JPS63112615A - Resin composition for rim formation - Google Patents

Abstract

PURPOSE:To obtain the title composition comprising a resin solution containing a specified (meth)acrylate compound and a urethane formation catalyst and a resin solution containing an isocyanate compound and a radical polymerization initiator, freed from troubles such as gelation in an apparatus and rapidly curable when both solutions are mixed together. CONSTITUTION:The title composition comprising two components of a solution (A) comprising a compound of mixture (a) mainly consisting of a component comprising at least one monomer (I) containing a (meth)acryloyl group and a hydroxyl group, wherein the (meth)acryloyl group content is equal to or greater than 2mol per 1,000g of said compound of mixture (a) and said compound or mixture (a) contains at least 25wt%, based on the total weight of monomer (I), monomer (I-a) having an internal hydroxyl group and a terminal (meth) acryloyl group, having an MW of 30-2,000 and having a main chain comprising a saturated ester and/or an alkyl ether chain, and a urethane formation catalyst and, optionally, a radical polymerization accelerator and a solution (B) comprising an isocyanate compound and a radical polymerization initiator.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a resin composition for RIM molding that simultaneously performs a radical polymerization reaction and a urethanization reaction, thereby achieving fast curing and excellent stability of the resin liquid. It is related to.

(Prior art) A resin check con molding method in which a preform or bricut reinforcement material is placed in a mold in advance, and after the mold is clamped, an unsaturated polyester resin containing a polymerization initiator and accelerator is injected. Although it is seen as a promising method for manufacturing medium-sized, high-mix FRP molded products, it has not yet become as popular as originally expected. One of the reasons for this is that the conventional resin molding method is limited in its ability to cure quickly due to mechanical limitations of its equipment, and compared to press molding methods such as SMC and SMC, it is less productive in terms of productivity. There are some points where it is clearly inferior.

In addition, in order to resolve the above-mentioned limitations, the use of RIM molding equipment, which has been put into practical use with urethane resins, etc., is being considered, but the stability of the resin liquid containing a polymerization initiator deteriorates as it is made to cure quickly. , troubles such as gelation occur frequently in the RIM molding apparatus, and are not necessarily satisfactory.

(Object of the Invention) Therefore, the object of the present invention is to make R
The object of the present invention is to provide a resin composition for RIM molding that does not cause troubles such as gelation in an IM molding apparatus and can exhibit fast curing properties by mixing two liquids.

(Structure of the Invention) As a result of intensive research, the present inventors have discovered that a resin liquid containing a specific (meth)acrylate compound and a urethanization reaction catalyst, and a resin liquid containing an isocyanate compound and a radical polymerization initiator. They discovered that the above object could be achieved by using a combination of the following, and thus failed to complete the present invention.

That is, the present invention provides [a monomer containing a (meth)acryloyl group and a hydroxyl group]
A compound or mixture (a) whose main component is one or more components of the compound (I) (hereinafter both collectively referred to as polymerizable reaction liquid (a)), the polymerizable reaction liquid The content m of (meth)acryloyl groups per 1000Q of (a) is at least 2 moles, and the monomer (I) has a hydroxyl group in the molecule and a (meth)acryloyl group at the end of the molecule, and has a molecular weight of 230 to 2000 and whose main chain is a saturated ester and/or alkyl ether chain (I-a) at least 25% by weight based on the total amount of monomer (1). Consists of two liquids: solution (8) containing liquid (a), a urethanization catalyst, and optionally a radical polymerization promoter, and solution (B) containing an isocyanate compound and a radical polymerization initiator. A resin composition for RIM molding characterized by:

The monomer (I) referred to in this application has at least 111 (meth)acryloyl groups and 111 hydroxyl groups each in one molecule! It is a compound represented by the following general formula (1).

General formula % formula % (1) However, n is 2 to 6! ! number, m is an integer from 1 to 5, and n
It is a value that satisfies the relational expression -m≧1, Ro is -H or -CH3, and R1 is an n-valent organic residue.

Examples of monomer (I) include R1 in general formula (1)
Typical examples include those whose groups fall under the following categories (a) to (c).

(a) When R1 is an alkyl or cycloalkyl organic residue of n(i[.

Specific examples of such monomer (I) include mono(meth)acrylates of glycols such as ethylene glycol, propylene glycol, butylene glycol, benzene glycol, hexylene glycol, cyclohexylene glycol, and hydrogenated bisphenol A: Examples include such compounds in mono(meth)acrylates or poly(meth)acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolethane, 1-limethylolpropane, pentaerythritol, and sorbitol.

