JPH0739460B2 - RIM molding resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a RIM molding resin composition capable of simultaneously performing a radical polymerization reaction and a urethanization reaction. More specifically, the present invention relates to a RIM molding resin composition that is fast-curing and has excellent stability of a resin solution.

[Conventional technology]

A resin injection molding method in which a preform or precut reinforcing material is installed in advance in a molding die, and after clamping the mold, an unsaturated polyester resin containing a polymerization initiator and a polymerization accelerator is injected Is seen as a promising method for manufacturing FRP molded products.

[Problems to be Solved by the Invention]

However, the resin injection molding method has not yet reached the prevalence as initially expected. As one of the causes, the conventional resin injection molding method has a limit to make the unsaturated polyester resin fast curable due to the restriction on the mechanism of the molding apparatus.
Compared with the press molding methods such as SMC and BMC, it is inferior in terms of productivity.

In addition, in order to solve the above-mentioned restrictions, the use of a RIM molding device that has been put to practical use with urethane resin or the like is also being considered. However, as the unsaturated polyester resin is made to cure faster, the stability of the resin solution containing the polymerization initiator becomes worse. For this reason, troubles such as gelation of the unsaturated polyester resin frequently occur in the RIM molding device, which is not always satisfactory.

The present invention has been made in view of the above-mentioned conventional problems, and its purpose is to cause troubles such as gelation in the RIM molding apparatus by being composed of two types of resin solutions having excellent stability. It is an object of the present invention to provide a RIM molding resin composition capable of exhibiting rapid curability by mixing both resin solutions without using the resin composition.

[Means for Solving the Problems]

The inventors of the present application, in order to achieve the above object, as a result of diligent studies on the resin composition for RIM molding, a resin solution containing a specific (meth) acrylate compound and a urethanization catalyst, an isocyanate compound and radical polymerization. By using in combination with a resin solution containing an initiator, without causing troubles such as gelation in the RIM molding apparatus, yet, RIM molding resin composition that can exhibit rapid curing property The present invention has been completed and the present invention has been completed.

That is, the present invention comprises a monomer having a (meth) acryloyl group and a hydroxyl group, a main chain consisting of a saturated ester and / or an alkyl ether, and a molecular weight of 230 to 2000, and a urethanization catalyst. (A) and a solution (B) containing an isocyanate compound and a radical polymerization initiator.

Further, the monomer has at least two (meta) in one molecule.
It is characterized by containing an acryloyl group.

The present invention will be described in detail below.

Monomer in the present invention (hereinafter referred to as monomer (I))
Is a compound containing at least one (meth) acryloyl group and one hydroxyl group in one molecule, and is a compound represented by the following general formula (1).

_{(CH 2 = CR 0 -COO)} m-R 1 - (OH) n - m ...... (1) ( where, n is an integer of from 2 to 6, m satisfies the relation n-m ≧ 1 1 To an integer of 5, R ₀ is hydrogen or a methyl group, R ₁
Is an n-valent organic residue. As a typical example of the above-mentioned monomer (I), compounds in which the R ₁ group in the general formula (1) corresponds to the following (A) to (C) can be mentioned.

(A) The R ₁ group is an n-valent alkyl-based organic residue or an n-valent cycloalkyl-based organic residue.

Specific examples of the monomer (I) corresponding to this are ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, cyclohexylene glycol, glycol mono (meta) such as hydrogenated bisphenol A. Acrylate: The compound or the like of mono (meth) acrylate or poly (meth) acrylate of a polyhydric alcohol having a valence of 3 or more, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.

(B) The case where the R ₁ group is a linear, star or branched, n-valent saturated or saturated organic residue having an ester bond and / or an ether bond.

In addition, the above-mentioned "saturability" means that "there is substantially no copolymerizability with a (meth) acryloyl group in a usual method". For example, tetrahydrophthalic anhydride,
Carbon-carbon double bond such as 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride and 3,6-endomethylene-1,2,3,6,7,7-hexachlorophthalic acid The double bond of the aromatic ring and the like are bonds corresponding to the above-mentioned saturation property.

