WO2007125787A1

WO2007125787A1 - Reaction injection molded body having coating film on surface and method for producing same

Info

Publication number: WO2007125787A1
Application number: PCT/JP2007/058400
Authority: WO
Inventors: Masaki Takeuchi; Tomohiko Takimoto
Original assignee: Rimtec Corporation; Miura, Takahiro
Priority date: 2006-04-27
Filing date: 2007-04-18
Publication date: 2007-11-08
Also published as: JP4832513B2; JPWO2007125787A1

Abstract

A reaction injection molded body having a uniform coating film over the entire surface can be easily produced by obtaining a molded body through bulk polymerization of a polymerizable composition within a mold and then forming a coating film on the surface of the molded body within the mold by an in-mold coating method. The polymerizable composition contains a norbornene monomer, a polymerization catalyst and an inorganic filler composed of a fibrous filler having an aspect ratio of 5-100 and a particulate filler having an aspect ratio of 1-2.

Description

Specification

Reaction injection molded body having a coating film on the surface and method for producing the same

Technical field

The present invention relates to a reaction injection molded body having a coating film on the surface and a method for producing the same.

More specifically, the present invention relates to a reaction injection molded body having a coating film free from coating defects, and a method for producing a reaction injection molded body having a coating film free from coating defects by in-mold coating subsequent to reaction injection molding. Background art

[0002] Automotive parts such as bumpers and air deflectors, construction of wheel loaders and power shovels, etc. 'recreational equipment such as industrial machines, golf cars and game machines, housing equipment such as wash bowls and unit baths, etc. Recently, large-sized molded products are manufactured by reaction injection molding. A coating film is formed in order to impart characteristics such as designability and weather resistance to the resin molded body used in each of these applications.

To form this coating film, the surface of a resin molded body obtained by bulk polymerization of a reaction stock solution composed of a monomer, a catalyst, etc. in a mold by a reaction injection molding method (RIM method) has been sprayed. The method of painting has been adopted.

[0003] However, the resin molded body on which the coating film is formed by this method has a problem in that the adhesiveness of the coating film is lowered due to aging, and the production cost is high.

As a method for solving this problem, an in-mold coating method is known. When a molded body is produced by the reaction injection molding method, the volume shrinks when the reaction stock solution becomes a molded body. This is called molding shrinkage, but this molding shrinkage usually causes a gap of 5 to 500 zm between the mold and the molded body. The in-mold coating method is a method in which a coating agent is injected into the gap between the molded body generated by the molding shrinkage and the mold surface, and is cured to form a coating film on the molded body. After the in-mold coating, the molded body having the coating film is taken out from the mold.

However, if this in-mold coating method is applied to a basin-shaped body such as a unit bath wash or a field pan, the coating agent will not penetrate into the vertical wall of the basin-shaped body. For this reason, in particular, a good coating film may not be formed on this portion.

[0004] In Patent Document 1, in addition to specifying the timing from the completion of bulk polymerization of the reaction stock solution used for reaction injection molding to the start of pouring the coating agent, the thickness of the vertical wall, the formation position of the rib, etc. It has been reported that by making each within a specific range, it is possible to prevent the coating from being poorly coated and the formation of wrinkles and cracks.

However, depending on the shape of the molded body, it may not be possible to adjust the thickness of the vertical wall or the formation of ribs may be unfavorable. Is not applicable.

In Patent Document 2, a molded product obtained by reaction injection molding is fixed by a molded product fixing means, and a coating agent is injected into the mold and cured to form a coating film on the surface of the molded product. A method of forming is disclosed.

However, depending on the shape of the molded product, fixing may not be sufficient, and coating defects may occur.

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-11152

Patent Document 2: International Publication No. 2005/046958 Pamphlet

Disclosure of the invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to obtain a reaction injection molded body having a uniform coating film without forming a rib or the like on the molded body or without providing a molded product fixing means. It is to provide a method for producing a reaction injection molded body. Another object of the present invention is to provide a reaction injection molded article by the above production method.

Means for solving the problem

[0007] In order to achieve the above object, the present inventors have conducted extensive research on the composition and the like of the reaction injection molding material. As a result, if a specific inorganic filler is contained in the reaction injection molded body, the reaction It was found that the shrinkage of the injection-molded product can be reduced, whereby a reaction injection-molded product having a good coating film can be obtained, and the present invention has been completed based on this finding.

[0008] According to the present invention, the norbornene-based monomer, the polymerization catalyst, and the aspect ratio Force ¾ ~: A polymerizable composition containing an inorganic filler composed of a fibrous filler of 100 and a particulate filler having an aspect ratio of 1 to 2 is bulk polymerized in a mold to obtain a molded body, There is provided a process for producing a reaction injection molded article having a coating film on its surface, characterized in that a coating film is formed on the surface of the molded article by an in-mold coating method in a continuous mold.

In the method for producing a reaction injection molded article of the present invention, it is preferable to use a metathesis polymerizable composition as the polymerizable composition.

In the method for producing a reaction injection molded article of the present invention, the content weight ratio (fibrous filler Z particulate filler) between the fibrous filler and the particulate filler is 95/5 to 55/45. preferable.

In the method for producing a reaction injection molded article of the present invention, it is preferable that the fibrous filler has a 50% volume cumulative diameter of 0.:! To 50 zm.