(b) When R1 is a linear, star-like or branched zero-valent saturated or saturated organic residue having an ester bond and/or an ethyl bond.

Incidentally, the term "saturation" here means "substantially no copolymerizability with (meth)acryloyl groups in normal methods", for example, tetrahydrophthalic anhydride, 3.6 endomethylene-1.2, 3.6 tetrahydrophthalic anhydride, 3.6 endomethylene 1.2
．． 3.6, 7.7 Carbon-carbon double bonds such as hexachlorophthalic acid, double bonds in aromatic rings, etc. correspond to the saturation described here.

Specific examples of such monomer (I) include the monomers shown in the following sections (Row 1) to (Row 3).

(Row 1) (Meth)acrylic acid and one or more of the monomers (I>) shown in item (a) have a cyclic structure typified by ethylene oxide, propionoquinide, glycidyl methacrylate, tetrahydrofuran, etc. The reaction product obtained by ring-opening addition reaction of one or more compounds having an ether group M4 structure.

(Row 2) (Meth)acrylic acid, one or more of the monomers (I) shown in (A) or (Row 1), and one lactone compound represented by ε-caprolactone. Or the reaction product obtained by subjecting two or more kinds of compounds, if necessary, to a ring-opening addition reaction of one or more kinds of compounds having a cyclic ether group structure as described above.

(Row 3) (meth)acrylic acid, (in ring or one or more of the monomers (I) shown in (Row 1), succinic acid, phthalic acid,
Ring-opening copolymerization reaction of one or more saturated or saturated dicarboxylic acid anhydrides such as tetrahydrophthalic acid and one or more compounds having a cyclic ether group structure as described above. The resulting reaction product.

(c) When R1 is a reactive residue of an epoxy resin having at least two or more epoxy groups in the molecule.

An example of such a monomer (I) is a reaction product of an epoxy resin and (meth)acrylic acid,
Examples include so-called epoxy (meth)acrylates.The epoxy resin used in this case is not particularly limited and can be arbitrarily selected from known epoxy resins.

The polymerizable reaction solution (a) in the present invention contains at least 2 moles of (meth)acryloyl group per 1000 (), and is composed of one or more selected from the monomer (1). It contains at least 50% by weight of the components, preferably 70% by weight or more, and contains at least 25% by weight of the monomer (I-a) described below based on the total amount of monomer (I). If the content of (meth)acryloyl group is less than 2 mol/1000g, the heat resistance and rigidity of the final molded product will be low, which is not preferable.Moreover, monomer (I) and monomer ( In the case of a polymerizable reaction liquid (a) in which the content of I-a) is less than the above range, when it is actually used, the rapid curing characteristics during molding, the heat resistance of the obtained molded product, This is undesirable because the balance of toughness etc. becomes poor.

Other components of the polymerizable reaction solution (a) include the above (a).
Polyhydric alcohols with a valence of 2 or more and polyhydroxy compounds used in the polyurethane industry such as those exemplified in Section 2 (for example, "Plastic Materials Course 2" published by Nikkan Kogyo Shimbun)
"Polyurethane Resin" (written by Keiji Iwata, November 3, 1961)
Polyhydroxy compounds described on pages 55 to 69 of the 2nd edition published on the 0th), terminal human O-oxy unsaturated polyesters,
Furthermore, alcoholic hydroxyl group-containing compounds such as monohydric alcohols such as methanol, ethanol, and octyl alcohol as modifiers; aromatic vinyl compounds such as styrene, methylstyrene, halogenated styrene, and divinylbenzene;
Allyl compounds such as diallyl phthalate and triallyl cyanurate, maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, methyl (meth)acrylate-1~, butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylene Polymerization of (meth)acrylates other than monomer (I) such as glycol di(meth)acrylate, dibropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. Examples include vinyl compounds, and one or more of these compounds can be appropriately selected and used.

The monomer (I-a) corresponds to the monomer (I), and [has a hydroxyl group in the molecule and a (meth)acryloyl group at the end of the molecule, and has a molecular weight of 230 to 2000] This is a compound that satisfies the conditions of Compound J, in which the main chain is a saturated ester and/or alkyl ether chain. Examples of monomer (I-a) include the compounds listed in items (1) and (c) listed as examples of monomer (I). Among these, the compound described in (B) is more preferred, and the compound described in (R1) and (R2) is particularly preferred.

