JP3071520B2 - Method for producing epoxy (meth) acrylates, epoxy (meth) acrylates obtained by the method, and polymerizable composition containing the epoxy (meth) acrylates - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel epoxy (meth)
A method for producing an acrylate, an epoxy (meth) acrylate obtained by the method, and a vinyl monomer copolymerizable with the epoxy (meth) acrylate and the epoxy (meth) acrylate It relates to a polymerizable composition.

[0002] Epoxy (meth) acrylates obtained by reacting bisphenol-type epoxy resins or novolak-type epoxy resins with (meth) acrylic acid are widely used. For example, molded articles obtained by curing a polymerizable composition containing the epoxy (meth) acrylates are used for bathtubs, water tank panels, outer plates and exterior materials of automobiles, and the like. There are various molding methods for curing the polymerizable composition to obtain a molded product, for example, a compression molding method using a sheet molding compound (SMC), a bulk molding compound (BMC)
Injection molding method, hand-up method or pultruding method for impregnating and curing the polymerizable composition in mats, fabrics and strands of reinforcing fibers, and introducing the polymerizable composition into the mold for rapid in-mold polymerization There are a resin transfer molding method (RTM) and a reaction injection molding method (RIM).

The present invention relates to a method for producing a novel epoxy (meth) acrylate which can be applied to the above-mentioned molded article or molding method, an epoxy (meth) acrylate obtained by the production method, and the epoxy (meth) acrylate And a polymerizable composition comprising a vinyl monomer copolymerizable with the epoxy (meth) acrylates.

[0004]

2. Description of the Related Art Conventionally, when an epoxy (meth) acrylate is produced by reacting a bisphenol type epoxy resin or a novolak type epoxy resin with (meth) acrylic acid, a catalyst is used in a reaction system. Such catalysts include, for example, quaternary ammonium salts, tertiary amines, lithium halides, phosphines, phosphonium halides and the like.

However, according to the above-mentioned conventional means, the resulting epoxy (meth) acrylate is colored brown due to the catalyst used, and the epoxy (meth) acrylate or a mixture containing the epoxy (meth) acrylate is obtained. When the polymerizable composition is cured, there is a drawback that the coloring is further induced and only a molded product having a poor hue can be obtained. Even if a pigment is added, the disadvantage impairs the color development.

[0006]

The problem to be solved by the present invention is that the epoxy (meth)
When the acrylates are colored brown, and when the epoxy (meth) acrylates or the polymerizable composition containing the same are cured, the acrylates are further colored, and only a molded article having a poor hue can be obtained. is there.

[0007]

Means for Solving the Problems Thus, the present inventors have
As a result of intensive studies to solve the above problems, an epoxy resin having at least two epoxy groups in the molecule,
Epoxy (meth) acrylates obtained by reacting an organic phosphonium sulfonate having a carboxyl group in the molecule with (meth) acrylic acid at a predetermined functional group molar ratio without using a catalyst are suitable and suitable. I found something.

That is, the present invention provides the following A, B and C
Is an epoxy group which is a functional group of A / a carboxyl group which is a functional group of B and C = 0.9 to 1.1 (functional group molar ratio)
A method for producing epoxy (meth) acrylates, characterized by reacting without using a catalyst, an epoxy (meth) acrylate obtained by the production method, and an epoxy (meth) acrylate and the epoxy The present invention relates to a polymerizable composition containing a vinyl monomer copolymerizable with (meth) acrylates.

A: an epoxy resin having at least two epoxy groups in a molecule B: an organic phosphonium sulfonate having a carboxyl group in a molecule C: (meth) acrylic acid

The epoxy resin of A used in the present invention includes 1) a bisphenol-type epoxy resin obtained from a bisphenol and epihalohydrin, 2) an average of 2 per molecule obtained from a condensed phenol or condensed alkyl-substituted phenol and epihalohydrin. Novolak type epoxy resins having more than two epoxy groups, 3) polybasic acid glycidyl ester type epoxy resin, 4) polyhydric alcohol glycidyl ether type epoxy resin, and the like.

The organic phosphonium sulfonates of B used in the present invention include: 1) phosphonium sulfonatomonocarboxylates such as phosphonium sulfobenzoate and phosphonium phthalene monocarboxylate; 2) phosphonium sulfonatophthalate and phosphonium sulfoisophthalate. ,
Sulfo aromatic dicarboxylic acid phosphoniums such as phosphonium terephthalate and phosphonaphthalenedicarboxylate, 3) α-sulfo fatty acid phosphoniums such as α-sulfopalmitate and α-sulfolaurate, and 4) monophosphonium sulfosuccinate And monoalkyl esters of phosphonium sulfoaliphatic dibasic acids such as alkyl esters and phosphonium sulfoalkyl succinic acid monoesters.

Examples of the phosphonium group constituting the organophosphonium sulfonate B include 1) tetraalkylphosphonium, 2) phosphonium having an alkyl group substituted with OH and CN, 3) aromatic phosphonium, 4)
And phosphonium having an aralkyl group.

