JPH1044356A - Polycarbonate laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve weather resistance, surface gloss and heat stability to avoid an initial coloring by blending a proper quantity of a hydroxyphenyl triazine compound and other two compounds with a polycarbonate base material to be coated. SOLUTION: This is a polycarbonate laminated sheet made by coating a composition containing 0.1-5wt.% of a hydroxyphenyl triazine compound indicated in a formula I, 0.001-1wt.% of a phenol compound indicated in formulas II, III and a 0.001-1wt.% of phosphorus compound indicated in a formula IV on a poly carbonate base material by a thickness of 10-100μm. In the formula I, RI is a hydrogen or an alkyl group with 1-18 carbons or an alkoxy group with 1-12 carbons or an alkyl group with 2-6 carbons replaced by a halogen or a benzyl group and R2 is a hydrogen or a methyl group. In the formulas II, III, R1 and R2 are alkyl groups with 1-4 carbons. R3 is the alkyl group with 1-30 carbons, n is 1-10. In the formula IV, R1 and R2 are alkyl groups with 1-4 carbons or hydrogens.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated polycarbonate sheet which is excellent in weather resistance, surface gloss and thermal stability, has little initial coloring, and prevents precipitation of an ultraviolet absorbent.

[0002]

2. Description of the Related Art Polycarbonate sheets are excellent in impact resistance, transparency, heat resistance, flame resistance, etc., and are used for building materials represented by window materials, carport roofing materials, veranda sills, and roads such as transparent soundproofing boards. It is used in various fields such as materials and railway vehicle materials, and its use is expected to expand in the future.

However, polycarbonate sheets have the disadvantage of poor weather resistance, and particularly when used in places exposed to ultraviolet light, such as outdoors, a decrease in optical performance such as yellowing or loss, a decrease in tensile strength, and a decrease in impact resistance. The mechanical properties such as the above were deteriorated, which was a problem. In recent years, as a method for improving the weather resistance of a polycarbonate sheet, a number of methods have been proposed in which a sheet surface is coated with a resin layer containing a large amount of an ultraviolet absorber.
Japanese Patent Publication No. 9929, Japanese Patent Publication No. 3-54626, and Japanese Patent Publication No. 6-41162.

[0004] According to these methods, strength reduction due to weathering discoloration and ultraviolet light deterioration is certainly solved. However,
In these methods, since a large amount of an ultraviolet absorber is added to the surface layer, the surface gloss, which is an excellent feature of the appearance of the polycarbonate sheet, is inferior. There was a problem that a large amount was precipitated on the surface. In addition, there is also a problem that the initial coloring due to sheet molding or the like is large due to lack of thermal stability.

The inventor of the present invention has proposed a method of improving these problems in Japanese Patent Application No. 7-309743, but it is insufficient to solve all problems, and further improvements have been desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to improve the weather resistance of a polycarbonate sheet, improve surface gloss, improve thermal stability, prevent initial coloring, and use the sheet outdoors for a long period of time. Another object of the present invention is to provide a polycarbonate sheet in which the ultraviolet absorbent does not precipitate.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies and found that the polycarbonate surface is coated with a polycarbonate composition containing at least three or four specific compounds in a specific amount. As a result, they have found that all of the above-mentioned problems can be solved, and have completed the present invention.

That is, according to the present invention, a polycarbonate (I) is used as a base material, and at least (A) 0.1 to 5% by weight of a hydroxyphenyltriazine compound represented by the following formula:
(B) A polycarbonate composition containing 0.001 to 1% by weight of a phenolic compound represented by the following chemical formula 6 and / or 7, and (C) 0.001 to 1% by weight of a phosphorus compound represented by the following chemical formula 8 10 to 100 μm depending on the product (II)
It is a polycarbonate laminated sheet coated with a thickness of m.

[0009]

Embedded image

(Wherein R1 is hydrogen or C 1-18)
An alkyl group or an alkyl group having 1 to 12 carbon atoms or an alkyl group having 2 to 6 carbon atoms substituted with halogen or a benzyl group, and R2 is hydrogen or a methyl group. )

[0011]

Embedded image

(Wherein, R1 and R2 are alkyl groups having 1 to 4 carbon atoms, R3 is an alkyl group having 1 to 30 carbon atoms, and n is 1 to 10.)

[0013]

Embedded image

(Wherein, R1 and R2 are alkyl groups having 1 to 4 carbon atoms, R3 is an alkyl group having 1 to 30 carbon atoms, and n is 1 to 10.)

