JP5013727B2 - Multi-layer reinforced sheet - Google Patents

Description

  The present invention relates to a multilayer reinforcing sheet having a styrenic resin layer reinforced with a filler.

FRP sheets are widely known as glass fiber reinforced sheets (see, for example, Patent Document 1). However, since a large amount of unreacted styrene monomer remains in the thermosetting type sheet, there is a problem that the concentration of volatile organic compounds (VOC) in the air, particularly the styrene monomer, increases when used in a sealed room or the like. there were.
Many types of glass fiber reinforced thermoplastic resins that can be substituted for the FRP are known, but those using crystalline resins such as nylon, PET, PP, etc. have low sheet formability, and secondary There were problems such as difficulty in adhesion during processing. In addition, glass fiber reinforced AS, which is well-known among amorphous resins, has a rough surface when it is made into a sheet, or glass fibers are lost when it is rubbed. There was a problem of doing. That is, there has not been a reinforced sheet having a smooth surface, low VOC, easy secondary processing, and little difference in physical properties in length and width.
Japanese Patent No. 3098308

  Conventional glass fiber reinforced styrenic resin is not used for appearance parts because glass fiber roughens the surface and its directionality can be confirmed even if the mold temperature is increased. It was. In the present invention, a reinforced styrene resin containing a filler having a specific shape in the main layer, and a multilayer sheet made of a styrene resin or an acrylic resin in the skin layer, a smooth surface, low VOC and secondary The present invention relates to providing a reinforced sheet that can be easily processed.

  The inventors of the present invention have repeatedly studied to solve the above problems and have arrived at the present invention.

That is, this invention is a multilayer reinforcement sheet | seat of following [1]-[ 4 ].
[1] A multilayer reinforced sheet of two or more layers including at least a surface layer and a main layer, wherein the surface layer is made of a styrene resin or an acrylic resin, and the main layer is made of glass fiber and flaky powder as a filler. And a total content of all fillers of 40 to 70% by weight, and has a linear expansion coefficient of 5 or less and a linear expansion coefficient ratio of 2 or less. Multi-layer reinforced sheet.
[ 2 ] The multilayer reinforcing sheet according to [1] , wherein 0.5 parts or more of a white pigment is added to the resin constituting the surface layer and the main layer.
[ 3 ] The multilayer reinforcing sheet according to [1] or [2] , wherein the styrene resin constituting the main layer is a copolymer of an unsaturated nitrile monomer and a styrene monomer.
[ 4 ] The multilayer reinforcing sheet according to any one of [1] to [ 3 ], wherein the surface layer is made of ABS resin having a thickness of 0.05 mm to 0.5 mm.

  The multi-layer reinforced sheet of the present invention has a smooth surface, low VOC, easy secondary processing, and excellent properties such as little vertical and horizontal physical property difference.

  As the styrene resin (A) used for the main layer and the surface layer of the present invention, (a1) a rubbery polymer is graft-polymerized with a monomer mixture containing an aromatic vinyl monomer and an unsaturated nitrile monomer. Graft polymer obtained, (a2) a polymer obtained by copolymerizing a monomer mixture containing an aromatic vinyl monomer and an unsaturated nitrile monomer, (a3) an aromatic vinyl monomer A graft polymer obtained by graft polymerization of a monomer mixture containing a monomer, a (meth) acrylic acid ester monomer and an unsaturated nitrile monomer, (a4) an aromatic vinyl monomer, (meth) acrylic Examples thereof include a graft polymer obtained by copolymerizing a monomer mixture containing an acid ester monomer and an unsaturated nitrile monomer, or a mixture thereof.

Here, as the rubbery polymer, specifically, polybutadiene (BR), diene rubber such as styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), polybutyl acrylate, etc. Acrylic rubber (AR), polyisoprene (IR), polychloroprene (CR), ethylene-propylene rubber (EPM), ethylene-propylene-diene terpolymer rubber (EPDM), styrene-butadiene block copolymer rubber, styrene -Block copolymers such as isoprene block copolymer rubber, hydrogenated products thereof and the like can be used.
Among these polymers, BR, SBR, NBR, AR and the like are preferable.

