JP2009263575A - Composite molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite molding excellent in impact resistance, weatherability and design properties. <P>SOLUTION: The composite molding includes a reaction-curable transparent resin layer having a specific haze value on at least a part of the surface of a norbornene resin molding obtained by bulk polymerization of a norbornene monomer in a die. The norbornene resin molding and the transparent resin layer are directly bonded to each other on the contact interface. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a composite molded body in which a reaction-curable transparent resin layer having a specific haze value is formed on at least a part of the surface of a norbornene-based resin molded body obtained by bulk polymerization of a norbornene-based monomer in a mold. About.

  Conventionally, it is practical to produce a resin molded body made of a norbornene resin by injecting a reaction liquid containing a norbornene monomer and a metathesis catalyst into a mold by a reaction injection molding (RIM) method and performing bulk ring-opening polymerization. It has become. The reaction liquid used in this reaction injection molding is usually obtained by instantaneously mixing two or more reaction stock solutions with a collision mixing device or the like. Such a reaction stock solution is not bulk polymerized by only one liquid, but when all the liquids are mixed, it becomes a reaction liquid containing each component at a predetermined ratio, and the norbornene monomer is bulk polymerized.

  The resin molded body obtained by such RIM method is used, for example, in the field of housing equipment materials such as ceilings, wall panels, kitchen counters, and wash bowls. When used in such applications, it has excellent rigidity. Is required. On the other hand, in order to make the resin molded body obtained by the RIM method highly rigid, a method of adding various fillers to the reaction liquid and molding is known. As a result, a highly rigid resin molded body is obtained using calcium carbonate.

  However, since the resin molded body described in Patent Document 1 is inferior in weather resistance, there is a problem that the color deteriorates with time. In particular, in the above-mentioned housing equipment material field, in addition to being excellent in rigidity, it is also required to have excellent design properties, so it is desired to prevent deterioration of color over time by improving weather resistance. Yes.

JP 2003-321597 A

  This invention is made | formed in view of such a real condition, and it aims at providing the composite molded object excellent in impact resistance, a weather resistance, and designability.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have found that at least a part of the surface of a norbornene-based resin molding obtained by bulk polymerization of a norbornene-based monomer in a mold has a reaction-curable type and a specific haze value. In the composite molded body having a transparent resin layer having the above, it has been found that the above object can be achieved by directly bonding the norbornene-based resin molded body and the transparent resin layer at the contact interface, and the present invention has been completed. It was.

  That is, according to the present invention, a composite having a reaction-curable transparent resin layer having a haze value of 80 or less on at least a part of the surface of a norbornene-based resin molding obtained by bulk polymerization of norbornene-based monomers in a mold. There is provided a composite molded body, wherein the norbornene-based resin molded body and the transparent resin layer are directly bonded at the contact interface.

In the composite molded article of the present invention, the transparent resin layer preferably has a thickness of 0.01 to 7 mm.
In the composite molded body of the present invention, the norbornene-based resin molded body is placed in a mold, and the transparent resin layer composition that will form the transparent resin layer is injected into the mold and injected. It is preferable that the transparent resin layer composition is produced by reaction curing.
In the composite molded article of the present invention, the transparent resin layer preferably contains an unsaturated polyester, a polymerizable compound, and an organic peroxide polymerization initiator.

  According to the composite molded body of the present invention, a transparent resin layer having a reaction curing type and a haze value of 80 or less is formed on at least a part of the surface of a norbornene resin molded body obtained by bulk polymerization of a norbornene monomer in a mold. Since it forms, the molded object which has the outstanding design property can be provided. Moreover, by directly bonding the norbornene-based resin molded body and the reaction-curing transparent resin layer at the contact interface, a composite molded body having excellent impact resistance and weather resistance in addition to design properties is provided. Can do. Such a composite molded article of the present invention can be suitably used for applications requiring particularly excellent design properties. In addition to this, since the composite molded article of the present invention is excellent in design and weather resistance, it is not necessary to perform coating and plating, and the coating process and the plating process can be omitted.

  The composite molded body of the present invention has a reaction-curable transparent resin layer having a haze value of 80 or less on at least a part of the surface of a norbornene-based resin molded body obtained by bulk polymerization of a norbornene monomer in a mold. The norbornene-based resin molded body and the transparent resin layer are directly joined at the contact interface.

Norbornene-based resin molded body First, the norbornene-based resin molded body of the present invention will be described. The norbornene-based resin molded product of the present invention is obtained by bulk polymerization of a norbornene-based monomer in a mold.

The norbornene-based monomer is not particularly limited as long as it is a compound having a norbornene ring structure; however, it is a bicyclic compound such as norbornene or norbornadiene; And the like. Tricyclics such as cyclopentadiene; tetracyclics such as tetracyclododecene; pentacyclics such as cyclopentadiene trimer; heptacyclics such as cyclopentadiene tetramer;
These norbornene monomers include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; alkenyl groups such as vinyl group; alkylidene groups such as ethylidene group; aryl such as phenyl group, tolyl group and naphthyl group; These norbornene monomers may have a polar group such as an ester group, an ether group, a cyano group, or a halogen atom.