[0015]

Embedded image

(In the formula, R1 and R2 are an alkyl group having 1 to 4 carbon atoms or one of them is hydrogen.) The present invention will be described in detail below. The polycarbonate used for the substrate part polycarbonate (I) and the coating layer polycarbonate composition (II) of the present invention has a main chain composed of a repeating unit represented by the following formula (9).

[0017]

Embedded image

(Where Ar is a divalent aromatic residue,
For example, phenylene, naphthylene, bifinylene, pyridylene and those represented by Chemical formula 10 can be mentioned. )

[0019]

Embedded image

(Wherein Ar ¹ and Ar ² are arylene groups, for example, each represents a group such as phenylene, naphthylene, biphenylene, pyridylene, etc., and Y is
An alkylene group or a substituted alkylene group represented by 2. )

[0021]

Embedded image

[0022]

Embedded image

(Wherein R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, optionally substituted with a halogen atom or an alkoxy group). K may be 3 to 11
Wherein the hydrogen atom of Chemical formula 12 is a lower alkyl group,
It may be substituted with an aryl group, halogen and the like. ) Further, a divalent aromatic residue represented by Chemical formula 13 may be contained as a copolymer component.

[0024]

Embedded image

(Wherein Ar ¹ and Ar ² are the same as in Chemical formula 2. Z is a mere bond or —O—, —CO—, —S—, —S
It is a divalent group such as O ₂ —, —CO ₂ —, —CON (R ¹ ) —, (R ¹ is as defined above). Examples of these divalent aromatic residues include those represented by the following chemical formulas 14 and 15.

[0026]

Embedded image

[0027]

Embedded image

(Wherein R ⁵ and R ⁶ are hydrogen, halogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, C ₁ -C ₁₀ cycloalkyl or phenyl, respectively. M and n Is an integer of 1 to 4; when m is 2 to 4, each R ⁵ may be the same or different; and when n is 2 to 4, each R ⁶ is the same or different. Among them, one represented by the following formula 16 is a preferable example. In particular, those containing 85 mol% or more of a repeating unit in which Chemical Formula 16 is Ar are preferable.

[0029]

Embedded image

The polycarbonate may contain a trivalent or higher aromatic residue as a copolymer component,
An aliphatic or aromatic ester component may be contained as a copolymer component. Although the molecular structure of the polymer terminal is not particularly limited, one or more terminal groups selected from a hydroxy group, an aryl carbonate group, and an alkyl carbonate group can be bonded. The aryl carbonate terminal group is represented by the following formula (17).
Is mentioned.

[0031]

Embedded image

(Wherein Ar ³ is a monovalent aromatic residue;
The aromatic ring may be substituted. )

[0033]

Embedded image

The alkyl carbonate terminal group is represented by the following formula:
And specific examples include, for example, the following Chemical Formula 20.

[0035]

Embedded image

(Wherein R ⁷ is a linear or branched alkyl group having 1 to 20 carbon atoms)

[0037]

Embedded image

Among them, a phenyl carbonate group,
A pt-butylphenyl carbonate group, a p-cumylphenyl carbonate group and the like are preferably used. Further, the ratio of the hydroxyl group terminal to the other terminal is preferably 1: 100 or more, more preferably 1:40 or more. The molecular weight of these polycarbonates is not particularly limited. Further, the content of hydrolyzable chlorine contained in the polycarbonate is preferably 1 ppm or less, more preferably 0.5 ppm or less. If chlorine in an amount exceeding 1 ppm is contained in the polycarbonate resin, it will be colored by being exposed to a high temperature for a long time, such as during molding, and the transparency characteristic of polycarbonate will be lost.

The polycarbonate can be produced by a known method. Specifically, a known method for reacting an aromatic dihydroxy compound with a carbonate precursor, for example, an interfacial polymerization method (phosgene method) in which an aromatic dihydroxy compound and phosgene are reacted in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent , An ester exchange method (melting method) in which an aromatic dihydroxy compound is reacted with diphenyl carbonate, and a method of solid-phase polymerization of a crystallized carbonate prepolymer (JP-A-1-158033, JP-A-1-2727)
1426, JP-A-3-68627) and the like.

The base material polycarbonate (I) may contain various additives as required, such as a heat stabilizer, an antioxidant, a weathering agent, an ultraviolet absorber, a release agent, a lubricant, and an antistatic agent. Agents, plasticizers, polymers such as other resins and rubbers, pigments, dyes, fillers, reinforcing agents, flame retardants and the like. The polycarbonate used in the coating layer polycarbonate composition (II) may contain a heat stabilizer, an antioxidant, a weathering agent, and an ultraviolet absorber other than the three or four compounds essential in the present invention. However, the total amount of these additives should be 2% by weight or less, preferably 1% by weight or less.