The above examples of the phosphonium organic sulfonate B have been exemplified above, but among these, tetraethylphosphonium sulfobenzoic acid, tetrabutylphosphonium sulfobenzoic acid, tetraethylphosphonium-5-sulfoisophthalic acid, tetrabutylphosphonium-5-sulfoisophthalic acid Acids are preferred.

The combination of the epoxy resin of A and the organic phosphonium sulfonate of B is not particularly limited, but when a bisphenol type epoxy resin is used as A, B
It is preferable to use a tetraalkylphosphonium sulfoaromatic dicarboxylate as A, and when using a novolak type epoxy resin having an average of more than two epoxy groups in the molecule as A, tetraalkylphosphonium sulfoorganomonocarboxylate as B It is preferably used.

In the present invention, one or more of the epoxy resin of A, one or more of the phosphonium organic sulfonate of B, and (meth) acrylic acid of C are the functional groups contained in A. Epoxy group / carboxyl group which is a functional group contained in B and C = 0.9 to 1.1 (functional group molar ratio)
To react. Outside of this range, the physical properties of the finally obtained molded product are reduced.

The ratio of the organic phosphonium sulfonate B and the (meth) acrylic acid C to be used in the reaction is such that the carboxyl group contained in B / the carboxyl group contained in B and C = 0.001 to 0.1 ( (Molar ratio of carboxyl group). This is because A, B and C are sufficiently reacted to further improve the physical properties of the finally obtained molded product.

In the present invention, the reaction of A, B and C itself can be carried out by a known method. However, since the organic phosphonium sulfonate B inherently has a catalytic effect, the reaction is carried out separately as in the prior art. There is no need to use a catalyst.
Predetermined amounts of A, B and C are charged into a reaction vessel and reacted under heating to obtain desired epoxy (meth) acrylates. The reaction temperature is usually 60 to 150 ° C,
Preferably it is 80-140 degreeC. Styrene in the reaction system,
A vinyl monomer copolymerizable with epoxy (meth) acrylates such as methyl methacrylate can also be used as a solvent.

In the reaction of A, B and C, a stabilizer is preferably used in order to prevent polymerization of (meth) acrylic acid of C and epoxy (meth) acrylates formed by the reaction. As such a stabilizer, a known radical inhibitor can be used. These include, for example, p-benzoquinone, hydroquinone, catechol, pt-butylcatechol, 2,5-di-t-butylhydroquinone, hydroquinone monomethyl ether, etc., among which pt-butylbutylcatechol and hydroquinone Monomethyl ether is preferred.

The epoxy (meth) acrylates thus obtained contain epoxy (meth) acrylates having a structure in which phosphonium sulfonate groups are introduced in a predetermined molar ratio in the molecule. Such epoxy (meth)
Acrylates can be used as a polymerizable composition prepared by adding a vinyl monomer copolymerizable therewith. Such vinyl monomers include 1) styrene,
Vinyl aromatic monomers such as methylstyrene, divinylbenzene and vinyltoluene; 2) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, ethyl acrylate, butyl acrylate and the like (Meth) acrylic esters, 3) vinyl acetate, 4) diallyl phthalate, and the like. One or more of these can be used as appropriate, but from the viewpoint of the physical properties of the finally obtained molded product, look,
Styrene, methyl methacrylate or mixtures thereof are preferred.

[0020] The above polymerizable composition is an epoxy (meth)
Acrylates 30 to 90% by weight and vinyl monomer 70
Those containing from 10 to 10% by weight are preferred. This is because the viscosity of the polymerizable composition is kept low to improve molding workability and further improve the physical properties of the finally obtained molded product.

The polymerizable composition of the present invention may further contain an inorganic powdery filler. Examples of such an inorganic powdery filler include alumina trihydrate (Al ₂ O ₃ .3H ₂ O), calcium carbonate, silica, talc, powdered glass and the like.

The epoxy (meth) acrylates and the polymerizable composition of the present invention can be cured to form a molded product. When curing, conventional epoxy (meta)
The formulations provided for acrylate resins and unsaturated polyester resins can be applied. For example, radical polymerization can be performed using various curing agents and curing accelerators.

The epoxy (meth) acrylates and the polymerizable composition of the present invention can be prepared by a pultruding method, an injection molding method using BMC, a compression molding method using SMC, a resin transfer molding method,
A molded product can be obtained by applying an in-mold molding method such as a reaction injection molding method.

Hereinafter, examples and the like will be described in order to make the configuration and effect of the present invention more specific, but the present invention is not limited to the examples. In the following examples, parts are parts by weight, and% is% by weight.

[0025]

【Example】

Test Category 1 {Production of epoxy (meth) acrylates and evaluation thereof} Example 1 In a reaction vessel, 380 parts of bisphenol A type epoxy resin (Epicoat 828, epoxy equivalent 190, manufactured by Yuka Shell Epoxy) (epoxy equivalent) 2.0 mol), 172 parts of methacrylic acid (corresponding to 2.0 mol of carboxyl equivalent), 2.0 parts of tetrabutylphosphonium-5-sulfoisophthalic acid (corresponding to 0.008 mol of carboxyl equivalent), as a stabilizer 0.2 part of methquinone was taken and heated gradually. When the temperature exceeded 90 ° C., the contents became transparent and generated heat, and reached 140 ° C. 130-140
C. for 3 hours to complete the reaction. The obtained product was an epoxy (meth) acrylate and had an acid value of 9.0.