Examples of the unsaturated nitrile monomer include acrylonitrile and methacrylonitrile. Acrylonitrile is preferred.
Examples of the (meth) acrylic acid ester monomer include methyl methacrylate, methyl acrylate, butyl acrylate, and ethyl acrylate.
Examples of the styrene resin (A) include acrylonitrile-styrene-butadiene copolymer (ABS), acrylonitrile-styrene copolymer (AS), (meth) acrylic acid methyl acrylonitrile-styrene-butadiene copolymer (MABS), Acrylonitrile-styrene-acrylic rubber copolymer (ASA), acrylonitrile-styrene-EPDM copolymer (AES) and the like are preferable.
The unsaturated nitrile monomer unit contained in the styrene resin (A) is preferably 2 to 40% by weight.

  Among these resins, ABS containing 10 to 40% by weight of acrylonitrile and 10 to 50% by weight of butadiene rubber, AS containing 20 to 40% by weight of acrylonitrile, 2 to 10% by weight of acrylonitrile and butadiene MABS containing 10 to 50% by weight of rubber is more preferable.

The method for producing the styrene resin (A) is not particularly limited, and emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, a combination of these polymerization methods, and the like can be used.
The molecular weight of the styrenic thermoplastic resin may be any, but it is preferably 1 to 30 g / 10 min, more preferably 2 to 20 g / 10 min in terms of MFR (ISO 1133: 220 ° C. 98 N). When the MFR is less than 1 g / 10 minutes, the extrudability of the styrene resin composition decreases, and when it exceeds 30 g / 10 minutes, it is difficult to make the thickness of the surface layer uniform during extrusion of the styrene resin composition.

Examples of the acrylic resin (B) in the present invention include methyl methacrylate polymer (PMMA), rubber-reinforced PMMA, methyl methacrylate-styrene copolymer (MS), and reinforced MS.
Preference is given to methyl methacrylate homopolymers, methyl methacrylate copolymers containing up to 15% by weight of methyl acrylate units or ethyl acrylate units, acrylic rubber reinforced PMMA, MS, butadiene rubber reinforced MS (MBS). In addition, acrylic acid ester, methacrylic acid ester, maleic anhydride, acrylic acid, methacrylic acid, styrene, p-methylstyrene, pt-butylstyrene, butyl acrylate, acrylonitrile, methacrylic acid are used within the range not impairing the effects of the present invention. It is also possible to use a copolymerizable vinyl monomer such as nitrile and N-phenylmaleimide.
Specific examples of acrylic esters and methacrylic esters include propyl acrylate, butyl acrylate, stearyl acrylate, glycidyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, glycidyl methacrylate Etc. The method for producing the acrylic resin (B) is not particularly limited, and emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, a combination of these polymerization methods, and the like can be used.

The “main layer” in the present specification means the thickest layer excluding the surface layer among a plurality of layers constituting the multilayer reinforcing sheet. In the present invention, the thickness of the main layer is preferably 50% or more of the total thickness, particularly preferably 70 to 90%.
Fillers mainly used for the main layer are metal oxides, metal hydroxides, metal carbonates, metal sulfates, metal silicates, carbon, ketjen black, carbon fibers, organic substances mainly composed of cellulose, metals Selected from fiber.

Examples of the metal oxide include silica, alumina, titanium oxide, calcium oxide, magnesium oxide, zinc oxide, iron oxide, antimony oxide, tin oxide, and diatomaceous earth. Examples of the hydroxide include calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.
Examples of the metal carbonate include calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, hydrotalcite and the like.
Examples of the metal sulfate include calcium sulfate and barium sulfate.

