JPS60229749A - Multilayer sheet and manufacture thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a composite sort of styrene-butadiene-methyl methacrylate copolymer and a methyl methacrylate-containing polymer containing ultraviolet rays, which has high impact resistance and scratch resistance. The present invention relates to a transparent multilayer sheet that has excellent properties such as hardness, weather resistance, and moldability, and a method for producing the same.

(Prior art) In recent years, among transparent plastic plates, methacrylic resin plates, hard polyvinyl chloride plates, and polycarbonate plates have generally ceased to be used.
Due to its weather resistance and surface scratch resistance, it is widely used in displays, nameplates, signboards, lighting, architectural fields, etc.

Among these, in the field of signboards and lighting, there is a strong demand for weight reduction these days, and reinforced acrylic resin plates, which can be made thinner in terms of strength, are being used. In addition, methacrylic resin plates or hard-coated methacrylic m-belt plates are beginning to be used as glass for organic gray songs, and these transparent plastic plates are now being molded with higher-strength materials. The current situation is that

By the way, as a reinforced acrylic resin,
41 Publication 5% Publication No. 48-552'55, Japanese Patent Application Publication No. 55-58554 and Japanese Patent Publication No. 57-12873
Although the same pressure is described in Publication No. 6, the strength level is still insufficient, and the reinforced acrylic resin board also has improved cutting, punching properties, solvent resistance, and strength compared to the methacrylic resin board. Although it is certainly useful to make the wall thinner, the reality is that it is still not satisfactory in terms of rigidity and strength.

Furthermore, the styrene-butadiene-methyl methacrylate copolymer described in Japanese Patent Publication No. 46-52748 has excellent transparency, rigidity, impact resistance, and moldability, and is used in the injection molding field of notebooks for packaging materials and light electrical miscellaneous goods. etc. are widely used. However, when considered as a raw material for industrial thick sheets, it is inferior to reinforced acrylic resin sheets in terms of abrasion resistance (hardness) and weather resistance, and its excellent impact resistance is used in displays, nameplates, signboards, buildings, etc. It was difficult to utilize it for purposes such as lighting.

(Problems to be Solved by the Invention) The present invention solves the known drawbacks by using a styrene-butadiene-methyl methacrylate copolymer and a methyl methacrylate-containing polymer containing an ultraviolet absorber. The present invention provides a transparent multilayer sheet that has excellent impact resistance, scratch resistance, weather resistance, and moldability of the multilayer sheet, and a method for producing the same.

(Means for Solving the Problems) The present invention comprises: 1. A methyl methacrylate-containing polymer containing a styrene-butadiene-methyl methacrylate copolymer layer and 0.1 to 3.0% by weight of an ultraviolet absorber. 2. A multilayer sheet comprising a styrene-butadiene-methyl methacrylate copolymer layer and 0.1 to 6.0% by weight of an ultraviolet absorber. 1. A method for producing a multilayer sheet, characterized in that at least one of a methyl methacrylate-containing polymer sheet layer is melt-extruded and bonded together.

(Function) The styrene-butadiene-methyl methacrylate copolymer of the present invention is disclosed in Japanese Patent Publication No. 46-62748 and Japanese Patent Publication No. 46-62748.
15 to 2 parts by weight of a butadiene polymer or a butadiene copolymer with a weight of 50 or more, which is not described in US Pat.
~98 parts by weight of styrene-butadieno-methyl methacrylate copolymer and/or styrene-butadiene-grafted by bulk polymerization or bulk-suspension two-stage polymerization
Acrylonitrile, styrene, Styrene-butadiene-methyl methacrylate copolymer and/or styrene-butadiene-methyl methacrylate-acrylonitrile copolymer 60-5 to which 40-150 parts by weight of a monomer mixture selected from methyl methacrylate is grafted by emulsion polymerization. Combine heavy f part &! The remaining copolymer is the main body.

In addition, the methyl methacrylate-containing polymer of the present invention includes polymethyl methacrylate, acrylic rubber-containing methyl methacrylate copolymer, such as Mitsubishi Rayon Co., Ltd. product name Highvent HBE, HBS, HBA, etc., styrene 6
These include a styrene/methyl methacrylate copolymer of 0 to 70% by weight and 70 to 50% by weight of methyl methacrylate, and a styrene-butadiene-methyl methacrylate copolymer as described above.