Specific examples of such norbornene-based monomers include dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene codimer, 5-ethylidene norbornene, norbornene, norbornadiene, 5-cyclohexenyl norbornene, 1,4,4 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4-methano-1,4,4a, 5,6,7,8,8a-octahydro Naphthalene, 6-ethylidene-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4-methano-1,4 4a, 5,6,7,8,8a-octahydronaphthalene, 1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-hex Tetrahydronaphthalene, ethylenebis (5-norbornene), and the like.
Norbornene monomers may be used alone or in combination of two or more.

  Among the norbornene-based monomers, tricyclic, tetracyclic or pentacyclic norbornene is available because it is easily available, has excellent reactivity, and can provide a molded article having excellent heat resistance. System monomers are preferred.

  Further, the ring-opening polymer produced by bulk polymerization is preferably a thermosetting type. For this purpose, among the norbornene monomers, a reactive double bond such as a symmetric cyclopentadiene trimer is used. It is preferable to use one containing at least two crosslinkable monomers. The ratio of such a crosslinkable monomer is preferably 2 to 30% by weight in the total norbornene-based monomer.

  In addition, monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, and cyclododecene that can be ring-opening copolymerized with a norbornene-based monomer may be used as a comonomer within a range that does not impair the object of the present invention.

  When bulk polymerizing norbornene-based monomers in a mold, it is common to prepare a reaction liquid obtained by adding a polymerization catalyst to a norbornene-based monomer, and then injecting the reaction liquid into the mold and bulk-polymerizing it. .

The polymerization catalyst is not particularly limited as long as it is a catalyst capable of ring-opening polymerization of a norbornene-based monomer. In the present invention, a metathesis polymerization catalyst is preferable.
The metathesis polymerization catalyst is a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom. As transition metal atoms, atoms of Groups 5, 6 and 8 (long-period periodic table, the same applies hereinafter) are used. Although the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum, examples of the Group 6 atom include molybdenum and tungsten, and examples of the Group 8 atom include: Examples include ruthenium and osmium.

  Metathesis polymerization catalysts having group 6 tungsten or molybdenum as the central metal include metal halogen atoms such as tungsten hexachloride; metal oxyhalides such as tungsten chloroxide; metal oxides such as tungsten oxide; tridodecylammonium molybdate And organic metal acid ammonium salts such as tri (tridecyl) ammonium molybdate can be used. Of these, organic ammonium molybdate is preferred.

In the present invention, it is also preferable to use a metal carbene complex having a metal atom of Groups 5, 6 and 8 as a central metal as a metathesis polymerization catalyst. Of the metal carbene complexes, Group 8 ruthenium and osmium carbene complexes are preferred, and ruthenium carbene complexes are particularly preferred. Since ruthenium and osmium carbene complexes have excellent catalytic activity during bulk polymerization, the use of these as catalysts can improve the productivity of norbornene-based resin molded products, and the resulting norbornene-based complexes The odor derived from the unreacted norbornene-based monomer of the resin molding can be reduced.
Among the ruthenium carbene complexes, a ruthenium carbene complex in which at least two carbene carbons are bonded to a ruthenium metal atom and a group containing a hetero atom is bonded to at least one of the carbene carbons is particularly preferable.

  The usage-amount of a metathesis polymerization catalyst is 0.01 mmol or more normally with respect to 1 mol of monomers used for reaction, Preferably it is 0.1-50 mmol, More preferably, it is 0.1-20 mmol. If the amount of the metathesis polymerization catalyst used is too small, the polymerization activity is too low and the reaction takes a long time, resulting in poor production efficiency. On the other hand, if the amount used is too large, the reaction becomes so intense that it becomes easy to cure before it is sufficiently filled in the mold, and the catalyst is liable to precipitate, making it difficult to store homogeneously.

  When such a metathesis polymerization catalyst is used, it is preferable to use an organoaluminum compound, an organozinc compound, or an organotin compound as an activator (cocatalyst) for the purpose of controlling the polymerization activity.

Examples of such an activator include, but are not limited to, organometallic compounds of metals in Groups 11 to 14 of the periodic table.
Examples of organometallic compounds of metals of Groups 11 to 14 of the periodic table include organoaluminum compounds such as alkylaluminum halides and alkoxyalkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; organotin compounds such as tetrabutyltin; diethylzinc and the like Organic zinc compounds; and the like.

The amount of the activator used is not particularly limited, but is preferably 0.1 mol or more, more preferably 1 mol or more with respect to 1 mol of the metathesis polymerization catalyst used in the reaction, and the upper limit of the amount used is preferably 100 mol or less, more preferably 20 mol or less. If the amount of the activator used is too small, the polymerization activity becomes too low, and the time required for the reaction becomes long, so that the production efficiency deteriorates. On the other hand, if the amount used is too large, the reaction becomes so intense that it may harden before it is sufficiently filled in the mold. However, when a ruthenium carbene complex is used as a metathesis polymerization catalyst, such an activator may or may not be used.
The activator is preferably used after being dissolved in the monomer. However, the activator is suspended in a small amount of solvent as long as it does not substantially impair the properties of the molded article obtained by the reaction injection molding method. By mixing, precipitation may be made difficult or solubility may be increased.