Metal silicates include calcium silicate (wollastonite, zonotlite), talc, mica, mica, clay, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, glass balloon, silica balun, Examples include glass flakes.
Examples of carbon include carbon black, graphite, carbon fiber, carbon balun, and charcoal powder.
Examples of organic substances mainly composed of cellulose include wood powder, pulp, rice bran powder, walnut powder, and paper sludge.

  As the glass fiber used in the present invention, the shape can be any shape such as roving, surfing mat, chopped strand mat, satin weave, lattice weave, plain weave, plain weave, twill weave, net, etc. Any type such as C-GF (alkali-containing glass fiber), alumina borosilicate glass (E glass) can be used. Moreover, a glass fiber with a diameter of 5-50 micrometers can be used, and a glass fiber of 5-20 micrometers is especially preferable. Moreover, in order to improve adhesiveness with a styrene-type thermoplastic resin, it is preferable to treat the glass fiber surface with commonly used surface treatment agents such as vinyl silane, aminosilane, and chromium compounds.

The main layer in the present invention comprises a styrenic resin (A) containing 25% or more of flaky powder filler and a total content of all fillers of 40 to 70% by weight. Flakes are flakes such as scales.
The filler of the flaky powder preferably has an average particle size of 0.5 μm to 1 mm, more preferably 1 μm to 500 μm. Further, the specific gravity of the bulk (JIS-K5101) is preferably 0.1 g / ml to 1 g / ml, more preferably 0.2 g / ml to 0.6 g / ml.
The use of such a flake-like filler having a small and low specific gravity lowers the difference in longitudinal and lateral physical properties of the sheet, improves the sheet surface property, and increases the flexural modulus.
Examples of such flaky powder include talc, mica, mica, and glass flakes. More preferred is talc.

The content of all fillers in the main layer is 40 to 70% by weight, preferably 40 to 60% by weight. If it is less than 40% by weight, the flexural modulus decreases, and if it exceeds 70% by weight, the impact property of the sheet decreases.
The multi-layer reinforced sheet of the present invention is produced by blending a styrene resin (A) and a filler, which is a flaky powder, within a predetermined range so as to balance physical properties such as sheet formability, sheet appearance, and sheet strength. Is done.

  In order to impart moldability, a plasticizer and a softener may be added to the surface layer and the main layer. The type is not particularly limited as long as it reduces the hardness, but fatty acids and fatty acid metal salts, terpene resins, petroleum resins, PE and PP waxes, paraffinic oils, naphthenic oils and ester oils are recommended. Is done.

Examples of preferable combinations of styrene resins constituting the main layer of the present invention include styrene resins in which glass fibers and talc are added to ABS resins, and styrene resins in which glass fibers and glass flakes are added to ABS resins. It is done.
Moreover, as a preferable styrene resin used for the surface layer, an ABS resin and an ABS resin to which an inorganic filler is added can be given.

  There is no particular limitation on the method for melt-mixing the styrene resin (A) of the present invention and each component such as a filler, and it is generally known, such as a single screw extruder, a twin screw extruder, a Banbury mixer, a pressure kneader, a mixing roll, This method can be used.

  Styrenic resin and acrylic resin used for the surface layer and main layer of the present invention are an antioxidant, a weathering agent, a metal deactivator, an ultraviolet absorber, a light stabilizer, a bleed / bloom agent, if necessary. Sealability improver, crystal nucleating agent, flame retardant, crosslinking agent, co-crosslinking agent, vulcanizing agent, antibacterial, antifungal agent, dispersant, softener, plasticizer, clay modifier, anti-coloring agent, foaming Agents, foaming aids, colorants such as titanium oxide and carbon black, metal powders such as ferrite, or other rubbery polymers such as SBR, NBR, BR, NR, IR, AR, CR, IIR, and others If necessary, thermoplastic resins other than the above components, such as polycarbonate resins, polyacetal resins, polyamide resins, polyester resins, polyether resins, polysulfone, polyphenylene sulfide Such as polyacetal resin, it can be appropriately compounded.