The coating layer polycarbonate composition (I)
Various additives may be added to the polycarbonate used in I), if necessary. For example, release agents, lubricants, antistatic agents, plasticizers, polymers such as resins and rubbers, pigments, dyes, fillers Agents, reinforcing agents, flame retardants and the like.
These additives and the like may be added while the polycarbonate after the polymerization is in a molten state, and after the polycarbonate is once pelletized, the additives may be added and re-melted and kneaded, or simultaneously with the polycarbonate during sheet molding or It may be added during molding.

The (A) hydroxyphenyltriazine compound used in the present invention is represented by the following formula (21). For example, 2,4-diphenyl-6- (2-hydroxy-4-
Methoxyphenyl) -1,3,5-triazine, 2,4
-Diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-propoxyphenyl)
-1,3,5-triazine, 2,4-diphenyl-6-
(2-hydroxy-4-butoxyphenyl) -1,3,3
5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-
Triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-
4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-
Benzyloxyphenyl) -1,3,5-triazine,
2,4-diphenyl-6- (2-hydroxy-4- (2
-Butoxyethoxy) phenyl) -1,3,5-triazine, 2,4-di-p-toluyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4- Di-p-toluyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine,
2,4-di-p-toluyl-6- (2-hydroxy-4
-Propoxyphenyl) -1,3,5-triazine,
2,4-di-p-toluyl-6- (2-hydroxy-4
-Butoxyphenyl) -1,3,5-triazine, 2,
4-di-p-toluyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine,
2,4-di-p-toluyl-6- (2-hydroxy-4
-Octyloxyphenyl) -1,3,5-triazine, 2,4-di-p-toluyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4- Di-p-toluyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4-di-p-toluyl-6- (2-hydroxy-4- (2- Hexyloxyethoxy) phenyl)
-1,3,5-triazine and the like. Of these, 2,4-diphenyl-6-, which is particularly excellent in an ultraviolet absorbing effect,
(2-hydroxy-4-hexyloxyphenyl)-
1,3,5-triazine is more preferred.

[0043]

Embedded image

(Wherein R1 is hydrogen or C 1-18)
An alkyl group or an alkyl group having 1 to 12 carbon atoms or an alkyl group having 2 to 6 carbon atoms substituted with halogen or a benzyl group, and R2 is hydrogen or a methyl group. The above-mentioned hydroxyphenyltriazine compound is used in the coating layer polycarbonate composition (II) of the present invention.
It is preferable that 0.1 to 5% by weight, preferably 0.5 to 3% by weight, more preferably 1 to 3% by weight is blended. If the compounding amount is less than 0.1% by weight, the ultraviolet ray cannot be completely absorbed by the coating layer polycarbonate composition (II) layer, and the polycarbonate (I) in the base material is exposed to the ultraviolet ray, so that the coloration and the transparency of the polycarbonate (I) are increased. Loss, strength reduction, etc., and so-called poor weather resistance. Conversely, if the content exceeds 5% by weight, the ultraviolet light can be absorbed almost completely, so that the weather resistance can be improved. The compound itself is colored by the compound, and not only the initial coloring when viewed as a laminated sheet is large, but also the surface gloss of the sheet surface is deteriorated due to the presence of a large amount of the compound in the surface layer, so-called gloss disappeared. Very serious problems occur in appearance, such as a state. In addition, when used outdoors for a long period of time, there arises a problem that a large amount of the incorporated ultraviolet absorber is precipitated on the sheet surface.

The phenolic compound (B) used in the present invention includes, for example, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexane Diol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n
-Octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N '
Hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3 5-trimethyl-2,4,6
-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like, and one or more kinds can be used. In particular, the following chemical formula 22 and / or chemical formula 2 which are excellent in the heat stability at the time of sheet molding and the effect of preventing coloring due to heat.
3, ie, octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate and / or pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate] is preferred.

[0046]

Embedded image

(Wherein, R1 and R2 are an alkyl group having 1 to 4 carbon atoms, R3 is an alkyl group having 1 to 30 carbon atoms, and n is 1 to 10.)