Specific examples of the monomer (1) corresponding to this include compounds corresponding to the following (b-1) to (b-3). That is, (b-1) one or more compounds of (meth) acrylic acid and the compounds exemplified in (a) above, and a cyclic ether represented by ethylene oxide, propion oxide, glycidyl methacrylate, tetrahydrofuran, or the like. The reaction product obtained by subjecting one or more compounds having a group structure to a ring-opening addition reaction.

(B-2) (meth) acrylic acid, one or more of the compounds exemplified in the above (a) or (b-1), and one of lactone compounds represented by ε-caprolactone or the like. The said reaction product obtained by ring-opening addition reaction of 2 or more types and 1 or 2 or more types of the compound which has the cyclic ether group structure shown in said (b-1) further as needed.

(B-3) (meth) acrylic acid, one or more of the compounds exemplified in the above (A) or (B-1), represented by succinic acid, phthalic acid, tetrahydrophthalic acid and the like. A ring-opening addition reaction is carried out between one or more kinds of saturated or saturated dicarboxylic acid anhydrides and one or more kinds of compounds having a cyclic ether group structure shown in (b-1) above. The reaction product obtained.

(C) The R ₁ group is a reaction residue of an epoxy resin having at least two epoxy groups in the molecule.

Specific examples of the monomer (I) corresponding to this include a so-called epoxy (meth) acrylate which is a reaction product of an epoxy resin and (meth) acrylic acid. The epoxy resin is not particularly limited and can be arbitrarily selected from known epoxy resins.

The above compound or mixture in the present invention (hereinafter, both are collectively referred to as a polymerizable reaction solution (a)) is 1000 g.
At least 50% by weight, preferably at least 70% by weight, of at least 2 mol of (meth) acryloyl group and at least one component selected from the monomer (I). In addition, at least 25% by weight of the below-mentioned monomer (hereinafter referred to as the monomer (Ia)) is contained with respect to the total amount of the above-mentioned monomer (I). If the content of the (meth) acryloyl group is less than 2 mol / 1000 g, the heat resistance and rigidity of the finally obtained molded article will be low, which is not preferable. Further, when the content of the monomer (I) or the monomer (Ia) is less than the above range, the polymerizable reaction liquid (a) may be used at the time of molding when actually used. It is not preferable because the rapid curing property of (2) and the heat resistance, toughness, etc. of the obtained molded product are unbalanced.

Other components of the polymerizable reaction liquid (a) include polyhydric alcohols having a valence of 2 or more as exemplified in (a) above, and polyhydroxy compounds used in the polyurethane industry (for example, published by Nikkan Kogyo Shimbun). Plastic material course 2 "Polyurethane resin" (Keiji Iwata, November 1969)
30-day edition, 2nd edition), pages 55-69, polyhydroxy compounds), terminal hydroxy unsaturated polyesters, and alcohols such as monohydric alcohols such as methanol, ethanol and octyl alcohol as modifiers. Hydroxyl group-containing compound; aromatic vinyl compound such as styrene, methylstyrene, halogenated styrene, divinylbenzene,
Allyl compounds such as diallyl phthalate and triallyl cyanurate, maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylene glycol di (meth)
Polymerizable vinyl compounds such as (meth) acrylates other than the monomer (I) such as acrylate, dipropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. Among these compounds, one kind or two or more kinds can be appropriately selected and used.

The monomer (I-a) is a compound corresponding to the monomer (I), and "has a hydroxyl group in the molecule, contains a (meth) acryloyl group at the end of the molecule, and has a molecular weight of 230 ~ 2000
And the main chain is a compound composed of a saturated ester and / or an alkyl ether. Examples of the monomer (Ia) include the compounds among the compounds described in (b) and (c) exemplified as the monomer (I). Among them, the compound among the compounds described in (b) is more preferable, and the compound among the compounds described in (b-1) and (b-2) is particularly preferable.