Further, as the ultraviolet absorber added to the methyl methacrylate-containing polymer, the pe/citriazole type, benzophenone type, and salicylic acid derivative type used for general plastics are used, and among them, the benzotriazole type is preferable, such as the one manufactured by Ciba Geigy, There are trade names such as Tinuvin P. In addition, this ultraviolet absorber is a radical scavenger Hifdartamine type, such as manufactured by Ciba Geigy, trade name Sanol L8.
It is even more effective when used in combination with 770, and the phenolic antioxidant BIT (2,6-sotbutyl/P
-cresol), Irganonx 1010°1076, and phosphorus compounds are also effective.

The amount of the ultraviolet absorber additive 71D is 0.1 to 6.0% by weight, preferably 006 to 1.5% by weight. Attachment 7+of is 0
．． If it is less than 11 it%, the ultraviolet absorbing ability will be insufficient and the notebook will turn yellow, and if it exceeds 6.0 weight and 11%, the transparency and physical properties will decrease, which is undesirable due to high cost. Further, the radical scavenger is sufficiently effective in the same amount as the ultraviolet absorber.

The multilayer sheet of the present invention is one in which a styrene-butadiene-methyl methacrylate copolymer note layer is integrated with a methyl methacrylate-containing monolithic note layer on at least one side of the styrene-butadiene-methyl methacrylate copolymer note layer. The wall thickness is Ll, 0311 or more, preferably 0.03 to 0.3
0 mm%, more preferably 0.05 to 0.20 m, and more preferably 20% or less on one side with respect to the thickness of the styrene/butatsuene-methyl methacrylate copolymer note layer. If the wall thickness is less than 0.05 part, the UV lfM absorption capacity is insufficient and the weather resistance deterioration of the styrene-butadiene/-methyl methacrylate copolymer sheet layer cannot be protected, and the blade base has no weather resistance effect. It is not economical due to the high cost.

Next, methods for producing the multilayer 7-sheet of the present invention include a coextrusion molding method and an extrusion lamination method.The coextrusion molding method uses a plurality of extrusion molding machines to bond resin in a molten state to form a multilayer sheet. There are two methods for kneading: a multi-manifold die, in which multiple resin layers are sorted and then bonded together, and a feed block die, in which multiple resins are bonded and then spread out in a sorted manner. .

The extrusion lamination method is a method in which one layer to be bonded is extruded into a notebook shape, while the other layer is bonded by heat or pressure after applying an adhesive.

(Example) Example 1 Styrene-butadiene copolymer (styrene/g Jl.

25%, 7.5 parts of butadiene weight [75%] to 74% of styrene.
25 parts of styrene to 70 parts of a graft copolymer (abbreviated as MBS-■) obtained by two-stage bulk polymerization method by dissolving it in a monomer mixture consisting of 2.5 parts of methyl methacrylate and 5765 parts of methyl methacrylate. , emulsion polymerization of 75 parts of butadiene K
A composition obtained by emulsifying 100 parts (solid content) of the thus obtained styrene-butadiene copolymer latex with a particle size of 100111 μm with a monomer mixture consisting of 40 parts of styrene, 10 parts of acrylonitrile, and 55 parts of methyl methacrylate. A styrene-butadiene-methyl methacrylate copolymer (hereinafter referred to as MBS-■) prepared by blending 60 parts of
Styrene/-methyl methacrylate copolymer (abbreviated as BS-〇), obtained by suspension polymerization of 45 parts of styrene and 55 parts of methyl methacrylate, and adding the radical scavenger and ultraviolet absorber shown in Table 1. (hereinafter abbreviated as MS) and 65 each
Coextrusion molding was carried out using a feed block type die combined with m/Ifl and 30 m/m extruders to obtain multilayer notebooks having the thickness configuration shown in Table 1.

Table 1 shows the results of measuring the physical properties of this sort.

Example 2 The fcMBS-■ obtained in Example 1 and a composition prepared by adding a radical scavenger and an ultraviolet absorber to commercially available polymethyl methacrylate (trade name Acrivera MD: manufactured by Mitsubishi Rayon Co., Ltd.) were each mixed at 65 m/m. Coextrusion molding was carried out using a multi-manifold Daizo die combined with a 30 ml extruder. Table 1 shows the thickness structure of the multilayer sheet and its physical properties.

Example 6 A radical scavenger and an ultraviolet absorber were added to MBS-■ obtained in Example 1 and a commercially available acrylic thread rubber reinforced methyl methacrylate resin ()-Ipet HBE (manufactured by Mitsubishi Shiion Co., Ltd.).
A preformed film having a thickness K of 0.0 and 0.05111 was extrusion laminated at a roll temperature of 80°C. The physical properties of the sheet are shown in Table 1.