The urethanization catalyst is a reaction catalyst for producing a urethane group by the reaction of a water F1 group and an incyane-1 group, and can be appropriately selected from catalysts known in the polyurethane industry. (For example, in the reference book "Polyurethane Resin" mentioned above, section [2, Chemistry of polyurethane and its applications J (pages 7 to 43), especially the 8 tables (Tables 2, 14 to 2, 18) and each figure (Figures 2, 19 to 2,
Among the various compounds described in 25), amine compounds and tin compounds are particularly preferred. ) The radical polymerization accelerator may be selected from the radical polymerization accelerators commonly used in the unsaturated polyester industry, depending on the type and type as necessary, in relation to the radical polymerization initiator used in the solution (B) mentioned above. Used by a selected group. Typical examples of radical polymerization accelerators are published by Nikkan Kogyo Shimbun.
"2" of Plastic Materials Course 10 "Polyester Resin" (written by Eiichi Takiyama, 9th edition published August 30, 1980)
・Section 7.2 “Catalysts and Promoters” (pages 76-9), especially (
11) As described in the section on accelerators (pages 85 to 97).

The isodicyanate compound is a liquid substance composed of one or more isocyanate compounds containing, on average, about two or more isocyanate groups in one molecule. The isocyanate compound can be appropriately selected from those commonly used in the polyurethane industry. For example, 3. of the reference book "Polyurethane Resin" mentioned above. Raw materials for polyurethane 3.1 Isocyanate section and 3.2 Polyisocyanate (pages 46-51), especially Table 3.1
(pages 46 to 47) and Tables 3 and 2 (page 48), and isocyanate group-containing reaction products of these compounds and polyhydric alcohols of dihydric or higher valence as exemplified in item (a) above. (Preferably, an isocyanate group-containing reaction product obtained by reacting both the compounds at a ratio of 0.5 or less hydroxyl groups per isocyanate group).

The radical polymerization initiator can be appropriately selected from those commonly used in the unsaturated polyester resin industry. For example, in the reference book "Polyester Resins" mentioned above, in the section 2.7.2 Catalysts and promoters, (1) Specific peroxide catalyst section (pages 76 to 85), especially Tables 2 and 17 (
Examples include the compounds described on pages 78 to 79) and diazo compounds typified by azobisisobutyronitrile.

Solution (8) in the present invention is the above polymerizable reaction solution (a)
and a urethanization catalyst and, if necessary, a radical polymerization promoter, and the solution (*fB) contains an isocyanate compound and a radical polymerization initiator. In actual use, solution (A) and solution (B) have m of 0.5 to 2 isocyanate groups contained in solution (B) per 1 hydroxyl group contained in solution (A), Preferably, they are mixed in a ratio of 0.87 to 1.2 so that they are as uniform as possible. If the above-mentioned usage ratio is exceeded, the physical properties of the molded article will deteriorate, which is undesirable.

Further, the urethanation catalyst is 0.001 to 3%, preferably 0.01 to 2% of the total amount obtained by mixing the solution (A) and the solution (8), and is a radical polymerization initiator. is 0
．． 01 to 5, preferably 0.1 to 3% by weight, and the radical polymerization accelerator used if necessary in relation to the radical polymerization initiator is O to 3, preferably O to 2% by weight.
This is a can. If the amount of urethanization catalyst or radical polymerization initiator used is smaller, the curing speed will be slower, and even if the amount of these compounds or radical polymerization accelerator used is larger, the curing speed will not be correspondingly faster. Both are impractical.

The solution (^) and the solution (B) are (1) mixed with each other in a predetermined ratio to form a cured product, and (11) the physical properties of the cured product are based on the (meth)acryloyl contained in the polymerizable reaction liquid as a component. Group-containing royal isocyanate compound, and further containing trifunctional or higher functional components contained in the polyfunctional alcohol component a
(ifi) Even when unsaturated groups other than (meth)acryloyl groups are used, residual unsaturated groups in the cured product can be controlled by considering copolymerizability with (meth)acryloyl groups. R is used to form a wide variety of molded products depending on the application because it can easily reduce the
1,M It is extremely suitable as a resin composition for molding equipment.

When molding solution (A) and solution (B) using a RIM molding device, solution FA) is placed in one resin tank,
Pour solution (B) into the other resin tank and mix solution (A) and solution (B) in a predetermined ratio according to the usual method, then add reinforcing material in advance if necessary! i! This is accomplished by injecting the resin into a mold, followed by curing and demolding as a molded article. At this time, the mixing ratio of solution (A) and solution (B) can be freely selected according to the mechanical characteristics of each RIM molding device, but it is usually 1:10 to 1:10.
The range is 10:1. Of course, even in this case, this mixing ratio cannot escape the stoichiometric constraints of the solution (A) and solution (B) described above.