The urethanization catalyst in the present invention is a catalyst provided when a hydroxyl group and an isocyanate group react to generate a urethane group, and can be appropriately selected and used from catalysts known in the polyurethane industry. (For example, in the above-mentioned reference book "Polyurethane resin", "2. Polyurethane chemistry and its application" (pages 7 to 43), particularly pages 26 to 31 (Tables 2-14 to 2).・ 18) and each figure (Fig. 2 ・ 19〜)
Various compounds shown in FIGS. 2 and 25) are preferable, and among them, amine compounds and tin compounds are preferable. ).

The radical polymerization accelerator is appropriately used in combination with the radical polymerization initiator used in the solution (B), if necessary, from among the radical polymerization accelerators generally used in the unsaturated polyester resin industry. The quantity and quantity are selected and used. A typical example of the radical polymerization accelerator is a plastic material course 10 "polyester resin" issued by Nikkan Kogyo Shimbun (Eiichiro Takiyama, published on August 30, 1980, No. 9).
Edition, "2.7.2 Catalysts and Promoters" (pages 76-79)
Page), especially as described in the section of (ii) accelerator (pages 85 to 97).

The isocyanate compound in the present invention means 1 on average.
It is a liquid substance composed of one or more isocyanate compounds containing about 2 or more isocyanate groups in the molecule. The isocyanate compound can be appropriately selected and used from the isocyanate compounds generally used in the polyurethane industry. For example, refer to “3. Polyurethane raw materials 3.
1 isocyanate and 3.2 polyisocyanate (pages 46 to 51) ”, particularly the compounds described in Table 3.1 (pages 46 to 47) and Table 3.2 (pages 48) and these compounds. Isocyanate group-containing reaction product with a dihydric or higher polyhydric alcohol as exemplified in (a) above (preferably obtained by reacting both compounds at a ratio of 0.5 equivalent or less per 1 equivalent of isocyanate group). And an isocyanate group-containing reaction product).

The radical polymerization initiator in the present invention can be appropriately selected and used from the radical polymerization initiators generally used in the unsaturated polyester resin industry. For example, refer to "2.
"7.2 Catalysts and promoters", (i) Organic peroxide catalyst (pages 76 to 85), particularly the compounds and azobis described in Table 2.17 (pages 78 to 79). Examples thereof include diazo compounds represented by isobutyronitrile.

The solution (A) in the present invention comprises the above-mentioned polymerizable reaction solution (a), a urethanization catalyst and, if necessary, a radical polymerization accelerator, and the solution (B) contains an isocyanate compound and a radical polymerization initiator. Comprises. In actual use, the solution (A) and the solution (B) contain 0.5 to 2, and preferably 0.7 to 2 isocyanate groups in the solution (B) per one hydroxyl group contained in the solution (A).
They are mixed so as to be as uniform as possible in a ratio of 1 to 1.2. When the amount exceeds the above range, the physical properties of the resulting molded article deteriorate, which is not preferable.

Further, the amount of the urethane-forming catalyst with respect to the amount (total amount) of the mixed solution obtained by mixing the solution (A) and the solution (B) is
0.001% to 3% by weight, preferably 0.01% to 2% by weight, and the amount of radical polymerization initiator is 0.01% to 5% by weight, preferably 0.1% to 3% by weight, Further, the amount of the radical polymerization accelerator optionally used in relation to the radical polymerization initiator is 0% by weight to 3% by weight, preferably 0% by weight to 2% by weight. If the amount of the urethanization catalyst used or the amount of the radical polymerization initiator used is less than the above-mentioned weight%, the curing rate will be slow, which is not practical. Further, even if the amount of the urethanization catalyst used, the amount of the radical polymerization initiator used, or the amount of the radical polymerization accelerator used is more than the above-mentioned weight%, the curing speed does not become so high as to be commensurate with it, so that it is not practical.