[0048]

Embedded image

(Wherein, R1 and R2 are alkyl groups having 1 to 4 carbon atoms, R3 is an alkyl group having 1 to 30 carbon atoms, and n is 1 to 10). In the composition (II), 0.001 to 1% by weight, preferably 0.01 to 0.5% by weight, and more preferably 0.01 to 0.1% by weight is blended.
When the compounding amount of the compound is less than 0.001% by weight, not only problems such as insufficient heat stability at the time of sheeting and large initial coloring occur, but also ultraviolet absorption when used outdoors for a long period of time. The agent is deposited on the surface of the sheet, causing a very serious problem in appearance, such as loss of gloss on the surface. Conversely, if the amount exceeds 1% by weight, the compound is added to the coating layer in such a large amount that the coating layer itself is colored by the compound, and the initial coloring when viewed as a laminated sheet is large. Not only that, since a large amount of the compound is present in the surface layer, the surface gloss of the sheet surface is deteriorated, resulting in a very serious problem in appearance, such as a loss of gloss. In addition, since the compound has poor weather resistance, when used outdoors for a long time,
Not only the weather resistance is poor such as coloring, but also the problem that the compound is deposited on the sheet surface occurs.

Examples of the phosphorus compound (C) used in the present invention include tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4, 4′-biphenylenediphosphite, tris (nonylphenyl) phosphite, triphenylphosphite, tris (ethylphenyl) phosphite, tris (butylphenyl) phosphite, tris (hydroxyphenyl) phosphite, etc. Alternatively, two or more kinds can be used. In particular, the following formula 2 which is excellent in heat stability at the time of sheet forming and prevention of coloring by heat.
4, ie, tris (2,4-di-
(t-Butylphenyl) phosphite is preferred.

[0051]

Embedded image

(In the formula, R1 and R2 are an alkyl group having 1 to 4 carbon atoms or either of them is hydrogen.) The above-mentioned phosphorus compound is used in the coating layer polycarbonate composition (II) of the present invention in an amount of 0.001 to 1 % By weight, preferably 0.001 to 0.5% by weight, more preferably 0.1% by weight.
It is preferable that 001 to 0.1% by weight be blended. When the compounding amount of the compound is less than 0.001% by weight, not only problems such as insufficient heat stability at the time of sheeting and large initial coloring occur, but also ultraviolet absorption when used outdoors for a long period of time. The agent is deposited on the surface of the sheet, causing a very serious problem in appearance, such as loss of gloss on the surface. Conversely, if the amount exceeds 1% by weight, the compound is added to the coating layer in such a large amount that the coating layer itself is colored by the compound, and the initial coloring when viewed as a laminated sheet is large. Not only that, since a large amount of the compound is present in the surface layer, the surface gloss of the sheet surface is deteriorated, resulting in a very serious problem in appearance, such as a loss of gloss. Further, since the compound is poor in weather resistance, when used outdoors for a long period of time, not only poor weather resistance such as coloring, but also problems such as precipitation of the compound on the sheet surface occur.

In the present invention, at least 0.1 to 5 parts by weight of (A) the hydroxyphenyltriazine compound and 0.001 to 1 part by weight of the (B) phenolic compound are contained in the coating layer polycarbonate composition (II). It is important that 0.001 to 1 part by weight of (C) the phosphorus compound is combined and blended. These (A), (B),
If any one of the compounds (C) is not compounded, or if the compounding amount is small, or if the compounding amount is large, the problems of the present invention cannot all be satisfied.

The timing and method of blending polycarbonate with (A) hydroxyphenyltriazine-based compound, (B) phenol-based compound, and (C) phosphorus-based compound to form coating layer polycarbonate composition (II) are particularly limited. There is no. For example, the polycarbonate after polymerization may be added during the molten state, after the polycarbonate is once pelletized, the additives may be added and then re-melted and kneaded, or added simultaneously with the polycarbonate during sheet molding or during the molding. May be.

The method for forming the polycarbonate laminated sheet is not particularly limited. For example, a coextrusion method in which the polycarbonate (I) and the coating composition (II) of the base portion are simultaneously melt extruded and laminated in a sheet die to form a sheet. Then, the coating layer polycarbonate composition (II) was added to the base material polycarbonate (I) formed by extruding a sheet,
A method of melt extrusion from a die and laminating to laminate,
A method of continuously laminating a coating layer polycarbonate composition (II) previously formed into a film shape on a sheet surface of a substrate portion polycarbonate (I) using a heating roll or the like in the middle of the sheet manufacturing process; And a method of laminating the polycarbonate (I) formed on the base portion and the polycarbonate composition (II) formed on the film in the form of a film by thermocompression bonding with a press.

Coating Layer The polycarbonate composition (II) is coated on one or both sides of the polycarbonate (I) of the base material, and the coating thickness is preferably from 10 to 100 μm, more preferably from 20 to 50 μm. If the coating thickness is less than 10 μm, the effect of improving the weather resistance is insufficient, and
When the thickness exceeds 00 μm, the coloring of the coating layer is conspicuous, and the initial coloring when viewed as a laminated sheet becomes large, which is a problem.