In the method for producing a reaction injection molded article of the present invention, the particulate filler preferably has a 50% volume cumulative diameter of 0.:! To 50 / m.

In the method for producing a reaction injection molded article of the present invention, the fibrous filler having an aspect ratio of 5 to 100 is preferably wollastonite or whisker-like calcium carbonate. In the method for producing a reaction injection molded article of the present invention, the particulate filler having an aspect ratio of 1 to 2 is preferably calcium carbonate or calcium hydroxide.

In the method for producing a reaction injection molded article of the present invention, the amount of the inorganic filler is preferably 5 to 55 parts by weight with respect to 100 parts by weight of the total amount of norbornene monomer and catalyst.

Furthermore, according to the present invention, there is provided a reaction injection molded article comprising a norbornene monomer bulk polymer containing an inorganic filler, which is obtained by the above reaction injection molded article production method, and having a coating film on the surface thereof. Provided.

The reaction injection molded article of the present invention is preferably a large panel.

The invention's effect

According to the present invention, a reaction injection molded article having a uniform coating film is obtained without making it necessary to form ribs on the molded article or using a molded article fixing means. Ability to do S.

The reaction injection molded article having a coating film obtained by the present invention is used for automobiles such as bumpers and air deflectors, construction of wheel loaders and power shovels, industrial machinery, leisure applications such as golf carts and game machines, It can be suitably used in medical applications such as medical equipment, industrial applications such as large panels and chairs, and residential equipment applications such as shower pans and wash bowls.

BEST MODE FOR CARRYING OUT THE INVENTION

[0010] The method for producing a reaction injection molded article having a coating film on the surface thereof according to the present invention comprises a norbornene monomer, a polymerization catalyst, a fibrous filler having an aspect ratio of 5 to 100, and an aspect ratio of 1 to 2. A polymerizable composition containing an inorganic filler, which is a particulate filler, is mass-polymerized in a mold to obtain a molded body, and subsequently is formed on the surface of the molded body by an in-mold coating method. A coating film is formed.

[0011] The polymerizable composition used in the present invention comprises a norbornene-based monomer, a polymerization catalyst, and an inorganic filler.

Specific examples of the norbornene-based monomer are those having a norbornene ring. Specific examples thereof include bicyclic compounds such as norbornene and norbornagen; tricyclic compounds such as dicyclopentagen and dihydridocyclopentagen; And the like; and pentacycles such as cyclopentadiene trimer; and heptacycles such as cyclopentagen tetramer. These bicyclic to heptacyclic compounds have hydrocarbon groups such as alkyl groups, alkenyl groups, alkylidene groups, and aryl groups, and polar groups such as ester groups, ether groups, cyan groups, and halogen atoms as substituents. You may do it. Among these, tricyclic or pentacyclic norbornene monomers are more preferable because they are easily available and have excellent reactivity, and tricyclic to pentacyclic norbornene monomers are more preferable.

[0012] Specific examples of norbornene monomers include dicyclopentagen, tricyclopentagen, cyclopentagen-methylcyclopentagen co-dimer, 5-ethylidene norbornene, norbornene, norbornagen, 5-cyclohexenyl. Norbornene, 1, 4, 5, 8—Dimethanone 1, 4, 4a, 5, 6, 7, 8, 8a—Old Kutahydronaphthalene, 1,4-methano —1, 4, 4, 4a, 5, 6, 7, 8 , 8a—octahydronaphthalene, 6-ethylidene 1, 4, 5, 8— Dimethanone 1,4,4a, 5,6,7,8,8-year-old Kutahydronaphthalene, 6-ethylidene 1,4, methanone 1,4,4a, 5,6,7,8,8-year-old Kutahydronaphthalene, 1,4,5,8-dimethanone 1,4,4a, 5,6,7,8,8a-aged kutahydronaphthalene, ethylenebis (5-norebonorenene) and the like.

Norbornene monomers may be used alone or in combination of two or more.

In addition, monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentagene, cyclootaten, and cyclododecene can be used as a comonomer.

[0013] The polymerization catalyst is preferably a metathesis polymerization catalyst.

The metathesis polymerization catalyst is not particularly limited as long as it is a catalyst capable of ring-opening polymerization of a norbornene-based monomer.

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 shall apply hereinafter) are used. 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. Examples of the Group 8 atom include: Examples include ruthenium and osmium.

[0014] Metathesis polymerization catalysts having Group 6 tungsten or molybdenum as the central metal include metal halides such as tungsten hexachloride; metal oxyhalides such as tungsten chloroxide; metal oxides such as tungsten oxide; Further, organometallic acid ammonium salts such as tridodecinoleammonum molybdate and tri (tridecyl) ammonium molybdate can be used.

Among these, organic molybdenum molybdate is preferred. When these metathesis polymerization catalysts are used, it is preferable to use an organic aluminum compound or an organic tin compound as an activator (cocatalyst) for the purpose of controlling the polymerization activity.

In the present invention, it is also preferable to use a metal carbene complex having a metal atom of Group 5, 6 and 8 as a central metal as a metathesis polymerization catalyst. Among the metal carbene complexes, the group 8 ruthenium and osmium carbene complexes are preferred, and the ruthenium carbene complex is particularly preferred. Is preferred. This is because the activity of the catalyst during bulk polymerization is excellent, so that the productivity of the norbornene-based resin molded article is excellent, and the resulting norbornene-based resin molded article has little odor derived from the unreacted norbornene-based monomer.