The solution (A) and the solution (B) become a cured product by mixing (i) with each other in a predetermined ratio, and (ii) the physical properties of the cured product are the same as those of the polymerizable reaction liquid (a) which is a constituent component. The content can be adjusted by the content of the (meth) acryloyl group contained, the content of the isocyanate compound, and the content of the trifunctional or higher functional component contained in the polyfunctional alcohol component (the component containing a hydroxyl group), and ( iii) Even when an unsaturated group other than the (meth) methacryloyl group is used in combination, the amount of the residual unsaturated group in the cured product can be easily adjusted by selecting in consideration of the copolymerizability with the (meth) acryloyl group. It is extremely suitable as a resin composition for a RIM molding apparatus that forms a wide variety of molded products depending on the application because it can be reduced. That is, the solution (A) and the solution (B) are extremely suitable as the RIM molding resin composition.

When molding the solution (A) and the solution (B) using the RIM molding device, the solution (A) is put into one resin tank and the solution (B) is put into the other resin tank, and a usual method is used. According to the procedure described above, the solution (A) and the solution (B) are mixed at a predetermined ratio, and if necessary, the mixed solution is injected into a molding die (mold) in which a reinforcing material is previously arranged. It is achieved by demolding as a molded product. At this time, the mixing ratio of the solution (A) and the solution (B) can be freely selected according to the mechanical characteristics of each RIM molding device, but is usually in the range of 1:10 to 10: 1. Of course, even in this case, the above mixing ratio cannot avoid the stoichiometric restriction of the solution (A) and the solution (B) described above.

The solution (A) and the solution (B) are cured only when mixed at a predetermined ratio. Moreover, even if the amounts of the urethanization catalyst, the radical polymerization accelerator, the radical polymerization initiator and the like used are selected so that the curing time is extremely short, the solution (A) and the solution (B) are independent of each other. In the state, it is stable for a very long time. Therefore, there is no trouble such as gelation of resin in the RIM molding device. Then, the solution (A) and the solution (B) having the above-mentioned constitutions are RIM
By molding using a molding apparatus, it is possible to obtain a molded product having various physical properties such as tensile strength, tensile elastic modulus, bending strength, bending elastic modulus, and Barcol hardness.

The RIM molding resin composition according to the present invention can be used together with various additives, fillers, reinforcing materials and the like. Such additives, fillers, reinforcing materials, etc.
For example, those used in the unsaturated polyester resin industry can be effectively used as they are. Specifically, the additives include ultraviolet absorbers, radical polymerization inhibitors and retarders, colorants, internal release agents, silane coupling agents, titanium coupling agents, thermoplastic resins and crosslinked rubber-like substances. Typical examples include low-contraction agents, fillers include calcium carbonate, clay, talc, glass balloons, etc., and reinforcing materials include polyester, vinylon, glass, stainless steel, iron, and other various fiber products. Etc.

[Work]

According to the above configuration, by being composed of two types of resin solutions having excellent stability, without causing troubles such as gelation in the RIM molding apparatus, by mixing both resin solutions, It is possible to provide a RIM molding resin composition capable of exhibiting rapid curability, that is, a RIM molding resin composition which is fast curable and has excellent stability of a resin solution.

Then, by molding the RIM molding resin composition of the above configuration using a RIM molding device, tensile strength and tensile modulus,
It is possible to obtain a molded product having various physical properties such as bending strength, bending elastic modulus, and Barcol hardness.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to these Examples. All "parts" described below represent "parts by weight".

(Example 1) Monomethacrylate 318 parts of tetrapropylene glycol obtained by addition reaction at a ratio of 4 mol of propylene oxide per mol of methacrylic acid and 216 parts of 2-hydroxypropyl methacrylate (above, monomer (a )) And 0.8 part of dibutyltin dilaurate and 37 parts of cobalt octenoate (metal content 8% by weight) (above,
Solution (A) obtained by mixing with (urethane-forming catalyst), and solution obtained by mixing 200 parts of tolylene diisocyanate (isocyanate compound) and 11 parts of t-butyl perbenzoate (radical polymerization initiator) (B ), RIM
Two resin tanks of the molding apparatus were separately charged.