Solution (8) and solution (8) are cured only after being mixed in a predetermined ratio, and in order to shorten the curing time, they contain a urethanization catalyst, a radical polymerization accelerator, a radical polymerization initiator, etc. No matter how much you choose, the solution (
Since A) and solution (B) are stable for an extremely long time when used alone, there is no gelation trouble in the RIM molding apparatus.

When using the RIM molding resin composition of the present invention, it can be used together with various additives, fillers, reinforcing materials, etc. As for such additives, fillers, reinforcing materials, etc., those used in the unsaturated polyester resin industry, for example, can be effectively used as they are. - Examples include ultraviolet absorbers, radical polymerization inhibitors and retarders, colorants, internal layer agents, silane coupling agents, titanium coupling agents, thermoplastic resins, crosslinked rubber-like materials, etc. Additives such as shrinking agents, fillers such as calcium carbonate, clay, talc, glass balloons, Tetron, vinylon, etc.
Reinforcing materials for various taHa products such as glass, stainless steel, and iron.

The present invention will be explained in more detail with reference to examples below.

In principle, "1 part" in the examples indicates F parts by weight J. Note that the present invention is not limited to the scope of these examples.

Example 1 4 propylene oxide per mole of methacrylic'la
318 parts of tetrapropylene glycol monomethacrylate, 1-216 parts of 2-hydroxypropyl methacrylate, 0.8 parts of dibutyltin dilaurate, and cobalt octenoate (metal content: 8,000% by molar ratio) ) solution obtained by mixing 37 parts (Δ-1
) and 200 parts of tolylene diisocyanate and Tashi P
A solution (B-1) prepared by mixing 11 parts of butyl perbenzoate was respectively charged into a resin tank of a RIM molding apparatus. Next, a glass mat (Continuous Mat (Asahi Fiber M8624)) was set in advance, and solution (A-1) and solution (B -1) was injected while mixing in a RIM molding device at a ratio of 27 parts of the former to 10 parts of the latter. The properties of the flat plate obtained by demolding 2 minutes after the completion of injection are shown in Table 1.

Example 2 408 parts of a monomer (I-a-1) with a hydroxyl value of 138 obtained by reacting 1 mole of methacrylic acid with 3 moles of propylene oxide and 1 mole of phthalic anhydride according to a known method, trimethylolpropanedi A solution (A-2) obtained by mixing 270 parts of methacrylate, 67 parts of trimethylolpropane, 2 parts of dibutyltin dilaurate, and 3 parts of cobalt octenoate was mixed with 290 parts of tolylene diisocyanate and 20 parts of tert-butyl perbenzoate. A flat plate was obtained in the same manner as in Example 1 using the solution (B-2) obtained in Example 1. Note that the ratio of solution (A-2) and solution (B-2) used at this time was 26 parts to 10 parts. The properties of the flat plate are shown in Table 1.

Example 3 A monomer (I
-a-2) A solution (A-3) obtained by mixing 386 parts of diethylene glycol monomethacrylate, 174 parts of diethylene glycol monomethacrylate, 40 parts of styrene, 1.8 parts of dibutyltin dilaurate, and 4.5 parts of cobalt octenoate and 38 parts of propylene glycol
reaction product 2 of 261 parts of tolylene diisocyanate and 261 parts of tolylene diisocyanate
A flat plate was obtained in the same manner as in Example 1 using a solution (B-3) obtained by mixing 99 parts of tert-butyl perbenzoate and 18 parts of tert-butyl perbenzoate. At this time, solution (A-3) and solution (B-
The usage ratio for 3) was 2 parts to 1 part. The properties of the flat plate are shown in Table 1.

Chapter 1 Table

Claims (1)

[Scope of Claims] 1. A compound or mixture (a) whose main component is one or more monomers (I) containing a (meth)acryloyl group and a hydroxyl group, The content of (meth)acryloyl groups per 1000 g of the compound or mixture (a) is at least 2 moles, and the monomer (I) has a hydroxyl group in the molecule and a (meth)acryloyl group at the end of the molecule. Molecular weight is 230~
2000 and whose main chain is a saturated ester and/or alkyl ether chain (I-a). A solution (A) comprising a compound or mixture (a) containing at least 25% by weight based on the total amount of (I), a urethanization catalyst, and optionally a radical polymerization promoter, and an isocyanate compound and a radical polymerization initiator. A resin composition for RIM molding, characterized in that it consists of two liquids: a solution (B) comprising: 2. The RIM molding resin composition according to claim 1, wherein the monomer (I) contains at least two (meth)acryloyl groups in one molecule.