In the ruthenium carbene complex, at least two carbene carbons are bonded to a ruthenium metal atom, and at least one of the carbene carbons is bonded to a group containing a heteroatom. Ben complexes are particularly preferred.

[0016] The amount of the metathesis polymerization catalyst used is usually 0.

01 millimeters or more, preferably f or 0.1 millimeters or more and 50 millimeters or less, preferably ί or 20 millimeters or less. If the amount of the metathesis polymerization catalyst used is too small, the polymerization activity will be too low and the reaction will take a long time. It tends to harden before being deposited and the catalyst is likely to deposit, making it difficult to store homogeneously.

[0017] The activator (cocatalyst) is not particularly limited, and specific examples thereof include organometallic compounds of metals in Groups 11 to 14 of the periodic table. Specific examples thereof include organoaluminum compounds such as alkylaluminum halides such as ethylaluminum dichloride and jetylaluminum chloride, and alkoxyalkylaluminum halides; organotin compounds such as tetrabutyltin; and the like. When a ruthenium carbene complex is used as a metathesis polymerization catalyst, an activator may or may not be used.

[0018] The amount of the activator to be used is not particularly limited, but usually 0.1 mol or more, preferably 1 mol or more and 100 mol or less is preferable with respect to 1 mol of the metathesis polymerization catalyst used for the reaction. Or less than 10 moles. If no activator is used or if the amount of 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, when the amount used is too large, the reaction is too intense, and the composition may be cured before the polymerizable composition is sufficiently filled in the mold.

The activator is used after being dissolved in the monomer, but within a range that does not substantially impair the properties of the molded article by the reaction injection molding method, it is suspended in a small amount of solvent and mixed with the monomer. You may use it, making it difficult to precipitate or improving solubility.

[0019] It is preferable to add an activity regulator. The activity regulator is a polymerization catalyst as described later. This is to prevent the polymerization from starting during the injection when the monomer solution of the medium and the monomer solution of the activator are mixed and injected into the mold to start the polymerization.

As a strong activity regulator, Noreis base is suitable, and ether, ester, nitrile and the like are used. Specific examples include butyl ether, ethyl benzoate, diglyme and the like. When a polar group-containing monomer is used as the copolymerization monomer, the monomer itself may be a Lewis base and may also have an action as an activity regulator. The activity regulator is preferably added to a solution containing the active agent. Also, alcohols can be suitably used as the activity regulator.

Furthermore, it is preferable to add a polymerization accelerator in order to improve the polymerization conversion of the monomer. As the polymerization accelerator, among the chlorine atom-containing compounds, organic chlorinated compounds and chlorinated silicon compounds are preferable. Specific examples thereof include hexaclonal-p-xylene, 2,4-dichroic one-triclonal toluene, and tetrachlorosilane. The addition amounts of the activity regulator and the polymerization accelerator are not particularly limited, but are each approximately 1 Oppm to 10% of the weight of the polymerizable composition.

In the present invention, as an essential component of the polymerizable composition, an inorganic filler comprising a fibrous filler having an aspect ratio of 5 to 100 and a particulate filler having an aspect ratio of! To 2 is used. . In the present invention, 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 of 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.

[0021] The weight ratio of fibrous filler and particulate filler (fibrous filler Z particulate filler) is a force of 95/5 to 55/45 S, preferably 80/20 to 60/40 It is better than the power.

When this ratio is within the above range, it becomes easier to obtain a molded body having a coating film free from coating film defects.

[0022] The fibrous filler used in the present invention has an aspect ratio of 5 to 100. It is essential and preferably has an aspect ratio of 10 to 50. The 50% volume cumulative diameter of the fibrous filler is preferably 0.1 to 50 / m, more preferably 1 to 30 / im. If the 50% volume cumulative diameter is too small, the rigidity and dimensional stability of the molded product obtained using this may be insufficient. Conversely, if the 50% volume cumulative diameter is too large, when the polymerization reaction solution is injected into the mold, the polymerization reaction solution may settle in the tank or piping or the injection nozzle may become clogged.

[0023] Specific examples of the fibrous filler include glass fiber, wollastonite, potassium titanate, zonolite, basic magnesium sulfate, aluminum borate, tetrapod-type zinc oxide, gypsum fiber, phosphate fiber, and alumina. Examples thereof include fiber, whisker-like calcium carbonate, and whisker-like boehmite.

Of 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 preferred.

[0024] The particulate filler used in the present invention must have an aspect ratio of 1 to 2, and preferably has an aspect ratio of 1 to 5.

The 50% volume cumulative diameter of the particulate filler is preferably 0.1-50 / m, more preferably:! To 30 μΐη, and particularly preferably 1 to 10 μ μη. If the 50% volume cumulative diameter is too small, the rigidity and dimensional stability of the molded product obtained using this may become insufficient. Conversely, if the 50% volume cumulative diameter is too large, when the polymerization reaction liquid is injected into the mold, the polymerization reaction liquid may settle in the tank or piping, or the injection nozzle may be clogged.