  Moreover, it is preferable to add an activity regulator further to the reaction solution used in the present invention. As described later, the activity modifier is divided into two or more reaction stock solutions (for example, a monomer solution of a polymerization catalyst and a monomer solution of an activator), and these are mixed and injected into a mold for polymerization. This is to prevent the polymerization from starting during the injection.

Examples of such activity regulators include Lewis bases such as ethers, esters and nitriles, alcohols, acetylenes and α-olefins.
Specific examples of the Lewis base include butyl ether, ethyl benzoate, diglyme and the like. Specific examples of alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, t-butyl alcohol, 1,3-dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol is mentioned. Specific examples of acetylenes include phenylacetylene. Specific examples of α-olefins include vinyl norbornene.
On the other hand, when a polar group-containing monomer is used as a copolymerization monomer, the monomer itself may be a Lewis base, and in this case, it may also function as an activity regulator. The activity regulator is preferably added to a solution containing an activating component such as the above-described activator.

  Moreover, it is preferable to add a polymerization accelerator to the reaction solution used in the present invention in order to improve the polymerization conversion rate of the monomer. As the polymerization accelerator, a chlorine atom-containing compound is preferable, and among them, an organic chlorine compound and a chlorinated silicon compound are preferable. Examples of such compounds include 2,4-dichlorobenzotrichloride, hexachloro-p-xylene, 2,4-dichloro-trichlorotoluene, and silicon tetrachloride.

  Although the addition amount of the said activity regulator and a polymerization accelerator is not specifically limited, It is about 10 ppm-10% by weight ratio with respect to the whole reaction liquid used for this invention.

In the present invention, the norbornene resin molded product preferably contains a colorant. Examples of the colorant include organic pigments, inorganic pigments, dyes, and the like. As organic pigments, azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow, pyrazolone red, resol red, helio bordeaux, pigment scarlet, permanent red 2B; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; quinacridone red, Quinacridone pigments such as quinacridone magenta; perylene pigments such as perylene red, perylene scarlet and perylene black; isoindolinone pigments such as isoindolinone yellow and isoindolinone orange; pyranthrones such as pyranthrone red and pyranthrone orange Examples thereof include pigments. Examples of the inorganic pigment include Bengala, titanium yellow, titanium black, ketjen black, black iron oxide, graphite, carbon black, titanium oxide (white pigment), copper chromate, zinc sulfide, barium sulfate, and calcium carbonate. . Examples of the dye include anthraquinone and carbon black-containing black dyes.
As a compounding quantity of a coloring agent, it is 0.001-10 weight part with respect to 100 weight part of norbornene resin moldings, Preferably it is 0.01-5 weight part.

  You may mix | blend a filler as an arbitrary component with the reaction liquid used by this invention. Various fillers can be used as the filler, and although not particularly limited, an inorganic filler composed of a fibrous filler having an aspect ratio of 5 to 100 and a particulate filler having an aspect ratio of 1 to 2 is used. It is preferable. The aspect ratio of the filler refers to the 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 content weight ratio (fibrous filler / particulate filler) of the fibrous filler and the particulate filler is preferably 95/5 to 55/45, more preferably 80/20 to 60/40. is there. By setting these ratios within the above range, it becomes easier to obtain a molded article having excellent rigidity and dimensional stability.

  The fibrous filler preferably has an aspect ratio of 5 to 100, and more preferably has an aspect ratio of 10 to 50. 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 too small, the rigidity and dimensional stability of a molded product obtained using this may become insufficient. Conversely, if the 50% volume cumulative diameter is too large, the polymerization reaction solution may settle in the tank or piping or the injection nozzle may be clogged when the polymerization reaction solution is injected into the mold.

  Specific examples of such fibrous fillers include glass fiber, wollastonite, potassium titanate, zonolite, basic magnesium sulfate, aluminum borate, tetrapod-type zinc oxide, gypsum fiber, phosphate fiber, alumina fiber, Examples include whisker-like calcium carbonate and whisker-like boehmite. Among these, wollastonite and whisker-like calcium carbonate that can increase the rigidity of the resulting molded body with a small amount of use without inhibiting bulk polymerization are preferable.

  Further, the particulate filler preferably has an aspect ratio of 1 to 2, and more preferably has an aspect ratio of 1 to 1.5. The 50% volume cumulative diameter of the particulate filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm, and particularly preferably 1 to 10 μm. If the 50% volume cumulative diameter is too small, the rigidity and dimensional stability of a molded product obtained using this may become insufficient. Conversely, if the 50% volume cumulative diameter is too large, the polymerization reaction solution may settle in the tank or piping or the injection nozzle may be clogged when the polymerization reaction solution is injected into the mold.

  Specific examples of such particulate fillers include calcium hydroxide, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, red phosphorus, various metal powders, clay, various ferrites, hydrotalcite, and the like. be able to.