The thickness of the polycarbonate laminated sheet of the present invention is not particularly limited, and is preferably 0.5 to 20 mm.
More preferably, it is 2 to 15 mm. The polycarbonate laminated sheet of the present invention can be formed into various shapes by processing. For example, machining such as cutting, drilling, cutting, and polishing, push-up molding, free molding, thermoforming such as heater bending, vacuum forming, and pressure forming, cold working such as shear punching and cold bending, welding, and bonding , Printing, painting, etc., and these processes can be performed in any step during or after forming the laminated sheet. The laminated sheet of the present invention may have a flat plate shape or a corrugated plate shape formed from a flat plate. The corrugated shape is formed by pressing with a roll having a corrugated shape during or after forming the laminated sheet.

The treatment of the surface of the laminated sheet of the present invention by post-processing is not particularly limited. For example,
Examples thereof include a silicon or acrylic hard coat applied to increase the surface hardness, application of a water-repellent resin, application of an antistatic agent, and application of a light diffusing material.

[0059]

The effects of the present invention will be more specifically described below with reference to examples and comparative examples. The evaluation of each item was measured by the following method. (1) Weather resistance Sunshine super long life carbon was used with a sunshine weather meter manufactured by Suga Test Machine at a temperature of 6
The test piece was exposed for 3000 hours under the conditions of repeating a cycle of 2 hours without rainfall and 18 minutes of rainfall at a constant 3 ° C.

For evaluation, changes in yellowness and haze (cloudiness) before and after exposure were measured in accordance with JIS K 7103. Yellowing degree (ΔYI) = (yellowness before exposure) − (yellowness before exposure) When the value of yellowing degree (ΔYI) is large, the yellowness becomes deeper as a result of the weather resistance test as compared to the initial value ( When the yellowing degree exceeds 4, it is clearly visible that the pigment is colored.

Haze difference (ΔH%) = (haze after exposure)
-(Haze before exposure) A large value of the haze difference (ΔH%) means that the haze became large as a result of the weather resistance test as compared with the initial value, and if the haze difference (ΔH%) exceeds 2, The loss of clarity is clearly visible visually. In this evaluation, the case where the yellowing degree (ΔYI) was less than 4 and the haze difference (ΔH%) was less than 2, that is, neither yellowing nor fogging was defined as weather resistance ◎, and the yellowing degree (ΔYI) was 4
When the haze difference (ΔH%) was 2 or more, that is, when yellowing or clouding occurred, the weather resistance was evaluated as x.

(2) Surface Gloss The degree of gloss on the sheet surface was visually evaluated in comparison with the glass surface having a refractive index of 1.567. In this evaluation, the case where it was judged that the surface of the sheet was glossy or equal to the above glass was evaluated as ◎, and the case where it was judged that it was inferior compared to the above glass was evaluated as ×.

Also, the case where ◎ was obtained immediately after the production of the polycarbonate laminated sheet, but the case where the gloss of the sheet surface disappeared in the weather resistance test was indicated as △. (3) Initial coloring The yellowness immediately after forming the laminated sheet was measured in accordance with JIS K 7105. When the yellowness exceeds 4, it is clearly visible by visual observation that coloring has occurred.

In this evaluation, when the yellowness was less than 4, the initial coloring was evaluated as ◎, that is, the initial coloring was small.
The above cases were evaluated as initial color x, that is, the initial color was large. (4) Precipitation of Ultraviolet Absorber Fine powder adhering to the sample surface after the weather resistance test was collected with an adhesive tape, and the ultraviolet absorber contained in the collected fine powder was subjected to high-speed liquid chromatography (manufactured by Shimadzu Corporation, LC
The analysis was carried out according to -6A).

When the same evaluation was performed before the weather resistance test, no ultraviolet absorber was confirmed. Therefore, when the peak of the ultraviolet absorber was confirmed after the weather resistance test, it was concluded that the ultraviolet absorber was precipitated by the weather resistance test. Can be In this evaluation,
When the peak of the ultraviolet absorber could not be confirmed, ◎, that is, there was no precipitation of the ultraviolet absorber, and conversely, when the peak of the ultraviolet absorber was confirmed, ×, that is, the ultraviolet absorber precipitated as a result of the weather resistance test. It was evaluated as having done.

[0066]

[Example 1] Polycarbonate (trade name, manufactured by Teijin Chemicals Limited)
Panlite), 2,4-diphenyl-6- (2
-Hydroxy-4-hexyloxyphenyl) -1,
(A) 3% by weight of hydroxyphenyltriazine-based compound composed of 3,5-triazine, octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
(B) phenolic compound consisting of propionate
0.05% by weight of (C) a phosphorus-based compound composed of tris (2,4-di-t-butylphenyl) phosphite
% By weight, melt-kneaded at an extrusion temperature of 280 ° C. in a vented 30 mm twin-screw extruder, and extruded into pellets to obtain a coating layer polycarbonate composition (II).

