JP2007331378A - Composite molded object and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite molded object which possesses good moldability and rigidity in combination without the generation of warpage and excellent adhesive properties between artificial marble and a norbornene-based resin molded object. <P>SOLUTION: This composite molded object is comprised of a norbornene-based resin molded object prepared by bulk-polymerizing a norbornene-based monomer in a mold, and an artificial marble. In addition, the norbornene-based resin molded object contains a fibrous filler with a 5 to 100 aspect ratio and a particulate filler with 1 to 2 aspect ratio. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composite molded body useful in the field of housing equipment materials such as a ceiling, a wall panel, a kitchen counter, a wash bowl, and a waterproof pan (washing pan).

  In the field of housing equipment materials such as ceilings, wall panels, kitchen counters, wash bowls, and waterproof pans (washing pans), composite molded articles having excellent design and rigidity are required. As such a composite molded body, a composite molded body made of a norbornene-based resin molded body and artificial marble is known.

  Conventionally, a composite molded body composed of a norbornene-based resin molded body and an artificial marble is formed by placing the artificial marble in a mold, and a reaction liquid containing a norbornene-based monomer and a metathesis catalyst in the mold by a reaction injection molding (RIM) method. It is manufactured by injection and bulk ring-opening polymerization.

  However, conventional norbornene-based resin molded bodies and composite molded bodies made of artificial marble are prone to warp, and there is a problem that the adhesion between artificial marble and norbornene-based resin molded bodies is poor.

  The present invention has been made in view of such problems, and provides a composite molded body having both design and rigidity, no warpage, and excellent adhesion between an artificial marble and a norbornene-based resin molded body. For the purpose.

  As a result of intensive studies to solve the above problems, the present inventors have used a norbornene-based resin molded body containing two or more kinds of fillers having a specific aspect ratio, and used the norbornene-based resin molded body. It has been found that by placing liquid artificial marble after placing in a mold, the above-mentioned composite molded body can be obtained, and the present invention has been completed.

That is, the present invention
(1) A norbornene-based resin molded body obtained by bulk polymerization of norbornene-based monomers in a mold and a composite molded body made of artificial marble, the norbornene-based resin molded body having an aspect ratio of 5 to 100 A composite molded article comprising a fibrous filler and a particulate filler having an aspect ratio of 1 to 2;
(2) In the above (1), the fibrous filler and the particulate filler are contained in a proportion of 5 to 80 parts by weight with respect to 100 parts by weight of the fibrous filler. The composite molded article, and
(3) The method for producing a composite molded body according to (1) or (2), wherein the norbornene-based resin molded body is disposed in a mold, and liquid artificial marble is injected into the mold. ,
Is to provide.

  The composite molded body of the present invention has both design and rigidity, has no warpage, and has excellent adhesion between artificial marble and norbornene resin molded body, so that it can be used for ceilings, wall panels, kitchen counters, wash bowls, waterproof It is useful in the field of housing equipment materials such as bread (washing bread).

  The composite molded body of the present invention is a norbornene-based resin molded body obtained by bulk polymerization of norbornene-based monomers in a mold, and a composite molded body made of artificial marble, the norbornene-based resin molded body having an aspect ratio of 5 It contains ˜100 fibrous filler and particulate filler having an aspect ratio of 1-2.

(Norbornene resin molding)
The norbornene-based resin molded product used in the present invention is obtained by bulk polymerization of a norbornene-based monomer in a mold.
The norbornene-based monomer is a compound having a norbornene ring structure, and any compound may be used as long as it is such a compound. Especially, since the molded object which is excellent in heat resistance is obtained, it is preferable to use the polycyclic norbornene-type monomer more than tricyclic.

  Specific examples of norbornene-based monomers include bicyclics such as norbornene and norbornadiene; tricyclics such as dicyclopentadiene (cyclopentadiene dimer) and dihydrodicyclopentadiene; tetracyclics such as tetracyclododecene; Pentacycles such as pentadiene trimer; heptacycles such as cyclopentadiene tetramer; and substituted products thereof.

  The bulk polymerization method is not particularly limited, and examples thereof include a method in which a reaction stock solution prepared by dividing a norbornene-based monomer, a metathesis catalyst, a filler and an optional component into two or more liquids is mixed in a mold.

  The reaction stock solution is not bulk polymerized with only one liquid, but when all the liquids are mixed, it becomes a reaction liquid containing each component at a predetermined ratio, and the bulk polymerization reaction of the norbornene monomer starts.

