JP2003011159A - Method for manufacturing molded product having coating film and mold assembly - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a molded product having a coating film which is free from problems such as an appearance failure e.g. a mark of a visible coating agent injection aperture and the release of the coating film due to an adhesion failure. SOLUTION: This method for manufacturing a molded product having a coating film comprises the step to obtain the molded product 4 by injecting a reaction stock solution including a norbornene monomer into a mold and curing the stock solution and the step to inject a coating agent into a gap 60 between the inner face of the mold and the molded product 4 from coating agent injection apertures 24a to 24c formed in the inner face of the mold which is a part of the inner face of the mold and a part where the stock solution is molded into the molded product 4 by the inner face and corresponds to a part (82) to be cut after molding and/or in the inner face of the mold corresponding to a part (10) to be invisible from outside after assembling a finished product, and cure the coating agent to form the coating film 6 on the surface of the molded product 4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and a mold apparatus for producing a molded product having a coating film formed on the surface of a polynorbornene resin molded product in the same molding die.

[0002]

2. Description of the Related Art Conventionally, a polynorbornene-based resin molded product obtained by bulk polymerization of a norbornene-based monomer in a mold by a reaction injection molding (RIM) method in order to impart various properties such as designability and weather resistance. The surface of the resin has been spray-coated to form a film, but the film adhesion tends to be insufficient due to a change with time due to surface oxidation of the resin. Further, since the spray coating process is a separate process from the molding process, there is a problem that the production cost becomes high.

Therefore, various proposals have been made for forming a coating film on the surface of a polynorbornene resin molded article with good adhesion. The in-mold coating method is known as one of such proposals.

For example, in Japanese Unexamined Patent Publication No. 11-300776, a molding material containing dicyclopentadiene as a main component is molded in a cavity formed by a movable mold and a fixed mold by a reaction injection molding method, and the same mold is formed. In the interior, five kinds of components such as a polymerization initiator, a mold release agent, and an ethylenically unsaturated monomer are indispensable between the obtained molded product and the inner surface of the mold, and a coloring pigment that can be blended if necessary There is disclosed a method for producing a resin molded product, which comprises injecting a coating agent comprising:

In Japanese Patent Laid-Open No. 2001-71345, a molding material containing a cyclic olefin as a main component is injected from a resin injection port into a mold having a temperature difference between a cavity mold temperature and a core mold temperature. , A method for producing a crosslinked polymer molded article in which reaction injection molding by metathesis polymerization is performed, and then paint is injected from a paint injection port provided on the mold side on the high temperature side to coat the molded article and cure the paint. It is disclosed.

[0006]

Certainly, the method described in the above publication has an advantage that the steps can be simplified. However, as a result of examination by the present inventors, in the so-called in-mold coating method of this type, (1) not only the mark corresponding to the injection port remains on the coating surface in contact with the coating agent injection port, but not only the appearance is deteriorated. (2) Since the coating agent injection head is usually cooled by a cooling means such as a cold water jacket in order to prevent the coating agent from being hardened and clogged in the coating agent inlet, coating is performed around the coating agent inlet. It has been found that there is a problem that the agent is apt to cause curing failure, and the adhesion of the coating is apt to be insufficient due to the curing failure of the coating agent.

An object of the present invention is to provide a method for producing a molded article having a coating film free from the problem of peeling of the coating film due to poor appearance of coating agent injection port marks and poor adhesion, and a mold apparatus suitable for carrying out this method. Is to provide.

[0008]

Means for Solving the Problems The inventors of the present invention, in producing a polynorbornene-based resin molded product having a coating film in the same mold, after obtaining a polynorbornene-based resin molded product, and after molding the molded product. A coating agent is injected into a gap between the inner surface of the die and the molded body through a coating agent injection port provided in the die corresponding to a portion to be cut off and / or a portion to be invisible from the outside after assembly of the product, and then cured. As a result, it was found that the appearance of traces of the injection port of the coating agent and the peeling of the coating film due to poor adhesion do not occur, and the present invention has been completed.

That is, the method for producing a molded article having a coating film according to the present invention comprises the steps of placing a reaction stock solution containing a norbornene-based monomer in a mold and curing it to obtain a molded article, and cutting the molded article after molding. From the coating material injection port provided in the mold corresponding to the part to be exposed and / or the part that cannot be seen from the outside after the product is assembled, in the gap between the inner surface of the mold and the molded body, the coating material is put and cured, And a step of forming a coating film on the surface of the molded body.