  It is preferable that the surface of the filler is hydrophobized. By using the hydrophobized filler, the filler can be prevented from aggregating and settling in the reaction solution, and the filler can be uniformly dispersed in the resulting molded article. As a result, the rigidity and dimensional stability of the obtained molded body can be made uniform, and furthermore, the anisotropy can be reduced. Examples of the treating agent used for the hydrophobizing treatment include silane coupling agents such as vinyl silane, titanate coupling agents, aluminum coupling agents, fatty acids such as stearic acid, fats and oils, surfactants, and waxes. Hydrophobic treatment of the filler can be performed by mixing the hydrophobizing agent at the same time when preparing the reaction stock solution containing the norbornene monomer, the polymerization catalyst and the filler. It is preferable to prepare the reaction stock solution using the filler subjected to the above.

  The amount of the filler is preferably 5 to 55 parts by weight, more preferably 10 to 45 parts by weight with respect to 100 parts by weight of the total amount of the norbornene monomer and the polymerization catalyst. If the amount of the filler is too 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. Conversely, if the amount is too small, it is difficult to obtain the effect of adding the filler.

  Moreover, you may mix | blend various additives other than the above with the reaction liquid used by this invention in order to improve or maintain the characteristic at the time of setting it as a composite molded object. Such additives include reinforcing materials, antioxidants, heat stabilizers, light stabilizers, UV absorbers, foaming agents, antistatic agents, flame retardants, lubricants, softeners, tackifiers, plasticizers, release agents. Examples include molds, deodorants, fragrances, elastomers, dicyclopentadiene-based thermal polymerization resins and hydrogenated products thereof.

In particular, by adding an elastomer as an additive, the viscosity of the reaction stock solution is adjusted when the reaction solution is divided into two or more reaction stock solutions as described later, and the impact resistance of the resulting molded article is improved. Can do. Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), Mention may be made of ethylene-propylene-diene terpolymers, ethylene-vinyl acetate copolymers (EVA) and their hydrides.
The usage-amount of an elastomer is 0.5-20 weight part normally with respect to 100 weight part of norbornene-type monomers, Preferably it is 2-10 weight part.

  Various additives are added to the catalyst or activator monomer solution; used as a separate monomer solution and mixed with the catalyst or activator monomer solution during reaction injection molding; It is added by the method; What is necessary is just to select suitably the addition method with the kind of additive to be used.

  A method for preparing a reaction liquid comprising a norbornene-based monomer, a polymerization catalyst, and other components added as necessary is not particularly limited, and these components may be mixed by any method. Depending on whether the polymerization catalyst used requires an activator (cocatalyst), for example, the following two methods can be mentioned.

  That is, when the polymerization catalyst used does not require an activator, a reaction stock solution (i) containing a norbornene-based monomer and a reaction stock solution (ii) containing a polymerization catalyst are prepared and mixed. do it. Here, the reaction stock solution (ii) containing the polymerization catalyst can be prepared by dissolving or dispersing the polymerization catalyst in a small amount of an inert solvent.

  On the other hand, when the polymerization catalyst used requires an activator, a reaction stock solution containing a norbornene monomer and a polymerization catalyst (hereinafter sometimes referred to as “A solution”), a norbornene monomer, A reaction stock solution containing the activator (hereinafter sometimes referred to as “B solution”) may be prepared and mixed. At this time, a reaction stock solution consisting of only a norbornene-based monomer (hereinafter sometimes referred to as “C solution”) may be used in combination.

  When a filler is used, it may be blended in any of the above reaction stock solutions (“A solution”, “B solution” or “C solution”, or reaction stock solution (i) or reaction stock solution (ii)). However, it is preferable to mix | blend with the reaction stock solution containing a norbornene-type monomer. When using a fibrous filler and a particulate filler, these may be blended in separate reaction stock solutions or both may be blended in the same reaction stock solution. The method of blending in is preferable, whereby the sedimentation of the filler is suppressed and the storage stability of the reaction solution is improved.

Subsequently, the manufacturing method of the norbornene-type resin molding used by this invention is demonstrated. The norbornene-based resin molded product used in the present invention can be obtained by injecting the reaction solution described above into a mold and performing bulk polymerization in the mold.
In order to bulk-polymerize the reaction liquid described above in a mold, for example, a known collision mixing apparatus can be used as a reaction injection molding (RIM) apparatus.

Then, two or more reaction stock solutions (“A solution”, “B solution” and “C solution”, or reaction stock solution (i) and reaction stock solution (ii)) are separately introduced into the collision mixing apparatus. A norbornene-based resin molded article can be obtained by mixing instantaneously with a mixing head to obtain a reaction liquid, pouring the reaction liquid into a mold, and performing bulk polymerization in the mold. Note that a low-pressure injector such as a dynamic mixer or a static mixer can be used instead of the collision mixing device.
The temperature of the reaction stock solution before supply is preferably 10 to 60 ° C., and the viscosity of the reaction stock solution is usually 5 to 3,000 mPa · s, preferably 50 to 1,000 mPa · s at 30 ° C., for example. Degree.