  The metathesis catalyst used for the bulk polymerization is not particularly limited as long as the norbornene monomer can be ring-opening polymerized by a reaction injection molding method (RIM method), and may be a known one. Examples thereof include halides, oxyhalides, oxides, organic ammonium salts, oxyacid salts, and heteropolyacid salts of Group 5 or Group 6 transition metals. As the compounds of Group 5 or Group 6 transition metals, halides, oxyhalides and organic ammonium salts are preferable, and organic ammonium salts are more preferable.

  Moreover, as said transition metal, molybdenum, tungsten, and tantalum are preferable, and molybdenum and tungsten are more preferable. Particularly preferred specific examples of metathesis catalysts include tridodecyl ammonium molybdate and tungstate, methyl tricapryl ammonium molybdate and tungstate, tri (tridecyl) ammonium molybdate and tungstate, and trioctyl ammonium. Examples thereof include molybdate and tungstate.

  An activator such as ethylaluminum dichloride and diethylaluminum chloride and an activity regulator such as alcohols, haloalcohols, esters, ethers and nitriles may be used in combination.

  Examples of the optional component include an activator, an activity regulator, an elastomer, and an antioxidant.

  The norbornene-based resin molded body used in the present invention contains a fibrous filler having an aspect ratio of 5 to 100 and a particulate filler having an aspect ratio of 1 to 2.

  The fibrous filler is a solid material insoluble in the norbornene-based monomer, and has an aspect ratio of 5 to 100, preferably 10 to 50, more preferably 15 to 35. If the aspect ratio is excessively small, the strength and dimensional stability of the molded product may be insufficient. If the aspect ratio is excessively large, the injection nozzle may be clogged when being injected into the mold.

  In the present invention, the aspect ratio of the filler is a ratio between the average major axis diameter of the filler and the 50% volume cumulative diameter. Here, the average major axis diameter is a number average major axis diameter calculated as an arithmetic average value obtained by measuring the major axis diameters of 100 fillers randomly selected from an optical micrograph. The 50% volume cumulative diameter is a value obtained by measuring the particle size distribution by the X-ray transmission method.

  The 50% volume cumulative diameter of the fibrous filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm. If the 50% volume cumulative diameter is excessively small, the strength and dimensional stability of the molded body are insufficient (the dimensional stability of the molded body is insufficient. If it is excessively large, it may settle in the tank or piping when the reaction solution is injected into the mold or the injection nozzle may be clogged.

  Specific examples of the fibrous filler include glass fiber, wollastonite, potassium titanate, zonolite, basic magnesium sulfate, aluminum borate, tetrapot type zinc oxide, gypsum fiber, phosphate fiber, alumina fiber, acicular carbonate Examples include calcium and acicular boehmite.

  The particulate filler is a solid material insoluble in the norbornene-based monomer, and has an aspect ratio of 1 to 2, preferably 1 to 1.5.

  Further, the 50% volume cumulative diameter of the particulate filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm. If the 50% volume cumulative diameter is excessively small, the strength and dimensional stability of the molded product may be insufficient. If it is excessively large, it may settle in the tank or piping when the reaction liquid is injected into the mold, The injection nozzle may become clogged.

  Specific examples of the particulate filler include calcium carbonate, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, barium titanate, silica, alumina, carbon black, graphite, antimony oxide, Examples include red phosphorus, various metal powders, clay, various ferrites, and hydrotalcite.

  It is preferable that the surface of the fibrous filler and the particulate filler is subjected to a hydrophobic treatment. By using the hydrophobized filler, the filler can be uniformly dispersed in the obtained molded body, and a molded body having uniform strength and dimensional stability and low anisotropy can be obtained.

  Examples of the treating agent used for the hydrophobizing treatment include silane coupling agents, titanate coupling agents, aluminum coupling agents, fatty acids, fats and oils, surfactants, waxes, and other polymers.

The content of the filler in the norbornene-based resin molded body is a total of the fibrous filler and the particulate filler, and is preferably 5 to 60% by weight, more preferably 10 to 50% by weight.
The particulate filler is usually 5 to 80 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the fibrous filler. Further, when the amount ratio of the fibrous filler to the particulate filler is within this range, the strength and dimensional stability of the obtained molded body are uniform and the anisotropy is small.

(Artificial marble)
The artificial marble used in the present invention exhibits a natural stone-like appearance by containing a filler in an acrylic resin.