[0025] Specific examples of the particulate filler include calcium carbonate, calcium hydroxide, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, barium titanate, silica, and alumina. , Carbon black, graphite, antimony oxide, red phosphorus, various metal powders, clay, various ferrites, hydrated talcite and the like.

Of these, calcium carbonate and calcium hydroxide are preferred because they do not inhibit the bulk polymerization reaction.

[0026] The filler used in the present invention preferably has a hydrophobic surface.

By using a hydrophobized filler, the aggregation and precipitation of the filler in the polymerizable composition It is possible to prevent falling, and to make the dispersion of the filler in the obtained molded body uniform, thereby making the molded body uniform in rigidity and dimensional stability and further reducing anisotropy. The power to do is S.

Examples of the treating agent used in the hydrophobizing treatment include silane coupling agents such as bursilane, titanate coupling agents, aluminum coupling agents, fatty acids such as stearic acid, fats and oils, surface active chiral IJ, and waxes. .

The hydrophobization treatment of the filler can be performed by mixing the hydrophobizing agent at the same time when preparing a polymerizable composition containing a norbornene-based monomer, a polymerization catalyst and a filler. It is preferable to prepare the polymerizable composition using the filler that has been subjected to the chemical treatment.

[0027] In the present invention, the amount of the inorganic filler is the total amount of the norbornene-based monomer and the catalyst.

It is preferably 5 to 55 parts by weight with respect to 100 parts by weight. It is preferably 10 to 45 parts by weight.

If the amount of inorganic 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, the resulting molded product may have insufficient rigidity and dimensional stability.

[0028] In the present invention, in order to improve or maintain the properties of the molded product, various additives are blended in the polymerizable composition within a range that does not impair the adhesion, adhesion, etc. between the cured coating and the molded product. You can do it. Possible additives include reinforcements, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, pigments, colorants, foaming agents, antistatic agents, flame retardants, lubricants, softeners, adhesives Agents, plasticizers, mold release agents, deodorants, fragrances, elastomers, dicyclopentagen-based thermal polymerization resins and hydrogenated products thereof.

In particular, by adding an elastomer, the viscosity of the reaction stock solution can be adjusted, and the impact resistance of the resulting molded product can be improved. Examples of elastomers include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer ( SIS), ethylene-propylene-diene terpolymers, ethylene monoacetate copolymers (EVA) and their hydrides. The amount of elastomer used is usually 0.5 per 100 parts by weight of norbornene monomer.

-20 parts by weight, preferably 2 to 10 parts by weight.

[0029] 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; And the like. The addition method may be appropriately selected depending on the type of additive.

[0030] A method for preparing a polymerizable composition comprising a norbornene-based monomer, a polymerization catalyst and an inorganic filler is not particularly limited, and these components may be mixed by any method, but typically Depending on whether the polymerization catalyst requires an activator (cocatalyst), the following two methods can be shown.

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

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

[0031] The filler may be incorporated into any of the above reaction stock solutions ("solution A", "solution B" or "solution C", or the reaction stock solution (i) or the reaction stock solution (ii)) It is preferably used by mixing in a reaction stock solution containing a norbornene monomer.

The fibrous filler and the particulate filler may be blended in separate reaction stock solutions, or both may be blended in the same reaction stock solution, but the latter blending method is preferred. Sedimentation of the filler is suppressed, and the storage stability of the polymerizable composition is improved.

[0032] In the method for producing a reaction injection molded article of the present invention, first, the polymerizable composition is bulk polymerized in a mold to obtain a molded article.

Polymerizable composition comprising norbornene-based monomer, polymerization catalyst and inorganic filler In order to perform bulk polymerization in a mold, for example, a collision mixing device known as a reaction injection molding (RIM) device can be used.

Two or more types of 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. Then, the reaction injection molded body can be obtained by instantaneously mixing with a mixing head, pouring the resulting polymerizable composition into a mold, and 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 f. C (This is usually about 5 to 3,000 cP, preferably about 50 to about 1, OOOcP.

[0033] 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.

The material of the mold is not particularly limited, and can indicate metals such as steel, aluminum, zinc alloy, nickel, copper, and chromium, and resin. Further, these molds may be manufactured by any method such as forging, forging, thermal spraying, electric plating, etc., or may be made by plating.

The structure of the mold may be determined in consideration of the pressure when the mixed liquid and the coating agent are injected into the mold. The mold clamping pressure is gauge pressure and is usually 0.:! To 9.8 MPa.

The molding time varies depending on the types of norbornene monomer, polymerization catalyst and polymerization activator (cocatalyst), their composition ratio, mold temperature, etc., but is not uniform, but generally 5 seconds to 6 minutes It is preferably 10 seconds to 5 minutes.

[0034] In the case where the reaction stock solution is supplied into a cavity formed by a mold having a male mold and a female mold as a pair, and bulk polymerization is performed, the mold temperature Tl (° C) of the male mold is set to the female mold. It is preferable to set it higher than the mold temperature T2 (° C). As a result, the surface of the molded body on which the coating film is formed can be made into a beautiful surface with no surface bubbles and can contribute to improving the adhesion of the coating film.

The difference between the mold temperature T1 of the male mold and the mold temperature T2 of the female mold (T1-T2) is preferably 5 ° C Above, more preferably 10 ° C or higher, and the upper limit is preferably 60 ° C or lower. T1 is preferably 110 ° C or lower, more preferably 95 ° C or lower, and the lower limit is preferably 50 ° C or higher. T2 is preferably 70 ° C or lower, more preferably 60 ° C or lower, and the lower limit is preferably 30 ° C or higher.