  The mold used for reaction injection molding is not particularly limited, but usually a mold formed of a male mold and a female mold is used. Further, the mold to be used is not necessarily an expensive metal mold with high rigidity, and is not limited to a metal mold, and a resin mold or a simple mold can be used. The material in the case of using a metal mold is not particularly limited, and examples thereof include steel, aluminum, zinc alloy, nickel, copper, chrome, etc., and can be manufactured by any method such as casting, forging, thermal spraying, and electroforming. Or may be plated.

The mold structure may be determined in consideration of the pressure when the reaction liquid is injected into the mold. The mold clamping pressure is a gauge pressure and is usually 0.1 to 9.8 MPa.
The molding time varies depending on the type of norbornene monomer, polymerization catalyst, polymerization activator (cocatalyst), composition ratio, mold temperature, etc., but is not uniform, but generally 5 seconds to 6 minutes, preferably Is from 10 seconds to 5 minutes.

  In the case where bulk reaction is performed by supplying a reaction stock solution into a cavity formed by a male mold and a female mold, the male mold temperature T1 (° C.) is set higher than the female mold temperature T2 (° C.). It is preferable to set. Thereby, the design surface (surface which forms the reaction hardening type and transparent resin layer which has a specific haze value mentioned later) can be made into the beautiful surface of the surface appearance without sink and a bubble.

The difference (T1−T2) between the male mold temperature T1 and the female mold temperature T2 is preferably 5 ° C. or more, more preferably 10 ° C. or more, and the upper limit thereof is preferably 60 ° C. or less. The male temperature T1 is preferably 110 ° C. or lower, more preferably 95 ° C. or lower, and the lower limit thereof is preferably 50 ° C. or higher. The temperature T2 of the female mold is preferably 70 ° C. or lower, more preferably 60 ° C. or lower, and the lower limit thereof is preferably 30 ° C. or higher.
As a method of adjusting the mold temperature, for example, a method of adjusting the temperature of the mold with a heater: a method of adjusting the temperature of the temperature control water circulated in a pipe embedded in the mold, the temperature of a heat medium such as oil; Etc.

Composite molded body The composite molded body of the present invention is formed by forming a reaction-curable transparent resin layer having a haze value of 80 or less on at least a part of the surface of the norbornene-based resin molded body. The body and the transparent resin layer are directly joined (joined without an adhesive layer) at the contact interface.

  In the present invention, the composite molded body obtained by forming a reaction-curable transparent resin layer having a haze value of 80 or less on the surface of the norbornene-based resin molded body has excellent design. Can do. Further, by directly bonding the norbornene-based resin molded body and the transparent resin layer at the contact interface, a composite molded body excellent in impact resistance and weather resistance in addition to design properties can be obtained. In the present invention, the reaction-curable transparent resin layer has a haze of 80 or less, preferably 50 or less, and particularly preferably 10 or less.

Such a composite molded article of the present invention can be produced by the following method.
That is, when a norbornene-based resin molded body is produced by the above-described method, if bulk polymerization proceeds in the mold, a norbornene-based resin molded body is obtained, and a gap is formed between the mold and the molded body due to molding shrinkage. Occurs.

  In the present invention, the transparent resin layer composition constituting the reaction-curable transparent resin layer is injected into the gap from the injection port, and the injected transparent resin layer composition is reacted in the mold. As a result, a reaction-curable transparent resin layer is formed on at least a part of the surface of the norbornene-based resin molded body. Alternatively, the male mold is slightly opened relative to the female mold, and after forming a sufficient gap between the inner surface of the male mold and the norbornene-based resin molded product, the composition for the transparent resin layer is injected. And may be reacted.

  Thus, by injecting the composition for the transparent resin layer into the mold and reacting the composition for the transparent resin layer in the mold to form a reaction curable transparent resin layer, a norbornene-based resin molded body, The reaction curable transparent resin layer may be directly bonded at the contact interface.

  Moreover, when injecting the composition for a transparent resin layer, a method of injecting simultaneously from a plurality of injection ports may be adopted in addition to the method of injecting into the mold from a single injection port. By injecting simultaneously from a plurality of injection ports, the transparent resin layer composition can be injected without injection unevenness. Note that the transparent resin layer composition may be injected between the inner surface of the male mold and the molded body at a pressure higher than the mold clamping pressure while the male mold and the female mold are closed. The gap for injecting the transparent resin layer composition may be appropriately determined in consideration of the thickness of the finally obtained reaction-curable transparent resin layer. In the present invention, the thickness of the reaction curable transparent resin layer is preferably 0.01 to 7 mm, more preferably 0.02 to 5 mm, and still more preferably 0.02 to 4 mm. If the thickness of the transparent resin layer is too thin, the strength and weather resistance may be inferior. On the other hand, if it is too thick, the impact resistance may be inferior.