  Acrylic resins include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and ethylene glycol dimethacrylate. Examples thereof include those obtained by radical polymerization using one kind or a mixture of two or more kinds of acrylates as a main component. Among these, those obtained from methyl methacrylate as the main component are preferred from the viewpoint of weather resistance, chemical resistance and transparency.

  As the filler, crushed stones such as olivine, nepheline, feldspar, wollastonite, apatite, calcite, rhodolite, barite, and the like; mica, glass, aluminum hydroxide, alumina, kaolin, etc. are preferable. Is particularly preferred.

  Specific examples of the artificial marble include DuPont Corian (manufactured by Mitsubishi Rayon Co., Ltd.), Grass Pure (manufactured by Dainippon Ink Co., Ltd.), Neopol (manufactured by Nippon Yupica Co., Ltd.), and the like.

(Production method of composite molded body)
The method for producing a composite molded body of the present invention is characterized in that a norbornene-based resin molded body is placed in a mold, and liquid artificial marble is injected into the mold.

  In the method for producing a composite molded body of the present invention, a mold having an inner surface shape is used in which a gap is formed between the surface and the inner surface of the norbornene resin molded body when the norbornene resin molded body is disposed. A composite molded body of the present invention can be obtained by placing a norbornene-based resin molded body in the mold and then injecting liquid artificial marble syrup into the gap.

The mold temperature at the time of pouring is usually 30 to 100 ° C. The injection pressure is usually 0.05 to 0.5 MPa in absolute pressure.
Moreover, as for the temperature of artificial marble syrup, 10-30 degreeC is preferable.

  According to the manufacturing method of the present invention, compared with the case where the norbornene resin molded body is formed by reaction injection molding (RIM) after placing the artificial marble in the mold, the artificial marble and the norbornene resin molded body A composite molded body having improved adhesiveness can be obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples. In addition, the part and% in an Example and a comparative example are a basis of weight unless there is particular notice. Moreover, each characteristic was measured by the method shown below.

(1) 50% volume cumulative diameter of the filler The 50% volume cumulative diameter of the filler is obtained by measuring the particle size distribution with an X-ray transmission method using a particle size distribution measuring device (Cedigraph, manufactured by Micromeritics). It was.
(2) Aspect ratio of filler The aspect ratio of filler is the number average major axis diameter calculated as the arithmetic average value of the major axis diameter of 100 fillers randomly selected from optical micrographs. And the above-mentioned 50% volume cumulative diameter.
(3) Linear expansion coefficient The linear expansion coefficient of the norbornene-based resin molded product was measured according to JIS K7197. However, a test piece having a length of 10 mm, a width of 5 mm, and a thickness of 4 mm was used.
(4) Adhesiveness The interface between the acrylic artificial marble and the norbornene-based resin molded body was pry open with a flat-blade screwdriver.

Example 1
In a mixed monomer composed of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene, 3 parts of a styrene-isoprene-styrene block copolymer (Quintac 3421, manufactured by Nippon Zeon Co., Ltd.) was dissolved. Next, after adding diethylaluminum chloride as an activator and 1,3-dichloro-2-propanol as an activity regulator to a concentration of 100 mmol / kg, 0.1 part of silicon tetrachloride was further added. The mixture was uniformly mixed and dispersed to obtain a reaction stock solution (solution A). The specific gravity of A liquid was 0.98.

  Separately, 3 parts of a styrene-isoprene-styrene block copolymer (Quintac 3421, manufactured by Nippon Zeon Co., Ltd.) was dissolved in a mixed monomer composed of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene. Next, 2 parts of a phenolic antioxidant (Irganox 1010, manufactured by Ciba Specialty Chemicals) and tri (tridecyl) ammonium molybdate as a polymerization catalyst were added to a concentration of 25 mmol / kg, and mixed and dispersed uniformly. As a result, a reaction stock solution (solution B) was obtained.

  Further, separately from the above, a mixed monomer composed of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene is used as a fibrous filler, and wollastonite (50% volume cumulative diameter is 20 μm, aspect ratio is 18, SH-400: 135 parts manufactured by Kinsei Matec Co., Ltd., surface treated with vinyl silane), heavy calcium carbonate as particulate filler (50% volume cumulative diameter is 1.4 μm, aspect ratio is 1, SCP-E # 2300, Sankyosei) 45 parts by a powder company, surface-treated with stearic acid) and 1.8 parts of an aluminate-based dispersant (Plenact KR TTS, Ajinomoto Fine-Techno Co., Ltd.) are added and mixed with stirring to obtain a reaction stock solution (C Liquid). The specific gravity of C liquid was 1.6.