Comparative example 1 MBS-〇 single notebook'& 65 m/m extruder-T
-Made with die equipment. Its physical properties are shown in Table 1.

Comparative Example 2 MBS-■ obtained in Example 1 and commercially available polymethyl methacrylate (Acryvet Mb° manufactured by Mitsubishi Shiyon Co., Ltd.) were fed using a combination of Sonezawa 65111/m and RoQ m/m extruders. Coextrusion molding was performed using a block type die. Table 1 shows the thickness structure of the multilayer notebook and its sheet properties.

Comparative Example 6 MBS-■ obtained in Example 1 and styrene- obtained in Example 1
Methyl methacrylate copolymer usi'cJ
Coextrusion molding was performed using a multi-manifold type die combined with a 30m1II extruder. Table 1 shows the thickness structure of the multilayer 7-sheet and its sheet properties.

Comparative Example 4 MBS-■ obtained in Example 1 and Styrene/- obtained in Example 1
Methyl methacrylate copolymer MSK% Extrusion lamination was carried out at a roll temperature of 80° C. by adding an external ray absorber and forming a film in advance to a thickness of 0.02 mm, which is less than the specified thickness. The physical properties of the notebook are shown in Table 1.

Comparative Example 5 The physical properties of commercially available methacrylic resin plates (trade name: Sumipex E: Sumitomo Chemical Co., Ltd. Jkl) having the same thickness (3.0 m) were measured. The results are shown in Table 1.

Comparative Example 6 Commercially available reinforced acrylic 4II fat plate with the same thickness (6.0 layers) (
The physical properties of Acrylite R (manufactured by Mitsubishi Rayon Co., Ltd.) were measured. The results are shown in Table 1.

Example 4 Styrene-butadiene copolymer (styrene weight 25%,
A graft copolymer (hereinafter referred to as MBS-■), 45 parts of styrene, and 55 parts of methyl methacrylate were suspended to form a radical scavenger shown in Table 2, Ultraviolet 118! Styrene-methyl methacrylate copolymer composition obtained by adding an absorbent (MS
(abbreviated as ) and f165 m, mu, and 3 CI In, respectively.
Co-extrusion molding was carried out using a Feed Pronk Tyzo die combined with a /m extruder to obtain Poly 1@7-1 having a Kishi-shaped structure. Table WJ2 shows the results of measuring the physical properties of this notebook.

Example 5 fcMBS-■ obtained in Example 4 and a commercially available polymethyl methacrylate (trade name: Acrivet MD, manufactured by Mitsubishi Rayon Co., Ltd.) K radical scavenger and ultraviolet absorber were added to it. Co-extrusion molding was carried out using a multi-manifold type die combining seven extruders, each having a length of 65 m and 30 m. Table 2 shows the thickness structure of the polyester M7-) and the physical properties of the sheet.

Example 6 fcMBB-■ obtained in Example 4 and commercially available acrylic rubber-reinforced methyl methacrylate resin (trade name Hypet, HBE
A radical scavenger and an ultraviolet absorber were added to Mitsubishi Rayon Co., Ltd. (711), and a film of 0.05 m++ thickness K was preformed by extrusion heat lamination at a roll temperature of 80°C. Its physical properties are shown in Table 2.

Comparative Example 7 A single notebook of MBS-■ was prepared using a 651n/m extruder-T-die equipment. The notebook physical properties are shown in Table 2.

Comparative Example 8 fCMBS-■ obtained in Example 4 and commercially available polymethyl methacrylate (trade name Acrypent MD = Mitsubishi Rayon (a)
Co., Ltd.) were co-extruded using a feed block type die combined with a 65 m/m% 30 m/m extruder. Table 2 shows the thickness structure and physical properties of the polyester.

Comparative Example 9 The fcMBS-■ obtained in Example 4 and the composition to which the styrene-methyl methacrylate copolymer MSK ultraviolet absorber obtained in Example 4 was added in a specified amount or less were mixed at 65 m/m, respectively.
Coextrusion molding was performed using a multi-manifold type die combined with a 30 ml extruder. Multilayer notebook thickness 11#
: and its sheet properties are shown in Table 2.