  The reaction curable transparent resin layer may be formed on at least a part of the surface of the norbornene-based resin molded body. For example, it may be formed only on one surface of the molded body, or formed on the entire surface of the molded body. However, in the present invention, it is preferable to form a reaction-curable transparent resin layer on at least the entire portion of the composite molded body that becomes the design surface.

  Although it does not specifically limit as a composition for transparent resin layers for forming a reaction-curable transparent resin layer, It has reaction sclerosis | hardenability, is reaction-cured, and is reactive-curable transparent on the norbornene-type resin molding surface. From the viewpoint that UV absorption and oxygen barrier properties can be imparted to the composite molded body by forming a resin layer, an unsaturated polyester, a polymerizable compound, and an organic peroxide polymerization initiator as a curing agent, The thing to contain is mentioned.

  In the present invention, by using a composition for a transparent resin layer containing such an unsaturated polyester, a polymerizable compound, and an organic peroxide polymerization initiator as a curing agent, the effect of the unsaturated polyester is mainly obtained. Thereby, the designability in the surface in which the reaction hardening type transparent resin layer was formed can be improved. In addition, by using the composition for a transparent resin layer having such a configuration and forming a reaction-curable transparent resin layer by the above-described method, a polymerizable compound and a polymer existing near the surface of the norbornene-based resin molded body Direct chemical bonds with molecules. As a result, the norbornene-based resin molded product and the reaction-curable transparent resin layer can be directly bonded at the contact interface. As a result, the UV-absorbing property and oxygen of the reaction-curable transparent resin layer can be obtained. The barrier property can be sufficiently exhibited, and the resulting composite molded article can be made excellent in impact resistance and weather resistance.

  The unsaturated polyester used in the present invention is synthesized by addition reaction or dehydration condensation reaction of α, β-olefin unsaturated dicarboxylic acid or its anhydride and glycol. In addition to these, saturated dicarboxylic acids and aromatic dicarboxylic acids, or anhydrides thereof, dicyclopentadiene that reacts with carboxylic acids, and the like can also be used in combination.

Examples of the α, β-olefin unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and anhydrides of these dicarboxylic acids.
Examples of the saturated dicarboxylic acid used in combination with the α, β-olefin unsaturated dicarboxylic acid include adipic acid, sebacic acid, succinic acid, phthalic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, and tetrahydrophthalic acid. And tetrachlorophthalic acid.
Among these, it is preferable to use fumaric acid as the α, β-olefin unsaturated dicarboxylic acid, and to use isophthalic acid as the saturated dicarboxylic acid in combination.

Examples of glycols include the following.
That is, examples of the diol include alkanediol, oxaalkanediol, hydrogenated bisphenol A, diol obtained by adding ethylene oxide or propylene oxide to bisphenol A, and hydrogenated products thereof.
Moreover, as alkanediol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Examples include 6-hexanediol and cyclohexanediol.
Examples of oxaalkanediol include diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol.
In addition to these glycols, monools such as octyl alcohol and oleyl alcohol; triols such as trimethylolpropane;
Among these, it is preferable to use hydrogenated bisphenol A, neopentyl glycol, and 1,6-hexanediol in combination.

  Examples of the polymerizable compound include styrene, divinylbenzene, chlorostyrene, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclohexane. Pentenyloxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, bisphenol A alkylene oxide Examples include di (meth) acrylate and trimethylolpropane tri (meth) acrylate.

  The content ratio of the polymerizable compound in the composition for transparent resin layer is preferably 10 to 900 parts by weight, more preferably 30 to 500 parts by weight with respect to 100 parts by weight of the unsaturated polyester. When the content ratio of the polymerizable compound is too low, the transparent resin layer is not sufficiently cured, and the impact resistance and weather resistance may be lowered. On the other hand, when the content ratio is too high, the stability of the composition for a transparent resin layer is impaired.

  As the curing agent, an organic peroxide polymerization initiator is preferably used. Examples of such organic peroxide polymerization initiators include bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, t-butylperoxyneodecanoate, and t-butylperoxy. Neohexanoate, t-butylperoxyneoheptanoate, t-hexylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-hexylperoxyneodecanoate, t-butylperoxy Pivalate, lauroyl peroxide, 2,4,4-trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxy-2- Examples thereof include ethyl hexanoate.

  The content of the curing agent in the transparent resin layer composition is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the unsaturated polyester. When there are too few hardening agents, hardening of a transparent resin layer will become inadequate and impact resistance and a weather resistance may fall. On the other hand, when too much, the stability of the composition for transparent resin layers will be impaired.

In addition, in the composition for transparent resin layers, the promoter for organic peroxide polymerization initiators and the mold release agent may contain as needed.
Examples of the accelerator for the organic peroxide polymerization initiator include cobalt naphthenate, cobalt octylate, zinc naphthenate, zinc octylate, manganese naphthenate, and lead naphthenate. The content of the organic peroxide polymerization initiator accelerator in the transparent resin layer composition is 0.01 to 20 parts by weight, preferably 0.04 to 10 parts by weight, based on 100 parts by weight of the unsaturated polyester. It is.
Examples of the release agent include stearic acid, hydroxystearic acid, zinc stearate, soybean oil lecithin, silicone oil, fatty acid ester, fatty acid alcohol dibasic acid ester and the like. The content rate of the mold release agent in the composition for transparent resin layers is 0.01-20 weight part with respect to 100 weight part of unsaturated polyester, Preferably it is 0.04-10 weight part.