  One of the reaction injection molds having a space (cavity) of 500 mm length × 500 mm width × 4 mm thickness inside was heated to 90 ° C. and the other was heated to 60 ° C. Liquid A 26.8 parts, liquid B 26.8 parts, and liquid C 46.4 parts are fed into the mixing head, and then injected into the reaction injection mold at an injection pressure of 5 MPa or less to perform bulk polymerization. The reaction was carried out for 3 minutes after the start. The mixing ratio of liquid A, liquid B, and liquid C at this time is 1: 1: 1 by volume, the amount of fibrous filler injected is 22.5 parts, and the amount of particulate filler is 7 .5 parts. Thereafter, the molded body was taken out of the mold, and an A4 size (length 347 mm, width 210 mm) plate was cut out from the molded body.

  340 g of methyl methacrylate monomer and 30 g of styrene-isoprene-styrene block copolymer (Quintac 3421: manufactured by Nippon Zeon Co., Ltd.) were placed in a 2 liter separable flask and mixed and dissolved at 60 ° C. Thereto, 27 g of polymethyl methacrylate (average molecular weight: 500,000) and 3 g of trimethylolpropane trimethacrylate were added and mixed and dissolved, and then allowed to stand overnight at room temperature to obtain acrylic syrup.

  Next, 50 g of silane coupling agent-treated mica (manufactured by Toshin Kasei Co., Ltd.) and 550 g of silane coupling agent-treated aluminum hydroxide (made by Nippon Light Metal Co., Ltd.) are uniformly added to and mixed with the acrylic syrup. Acrylic syrup was prepared. Next, 3 g of stearic acid and 6 g of bis (4-t-butylcyclohexyl) peroxydicarbonate (Perkadox 16, manufactured by Kayaku Akzo) as a radical polymerization initiator were added and the whole volume was stirred and mixed for about 30 minutes. The desired acrylic artificial marble syrup was obtained by degassing under reduced pressure.

  Between the two stainless steel plates of 300 mm × 210 mm × thickness 3 mm, the above-described norbornene-based resin molded body and the soft rubber gasket are interposed to create a space (cavity) of 260 mm long × 160 mm wide × 5 mm thick. Acrylic artificial marble syrup was poured into it and cured in warm water at 50 ° C. for 40 minutes and then in warm water at 90 ° C. for 1 hour to obtain a composite molded body 1 comprising a norbornene-based resin molded body and acrylic artificial marble. . The obtained composite molded body 1 was evaluated for warpage.

(Comparative Example 1)
A composite molded body 2 comprising a norbornene-based resin molded body and an acrylic artificial marble was obtained in the same manner as in Example 1 except that the fibrous filler and the particulate filler were not added. The obtained composite molded body 2 was evaluated for warpage.

  Aspect ratio and amount of fibrous filler and particulate filler used in Example 1 in the molded body, linear expansion coefficient of norbornene-based resin molded body used in Example 1 and Comparative Example 1, and Examples Table 1 summarizes the results of evaluation of the presence or absence of warpage and adhesiveness of the composite molded bodies obtained in 1 and Comparative Example 1.

  From Table 1, a composite molded body 1 of Example 1 using a norbornene-based resin molded body containing a fibrous filler having an aspect ratio of 5 to 100 and a particulate filler having an aspect ratio of 1 to 2. No warpage occurred, and the adhesion between the norbornene-based resin molding and the acrylic artificial marble was good. On the other hand, warpage was observed in the composite molded body 2 of Comparative Example 1 using a norbornene-based resin molded body containing no filler.

Claims (3)

  A norbornene-based resin molded body obtained by bulk polymerization of norbornene-based monomers in a mold, and a composite molded body made of artificial marble, wherein the norbornene-based resin molded body has a fibrous filling with an aspect ratio of 5 to 100 A composite molded body comprising a material and a particulate filler having an aspect ratio of 1 to 2.   2. The composite according to claim 1, wherein the fibrous filler and the particulate filler are contained in a proportion of 5 to 80 parts by weight of the particulate filler with respect to 100 parts by weight of the fibrous filler. Molded body.   The method for producing a composite molded body according to claim 1 or 2, wherein the norbornene-based resin molded body is placed in a mold, and liquid artificial marble is injected into the mold.