The thus-obtained coating layer polycarbonate composition (II) was manufactured by Toshiba Machine Co., Ltd.
/ D = 32, and at the same time, co-extrusion of the base material polycarbonate (I) (trade name: Panlite manufactured by Teijin Chemicals Co., Ltd.) using an extruder having a diameter of 100 mm and L / D = 32 manufactured by Toshiba Machine Co. Thus, a polycarbonate laminated sheet having two and three layers in which the coating layer polycarbonate composition (II) was coated on both sides of the polycarbonate (I) was obtained. The co-extrusion die uses a feed block method, and the die set temperature is 2
The test was carried out at 70 ° C and the extruder cylinder temperature was 290 ° C. The thickness of the coating layer polycarbonate composition (II) was adjusted by adjusting the discharge rate of both extruders and the flow rate adjustment bolt of the die so that the thickness of each side of the polycarbonate composition (II) was 30 μm. In addition, the laminated molten resin discharged from the die is adjusted to a plate thickness of 5 mm by a glazing roll controlled at 120 ° C.
A polycarbonate laminated sheet having good appearance was obtained.

The obtained polycarbonate laminated sheet was evaluated according to the evaluation method described above. As a result, it was excellent in weather resistance (yellowing degree = 2, haze difference = 0.5%), excellent in surface gloss, and less in initial coloring. (Yellowness = 1) and no precipitation of the ultraviolet absorber was confirmed by the weather resistance test. Table 1 shows the results.

[0069]

Example 2 Coating layer Among the compounds to be blended in the polycarbonate composition (II), (B) octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate was used as a phenolic compound. 04% by weight of pentaerythrityl-tetrakis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]
A polycarbonate laminated sheet was obtained in the same manner as in Example 1 except that 0.03% by weight of 0.07% by weight was used.

The obtained polycarbonate laminated sheet was evaluated according to the above-mentioned evaluation method. As a result, as in Example 1, it was excellent in weather resistance (yellowing degree = 2, haze difference = 0.5%), and excellent in surface gloss. (60 degree specular gloss = 150), little initial coloring (yellowness = 1), and no precipitation of the ultraviolet absorber by the weather resistance test. The results are shown in Table 1 together with Example 1.

[0071]

Comparative Example 1 A polycarbonate laminated sheet was obtained in the same manner as in Example 1 except that the hydroxyphenyltriazine compound (A) was not blended among the compounds blended in the coating layer polycarbonate composition (II). As a result of evaluating the obtained polycarbonate laminated sheet according to the evaluation method described above, the weather resistance was poor (yellowing degree = 15, haze difference =
20%).

The results are shown in Table 1 together with the examples.

[0073]

Comparative Example 2 A polycarbonate laminated sheet was obtained in the same manner as in Example 1, except that the phenolic compound (B) was not blended among the compounds blended in the coating layer polycarbonate composition (II). The obtained polycarbonate laminated sheet was evaluated according to the evaluation method described above. As a result, it was found that the thermal stability was poor, and the coating layer polycarbonate composition (II) was colored during the formation of the laminated sheet, and the initial coloring was large. (Yellowness = 5) In the weather resistance test, it was confirmed that the surface gloss was lost and that the ultraviolet absorbent was precipitated on the sheet surface.

The results are shown in Table 1 together with the examples.

[0075]

Comparative Example 3 A polycarbonate laminated sheet was obtained in the same manner as in Example 1 except that, among the compounds to be blended into the coating layer polycarbonate composition (II), (C) the phosphorus compound was not blended. The obtained polycarbonate laminated sheet was evaluated according to the evaluation method described above. As a result, the thermal stability was poor as in Comparative Example 2, and the coating layer polycarbonate composition (II) was colored at the time of molding the laminated sheet, and the initial coloring was large. I understand. (Yellowness = 5) In the same manner as in Comparative Example 2, it was confirmed by the weather resistance test that the surface gloss was lost and that the ultraviolet absorbent was precipitated on the sheet surface.

The results are shown in Table 1 together with the examples.

[0077]

Comparative Example 4 The same procedure as in Example 1 was carried out except that the coating thickness of the coating composition polycarbonate composition (II) was reduced to 5 μm by adjusting the discharge rate of the laminated sheet extruder. Obtained. As a result of evaluating the obtained polycarbonate laminated sheet according to the evaluation method described above, the weather resistance was poor (yellowing degree = 8, haze difference = 8).
%), And the weather resistance test confirmed that not only the gloss of the sheet surface was lost, but also the precipitation of the ultraviolet absorber.