In the present invention, the center of the coating material inlet is
The edge of the portion cut off after molding the molded body and / or
Alternatively, it is preferably arranged at least 5 mm inward from the end of the part that cannot be seen from the outside after the product is assembled.

In the present invention, it is preferable to introduce the coating agent from two or more coating agent injection ports, and more preferably, the coating agent is simultaneously injected from two or more coating agent injection ports.

The mold apparatus according to the present invention is a mold apparatus for manufacturing a molded body having a coating film, and corresponds to a portion cut off after molding of the molded body and / or a portion hidden from the outside after product assembly. The mold is provided with a coating material injection port.

The "portion cut out after molding of the molded product" in the present invention is a part of the molded product formed for the purpose of improving the norbornene-based monomer in the mold, and is useful during molding. However, it means a portion that becomes unnecessary after molding. As such a material, although not particularly limited, in a molded body further having a hole such as a drainage hole with the coating, such as a bathtub, a washing bath pan or a wash bowl of a unit bath, a hole such as a drainage hole cut after molding is formed. Corresponds to the part without. In this case, it is preferable to insert the coating agent from the coating agent injection port provided in the mold corresponding to the cut-out portion of the hole cut out after molding.

The "portion of the molded product which cannot be seen from the outside after the product is assembled" in the present invention is an essential part of the molded product, and the molded product having a coating is combined with other members to form a higher-order assembly. When used as a product, it means the part that becomes difficult to see under normal use. Such a thing is not particularly limited, but in a molded product that further has a wall-standing surface together with a coating, such as a washing bath pan of a unit bath, a hidden portion that becomes the wall-standing surface after molding corresponds to the molded product. In this case, it is preferable that the coating material is introduced from the coating material injection port provided in the mold corresponding to the wall-standing portion that cannot be seen from the outside after the product is assembled.

The term "drainage port" as used in the present invention means a space for discharging drainage formed in a part of a molded article having a coating film to the outside. As such a drainage port, for example, a hole formed in a part of the bowl-shaped portion formed on the bottom wall of the molded article having a coating and having an area of about 1/10 of the opening area of the bowl-shaped portion can be cited. To be The "hole" referred to in the present invention is formed in a part of a molded article having a coating, and is a space when various objects such as water and bolts pass from one surface side of the molded article having the coating to the other surface side. Say. In the present invention, the "extracted portion" means
It is a part that is useful when molding a molded product having a coating film, but is unnecessary after molding. The "wall standing surface" in the present invention is a part of a molded product having a coating film, for example, a surface on which a wall material such as a wall panel is arranged and which is difficult to see in a normal use state.

[0016]

In the method for producing a molded article having a coating film using the mold device according to the present invention, a part of the coating film formed on the surface of the polynorbornene resin molded article corresponds to (1) a coating agent injection port. Even if there is a trace (a mark of the coating material injection port), or peeling of the coating around the coating material injection port occurs due to poor adhesion due to poor curing of the coating material that has occurred around the coating material injection port, Remove the coating material injection marks and the peeled film,
By cutting off after molding or making it invisible from the outside after assembling the product, it is possible to solve the problem of the appearance of the coating agent injection port trace and the peeling of the coating film due to poor adhesion.

In the present invention, the center of the coating material inlet is
The edge of the portion cut off after molding the molded body and / or
Alternatively, it is possible to surely cut off the coating agent injection port mark or the peeled coating film after molding by arranging it 5 mm or more (more preferably 8 mm or more) inside from the end of the part that cannot be seen from the outside after product assembly. Or it can be reliably hidden from the outside after product assembly.

In the present invention, a coating having a uniform thickness can be formed on the surface of the cured product by introducing the coating from two or more coating agent injection ports. Moreover, it is expected that the thickness of the coating film to be formed will be further uniformized by simultaneously introducing the coating material from the two or more coating material injection ports.

The molded product having the coating film according to the present invention includes:
The present invention is not limited to the above-mentioned bathtub, unit bath washing pan, wash bowl, and the like, and can be widely applied to other molded products having holes such as drainage ports or molded products having wall standing surfaces.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a sectional view of a mold apparatus according to an embodiment of the present invention, and FIGS. 2A to 2D show a molded product using the mold apparatus according to an embodiment of the present invention. FIG. 3 (A) and FIG. 3 (B) are process diagrams for explaining the manufacturing method, and are views showing an example of arrangement of the coating material injection ports in the present embodiment.

