JPH0596692A - Polycarbonate resin laminated product - Google Patents

Abstract

PURPOSE:To improve the weatherability of a laminated product for use in natural lighting material and the heat resistance thereof at the time of its formation by laminating the acryl resin film consisting of a specific copolymer, an acryl polymer and a multilayer elastic body on the surface of a polycarbonate resin plate. CONSTITUTION:An acryl resin mixture is made up consisting of 1-100wt.% of the copolymer of 98-40wt.% of methyl methacrylate, 1-30wt.% of N- cyclohexylmaleimide and 1-30wt.% of aromatic vinyl compound and 99-0wt.% of the acrylic polymer containing at least 70% of methyl methacrylate. An elastic body of multi-layer structure is formed by polymerizing 70-90 pts.wt. of the cross-linked acrylic ester copolymer of the acrylic alkyl ester having alkyl group of 1-8 carbon atoms, styrene or its derivative and multifunctional monomers and 10-30 pts.wt. of the cross-linked monomer mixture of the same kind. The acryl resin film 2 to be laminated on a polycarbonate resin plate 1 is composed of 50-98 pts.wt. of the acryl resin mixture and 2-50 pts.wt. of the elastic body.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin laminate having improved weather resistance which is used in exterior fields such as daylighting materials, soundproof walls and sunroofs.

[0002]

2. Description of the Related Art It is known to laminate an acrylic resin film in order to improve the weather resistance of a polycarbonate resin plate, and when such a polycarbonate resin plate is formed into a dome shape or a curved surface for use. Is heated in a heating furnace or infrared rays to be secondary molded. In this case, as a film containing an acrylic resin as a main component, it is known to use a composition composed of a multilayer structure elastic body known in JP-A-51-129449 and JP-A-52-56150. Has been. On the other hand, as a method for improving the heat resistance of acrylic resin, Japanese Patent Publication No.
56, 56-43232, JP-A-56-
As disclosed in JP-A-81322 and JP-A-62-270648, it is known to copolymerize methyl methacrylate with α-methylstyrene, maleic anhydride, cyclohexylmaleimide and the like.

[0003]

When molding a polycarbonate resin, the molding temperature of the polycarbonate resin is 15
Since it is 0 to 220 ° C., which is higher than the molding temperature of the acrylic resin, the acrylic resin film layer is considerably softened and becomes sticky. Therefore, when the heated sheet is moved or molded, marks are likely to be left on the hands or marks on the surface of the mold. Even if an acrylic resin having improved heat resistance is simply used in order to increase the heat resistance during molding, it cannot be used because the physical properties of the film such as spinnability cannot be obtained.

[0004]

SUMMARY OF THE INVENTION Therefore, the inventors of the present invention have earnestly studied to provide a polycarbonate resin laminate having improved weather resistance of a polycarbonate resin plate and improved heat resistance of the surface during secondary molding. As a result, the present invention has been completed.

On at least one side of a polycarbonate resin plate, a copolymer of a monomer mixture consisting of 98 to 40% by weight of methyl methacrylate, 1 to 30% by weight of N-cyclohexylmaleimide and 1 to 30% by weight of an aromatic vinyl compound ( The carbon number of the alkyl group is based on 50 to 98 parts by weight of an acrylic resin mixture consisting of I) 1 to 100% by weight and acrylic polymer (II) 99 to 0% by weight containing 70% by weight or more of methyl methacrylate. Obtained by polymerizing at least one of alkyl acrylates 1 to 8 and styrene alone or a mixture of styrene and its derivative, and a polyfunctional monomer having two or more carbon-carbon double bonds in one molecule. Crosslinked acrylic acid ester-based copolymer 70
In the presence of ˜90% by weight, at least one of methyl methacrylate and an acrylic acid alkyl ester having 1 to 8 carbon atoms of an alkyl group, other vinyl-based monomer copolymerizable therewith and one molecule Crosslinkable monomer mixture 30 comprising polyfunctional monomer having two or more carbon-carbon double bonds
The present invention relates to a polycarbonate resin laminate in which an acrylic resin film made of a resin composition obtained by mixing 2 to 50 parts by weight of a multilayer structure elastic body (III) obtained by polymerizing 10 to 10% by weight is laminated.