The results are shown in Table 1 together with the examples.

[0079]

Comparative Example 5 The same procedure as in Example 1 was carried out except that the coating thickness of the coating layer polycarbonate composition (II) was increased to 150 μm by adjusting the discharge rate of the laminated sheet extruder. Obtained. The obtained polycarbonate laminated sheet was evaluated according to the evaluation method described above. As a result, although the weather resistance was good (yellowing degree = 2, haze difference = 0.5%), initial coloring was noticeable (yellowness = 7).
It is a problem.

The results are shown in Table 1 together with the examples.

[0081]

Comparative Example 6 A coating layer was prepared in the same manner as in Example 1 except that the amount of the hydroxyphenyltriazine-based compound (A) was reduced to 0.05% by weight among the compounds to be added to the polycarbonate composition (II). A polycarbonate laminated sheet was obtained. The obtained polycarbonate laminated sheet was evaluated according to the above-mentioned evaluation method. As a result, the weather resistance was poor (yellowing degree = 10, haze difference = 10%), and not only the sheet surface was not glossy by the weather resistance test, but also ultraviolet rays. Precipitation of the absorbent was also confirmed.

The results are shown in Table 1 together with the examples.

[0083]

Comparative Example 7 The same procedure as in Example 1 was repeated except that the amount of the hydroxyphenyltriazine-based compound (A) was increased to 10% by weight among the compounds blended in the coating layer polycarbonate composition (II). I got a sheet. The obtained polycarbonate laminated sheet was evaluated according to the evaluation method described above. As a result, the weather resistance was very good (yellowing degree = 1, haze difference = 0.2%), but the coating layer polycarbonate composition (II) was large in amount. (A) Colored by a hydroxyphenyltriazine compound, the initial coloring as a laminated sheet becomes large (yellowness = 4), and the surface gloss is deteriorated due to the large amount of the compound in the surface layer, and the weather resistance test As a result, precipitation of the ultraviolet absorber was observed.

The results are shown in Table 1 together with the examples.

[0085]

Comparative Example 8 A polycarbonate laminate was prepared in the same manner as in Example 1 except that the amount of the phenolic compound (B) was reduced to 0.0005% by weight among the compounds blended in the coating layer polycarbonate composition (II). I got a sheet. As a result of evaluating the obtained polycarbonate laminated sheet according to the above-mentioned evaluation method, the weather resistance was good (yellowing degree =
2, haze difference = 0.5%), poor thermal stability, coloring of the coating layer polycarbonate composition (II) at the time of forming the laminated sheet, and large initial coloring. (Yellowness = 5) Further, it was confirmed by the weather resistance test that the surface gloss was lost and that the ultraviolet absorbent was precipitated on the sheet surface.

The results are shown in Table 1 together with the examples.

[0087]

Comparative Example 9 The same procedure as in Example 1 was repeated except that the amount of the phenolic compound (B) was increased to 1.5% by weight among the compounds to be added to the coating layer polycarbonate composition (II). I got a sheet. The obtained polycarbonate laminated sheet was evaluated according to the evaluation method described above, and as a result, the weather resistance was poor (yellowing degree = 5, haze difference =
1.5%), the coating layer polycarbonate composition (II) is colored by a large amount of the (B) phenolic compound, and the initial coloring as a laminated sheet increases (yellowness =
4) In addition, since a large amount of the compound is present in the surface layer, the surface gloss is deteriorated.

The results are shown in Table 1 together with the examples.

[0089]

Comparative Example 10 Coating Layer Polycarbonate Composition (II)
Was carried out in the same manner as in Example 1 except that the amount of the phosphorus-based compound (C) was reduced to 0.0005% by weight among the compounds to be mixed, to obtain a polycarbonate laminated sheet. As a result of evaluating the obtained polycarbonate laminated sheet according to the above-described evaluation method, the weather resistance was good (yellowing degree = 2,
(Haze difference = 0.5%), heat stability was poor, and the coating layer polycarbonate composition (II) was colored during the formation of the laminated sheet, indicating that the initial coloring was large. (Yellowness = 5) Further, it was confirmed by the weather resistance test that the surface gloss was lost and that the ultraviolet absorbent was precipitated on the sheet surface.

The results are shown in Table 1 together with the examples.