  In the composition for transparent resin layer, if necessary, a release agent other than the above, a curing accelerator, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, a modified resin, a surface preparation agent, and the like are blended. Can do.

And the composite molded object of this invention can be manufactured by the said method using the above-mentioned norbornene-type resin molded object and the composition for transparent resin layers.
The timing for injecting the composition for the transparent resin layer into the mold is that after injecting each component constituting the norbornene-based resin molded body, a bulk polymerization reaction occurs inside the mold, and the temperature of the molded body is the highest temperature. From the point of time, it is preferably within 20 minutes after 5 seconds, more preferably within 10 minutes after 5 seconds, and particularly preferably within 5 minutes after 10 seconds. If the timing for injecting the composition for the transparent resin layer is too early, the reaction of the reaction stock solution is insufficient, and the injection pressure of the composition for the transparent resin layer changes, making it impossible to form a good transparent resin layer. There is a fear. On the other hand, if the injection timing of the transparent resin layer composition is too late, the bonding between the norbornene-based resin molded product and the transparent resin layer may be insufficient.

The injection pressure of the transparent resin layer composition is preferably 1 to 50 MPa, more preferably 3 to 30 MPa, and still more preferably 5 to 22 MPa.
Moreover, it is preferable to harden | cure by hold | maintaining at predetermined temperature for predetermined time after inject | pouring the composition for transparent resin layers. The curing temperature of the composition for transparent resin layer is preferably 70 to 130 ° C, more preferably 80 to 120 ° C, and the curing time is preferably 20 seconds to 6 minutes, more preferably 60 seconds to 4 minutes. .

  The composite molded body of the present invention thus obtained is used for housing equipment materials such as ceilings, wall panels, kitchen counters, and wash bowls, taking advantage of the excellent impact resistance and weather resistance in addition to the design properties. It can be suitably used for vehicle use, construction civil engineering material use, play equipment related use, use and the like.

In the above description, the method for producing the composite molded body of the present invention is performed by injecting the composition for the transparent resin layer into the mold and reacting and curing it with the norbornene-based resin molded body placed in the mold. However, the method for producing the composite molded article of the present invention is not particularly limited, and the production is such that the norbornene resin molded article and the reaction-curing transparent resin layer are directly joined. Any method is acceptable.
For example, the above-mentioned composition for a transparent resin layer is heat-molded at 70 to 200 ° C. to form a semi-polymerized molded body, and this semi-polymerized molded body is laminated on a norbornene-based resin molded body and heated under heating. It is good also as a structure which a norbornene-type resin molding and a reaction hardening type transparent resin layer join directly by pressing.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” are based on weight unless otherwise specified.
Moreover, each characteristic was measured by the method shown below.

A test piece having a length of 100 mm, a width of 100 mm, and a thickness of 5 mm was prepared from the DuPont impact strength composite molded body. About the prepared test piece, using a DuPont impact tester, R = 24.7 mm hemispherical core, load 500 g, At a temperature of 23 ° C., 50% fracture energy was measured according to JIS K7211.

A test piece having a length of 100 mm, a width of 100 mm, and a thickness set in each test was prepared from the fading composite molded body, and the hue of the prepared test piece was measured using a spectral color difference meter (manufactured by Nippon Denshoku Co., Ltd., model name “SE2000”). ) In the L * a * b * color system. Next, the same test piece was irradiated with light by a xenon lamp for 1,200 hours, and the hue of the test piece after the light irradiation was measured in the same manner using the L * a * b * color system. Then, the fading property was evaluated by obtaining hue changes ΔL, Δa, and Δb before and after the light irradiation. It can be evaluated that the smaller the values of ΔL, Δa, and Δb, the lower the color fading and the better.

Haze value The haze value was measured according to JIS K 7105 in a room temperature atmosphere.

Example 1
In a mixed monomer composed of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene as a norbornene-based monomer mixture, 5.7 parts of a styrene-butadiene-styrene block copolymer was dissolved as an elastomer. Next, 0.7 parts of diethylaluminum chloride as an activator, 0.7 parts of 1,3-dichloro-2-propanol and 0.07 part of silicon tetrachloride as activity regulators were added, and the reaction stock solution (solution A) Got.

  On the other hand, 5.6 parts of a styrene-butadiene-styrene block copolymer was dissolved as an elastomer in a mixed monomer consisting of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene as a norbornene-based monomer mixture. . Subsequently, 1.7 parts of di-t-butylhydroxytoluene as an antioxidant, 1.9 parts of tri (tridecyl) ammonium molybdate as a polymerization catalyst, and 2.0 parts of a white pigment were added, and the reaction stock solution (B Liquid).