Examples of methods for adjusting the mold temperature include adjusting the mold temperature with a heater; adjusting the temperature of a heat medium such as temperature-controlled water or oil that is circulated in a pipe embedded in the mold; It is.

[0035] When bulk polymerization proceeds in the mold, a molded body made of norbornene-based resin is obtained, and a gap between the mold and the molded body due to molding shrinkage (hereinafter, this gap is simply referred to as "gap"). ) Occurs.

In the present invention, a coating agent is injected into the gap from the coating agent injection port to form a coating film on the surface of the molded body. In order to more reliably inject the coating agent, the male mold is slightly opened relative to the female mold, and a sufficient gap is provided between the inner surface of the male mold and the molded body. After forming, a coating agent may be injected.

In the case where a plurality of coating agent injection ports are provided, the coating agent is preferably injected simultaneously from all the injection ports. By injecting at the same time, it is possible to insert the coating agent without uneven injection. Note that the coating agent 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 should be determined appropriately in consideration of the final coating thickness.

[0036] The composition of the coating agent is not particularly limited. For example, an oligomer and / or unsaturated polyester resin (vehicle component) having at least two (meth) atta leuroleno groups and an ethylenically unsaturated monomer (monomer component). ), A polymerization initiator, an accelerator for an organic peroxide polymerization initiator, and a mold release agent having a melting point of 125 ° C. or lower.

[0037] As an oligomer having at least two (meth) atallyloyl groups used as a vehicle component, epoxy (meth) acrylate oligomer, urethane (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether ( (Meth) acrylate oligomer etc. are mentioned. [0038] The epoxy (meth) acrylate oligomer is an epoxy compound and (meth) acrylic acid in a ratio such that the equivalent amount of carboxynole group per equivalent of epoxy group is 0.5 to 1.5. It is produced by subjecting an acid to a ring-opening addition reaction to an epoxy group. Here, instead of (meth) acrylic acid, other unsaturated carboxylic acids may be used.

[0039] The urethane (meth) acrylate oligomer can be obtained by mixing and reacting a diisocyanate compound, a diol compound and a hydroxy group-containing (meth) acrylate. Alternatively, the dioli compound and the diisocyanate compound can be reacted to form a urethane isocyanate intermediate containing one or more isocyanate groups per molecule, and then this intermediate A method of reacting a compound with a hydroxy group-containing (meth) acrylate, reacting a diisocyanate compound with a hydroxy group-containing (meth) acrylate, and containing one or more isocyanate groups per molecule Examples thereof include a method of forming a urethane (meth) ate acrylate intermediate and then reacting this intermediate with a diol compound.

Here, various known materials can be used as the diisocyanate compound. Specifically, tolylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate, 1,2-diisocyanatoethane, hexamethylene diisocyanate, 1,3-bis Mention may be made of organic diisocyanates such as (isocyanatomethyl) cyclohexane. These diisocyanate compounds may be used alone or as a mixture.

Representative examples of the diol compound include alkylene diols such as ethylene glycol, propylene glycol, polyethylene glycol, polyethylene glycol and polypropylene glycol, and diester diol which is a diester reaction product of dicarboxylic acid or its anhydride. As mentioned.

Furthermore, as a hydroxy group containing (meth) acrylate, for example, the general formula: CH 2 = CRCO

twenty two

— (C H) —〇H (denotes, R is 1 H or 1 CH, and n is an integer of 2 to 8) n 2n 3

Are useful.

[0040] The polyester (meth) acrylate oligomer can be produced, for example, by a reaction between a polyester polyol having a hydroxyl group at the terminal and (meth) acrylic acid. (Meth) Other unsaturated carboxylic acids can be used instead of acrylic acid. The polyether (meth) acrylate oligomer can be produced, for example, by reacting a polyether polyol such as polyethylene glycol or polypropylene glycol with (meth) acrylic acid. Instead of (meth) acrylic acid, other unsaturated carboxylic acids may be used.

[0041] The unsaturated polyester resin used as the vehicle component is produced, for example, by a condensation reaction between an unsaturated dibasic acid such as maleic acid fumaric acid and a polyhydric alcohol such as ethylene glycol, propylene glycol, or trimethylolpropane. be able to.

[0042] Examples of the ethylenically unsaturated monomer used as the monomer component include styrene, a-methylstyrene, chlorostyrene, butanolene, dibutylbenzene, methinole (meth) acrylate, 1, 6-hexanediol di (meth) ) Atallate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, silicone (meth) acrylate, silicone di (meth) acrylate, etc. It is not limited to.

The blending amount of the monomer component is 20 to 200 parts by weight, preferably 40 to 160 parts by weight with respect to 100 parts by weight of the vehicle component, and a coating agent having appropriate curing characteristics and viscosity within this range. can get.

[0043] As the polymerization initiator used in the coating agent, an organic peroxide polymerization initiator is preferred.