The basic structure of the polycarbonate resin laminate of the present invention comprises a polycarbonate resin plate 1 as a base material and an acrylic resin film 2 laminated on the surface as shown in FIG. Further, FIG. 2 shows the polycarbonate resin laminate of the present invention formed into a dome shape by free blow molding. Such a dome is often used as a daylighting material. According to the present invention, the heat resistance of the acrylic resin film as the surface layer is greatly increased to make it difficult for marks such as a hand or a mold to be left on the surface of the laminate during thermoforming.

The polycarbonate resin used in the present invention means 2,2'-bis (4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4).
It is obtained by reacting -hydroxyphenyl) propane with phosgene by a known method, and a suitable molecular weight is 20,000 to 40,000 in terms of viscosity average molecular weight.
A suitable ultraviolet absorber may be added to the polycarbonate resin plate of the present invention in order to impart weather resistance. Further, it is possible to add a colorant or a pigment. Further, when used for a dome or the like, a minute embossed pattern can be provided on the surface in order to diffuse the transmission of direct light.

In the present invention, the methyl methacrylate component constituting the copolymer (I) retains the original optical properties, weather resistance or mechanical properties of the methacrylic resin, and has compatibility with the acrylic polymer (II). It is a component for improving the amount and is used in an amount of 40 to 98% by weight in the copolymer (I). If it is less than 40% by weight, the above properties are lost, and
If it exceeds 8% by weight, improvement in heat resistance cannot be expected.

Further, N which is a constituent component of the copolymer (I)
-Cyclohexylmaleimide is a component for improving heat resistance, and the amount thereof is 1 to 30% by weight, preferably 3 to 25% by weight in the copolymer (I). If it is less than 1% by weight, the heat resistance is inferior, and if it exceeds 30% by weight, the resin composition tends to become brittle and the polymerization system tends to become unstable, resulting in a decrease in productivity. The aromatic vinyl compound, which is a constituent component of the copolymer (I), has a synergistic effect of directly improving the heat resistance when, for example, α-methylstyrene is used, but is rather a heat resistant component. By increasing the copolymerization reaction of a certain N-cyclohexylmaleimide, the heat resistance is indirectly improved and a remarkable effect is exerted on the improvement of productivity. Further, the fluidity and the compatibility with the acrylic polymer (II) are improved by this component.

That is, the mixture of the acrylic polymer (II) and the binary copolymer of methyl methacrylate and N-cyclohexylmaleimide maintains transparency, and the mechanical properties are similar to those of the acrylic polymer (II). The characteristics are exhibited only when the copolymerization ratio of N-cyclohexylmaleimide is very limited, and in general, this mixture not only has no synergistic effect, but also has cloudiness and turbidity and has poor optical properties. I can only get it. Further, considering that the mixture of the copolymer of methyl methacrylate and the aromatic vinyl compound and the polymer (II) has poor compatibility and generally becomes opaque, the method according to the present invention has excellent physical properties and is transparent. It was a surprising result that a resin was obtained.

Examples of the aromatic vinyl compound of the present invention include styrene, o-, m-, p-methylstyrene, 1,
3-dimethylstyrene, 2,4-dimethylstyrene, p
Monovinylidene aromatic hydrocarbons such as -t-butylstyrene, α-methylstyrene, α-ethylstyrene, α-methyl-p-methylstyrene, o-, m-, p-chlorostyrene, 2,4-dibromostyrene , 2-methyl-4
-Alhalomonovinylidene aromatic hydrocarbons such as chlorostyrene and the like. Particularly, at least one selected from the group consisting of styrene, vinyltoluene and α-methylstyrene is preferable, and it is more preferable to contain α-methylstyrene having a large effect of improving heat resistance.