  In addition to the above, 100 parts of anhydrous silica separated by a centrifuge from a mixture of unsaturated polyester, styrene and anhydrous silica (trade name: Gelcoat UG-501, Nippon Iupika Co., Ltd.), and a curing agent As an organic peroxide (trade name: Parroyl TCP, manufactured by NOF Corporation), 0.5 part of organic peroxide (trade name: Percure HO (N), manufactured by NOF Corporation) was mixed. Then, a transparent resin layer composition was prepared.

  Next, an aluminum male mold and a female mold for producing a plate-shaped molded body having a length of 500 mm × width of 500 mm × thickness of 5 mm are prepared, and the composition for transparent resin layer is injected into one place in the central portion. An injector with a maximum injection pressure of 35 MPa was attached. The male mold and female mold were clamped at a pressure of 0.5 MPa, and the male mold was heated to 90 ° C. and the female mold was heated to 40 ° C., respectively.

  And while mixing A liquid and B liquid prepared above in the ratio of A liquid: B liquid = 1: 1 (weight ratio) with a static mixer, from the reaction liquid injection hole, inside the reaction injection mold And a bulk polymerization reaction was performed for 1 minute, and then a norbornene-based resin molded body that was polymerized and cured was obtained. Next, the transparent resin layer composition prepared above was poured into the mold at a pressure of 20 MPa, and held at the mold temperature for 3 minutes to react the transparent resin layer composition.

Thereafter, the mold was opened, and a composite molded body having a reaction-curing transparent resin layer having a thickness of 0.1 mm on the surface of the norbornene-based resin molded body was taken out. And according to the said method, the DuPont impact strength and the fading property were evaluated about the obtained composite molded object. The results are shown in Table 1.
Separately, only the transparent resin layer was molded so as to have a thickness of 0.1 mm, and the haze value of the molded product was measured and found to be 2.

Example 2
A composite molded body was produced in the same manner as in Example 1 except that the thickness of the reaction curable transparent resin layer was changed to 2 mm, and evaluated in the same manner. The results are shown in Table 1.
Further, when the haze value of only the transparent resin layer was measured in the same manner as in Example 1, it was 10.

Comparative Example 1
Except that the reaction-curable transparent resin layer was not formed, a molded body was produced in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 2
When preparing the composition for a transparent resin layer, a composite molded body was produced in the same manner as in Example 1 except that peroyl TCP and percure HO (N) were not used as curing agents, and evaluated in the same manner. Went. The results are shown in Table 1.

Comparative Example 3
Using the composition for a transparent resin layer prepared in the same manner as in Example 1, a molded article for a transparent resin layer having a thickness of 2 mm was produced under the conditions of a curing temperature of 130 ° C. and a curing time of 7 minutes. Next, JKS-100 as an adhesive was applied to the surface of the norbornene-based resin molded body obtained in the same manner as in Example 1, and a transparent resin layer molded body was laminated thereon, with a curing temperature of 23 ° C. A composite molded body was produced by curing the adhesive under the conditions of a curing time of 1 week. Then, the obtained composite molded body was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  As shown in Table 1, with the norbornene-based resin molded body arranged in the mold, the composition for the transparent resin layer is injected into the mold and reacted and cured, so that the norbornene-based resin molded body and the reaction-curable mold are When it is configured to be directly bonded to the transparent resin layer, it is excellent in impact resistance (50% fracture energy of DuPont impact strength), and almost no change occurs in all hues. As a result, almost no fading occurred (Examples 1 and 2). Moreover, the composite molded bodies of Examples 1 and 2 were excellent in design.

On the other hand, when the reaction-curable transparent resin layer was not formed, the impact resistance was inferior and the hue (Δa, Δb) changed greatly, resulting in inferior fading (Comparative Example 1). .
In addition, when the organic peroxide initiator as a curing agent is not added to the composition for the transparent resin layer, the composition for the transparent resin layer is insufficiently cured, and interface peeling occurs. A sample capable of performing various measurements could not be obtained (Comparative Example 2).
Furthermore, when a norbornene-based resin molded product and a reaction-curing transparent resin layer are laminated via an adhesive layer, the impact resistance is inferior and the change in hue (Δb) increases, fading. (Comparative Example 3). Moreover, the composite molded body of Comparative Example 3 was poor in color and poor in design.

Claims (4)

  A composite molded body having a reaction-curing type transparent resin layer having a haze value of 80 or less on at least a part of a surface of a norbornene-based resin molded body obtained by bulk polymerization of a norbornene-based monomer in a mold, the norbornene A composite molded body, wherein the resin-based molded body and the transparent resin layer are directly joined at the contact interface.   The composite molded body according to claim 1, wherein the transparent resin layer has a thickness of 0.01 to 7 mm.   The norbornene-based resin molded body is placed in a mold, a transparent resin layer composition that will form the transparent resin layer is injected into the mold, and the injected transparent resin layer composition is injected into the mold. The composite molded article according to claim 1 or 2, which is produced by reaction curing.   The composite molded article according to any one of claims 1 to 3, wherein the transparent resin layer contains an unsaturated polyester, a polymerizable compound, and an organic peroxide polymerization initiator.