If necessary, the multilayer reinforcing sheet of the present invention can be textured using a textured roll during sheet extrusion. Both sides may be textured. Particularly preferably, it is a sheet obtained by applying a texture on one side using a texture roll on one of the three rolls.
The wrinkle-patterned wrinkle pattern may be any pattern such as sand blast, pear texture, or leather wrinkle. is there.

  The multilayer reinforcing sheet of the present invention can be printed or painted on the surface, and can be bonded to other materials using an adhesive. The surface of the sheet can be painted, or various designs and designs can be printed on the surface by gravure printing or the like to improve the appearance. Moreover, the multilayer reinforcement sheet of this invention can be combined and used for a part of product by adhere | attaching using another raw material and an adhesive agent.

The multi-layer reinforced sheet of the present invention exhibits an appropriate swelling property with respect to a solvent, and can be in close contact with a paint, ink, or resin material by swelling with a solvent contained in the paint, printing ink, or adhesive. It becomes.
Here, examples of the solvent in which the multilayer reinforcing sheet of the present invention exhibits swelling include methyl ethyl ketone (MEK), acetone, toluene, cyclohexane, normal hexane, ethyl acetate, butyl acetate, isopropyl acetate, methylene chloride, or a mixture thereof. It is done.

By using such a solvent-containing paint, printing ink, or adhesive, the multilayer sheet of the present invention can be adhered to the paint, ink, or resin material. For example, in the gravure printing ink, the resin component is EVA, modified vinyl chloride or the like, the solvent is a mixture of MEK, toluene, cyclohexane, butyl acetate, and the like, and can be suitably used for printing the sheet of the present invention. .
Further, for example, as an adhesive, it can be satisfactorily bonded to other materials by a urethane adhesive or a synthetic rubber adhesive using a mixed solvent such as acetone, normal hexane, and butyl acetate.

Hereinafter, the present invention will be described in more detail with reference to examples. In the following examples, parts and percentages are by weight unless otherwise specified.
(1) Raw materials used in Examples and Comparative Examples <Styrenic resin>
AS30: Asahi Kasei Chemicals Corporation 70% styrene, 30% acrylonitrile
ABS: Stylac A4521 manufactured by Asahi Kasei Chemicals Corporation
(ABS grade for extrusion MFR 3.0 g / 10 min: ISO 1133)
<Acrylic resin>
・ PMMA: Asahi Kasei Chemicals Corporation Delpet 80N
<Filler>
GF1 (shape: fiber): Asahi Fiber Glass Co., Ltd. Glasslon CSA-17F05
Diameter 13μm, length 3mm ± 1.5
・ GF2 (shape: flake powder): Nippon Sheet Glass Co., Ltd. Micro glass flakes
REF-140 (particle size distribution: 70 μm to 300 μm is 80 wt% or more)
-Talc (shape: flake powder): Matsumura Sangyo Co., Ltd. Crown Talc PP
(Average particle size 6.0-10.0 μm, bulk density 0.28-0.36 g / ml)

(2) Production of Styrenic Resin Composition The raw materials were supplied to a melt kneader (Toshiba Machine TEM35B) (glass fibers were side fed) and melt kneaded to obtain a styrene resin composition, which was pelletized.
(3) Sheet preparation The styrenic resin containing the filler for the main layer obtained above was extruded at 190 ° C from Extruder X (Toshiba Machine single screw extruder 65 mm) into a sheet of 0.1 mm thickness, while extrusion From machine Y (Toshiba machine single screw extruder 40 mm), styrene resin or acrylic resin is extruded at 190 ° C. so as to be laminated on the surface layer and lower layer in a sheet shape of about 0.1 mm thickness, and multilayer reinforced sheet Z (see FIG. 1 (shown in a schematic diagram in FIG. 1)) (total thickness 0.9 to 1 mm).
Table 1 shows the configuration of the multilayer reinforcing sheet and the evaluation results thereof.