In the present embodiment, a washing bath pan of a unit bath is exemplified as a molded body having a coating, first the constitution of the washing bath pan will be briefly explained, and then a mold apparatus and a manufacturing method for manufacturing the washing bath pan will be explained. To do. However, the method for manufacturing a molded product having a coating film according to the present invention and the mold apparatus are not limited to the case of manufacturing such a washing pan, and a molded product having a hole cut out after molding, It can also be applied to the case of manufacturing a molded body having a wall-standing surface that is hidden from the outside after product assembly and cannot be seen.

As shown in FIG. 2D, the unit-bath washing pan according to the present embodiment serves as a bath for the bather, and the molded body 4 made of polynorbornene resin is used.
The coating film 6 is formed on the surface of, and has a rectangular shape when seen in a plan view.

The washing place pan 2 is provided with a drainage port 8 as a hole. The diameter of the drainage port 8 is, for example, 50 mm
It is about 200 mm. Drainage can be performed from the drainage port 8 to the outside. Further, a wall standing surface 10 for arranging a wall panel (not shown) of the unit bath is formed in the vicinity of the upper end portion of the outer periphery of the washing place pan 2. Wall stand 10
Has a width of, for example, about 20 to 100 mm.

To manufacture the washroom pan 2 according to this embodiment, for example, the mold apparatus 20 shown in FIGS. 1 and 2A can be used. The mold apparatus 20 according to the present embodiment has a male mold 24 and a female mold 26 that can be divided in a direction X perpendicular to the dividing surface 22. Then, the male mold 24 and the female mold 26 are clamped at the dividing surface 22 to form a cavity 28 inside. The male mold 24 and the female mold 26 are made of, for example, synthetic resin or metal.

In this embodiment, a portion of the male mold 24 that is cut off after molding of the molded body (corresponding to the removed portion 82 of the drainage port 8) and / or a portion that cannot be seen from the outside after product assembly (corresponding to the wall-standing surface 10). ) Has a coating material injection port 24
a, 24b, 24c are provided, and the coating material injection device 32 is attached thereto. In addition, in FIG. 1, the coating material injection device 32 mounted on the coating material injection ports 24a and 24c is omitted. The inner diameters of the coating material injection ports 24a to 24c may be, for example, about φ10 to φ15. The inner diameter may be different for each injection port. The coating agent described later is filled with a gap 60 (see FIG.
(See (C)).

Further, in the present embodiment, an injection port for the reaction stock solution of norbornene-based monomer, which will be described later, is formed in a part of the dividing surface 22, and a mixer for injecting the reaction stock solution of the norbornene-based monomer is provided therein. 30 are equipped.

In this embodiment, such a mold device 20 is used.
Using the above, a washing place pan (molded body having a film) is manufactured as follows.

First, the male mold 24 is combined with the female mold 26 at the dividing surface 22 to form a cavity 28 between the male mold 24 and the female mold 26, and the reaction stock solution of the norbornene-based monomer is supplied thereto from the mixer 30. To do. 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 3000 cp at 30 ° C., for example.
s, preferably about 50 to 1000 cps.

The norbornene-based monomer contained in the reaction stock solution used in the present embodiment may be any one having a norbornene ring, and specific examples thereof include a bicyclic compound such as norbornene and norbornadiene, dicyclopentadiene (cyclopentadiene). Dimers), tricycles such as dihydrodicyclopentadiene, tetracycles such as tetracyclododecene, pentacycles such as cyclopentadiene trimer, heptacycles such as cyclopentadiene tetramer, and the like. Cyclic to heptacyclic alkyl such as methyl, ethyl, propyl and butyl, alkenyl such as vinyl, alkylidene such as ethylidene, substituted phenyl such as phenyl, tolyl and naphthyl, and further these bicyclic to heptacyclic compounds. A cyclic ester group,
Examples thereof include substituents having a polar group such as an ether group, a cyano group, and a halogen atom. Above all, it is easy to obtain,
A polycyclic norbornene-based monomer having three or more rings is preferred because of its excellent reactivity, and more preferably a tricyclic, tetracyclic, or pentacyclic norbornene-based monomer. The norbornene-based monomers may be used alone or in combination of two or more. In addition to the above-mentioned norbornene-based monomer, a monocyclic cycloolefin such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, or cyclododecene which can be subjected to ring-opening copolymerization therewith can be used as a comonomer.