Comparative Example 10 MBS-■ obtained in Example 4 and Styrene- obtained in Example 4
An ultraviolet m absorber was added to the methyl methacrylate copolymer MS, and a preformed film having a thickness of 0.02 inches, which is below the specified thickness, was extrusion laminated at a roll temperature of 80°C. The physical properties of the sheet are shown in Table 2.

Comparative Example 11 The physical properties of commercially available methacrylic resin plates (trade name SUMIPEX E, manufactured by Sumitomo Chemical Co., Ltd.) with the same thickness (10ii+) were measured.The results are shown in Table 2.

Comparative Example 12 Commercially available reinforced acrylic resin plate with the same thickness (3,0111) (
The physical properties of Acrylite IR (trade name: manufactured by Mitsubishi Rayon Co., Ltd.) were measured. The results are shown in Table 2.

The distance measurement of physical properties between the example and the comparative example is as follows.

1. Total light transmittance: ASTM D-1003 compliant 2.
Falling Weight Strength = 11 Using a vapor chemical measurement method, a 5R steel ball tipped with a soo and p load, the height of the 70% retention rate of the sample was measured.

6. Izond impact strength 11: ASTM D-2564
Hardness: JISD-0202 5, Tensile strength: ASTM D-6386 weather resistance
Gender: Sunshine Weather Meter JISA-14
15 Yellow Storm: JISK-7103 (Effects of the Invention) The present invention provides a polyethylene 17-) of a styrene/-butadiene/-methyl methacrylate copolymer and a methyl methacrylate-containing polymer containing an ultraviolet 11M absorber. When used, it has excellent impact resistance, scratch resistance, weather resistance, transparency, extrudability of multilayer sheets, and secondary sword resistance, so it can be used for indoor and outdoor displays, nameplates, signboards, architectural lighting, etc. It is useful for this purpose.

Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedural Amendment June 9, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1, Indication of Case 1986 Patent Application No. 86526 2, Title of Invention Multilayer sheet and method for manufacturing the same 6 Relationship with the case of the person making the amendment Patent applicant address: 44-44, 1-4, Yurakucho, Chiyoda-ku, Tokyo Column 5 of the detailed description of the invention in the specification subject to the amendment, Contents of the amendment 1) Page 1 of the specification In the bottom row, change “Contains ultraviolet rays” to “
Contains ultraviolet absorbers.''

``Ryl resin board'' is corrected to ``Reinforced 7-krylic resin board,'' ``Architectural lighting'' in line 16 is corrected to ``lighting, architecture,'' and ``obvious defect'' in line 19 is corrected to ``such defect.''

4) Change “Contains ultraviolet absorber” to “Ultraviolet absorber included” in the first line of page 4 of the specification.
Contains ultraviolet absorbers.''

5) Replace “radical scavenger” on page 6, line 16 of the specification with “
Radical scavenger”, corrected.

6) "Acribet Mb" in the second line of page 11 of the specification is corrected to "Acribet MDJ."

7) Table 1 on page 13 of the specification is corrected as shown in the attached sheet.

8) Table 2 on page 18 of the specification is corrected as shown in the attached sheet.

9) Change "rsoog load" on page 19, line 4 of the specification to "5.
0I load" and "by using a multilayer sheet" in the 6th to 4th lines from the bottom are corrected to "by using a multilayer sheet."

10) "Architectural lighting" in the first line of page 20 of the specification is corrected to "1 lighting, architecture."

Procedural amendment 1. Display of the case 1986 Patent Application No. 86526 2 Name of the invention Multilayer sheet and its manufacturing method 6 Person making the amendment Relationship to the case Patent applicant address 1-4-1 Yurakucho, Chiyoda-ku, Tokyo In the specification Detailed Description of the Invention Column 5, Contents of Amendment 1) Next to “Tomo on one side” on page 7, line 11 of the specification, “
Contains ultraviolet absorber.”

join.

3) Table 1 on page 16 of the specification is corrected as shown in the attached sheet.

4) Table 2 on page 18 of the specification is corrected as shown in the attached sheet.

Claims (1)

[Claims] (11 Styrene/-butadiene/-methacrylate) methyl copolymer notebook layer and methyl methacrylate-containing polymer sheet layer containing 0.1 to 3.0% by weight of ultraviolet absorber are integrally bonded. (2) At least a styrene-butadiene-methyl methacrylate copolymer sheet layer and a methyl methacrylate-containing polymer sheet m containing 0.1 to 3.0% by weight of an ultraviolet absorber. A method for producing a multilayer sheet, characterized in that one of the sheets is melt-extruded and bonded together.