In order to achieve the above effects, the copolymer (I)
The proportion of the aromatic vinyl compound used therein is in the range of 1 to 30% by weight, preferably 2 to 20% by weight, more preferably 2 to 15% by weight. If less than 1% by weight, no synergistic effect is observed, and conversely if more than 30% by weight,
The compatibility with the polymer (II) decreases, and the transparency of the obtained resin composition decreases.

In the present invention, the copolymer (I) is N-cyclohexyl in consideration of the balance of resin properties such as heat resistance, mechanical properties, optical properties or molding processability of the finally obtained resin composition. When the number of moles of maleimide is α and the number of moles of aromatic vinyl compound is β, the compounding ratio (β / α) of both components is preferably in the range of 0.2 to 5, and is 0.5 to 2. The range is particularly preferable in terms of synergistic effect. When the compounding ratio is less than 0.2 or exceeds 5, a decrease in compatibility with the acrylic polymer (II) is recognized and the transparency tends to decrease.

The acrylic polymer (II) constituting the resin composition of the present invention is for imparting the original weather resistance, mechanical properties, optical properties and molding processability of the methacrylic resin. Methyl methacrylate, which is the main component in the acrylic polymer (II), is for imparting the original weather resistance, optical properties, and mechanical properties of the methacrylic resin, and if the amount used is less than 70% by weight. The physical properties are deteriorated. It is more preferably 80% by weight or more. Monomers used for copolymerization with methyl methacrylate include methyl acrylate, acrylic acid esters such as ethyl acrylate, methacrylic acid esters such as ethyl methacrylate and butyl methacrylate, styrene, acrylonitrile, maleic anhydride. Etc., and one or more of these monomers are copolymerized in an amount of 30% by weight or less, preferably 20% by weight or less.

The amount of the polymer (I) constituting the resin composition of the present invention is 1 to 100% by weight, preferably 5 to 95% by weight, and the heat resistance is less than 1% by weight. Inferior The amount of acrylic polymer (II) used is 0 to
It is 99% by weight, preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and if it exceeds 99% by weight, improvement in heat resistance cannot be expected.

Multilayer elastic body (III) in the present invention
Is a component that imparts impact resistance without impairing the optical properties and weather resistance of the acrylic resin, and at the same time imparts film-forming properties. The multilayer structure elastic body (III) used in the present invention is an elastic body having a two-layer structure. The first layer is a layer for imparting elasticity, and preferably 70 to 90 parts by weight of at least one kind of alkyl acrylate whose alkyl group has 1 to 8 carbon atoms, and styrene alone or a mixture of styrene and its derivative 30. It is a crosslinked acrylic acid ester-based copolymer obtained by polymerizing 10 to 10 parts by weight and 0.5 to 20 parts by weight of a polyfunctional monomer having two or more carbon-carbon double bonds in one molecule. Here, the ratio of the acrylic acid alkyl ester to the styrene-based monomer is (I)
Since it is necessary to match the refractive index with the acrylic resin mixture composed of (II) and (II) to maintain transparency, it is desirable to select from the above ratio, and if it deviates from this region, haze will occur. Further, the second layer is preferably 85 to 99 parts by weight of methyl methacrylate and 15 to 1 parts by weight of at least one kind of an alkyl acrylate having 1 to 8 carbon atoms of an alkyl group, and another vinyl type copolymerizable with this. It is a crosslinked resin layer comprising 0.5 to 20 parts by weight of a polyfunctional monomer having two or more monomers and carbon-carbon double bonds, and a phase of an acrylic resin mixture comprising (I) and (II). It is a layer that imparts solubility.