The organic peroxide polymerization initiator is used for polymerizing the vehicle component and the monomer component. The organic peroxide polymerization initiator preferably has a 1 minute half-life temperature of 90 ° C to 135 ° C. Examples of such organic peroxides include bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, t_butylperoxyneodecanoate, and t_butyl. Peroxyneohexanoate, t—Butinoleperoxyneoheptanoate, t_Hexenoleperoxyneodecanoate, t_Butylperoxybivalate, Lauroyl peroxide, 2, 4, 4_ Representative examples include trimethylpentylperoxy-2-ethylhexanoate, t-aminoleperoxy-2-ethylhexanoate, benzoyl peroxide, t_butylperoxy_2_ethylhexanoate, and the like. Les, not limited to these.

[0044] A cured product of a norbornene-based monomer is usually molded at a mold temperature of 65 to 95 ° C. Therefore, when the 1-minute half-life temperature of the organic peroxide polymerization initiator is higher than 135 ° C, the curing time of the coating agent becomes remarkably long, and in some cases, it does not cure at all. In addition, if the half-life temperature for 1 minute is lower than 90 ° C, the pot life of the coating agent is remarkably shortened and gelation occurs in the coating agent injection apparatus, which makes it impossible to inject the coating agent. The organic peroxide polymerization initiator is used in an amount of 0.:! To 15 parts by weight, preferably :! to 8 parts by weight per 100 parts by weight of the vehicle component.

[0045] Examples of the accelerator for the organic peroxide polymerization initiator include naphthenic acid conolate, octyl acid cobalt, zinc naphthenate, zinc octylate, manganese naphthenate, lead naphthenate, or a mixture thereof. , But not limited to these. An appropriate amount of the accelerator is 0.01 to 20 parts by weight, preferably 0.04 to 10 parts by weight per 100 parts by weight of the vehicle component.

[0046] As the release agent, a release agent having a melting point of 125 ° C or lower is preferably used. Typical examples of such a releasing agent include stearic acid, hydroxystearic acid, zinc stearate, soybean oil lecithin, silicone oil, fatty acid ester, and fatty acid alcohol dibasic acid ester.

If the melting point of the release agent is higher than 125 ° C, the molding temperature of the norbornene monomer is usually 65 to 95 ° C, and the surface temperature of the cured product rises due to the reaction heat of the norbornene monomer. However, the release agent does not melt sufficiently and the original release effect cannot be obtained. The release agent may be liquid at normal temperature.

The compounding amount of the release agent is appropriately from 0.:! To 15 parts by weight, preferably from 0.3 to 5 parts by weight per 100 parts by weight of the vehicle component, and the release effect is exhibited within this range.

[0047] The coating agent may include metal powder, a mold release agent other than the above, a curing accelerator, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, a coloring pigment, an extender pigment, a conductive pigment, if necessary. A modified resin, a surface conditioner, etc. can be blended.

Examples of mold release agents other than the above include fluorine compounds such as silicone oil and hexafluoropropene oligomer, and wax.

Examples of the polymerization inhibitor include hydroquinone, benzoquinone, p_t-butylcatechol and the like. Typical examples of the ultraviolet absorber and the light stabilizer include benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers.

Examples of the color pigment include titanium oxide, iron oxide, phthalocyanine blue, phthalocyanine green, and carbon black.

Examples of extender pigments include calcium carbonate, Tanorek, silica, clay, My strength, barium sulfate, aluminum hydroxide, and the like.

Examples of the conductive pigment include conductive carbon black and graphite.

The modified resin needs to have good compatibility with the vehicle component, and specific examples thereof include polymethylmetatalylate, polyacetate butyl, saturated polyester, chlorinated polyolefin and the like.

[0048] The viscosity of the coating is measured with a B-type viscometer at 30 ° C (rotor # 2, 3 (kpm), 500 to 10 to reduce the spread of the coating and foaming. , OOOmPa's force S, preferably 600 ~ 7, more preferable than OOOmPa's force S, 700 ~ 6, OOOmPa's force S, especially preferred.

[0049] The timing of injecting the coating agent from the coating agent injection port is such that after each component of the polymerizable composition such as a norbornene monomer is injected into the mold, a bulk polymerization reaction occurs inside the mold. It is preferably within 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes from the time when the body temperature reaches the maximum temperature. If the timing of injecting the coating agent is too early, the reaction of the reaction solution of the molding material may be insufficient and the coating agent may be deformed by the injection pressure of the coating agent. On the other hand, if the timing of injecting the coating agent is too late, the difference between the location where the shrinkage of the molded body increases and the location where it does not increase becomes significant, and the appearance of the coating film may be greatly reduced.

The mold temperature of the male mold when injecting the coating agent into the gap may be lower than the curing temperature of the coating agent, but it is preferable to set it above the curing temperature of the coating agent after injection of the coating agent. . The injection pressure of the coating agent is not particularly limited, but is preferably 1 to 50 MPa, more preferably 3 to 30 MPa, and particularly preferably 5 to 22 MPa. If the pressure is too low, the coating material may not penetrate sufficiently. Conversely, if the injection pressure is too high, the equipment costs will be excessive, and the mold structure will need to be pressure resistant, making it economical. May be inferior. [0050] After the coating agent is injected, the coating agent is cured by being held at a predetermined temperature for a predetermined time. The curing temperature of the coating agent is preferably 70 to 110 ° C, more preferably 80 to 100 ° C, and the curing time is preferably 20 seconds to 6 minutes, more preferably 60 seconds to 4 minutes. If the curing temperature is too high, the coating agent and the surface of the molded article may not be sufficiently adhered, and the coating agent may be peeled off.On the other hand, if the curing temperature is too low, the coating agent will begin to cure while being injected. Not only is it impossible to inject the coating material to every corner, but the injection pressure becomes higher than this, which may damage the injector and the mold. If the curing time is too short, the coating may not be cured sufficiently and the coating may be peeled off. On the other hand, if the curing time is too long, the productivity may decrease.

