 50 μm was prepared and wound into a roll. The processability of the film thus obtained was evaluated according to the criteria described below. Table 1 shows the results. Next, a graft polymer obtained by emulsion graft polymerization of 50% by weight of butadiene rubber, 35% by weight of styrene and 15% by weight of acrylonitrile, and styrene 73
ABS resin having a rubber content of 12%, which is composed of a copolymer obtained by emulsion polymerization of acrylonitrile and 27% by weight of acrylonitrile.
A sheet having a width of 400 mm and a thickness of 3 mm was extruded at 0 ° C. At that time, a film of a polycarbonate resin composition prepared in advance by a T-die was laminated. The impact resistance and weather resistance of the thus obtained weatherable styrene resin laminate were evaluated. Table 1 shows the results. Example 2 Preparation of a film, evaluation of film processability, and preparation of a weatherable styrene-based resin laminate in the same manner as in Example 1 except that the bisbenzotriazole-based compound obtained in Synthesis Example 2 was used. , And impact resistance and weather resistance were evaluated. Table 1 shows the results.

Comparative Examples 1 and 2 Polycarbonate resin 1 having a viscosity average molecular weight of 23,000
With respect to 00 parts by weight, commercially available ultraviolet absorbers (trade name “Tinuvin 900” (Comparative Example 1), “Tinuvin 1130”)
(Comparative Example 2) 10 parts by weight of Ciba-Geigy Co., Ltd. were added, and then a film was prepared in the same manner as in Examples 1 and 2, wound up in a roll, and evaluated for film processability. Table 1 shows the results. Next, a weather-resistant styrene-based resin laminate was prepared in the same manner as in Examples 1 and 2, except that the above-mentioned film was used, and its impact resistance and weather resistance were evaluated. Table 1 shows the results.

The method for evaluating the processability of the polycarbonate resin composition film and the impact resistance and weather resistance of the weatherable styrene resin laminate are as follows.

[Film workability] The film formability of the film was evaluated by the T-die casting method, and the workability was evaluated according to the following criteria. A: The processability of the film was extremely good. ：: The processability of the film was good. Δ: Film processability was practically insufficient. X: The workability of the film was remarkably insufficient.

[Impact resistance] A steel ball of 5 kg was applied to a thickness of 3 mm ±
Drop from above (maximum 1 m) above the 50 μm cut-out test piece, the maximum energy (k
g · m) was measured to evaluate the impact resistance. The larger the numerical value of the maximum energy is, the more excellent the impact resistance is, and it is required that the maximum energy is practically 3 kg · m or more. In addition, when neither destruction nor cracking occurs even when dropped from the maximum height of 1 m, it was determined as NB (non-destructive).

[Weather Resistance] Ultraviolet irradiation was performed for 500 hours using an ultraviolet irradiation device (I-Super) manufactured by Iwasaki Electric Co., Ltd., and the difference (ΔYI) between the YI value after irradiation and the initial YI value was evaluated. Irradiation of ultraviolet rays is performed by using a metal halide lamp as a light source, at a temperature of 70 ° C. and an ultraviolet intensity of 100 mW / cm ^2.
Was performed under the following conditions.

The smaller the ΔYI, the better the weather resistance. The preferred value of ΔYI is not particularly limited,
It is preferably less than or equal to the degree.

[0060]

[Table 1] As is clear from Table 1, Comparative Examples 1 and 2 using a commercially available ultraviolet absorber had insufficient film workability and could not obtain sufficient weather resistance. As a result, it was found that the film had good workability and that sufficient weather resistance could be imparted without impairing the impact resistance of the styrene resin.

[0061]

As described in detail above, according to the present invention,
A styrene-based resin laminate having excellent impact resistance and weather resistance can be obtained. The weatherable styrenic resin laminate obtained in this way is suitable for applications requiring a sufficient ultraviolet absorption capacity for a long period of time, such as outdoor use.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁶ , DB name) B32B 1/00-35/00 C08J 5/18 C08K 3/00-13/08 C08L 1/00-101 / 14 C07D 249/20 C09K 3/00

Claims (1)

(57) [Claims] [Claim 1] General formula (1): [Wherein, A is a direct bond or an alkylene group having 1 to 6 carbon atoms, a group: -O-, a group: -NH-, a group: -S-, a group:-
SO— or a group: —SO ₂ —. R ¹ and R ³ are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. R ² and R ⁴ are the same or different and represent a group (2): (Wherein, R ⁵ is a direct bond or a linear or branched alkylene group having 1 to 12 carbon atoms. R ⁶ and R ⁷
Are the same or different and are each a hydrogen atom or a carbon number of 1 to 10
Represents an alkyl group. m represents an integer of 1 to 20, and n represents an integer of 1 to 10. ). A film made of a polycarbonate-based resin composition containing 1 to 50% by weight of a bisbenzotriazole-based compound represented by the following formula: is laminated on at least one surface of a styrene-based resin substrate. .