The metathesis catalyst is not particularly limited as long as it is a catalyst capable of ring-opening polymerization of norbornene type monomers. The metathesis catalyst is a complex in which a transition metal atom is a central atom and a plurality of ions, atoms, polyatomic ions, and / or compounds are bound to each other. The transition metal atoms include groups 5, 6, and 8 (long-periodic periodic table,
The same shall apply hereinafter). The atoms of each group are not particularly limited, but examples of the atoms of group 5 include tantalum, examples of the atoms of group 6 include, for example, molybdenum and tungsten, and examples of the atoms of group 8 include, for example, ruthenium and osmium. Can be mentioned.

Examples of the metathesis catalyst containing a group 6 tungsten or molybdenum as a central metal include metal halides such as tungsten hexachloride; metal oxyhalides such as tungsten chloroxide; metal oxides such as tungsten oxide; and tridodecyl. Organometallic acid ammonium salts such as ammonium molybdate and tri (tridecyl) ammonium molybdate can be used. Of these, organic molybdate ammonium salts are preferred. When using these metathesis catalysts, it is preferable to use an organoaluminum compound or an organotin compound in combination as an activator (cocatalyst) for the purpose of controlling the polymerization activity.

In the present invention, as the metathesis catalyst, 5
It is also preferable to use a metal carbene complex having a group A, a group 6 and a group 8 metal atom as a central metal. Among the metal carbene complexes, group 8 ruthenium and osmium carbene complexes are preferable, and ruthenium carbene complexes are particularly preferable. Since the activity of the catalyst during bulk polymerization is excellent, the productivity of the norbornene-based resin molded product is excellent, and the obtained norbornene-based resin molded product has little odor (derived from unreacted norbornene-based monomer) and is excellent in productivity. Is.

The metal carbene complex has a structure (M = C) in which a carbene compound is bonded to the central metal atom and the metal atom (M) and the carbene carbon (> C :) are directly bonded to each other. . The carbene compound is a general term for compounds having a carbene carbon, that is, a methylene free group.

In the ruthenium carbene complex, at least two carbene carbons are bound to a ruthenium metal atom, and at least one of the carbene carbons is a ruthenium carbene complex to which a group containing a hetero atom is bound. Particularly preferred. Here, the hetero atom means an atom of groups 15 and 16 of the periodic table, and specifically,
Examples thereof include N, O, P, S, As and Se atoms. Among these, N, O, P, and S atoms are preferable, and N atom is particularly preferable, from the viewpoint of obtaining a stable carbene compound. Among the hetero atom-containing carbene compounds,
The carbene carbon preferably has a hetero atom adjacently bonded to both sides thereof, and more preferably has a hetero ring containing a carbene carbon atom and hetero atoms on both sides thereof. It is particularly preferable that the hetero ring has a saturated ring structure containing no double bond. Further, it is preferable that the hetero atom adjacent to the carbene carbon has a bulky substituent. When a ruthenium carbene complex having a carbene compound having the above-described preferable structure is used as a metathesis catalyst, the bulk polymerization activity is particularly high, and the production efficiency of the norbornene-based resin molded product is particularly good. Specific examples of the ruthenium carbene complex are described in WO97 / 06185 and Japanese Patent Publication No.
No. 508891 and Japanese Patent Laid-Open No. 11-322953.

The amount of the metathesis catalyst used is usually 0.01 mmol or more, preferably 0.1 mmol or more and 50 mmol or less, preferably 20 mmol or less with respect to 1 mol of the monomer used in the entire reaction solution. If the amount of metathesis catalyst used is too small, the polymerization activity will be too low and the reaction will take time, resulting in poor production efficiency.If the amount used is too large, the reaction will be too vigorous and the resin will cure before it is sufficiently filled in the mold. Or, the catalyst is likely to be deposited and it becomes difficult to store it homogeneously.

As the activator (cocatalyst), there is disclosed in JP-A-58-58.
No. 127728, Japanese Patent Laid-Open No. 4-226124,
Japanese Unexamined Patent Publication No. 58-129013 and Japanese Unexamined Patent Publication No. 4-1452.
There is no particular limitation as long as it is a known activator as disclosed in Japanese Patent Publication No. 47, for example, alkyl aluminum halides such as ethyl aluminum dichloride and diethyl aluminum chloride, organic aluminum compounds such as alkoxyalkyl aluminum halides, and organic tin. A compound etc. are mentioned. When a ruthenium carbene complex is used as the metathesis catalyst, an activator may or may not be used.