[0051] After the coating agent is cured, the mold is completely opened and removed to remove the mold, and more specifically, the molded body on which the coating film is formed. It is possible to obtain panels (which may be in the form of a tray).

The reaction injection molded article of the present invention is suitably used as a large panel (particularly a basin-shaped article) such as a concrete panel serving as a guide when pouring concrete; an outer wall panel for storing water or storing water-soluble chemicals, and the like. The length of the long side of the large panel (the longest side in the case of a basin-shaped body) is preferably 1,000 to 3,000 mm, and the length of the short side (the shortest side in the case of a basin-shaped body) The thickness is preferably 400 to 2,000 mm.

Example

[0052] The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited thereto. In the following, “part” and “%” are based on weight unless otherwise specified.

[Example 1]

(Mold)

Forged aluminum female mold and electric aluminum male mold for forming a bonnet-shaped body with an upper end force of S 1,200 mm, width 600 mm, and a lower end force S of 1, 190 mm, width 590 mm, height 150 mm The male mold has a coating agent injection port at the center and apex of both longitudinal sides, and an injector with a maximum injection pressure of 40 MPa was attached to each coating material injection port. Guides and weirs for forming burrs with a width of 30 mm and a thickness of 0.5 mm are formed around the basin-shaped body and the runner part on the upper outer periphery of the female mold. Protruding parts for preventing leakage of coating with a right-angled triangular cross-section with 5 mm sides The groove to be formed was provided. The groove was formed so that the vertical portion of the protrusion for preventing leakage of the coating faced the molded product side. In addition, the male groove has a length as a protrusion defect part for air discharge at one place.

Filled with a 10mm putty.

[0054] (Reaction stock solution and coating agent)

As a reaction stock solution component for reaction injection molding, a mixed monomer composed of 90 parts of dicyclopentagen and 10 parts of tricyclopentagen, an elastomer, styrene-isoprene-styrene block copolymer (made by Nippon Zeon Co., Ltd., trade name “Quin 3 parts of Tack 3421 ”) were dissolved. Next, add jetyl aluminum chloride as the activator and 1,3-dichloro 1-propanol as the activity regulator to a concentration of 100 mmol / kg. Got. The specific gravity of solution A was 0.98.

Separately, 90 parts of dicyclopentagen and 10 parts of tricyclopentagen are mixed with styrene / isoprene / styrene block copolymer (trade name “Quintac 3421” manufactured by Nippon Zeon Co., Ltd.) as an elastomer. ) Was dissolved in 3 parts. Next, 2 parts of phenolic antioxidant (thiojetylene bis [3- (3,5-di-tert-butylenoyl 4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals Co., Ltd., trade name “Ilganox 1010”) is dissolved here. In addition, tri (dodecyl) ammonium molybdate as a polymerization catalyst was added to a concentration of 25 mmol / kg, and hexaclonal p-xylene was added as a polymerization accelerator to a concentration of 8.5 mmol / kg. And uniformly mixed and dispersed.

Wollastonite (manufactured by Kinsei Matech Co., Ltd., manufactured by Kinsei Matec Co., Ltd.) having a 50% volume cumulative diameter of 20 μm and an aspect ratio of 18 that has been surface-treated with bursilane as a fibrous filler. SH-400 ”) 42.75 parts by weight, heavy carbonated lucium (surface-treated with stearic acid as a particulate filler, 50% volume cumulative diameter 1.4 zm and aspect ratio 1) Sanyo Seimitsu Co., Ltd., trade name “SCP_E # 2300”) 14.25 parts by weight was added and mixed by stirring to obtain a reaction stock solution (solution B). The specific gravity of the obtained B liquid was 1.46.

[0055] (Formation and formation of coating film)

The male mold and the female mold are clamped, the female mold and the male mold are heated to 40 ° C and 90 ° C, respectively, and clamped at a pressure of 0.47 MPa per area of the molded body, and a RIM molding machine is used. Then, in the mixing head, 100 parts of A volume and 146 parts of B liquid were collided and mixed. The liquid was poured into the mold. After filling the reaction stock solution, the mold temperature was maintained for about 1 minute. Next, 200 mL of the coating agent was injected into the mold at a pressure of 20 MPa, and the mold temperature was maintained for 3 minutes. As the coating agent, 100 parts of paint mainly composed of urethane acrylate oligomer (manufactured by Dainippon Paint Co., Ltd., trade name “Praglas # 400”), 1 part of dibutyl phthalate and bis- (4_t-butylcyclohexyl) par Oxidicarbonate (trade name “Per-force Dox 16” manufactured by Kayaku Akuzo Co., Ltd.) A mixture of 1 part paste was used.

Thereafter, the mold was opened, and a bonnet-shaped body having a coating film was taken out. When the design appearance of the basin-shaped compact was visually observed, the coating film was coated on all surfaces with a thickness of 100 to 300 zm with no defects on the entire inner surface. Further, the total filler content in the molded resin portion was 30%.