The mixing ratio of the resin composition of the present invention is (I)
50 to 98 parts by weight of the acrylic resin mixture consisting of (II) and (II), and 50 to 2 parts by weight of the multilayer structure elastic body (III). Within this range, the impact resistance and the film can be obtained without impairing the heat resistance. You will be able to add physical properties when you do. When the proportion of the multilayer elastic body exceeds 50 parts by weight, the impact resistance increases, but
Molding such as injection molding and extrusion molding becomes extremely difficult because the fluidity of the resin is greatly reduced. On the other hand, if the amount is less than 2 parts by weight, the moldability will not be a problem, but it will be difficult to obtain a thin sheet or film because of poor porosity, and physical properties such as tensile strength / elongation and impact strength of the film will not be obtained. ..

The acrylic resin layer 2 used in the present invention has good weather resistance by itself, but a general ultraviolet absorber can be added to impart further weather resistance. For example, benzophenone-based, triazole-based, and salicylic acid-based ultraviolet absorbers can be used.

As a method for laminating the acrylic resin layer 2 and the polycarbonate resin plate 1 used in the present invention, a generally known method can be applied. There are methods such as coextrusion molding, laminating a film on a substrate, and further applying an acrylic resin by dissolving it in a solvent or the like. In the simplest case, an acrylic resin film is formed in advance, and when the polycarbonate resin plate of the base material is extruded, the surface temperature is 130%.
There is a method of heat lamination in the region of 150 ° C. There is also a method of making a laminate by thermocompression-bonding the produced polycarbonate resin plate and an acrylic resin film.

[0020]

The present invention will be described in more detail with reference to the following examples. The physical properties in the examples were evaluated according to the following methods. 1. Total light transmittance and haze value are according to ASTM D1003
Was carried out according to. 2. The heat distortion temperature (HDT) was performed according to JIS K-6714. 3. Yield strength, breaking strength and elongation are according to ASTM D8
82. 4. For the heating test of the laminated product, the film obtained in each Example was used as a polycarbonate resin plate (Dialite P1).
001: Mitsubishi Rayon heat laminated with laminate products to KK) and heated predetermined time flat position to the film side up, placing the panel on the film surface was cooled under a load of 25 g / cm ² weight The surface condition after removing was observed.

(1) Two kinds of resins having the following compositions were prepared as an acrylic resin mixture. A. A copolymer composed of 75% by weight of methyl methacrylate, 5% by weight of α-methylstyrene, 5% by weight of styrene and 15% by weight of cyclohexylmaleimide was used as an acrylic resin mixture A. B. 80 parts by weight of a copolymer consisting of 85% by weight of methyl methacrylate, 5% by weight of α-methylstyrene and 10% by weight of cyclohexylmaleimide, and a commercially available acrylic resin:
20 parts by weight of Acrypet VH (product of Mitsubishi Rayon Co., Ltd.) was mixed to prepare an acrylic resin mixture B. (2) Acrypet I as the multilayer elastic body (III)
R320 (manufactured by Mitsubishi Rayon Co., Ltd.) was prepared.

Example 1 Acrypet I to 60 parts by weight of acrylic resin mixture A
40 parts by weight of R320 and 1.5 parts by weight of TINUVIN P (manufactured by Ciba Geigy) as an ultraviolet absorber were added and mixed to obtain a resin composition. The HDT of the obtained resin composition was 110 ° C. Next, this resin composition was molded at a die temperature of 240 ° C. to produce a film of 50 μm.
The total light transmittance of the film is 90.6%, the haze value is 1.8%
And the transparency was good. Table 1 shows the evaluation results of the obtained film laminate.

Example 2 A resin composition was obtained by adding 24 parts by weight of Acrypet IR320 and 1.5 parts by weight of Tinuvin P to 76 parts by weight of the acrylic resin mixture B and mixing them. H of the obtained resin composition
The DT was 103 ° C. In addition, H of the copolymer B alone
The DT was 115 ° C., and the heat resistance was lowered by 12 ° C. due to the addition of the elastic material having a multilayer structure, but the heat resistance was still higher than that of a general acrylic resin. Next, this resin composition was molded at a die temperature of 240 ° C. to produce a film of 50 μm. The total light transmittance of the film is 92.8%,
The haze value was 1.3% and the transparency was good. Further, the tensile strength and elongation are the yield strength 673 kg / cm ² and the breaking strength 55.
It was 6 kg / cm ² and the elongation was 36%. Table 1 shows the evaluation results of the obtained film laminate.