The amount of the activator used is not particularly limited,
Usually, 0.1 mol or more, preferably 1 mol or more, and 1 mol per 1 mol of the metathesis catalyst used in the entire reaction solution.
The amount is 00 mol or less, preferably 10 mol or less. If the activator is not used or the amount of the activator used is too small, the polymerization activity is too low and the reaction takes time, resulting in poor production efficiency. On the other hand, if the amount used is too large, the reaction may be too vigorous and the resin may be cured before being sufficiently filled in the mold.

The activator is used by dissolving it in the monomer,
As long as the properties of the molded product by the RIM method are not substantially impaired, it may be suspended in a small amount of a solvent and then mixed with a monomer to prevent precipitation or increase the solubility. Good.

If desired, the reaction stock solution contains a reinforcing material, an antioxidant, a filler, an elastomer, a pigment, a coloring agent, a foaming agent, a flame retardant, a sliding agent, a dicyclopentadiene-based thermopolymerization resin and its hydrogenation. You may mix | blend various additives, such as a thing.

When a norbornene-based monomer, a liquid containing a metathesis catalyst and, if necessary, a liquid containing an activator are prepared and mixed, bulk polymerization occurs. When performing bulk polymerization, the above liquids are instantaneously mixed using a mixing head or the like, and the mixed liquid is immediately injected into the cavity of the mold to start the polymerization. Then, the bulk polymerization (reaction injection molding) in the cavity of the mold apparatus is completed, and the mold is opened at the stage when the molded body is solidified to obtain the molded body. The material and size of the mold to be used, the polymerization time at the time of molding, the mold temperature and other conditions may be the same as those for molding by ordinary bulk polymerization of a polynorbornene-based resin.

When the reaction stock solution is supplied into the cavity 28 for curing, the mold temperature T1 (° C.) of the male mold 24 is set.
Is preferably set higher than the mold temperature T2 (° C.) of the female mold 26 (T1> T2). By doing so, the surface of the molded body 4 on which the coating film 6 is formed can be made to have a beautiful surface appearance without sink marks and air bubbles, which in turn can contribute to improving the adhesion of the coating film 6. In this embodiment, T1-T2
Is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and the upper limit is preferably about 50 ° C. T1 is preferably 85 ° C. or lower, more preferably 80 ° C. or lower, and the lower limit is preferably about 50 ° C. T2 is preferably 70 ° C. or lower, more preferably 60 ° C. or lower,
The lower limit is preferably about 30 ° C.

As a method of adjusting the mold temperature, for example, the mold temperature is adjusted by a heater; the temperature of circulating a heat medium such as temperature-controlled water or oil in a pipe embedded in the mold; Is mentioned.

When the bulk polymerization in the cavity 28 is completed, a molded body 4 made of polynorbornene resin is obtained as shown in FIG. 2 (B).

Next, as shown in FIG. 2C, the male mold 24
Is slightly opened relative to the female mold 26, and the male mold 24
A void (gap 60) is formed between the inner surface of the mold and the molded body 4, and the coating agent is injected into the void through the coating agent inlet 34 shown in FIG.

The coating agent is injected from the coating agent injection ports 24a to 24c provided at specific positions of the male die 24, but in the present embodiment, it is preferable to inject it from these three injection ports at the same time. By injecting at the same time, the coating agent can be evenly injected. In this case, as shown in FIG. 3A, the center of the coating material injection port 24b is preferably inside the edge portion 822 of the drain portion 8 of the drainage port 8 (see FIG. 2D) preferably at a predetermined value R1 or more. It is preferable to arrange and inject the coating agent from here. R1 is preferably 5 mm, more preferably 8 mm.

Further, as shown in FIG. 3B, the center of the coating material injection ports 24a, 24c is preferably inside the end portion 102 of the wall-standing surface 10 (see FIG. 2D) preferably at a predetermined value R2 or more. Is preferably disposed, and the coating agent is injected from there. R2 is preferably 5 mm, more preferably 8 mm
Is.

While the male mold 24 and the female mold 26 are closed, the coating material is injected between the inner surface of the mold of the male mold 24 and the molded body 4 at a pressure higher than the mold clamping pressure (usually about 10 MPa). You may. The gap 60 may be appropriately determined in consideration of the thickness of the coating film finally obtained, and is usually about 5 to 500 μm,
It is preferably set to about 10 to 200 μm.