[Comparative Example 1]

A basin-shaped product was obtained in the same manner as in Example 1 except that neither the fibrous filler nor the particulate filler was added. When the design appearance of the basin-shaped compact was visually observed, there was a linear unpainted portion in the concave portion of the basin-shaped compact, and a coating film could not be formed on the entire basin-shaped compact.

[Comparative Example 2]

A reaction stock solution (liquid B) was obtained in the same manner as in Example 1, except that the amount of the fibrous filler was 57 parts by weight and no particulate filler was added. The specific gravity of the obtained B liquid was 1.46. The molding and the formation of the coating film were performed in the same manner as in Example 1. When the design appearance of the obtained bonnet-shaped body was visually observed, the corner portions of the basin-shaped body were not painted. Further, the total filler content in the resin part of the molded body was 30%.

[Example 2]

Covers one central part of the female die of a forged aluminum male die and female die for forming a thin box-shaped concrete panel with a length of 1,500 mm, a width of 1,300 mm, and a height of 100 mm An injector with a maximum injection pressure of 40 MPa was used to inject the agent. Guides and weirs for forming burrs with a width of 30 mm and a thickness of 0.5 mm around the molded body and the runner part are formed on the outer periphery of the upper part of the female mold, and the two perpendicular lengths are 5 mm. To form a coating leakage preventing projection having a triangular cross section A groove was provided in the burr end of the male mold. The groove was formed so that the vertical portion of the protrusion for preventing leakage of the coating faced the molded body. In addition, a putty with a length of about 10 mm was carried in one part of the male mold groove as a projection defect for air discharge.

The male mold and female mold are clamped, the male mold and female mold are heated to 40 ° C and 90 ° C, respectively, and clamped at a pressure of 0.49 MPa per area of the molded body. In the mixing head, 400 parts of the same volume of A liquid (same as in Example 1) and 584 parts of B liquid (same as in Example 1) were collided and mixed, and the resulting reaction stock solution was The mold was poured and held at the mold temperature for about 1 minute.

Next, 800 mL of the same coating agent used in Example 1 was injected into the mold at a pressure of 20 MPa, and the mold temperature was maintained for 3 minutes.

Thereafter, the mold was opened, and a bonnet-shaped body having a coating film was taken out. When the design appearance of the basin-shaped compact was visually observed, the coating film was coated on all parts with a thickness of 100 to 300 / m with no defects on the entire inner surface. Further, the total filler content in the molded resin portion was 30%.

The following can be understood from the results of the examples and comparative examples.

That is, a polymerizable composition comprising a norbornene-based monomer, a polymerization catalyst, and 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. A molded body is obtained by bulk polymerization in the mold, and then a coating film is formed on the surface of the molded body by the in-mold coating method in the mold, thereby obtaining a coating film having no defects on the entire coated surface. I understand that. On the other hand, when only the fibrous filler is used, non-painted parts are produced in the corners of the basin-shaped molded body (Comparative Example 2), and if the filler is not used at all, It can be seen that a coating defect occurs in the concave portion of the basin-shaped compact (Comparative Example 1).

Claims

The scope of the claims

[1] A polymerizable composition comprising a norbornene monomer, a polymerization catalyst, and an inorganic filler comprising a fibrous filler having an aspect ratio of 5 to 100 and a particulate filler having an aspect ratio of 1 to 2. A reaction injection having a coating film on the surface thereof, characterized in that a molded body is obtained by bulk polymerization in a mold, and subsequently a coating film is formed on the surface of the molded body by an in-mold coating method in the mold. Manufacturing method of a molded object.

[2] The method for producing a reaction injection molded article according to claim 1, wherein the polymerizable composition is a metathesis polymerizable composition.

[3] The first or second claim, wherein the weight ratio of the fibrous filler to the particulate filler (fibrous filler / particulate filler) is 95/5 to 55/45 A method for producing the reaction injection molded article according to 1.

[4] The reaction injection molded article according to any one of claims 1 to 3, wherein the fibrous filler has a 50% volume cumulative diameter of 0.:! To 50 / m. Production method.

[5] The reaction injection molded article according to any one of claims 1 to 4, wherein the particulate filler has a 50% volume cumulative diameter of 0.:! To 50 / im. Production method.

[6] The reaction injection molding according to any one of claims 1 to 5, wherein the fibrous filler having an aspect ratio of 5 to 100 is wollastonite or whisker-like carbonic acid lucium. Body manufacturing method.

[7] The method for producing a reaction injection molded article according to any one of claims 1 to 6, wherein the particulate filler having an aspect ratio of 1 to 2 is calcium carbonate or calcium hydroxide.

[8] The force according to any one of claims 1 to 7, wherein the amount of the inorganic filler is 5 to 55 parts by weight with respect to 100 parts by weight of the total amount of the norbornene monomer and the catalyst. Reaction injection Molded body manufacturing method.

[9] A bulk polymer of a norbornene-based monomer containing an inorganic filler, obtained by the method for producing a reaction injection molded article according to any one of claims 1 to 8. A reaction injection molded article having a coating film on its surface.

[10] The reaction injection molded article having a coating film according to claim 9, which is a large panel.