(4) Evaluation method (4-1) Sheet surface state It confirmed using visual observation and the touch.
◯: Sheet that is smooth and not rough to the touch Z: The surface is rough.
L: A line-shaped striped pattern is visible.

(4-2) Residual Styrene Monomer Concentration Since the styrene monomer concentration in the air is proportional to the styrene monomer concentration in the sheet, it was determined using the amount of residual styrene monomer in the sheet.
The residual styrene monomer was measured by dissolving 2 g of a sample in 20 ml of DMF (dimethylformamide) and using a Shimadzu GC-14A gas chromatography (INJ temperature 250 ° C./capillary column). Quantification was performed using a calibration curve prepared in advance.
When the residual styrene monomer concentration is 0.5% or more, the styrene monomer concentration in the air becomes high.

(4-3) Bending elastic modulus Using a sheet cut in the form of a strip of 80 mm × 10 mm (in a direction parallel to sheet extrusion) from the sheet produced as described above, the bending elastic modulus is measured using the test method of ISO178. did.
If the flexural modulus is 5000 MPa or more, it is considered acceptable.

(4-4) Linear Expansion Coefficient From the sheet produced as described above, the linear expansion coefficient was measured using two types of samples in the direction parallel to the sheet extrusion and in the vertical direction (ASTM D696).
A linear expansion coefficient of 5 or less is considered acceptable.
If the linear expansion coefficient exceeds 5, warpage or the like is generated due to expansion during heating, so that FRP or the like cannot be substituted. (Requires linear expansion coefficient equivalent to FRP)

(4-5) Linear expansion coefficient ratio The ratio of the linear expansion coefficients of the two types of samples in the direction parallel to the sheet extrusion and in the vertical direction was defined as the linear expansion coefficient ratio.
Linear expansion coefficient ratio = Vertical linear expansion coefficient / Parallel linear expansion coefficient A large ratio indicates that there is a difference in the thermal expansion between the vertical and horizontal directions of the sheet. FRP or the like cannot be substituted because warpage or the like occurs due to the expansion of.

(4-6) Secondary workability (punchability)
A punching blade with which a square of 10 cm square was punched out was produced, and the punchability when the sheet was punched out was confirmed. ○ Passed above.
◎: 1 out of 10 shots did not crack.
○: 1 to 2 pieces out of 10 pieces were broken.
X: 3 or more pieces out of 10 pieces were cracked.

[Examples 1 to 3, Reference Example 1, and Comparative Examples 1 to 4]
The raw materials were used at the blending ratios shown in Table 1 and melt kneaded (glass fiber side feed) using Toshiba Machine TEM35B to produce pellets of a styrene resin composition. The pellets were used for evaluation by the above evaluation method, and the evaluation results are shown in Table 1.

  The present invention is a glass fiber reinforced sheet having a smooth surface, low VOC, and easy secondary processing, and can be used instead of the current FRP sheet. For example, a bath lid, a bath apron, a bus counter, a wall, a partition, etc. are mentioned.

It is a figure which shows an example of the laminated constitution of the multilayer reinforcement sheet | seat of this invention.

Claims (4)

A multilayer reinforced sheet of two or more layers including at least a surface layer and a main layer, wherein the surface layer is made of a styrene resin or an acrylic resin, and the main layer has 25 weights of glass fiber and flaky powder as a filler. Comprising a styrene-based resin having a total content of 40% to 70% by weight.
A multilayer reinforcing sheet having a linear expansion coefficient of 5 or less and a linear expansion coefficient ratio of 2 or less. The multilayer reinforcing sheet according to claim 1 , wherein 0.5 parts or more of a white pigment is added to the resin constituting the surface layer and the main layer. The multilayer reinforced sheet according to claim 1 or 2 , wherein the styrene resin constituting the main layer is a copolymer of an unsaturated nitrile monomer and a styrene monomer. The multilayer reinforcing sheet according to any one of claims 1 to 3 , wherein the surface layer is made of ABS resin having a thickness of 0.05 mm to 0.5 mm.

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