The composition of the coating agent is not particularly limited, but for example, an oligomer and / or unsaturated polyester resin having at least two (meth) acrylate groups (component A) and an ethylenically unsaturated monomer (component B).
And an organic peroxide polymerization initiator having a 1-minute half-life temperature of 90 to 135 ° C. (component C), an accelerator for organic peroxide polymerization initiator (component D), and a melting point of 125 ° C. or less. Mold agent (E
It is preferable to use a coating agent containing

Examples of the oligomer (component A) having at least two (meth) acrylate groups usable in the present invention include epoxy acrylate oligomer, urethane acrylate oligomer, polyester acrylate oligomer and polyether acrylate oligomer.

The epoxy acrylate oligomer is a normal epoxy group ring-opening of an epoxy compound and an unsaturated carboxylic acid at a ratio such that the carboxyl group equivalent is 0.5 to 1.5 per 1 equivalent of the epoxy group. It is produced by an addition reaction. Here, as the unsaturated carboxylic acid, acrylic acid and methacrylic acid are typical examples.

The urethane acrylate oligomer can be obtained by mixing and reacting a diisocyanate compound, a diol compound and a hydroxyl group-containing (meth) acrylate all together. As another method, a diol compound and a diisocyanate compound are reacted to form a urethane isocyanate intermediate containing one or more isocyanate groups per molecule, and then this intermediate and a hydroxyl group-containing (meth) acrylate group are added. To react a diisocyanate compound with a hydroxyl group-containing (meth) acrylate to form a urethane (meth) acrylate intermediate containing one or more isocyanate groups per molecule, and then the intermediate and a diol. Examples thereof include a method of reacting with a compound.
As the diisocyanate compound, various known compounds can be used, and specifically, toluene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate, 1,2-diisocyanatoethane, hexamethylene diisocyanate, 1 ，
Organic diisocyanates such as 3-bis (isocyanatomethyl) cyclohexane can be mentioned. These diisocyanate compounds may be used alone or as a mixture. Further, typical examples of the diol compound include alkylene diols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol and polypropylene glycol, and diester diol which is a diester reaction product of dicarboxylic acid or an anhydride thereof. To be Furthermore, as the hydroxyalkyl (meth) acrylate, for example, a general formula: CH ₂ ═CRCO ₂ — (C _n H _2n ) —OH is used.
(Wherein, R is -H or -CH _3, n is a positive number of 2 to 8) are useful compounds represented by.

The polyester acrylate oligomer is
For example, it can be produced by reacting a polyester polyol having a hydroxyl group at the terminal with the aforementioned unsaturated carboxylic acid.

The polyether acrylate oligomer is
For example, it can be produced by reacting a polyether polyol such as polyethylene glycol or polypropylene glycol with the aforementioned unsaturated carboxylic acid.

The unsaturated polyester resin (component A) usable in the present invention is, for example, an unsaturated dibasic acid such as maleic acid or fumaric acid and a polyhydric alcohol such as ethylene glycol, propylene glycol or trimethylolpropane. Can be produced by the condensation reaction of.

Examples of the ethylenically unsaturated monomer (component B) usable in the present invention include styrene, α-methylstyrene, chlorostyrene, vinyltoluene, divinylbenzene, methyl (meth) acrylate, and 1,6-
Hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane tri (meth) acrylate, silicone acrylate, silicone diacrylate and the like are mentioned as representative ones, but not limited to these. The mixing amount of the ethylenically unsaturated monomer is 100 parts by weight of the component A,
20 to 200 parts by weight, preferably 40 to 160 parts by weight is suitable, and a coating agent having appropriate curing characteristics and viscosity is obtained in this range.

The organic peroxide polymerization initiator (component C) that can be used in the present invention includes the vehicle components (component A) and (B).
It is used to polymerize (component). The organic peroxide polymerization initiator needs to have a one-minute half-life temperature of 90 ° C to 135 ° C. Examples of such an organic peroxide include bis (4-t-butylcyclohexyl) peroxydiene. Carbonate, diisopropyl peroxy dicarbonate, t-butyl peroxy neodecanoate, t-
Butyl peroxy neohexanoate, t-butyl peroxy neo heptanoate, t-hexyl peroxy neodecanoate, t-butyl peroxypivalate, lauroyl peroxide, 2,4,4-trimethylpentyl peroxy 2-ethylhexanoate, t-amylperoxy 2-ethylhexanoate, benzoyl peroxide, t-butylperoxy 2-ethylhexanoate and the like are mentioned as typical ones, but not limited thereto. Not a thing.