Next, glass mat (Continuous mat; Asahi Fiber Co., Ltd., M8624) 9 mold (45 cm) as a reinforcing material
(For a 45 cm flat plate), and the above solution (A) and solution (B) were charged from the injection port on the lower side of the mold kept at a temperature of 120 ° C. to 27 parts of solution (A): solution (B ) The mixture was poured into the RIM molding apparatus while mixing so that the ratio was 10 parts.
Two minutes after the completion of the injection, the mold was removed to obtain a flat plate (molded product). The physical properties of this flat plate (tensile strength, tensile elastic modulus, bending strength, bending elastic modulus, barcol hardness) were measured, and the results are shown in Table 1.

Example 2 According to a known method, 1 mol of methacrylic acid was reacted with 3 mol of propylene oxide and 1 mol of phthalic anhydride to obtain 408 parts of a monomer (Ia) having a hydroxyl value of 138, and trimethylolpropanediene. Methacrylate 270 parts (or more, monomer (a)), and trimethylolpropane (other components of the polymerizable reaction liquid (a)) 67 parts, dibutyltin dilaurate 2 parts and cobalt octenoate 3 parts (or more, (Urethane-forming catalyst) and a solution (A) obtained by mixing
Tolylene diisocyanate (isocyanate compound) 29
Using the solution (B) obtained by mixing 0 parts and 20 parts of t-butyl perbenzoate (radical polymerization initiator), the same molding as in Example 1 was carried out to obtain a flat plate (molded product). The use ratio of the solution (A) and the solution (B) was 26 parts of the solution (A): 10 parts of the solution (B). The physical properties of this flat plate were measured, and the results are shown in Table 1.

Example 3 According to a conventional method, 1 mol of succinic anhydride was added to 1 mol of 2-hydroxypropyl methacrylate, and then 1.1 mol of glycidyl methacrylate was added and reacted to obtain 386 parts of a monomer (Ia), diethylene glycol. 174 parts of monomethacrylate (above, monomer (a)) and 40 parts of styrene (other components of the polymerizable reaction liquid (a)), 1.8 parts of dibutyltin dilaurate and 4.5 parts of cobalt octenoate (above, urethane (A), a reaction product (isocyanate compound) of 38 parts of propylene glycol and 261 parts of tolylene diisocyanate, and t-butyl perbenzoate (radical polymerization initiator). Solution (B) obtained by mixing 18 parts
Is used to perform the same molding as in Example 1 to obtain a flat plate (molded product)
Got The ratio of the solution (A) and the solution (B) used was 2 parts of the solution (A): 1 part of the solution (B). The physical properties of this flat plate were measured, and the results are shown in Table 1.

[Effect of the invention] According to the above configuration, by comprising two types of resin solutions having excellent stability, without causing troubles such as gelation in the RIM molding apparatus, both resin solutions By mixing, RIM molding resin composition capable of exhibiting rapid curing property, that is, an effect that it is possible to provide a RIM molding resin composition that is fast curing and has excellent stability of the resin solution. Play.

Then, by molding the RIM molding resin composition of the above configuration using a RIM molding device, tensile strength and tensile modulus,
It is possible to obtain a molded product having various physical properties such as bending strength, bending elastic modulus, and Barcol hardness.

Claims (2)

[Claims] 1. A monomer containing a (meth) acryloyl group and a hydroxyl group, having a main chain of a saturated ester and / or an alkyl ether and having a molecular weight of 230 to 2000, and a urethanization catalyst. And a solution (B) containing an isocyanate compound and a radical polymerization initiator. 2. The RIM molding resin composition according to claim 1, wherein the monomer contains at least two (meth) acryloyl groups in one molecule.