[0091]

Comparative Example 11 Coating Layer Polycarbonate Composition (II)
Was carried out in the same manner as in Example 1 except that the amount of the phosphorus-based compound (C) was increased to 1.5% by weight among the compounds to be mixed, to obtain a polycarbonate laminated sheet.

The obtained polycarbonate laminated sheet was evaluated according to the above-mentioned evaluation method. As a result, the weather resistance was poor (yellowing degree = 5, haze difference = 1.5%), and the coating layer polycarbonate composition (II) contained a large amount. (C) It is colored by a phosphorus compound, the initial coloring as a laminated sheet becomes large (yellowness = 4), and the surface gloss is deteriorated due to the presence of a large amount of the compound in the surface layer.

The results are shown in Table 1 together with the examples.

[0094]

Comparative Example 12 Coating Layer Polycarbonate Composition (II)
Benzotriazole-based compound consisting of 2- [2-hydroxy-3,5-bis (α, α'-dimethylbenzyl) phenyl] -2H-benzotriazole, wherein (A) the hydroxyphenyltriazine-based compound is Except having changed to 3 weight%, it carried out similarly to Example 1 and obtained the polycarbonate laminated sheet.

The obtained polycarbonate laminated sheet was evaluated according to the evaluation method described above. As a result, it was found that the weather resistance was poor (yellowing degree = 6, haze difference = 3%), and that the gloss of the sheet surface was lost by the weather resistance test. No precipitation of the ultraviolet absorber was confirmed. The results are shown in Table 1 together with the examples.

[0096]

Comparative Example 13 Coating Layer Polycarbonate Composition (II)
Benzotriazole-based compound consisting of 2- [2-hydroxy-3,5-bis (α, α'-dimethylbenzyl) phenyl] -2H-benzotriazole, wherein (A) the hydroxyphenyltriazine-based compound is Except having changed to 5 weight%, it carried out similarly to Example 1, and obtained the polycarbonate laminated sheet.

The obtained polycarbonate laminated sheet was evaluated according to the evaluation method described above. As a result, although the weather resistance was good (yellowing degree = 3, haze difference = 1.5%), the initial coloring was large (yellowness = 4). ) And the weather resistance test confirmed that not only the gloss of the sheet surface was lost, but also the precipitation of the ultraviolet absorber. The results are shown in Table 1 together with the examples.

[0098]

Comparative Example 14 Coating Layer Polycarbonate Composition (II)
Benzotriazole-based compound consisting of 2- [2-hydroxy-3,5-bis (α, α'-dimethylbenzyl) phenyl] -2H-benzotriazole, wherein (A) the hydroxyphenyltriazine-based compound is Except having changed to 10 weight%, it carried out similarly to Example 1 and obtained the polycarbonate laminated sheet.

The obtained polycarbonate laminated sheet was evaluated according to the evaluation method described above. As a result, although the weather resistance was good (yellowing degree = 1, haze difference = 0.5%), the surface gloss was poor and the initial coloring was large. (Yellowness = 8), and not only the glossiness of the sheet surface was lost by the weather resistance test, but also the precipitation of the ultraviolet absorber was confirmed. The results are shown in Table 1 together with the examples.

[0100]

[Table 1]

[0101]

According to the present invention, the weather resistance of the polycarbonate sheet is improved, the surface gloss is improved, the thermal stability is improved, the initial coloring is prevented, and the ultraviolet absorbent is precipitated even when used outdoors for a long period of time. It is possible to provide a polycarbonate sheet which does not have any use, and it is expected that the use of the polycarbonate sheet outdoors will be further expanded in the future.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 69/00 LPU C08L 69/00 LPU

Claims (1)

[Claims] 1. A polycarbonate (I) base material comprising at least (A) 0.1 to 5% by weight of a hydroxyphenyltriazine-based compound represented by the following chemical formula (1), and (B) a compound represented by the following chemical formula (2) and / or (3): 0.001 to 1% by weight of a phenolic compound represented by the formula (C):
A polycarbonate laminated sheet which is coated with a polycarbonate composition (II) having a thickness of 10 to 100 μm. Embedded image (In the formula, R1 is hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 2 to 6 carbon atoms or a benzyl group substituted with halogen, and R2 is a hydrogen or methyl group. ) (Wherein, R1 and R2 are an alkyl group having 1 to 4 carbon atoms,
R3 is an alkyl group having 1 to 30 carbon atoms, and n is 1 to 10. ) (Wherein, R1 and R2 are an alkyl group having 1 to 4 carbon atoms,
R3 is an alkyl group having 1 to 30 carbon atoms, and n is 1 to 10. ) (In the formula, R1 and R2 are an alkyl group having 1 to 4 carbon atoms or any of them is hydrogen.)