Comparative Example 1 As an acrylic resin film, acryprene HBS001 (product of Mitsubishi Rayon Co., Ltd.) having a thickness of 50 μm was evaluated. The HDT was 77 ° C., the total light transmittance was 92%, and the haze value was 1%. .. In addition, the yield strength is 320 kg / c
The m ² and the elongation are 110%, which is superior to the product of the present invention, but the heat resistance is low. Table 1 shows the evaluation results of the obtained film laminate.

Comparative Example 2 60 parts of a commercially available acrylic resin Acrypet MD (manufactured by Mitsubishi Rayon Co., Ltd.) and 40 parts of Acrypet IR 320 were mixed, and then a 50 μm film was prepared.
DT 82 ° C, total light transmittance 93%, haze value 0.9%
Met. Further, the yield strength is 450 kg / cm ² , the elongation is 110%, and the heat resistance is 15 to 20 compared with the product of the present invention.
Only what was lower by ℃ was obtained. Table 1 shows the evaluation results of the obtained film laminate.

Reference Example Table 1 shows the results of heating test of only the polycarbonate resin plate without laminating the film.

[0027]

[Table 1]

From the above results, by using the polycarbonate resin laminate of the present invention, the manner of marking the flannel after applying a load is greatly improved and is close to the result of the polycarbonate resin itself. I understand.

[0029]

EFFECTS OF THE INVENTION The polycarbonate resin laminate of the present invention has improved heat resistance of the surface layer, so that it is less likely to leave marks on the mold during secondary molding or marks during handling, resulting in a molding process. It can be done easily and has great industrial significance.

[Brief description of drawings]

FIG. 1 shows a sectional view of a polycarbonate resin laminate of the present invention.

[Explanation of symbols]

 1 Polycarbonate resin plate 2 Acrylic resin film

FIG. 2 shows a cross-sectional view of the polycarbonate resin laminate of the present invention molded into a dome shape by free blow molding.

[Explanation of symbols]

 1 Polycarbonate resin plate 2 Acrylic resin film

FIG. 3 shows an example of steps for producing the polycarbonate resin laminate of the present invention by thermal lamination.

[Explanation of symbols]

 1 Polycarbonate resin plate 2 Acrylic resin film 3 Press roll 4 Forming roll 5 Extruder

Claims (1)

[Claims] 1. A polycarbonate resin plate having, on at least one surface thereof, a monomer mixture containing 98 to 40% by weight of methyl methacrylate, 1 to 30% by weight of N-cyclohexylmaleimide, and 1 to 30% by weight of an aromatic vinyl compound. Carbon of an alkyl group is added to 50 to 98 parts by weight of an acrylic resin mixture consisting of 1 to 100% by weight of the compound (I) and 99 to 0% by weight of an acrylic polymer (II) containing 70% by weight or more of methyl methacrylate. At least one of alkyl acrylates having a number of 1 to 8, styrene alone or a mixture of styrene and its derivatives, and carbon-in one molecule
Crosslinked acrylic acid ester-based copolymers 70 to 90 obtained by polymerizing a polyfunctional monomer having two or more carbon double bonds
In the presence of% by weight, at least one of methyl methacrylate and an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, another vinyl-based monomer copolymerizable therewith, and a carbon Crosslinkable monomer mixture 30 to 10 comprising a polyfunctional monomer having two or more carbon double bonds
An elastic body having a multi-layer structure (II
I) A polycarbonate resin laminate in which an acrylic resin film made of a resin composition in which 2 to 50 parts by weight is mixed is laminated.