When the one-minute half-life temperature of the organic peroxide polymerization initiator becomes higher than 135 ° C., the norbornene-based monomer cured product is usually molded at a mold temperature of 65 to 95 ° C., so that the coating agent is cured. The time will be significantly longer and in some cases will not cure at all. When the one-minute half-life temperature is lower than 90 ° C., the pot life of the coating material is remarkably shortened, and gelation occurs in the coating material injection device, so that the coating material injection operation cannot be performed, which is not preferable. The mixing amount of the organic peroxide polymerization initiator is 100 parts by weight of the component A,
0.1 to 15 parts by weight, preferably 1 to 8 parts by weight is suitable.

The accelerator (component D) usable in the present invention is
It is used for prompt activation of the organic peroxide polymerization initiator. As a promoter, cobalt naphthenate,
Representative examples include cobalt octylate, zinc naphthenate, zinc octylate, manganese naphthenate, lead naphthenate, and mixtures thereof, but are not limited thereto. A suitable amount of the accelerator is 0.01 to 20 parts by weight, preferably 0.04 to 10 parts by weight, based on 100 parts by weight of the component A.

The release agent (component E) usable in the present invention is
A release agent having a melting point of 125 ° C. or lower is used. Typical examples of the releasing agent include stearic acid, hydroxystearic acid, zinc stearate, soybean oil lecithin, silicone oil, fatty acid ester, and fatty acid alcohol dibasic acid ester. When the melting point of the release agent is higher than 125 ° C, the molding temperature of the norbornene-based monomer is usually 65 to 95 ° C, and even if the rise of the surface temperature of the cured product due to the reaction heat of the norbornene-based monomer is taken into consideration, The mold agent does not melt sufficiently, and it is difficult to obtain the original releasing effect. The release agent may be liquid at room temperature. The amount of the release agent is 0.1 to 15 parts by weight, preferably 0.3 to 100 parts by weight of the component A.
An appropriate amount is 5 parts by weight, and the releasing effect is exhibited in this range.

If necessary, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, a color pigment, an extender pigment, a conductive pigment, a modified resin, a surface modifier, etc. may be added to the coating agent. You can Examples of the polymerization inhibitor include hydroquinone, benzoquinone, paratertiarybutylcatechol and the like. Representative examples of the ultraviolet absorber and the light stabilizer include benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers. As the color pigment, for example, titanium oxide, iron oxide,
Examples thereof include phthalocyanine blue, phthalocyanine green and carbon black. Typical extender pigments include calcium carbonate, talc, silica, clay, mica, barium sulfate, and aluminum hydroxide. Examples of conductive pigments include conductive carbon black and graphite. The modified resin is required to have good compatibility with the component A, and examples thereof include polymethyl methacrylate, polyvinyl acetate, saturated polyester, and chlorinated polyolefin.

In the present embodiment, the coating agent is applied to the coating agent injection port 3
The timing of injecting from 4 is not particularly limited, and may be injected after the reaction stock solution is completely cured in the mold, and the reaction stock solution may properly withstand the injection of the coating agent and the flow pressure in the mold. It may be injected at the stage where it is cured to the extent possible,
Preferably, the time t at which the reaction stock solution is injected into the cavity
From a temperature T0 of 0, a time point t1 at which the polymerization reaction occurs inside the mold to reach the maximum temperature Tmax, and from the time point t1 is a time ts within a predetermined range. Time t within a predetermined range
s is from 5 seconds to 20 minutes, preferably from 5 seconds to 10 minutes, and particularly preferably from 10 seconds to 5 minutes. The injection pressure of the coating agent is not particularly limited, but is preferably about 1 to 50 MPa.

A mold release agent may be applied to the inner surface of the mold in advance before injecting the coating agent. By applying the release agent, the surface condition of the obtained molded product becomes good. Further, such a release agent may be included in the coating material. Examples of the releasing agent that can be used include silicone oil, fluorine compounds such as hexafluoropropene oligomer, and wax.

In this embodiment, when the coating material is injected into the gap 60, the mold temperature of the male mold 24 may be lower than the curing temperature of the coating material (currently about 90 ° C.). After the injection of the coating material, the mold temperature of the male mold 24 is set to be equal to or higher than the curing temperature of the coating material.

Thereafter, the mold temperature T1 of the male mold 24 is set to the coating agent curing temperature or higher, preferably 85 ° C. or higher, and the injected coating agent is cured. The curing time of the coating agent is preferably 1 to 10 minutes, more preferably 2 to 5 minutes.

Then, the mold is opened and released from the mold, and in this embodiment, the removed portion 82 of the drainage port 8 is removed to form a molded product having the coating film 6 as shown in FIG. 2D. 4 is obtained. The size and shape of the molded body 4 are not particularly limited, and can be a desired size and shape.

In the present embodiment, the inner surface of the mold corresponding to the portion formed in the molded body and cut out after the molding and / or the inner surface of the mold corresponding to the portion which cannot be seen from the outside after the product is assembled. Coating agent injection port 2 provided
Since the coating agent is introduced from 4a to 24c, a trace (coating agent injection port trace) corresponding to the coating agent injection ports 24a to 24c is formed on a part of the coating film 6, or the coating agent injection port 24a to 24c.
Even if peeling of the coating film around the coating material injection port occurs due to poor adhesion due to poor curing of the coating material that has occurred near 24c, the coating material injection port trace and the peeled coating film,
By cutting off after molding or making it invisible from the outside after assembling the product, it is possible to solve the problem of the appearance of the coating agent injection port trace and the peeling of the coating film due to poor adhesion.

Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments, and various modifications can be made without departing from the scope of the present invention. Of course.

For example, in the above-described embodiment, the coating film 6 is formed on only one surface of the molded body 4, but the coating film 6 may be formed on both surfaces. In this case, for example, a gap 60 is formed between the inner surface of the mold of the male mold 24 and the molded body 4, and a coating agent is put therein to cure it, and then the inner surface of the mold of the female mold 26 and the molded body 4 are separated. A gap 60 may be formed between them, and a coating agent may be put therein to cure.

[0070]

As described above, according to the present invention, in a method for coating a reaction injection molded product of a norbornene-based monomer in a mold, a coating film due to poor appearance of coating agent injection port marks and poor adhesion is formed. It is possible to provide a method for manufacturing a molded body that does not have a problem of peeling of the mold, and a mold apparatus suitable for performing this method.

[Brief description of drawings]

FIG. 1 is a sectional view of a mold device according to an embodiment of the present invention.

FIG. 2A to FIG. 2D are process diagrams for explaining a method for manufacturing a molded body using the mold device according to the embodiment of the present invention.

FIG. 3 (A) and FIG. 3 (B) are views showing an arrangement example of coating agent injection ports in the present embodiment.

[Explanation of symbols]

4. Molded product made of polynorbornene resin 6 ... film 20 ... Mold device 22 ... Dividing surface 24 ... Male 24a-24c ... Coating agent injection port 26 ... Female 28 ... Cavity 30 ... mixer 32. Coating material injection device 60 ... Gap 82 ... the removed part

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Koji Miyazaki             1-2-1, Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa               Zeon Corporation, General Development Center F-term (reference) 4F206 AA12 AC05 AG03 AG24 JA01                       JB23 JB24 JF01 JL02 JM04                       JN12 JQ81

Claims (6)

[Claims] 1. A step of placing a reaction stock solution containing a norbornene-based monomer in a mold and curing it to obtain a molded body, and a portion cut off after molding the molded body and / or a portion invisible from the outside after product assembly. From the coating agent injection port provided in the corresponding mold, in the gap between the inner surface of the mold and the molded body, the coating agent is cured and a step of forming a coating film on the surface of the molded body, A method for producing a molded article having a coating film having the same. 2. The center of the coating material injection port is arranged at least 5 mm inward from the edge of the portion cut off after the molding of the molded body and / or the end of the portion that cannot be seen from the outside after product assembly. A method for producing a molded article having a coating according to claim 1. 3. The method for producing a molded article having a coating according to claim 1, wherein the coating agent is introduced from two or more coating material injection ports. 4. The molded product having the coating film further has a drainage port, and a coating material is introduced from a coating material injection port provided in a mold corresponding to a drainage port cut-out portion cut out after molding of the molded product. A method for producing a molded article having a coating according to any one of claims 1 to 3. 5. The molding material having the coating film further has a wall-standing surface, and a coating material is injected from a coating material injection port provided in a mold corresponding to a wall-standing portion which cannot be seen from the outside after product assembly of the molding material. The manufacturing method of the molded object with a film in any one of Claims 1-3 characterized by the above-mentioned. 6. A mold device for producing a molded product having a coating, wherein a coating agent is poured onto a mold corresponding to a part cut off after molding of the molded product and / or a part hidden from the outside after product assembly. A mold apparatus having an inlet.