Examples 2 to 4 In the same manner as in Example 1, Examples 2 to 4 were performed to obtain epoxy (meth) acrylates.

Example 5 A novolak type epoxy resin (DEN4
31, average number of epoxy groups 2.2, epoxy equivalent 175,
350 parts (made by Dow Chemical Co., Ltd.)
0 mol), 172 parts of methacrylic acid (corresponding to 2.0 mol of carboxyl equivalent mol), tetrabutylphosphonium-
4.6 parts of 3-sulfobenzoic acid (corresponding to 0.02 mol of carboxyl equivalent), 263 parts of styrene, and 0.2 part of methquinone as a stabilizer are reacted at 80 ° C. for 40 hours to give an acid value of 6.5. Epoxy (meth) acrylates 6
A styrene solution containing 6.7% was obtained.

Comparative Example 1 The procedure of Example 1 was repeated, except that 2.0 parts of trimethylbenzylammonium chloride was used as a catalyst instead of 2.0 parts of tetrabutylphosphonium-5-sulfoisophthalic acid. ) Acrylates were obtained.
The acid value was 9.2.

Comparative Examples 2 to 4 Comparative Examples 2 to 4 were performed in the same manner as in Comparative Example 1 to obtain epoxy (meth) acrylates.

Comparative Example 5 4.6 tetrabutylphosphonium-3-sulfobenzoic acid
Parts, and 2.0 parts of trimethylbenzylammonium chloride was used as the catalyst, except that a styrene solution containing 66.7% of epoxy (meth) acrylates having an acid value of 6.4 was used. Obtained.

The epoxy resin, phosphonium organosulfonate, (meth) acrylic acid, the type and amount of catalyst used, and the acid value and hue of the epoxy (meth) acrylates obtained are shown in Table 1. Was.

[0032]

[Table 1]

Note) In Table 1, Amount used: upper part: parts, lower part: epoxy equivalent mole or carboxyl equivalent mole A: epoxy resin B: phosphonium organic sulfonate C: (meth) acrylic acid * 1: bisphenol A type epoxy resin ( Epicoat 8
No. 28, epoxy equivalent 190, manufactured by Yuka Shell Epoxy Co., Ltd.) * 2: Novolak type epoxy resin (DEN43)
1, average number of epoxy groups: 2.2, epoxy equivalent: 175, manufactured by Dow Chemical Company) * 3: tetrabutylphosphonium-5-sulfoisophthalic acid * 4: tetraethylphosphonium-5-sulfoisophthalic acid * 5: tetrabutylphosphonium-3 -Sulfobenzoic acid * 6: Methacrylic acid * 7: Trimethylbenzylammonium chloride * 8: Triethylamine * 9: Triphenylphosphine * 10: Tetrabutylphosphonium chloride * 11: Gardner number (JIS K-5400)

Test section 2 {Preparation of polymerizable composition and production of molded article by cast molding method and evaluation thereof} Preparation of polymerizable composition Epoxy (meth) acrylates obtained in test section 1 and vinyl monomer And the resulting mixture was uniformly dissolved to prepare a polymerizable composition shown in Table 2. However, Example 11 and Comparative Example 9
The styrene solution of the epoxy (meth) acrylates obtained in Test Category 1 was used directly as a polymerizable composition.

..Manufacture of molded articles Two glass plates (25 cm × 25 cm) each having a thickness of 5 mm and an outer diameter of 5 mm
, And a casting tank having a clearance of 3 mm was prepared. Then, a solution obtained by uniformly dissolving the radical initiator described in Table 2 in the polymerizable composition was poured into the casting tank, and the casting tank was left for 1 hour in a constant temperature bath at 80 ° C. Manufactured.

Evaluation of Molded Article The appearance of the molded article produced above was evaluated according to the following criteria, and the results are shown in Table 2. ◎: almost colorless ○: pale yellow ×: brown XX: dark brown

[0037]

[Table 2]

Note) In Table 2, the amount used: parts ST: styrene MMA: methyl methacrylate radical initiator: dibenzoyl peroxide

Test Category 3 {Preparation of Polymerizable Composition and Production of Molded Product by Resin Transfer Molding Method (RTM) and Its Evaluation} Preparation of Polymerizable Composition Epoxy (meth) acrylate obtained in Test Category 1 And a vinyl monomer were mixed and uniformly dissolved, and then an inorganic powdery filler and a curing accelerator were uniformly mixed therein to prepare a polymerizable composition shown in Table 3. However, in Example 16 and Comparative Example 12, the styrene solution of the epoxy (meth) acrylates obtained in Test Category 1 was used as it was, and the mixture obtained by uniformly mixing the inorganic powdery filler and the curing accelerator was polymerized. The composition was used.

..Production of molded articles into a nickel electroformed flat mold heated to 35.degree.
% Glass strand continuous mat (Unifilomat U-750, manufactured by Nippon Electric Glass Co., Ltd.)
Was charged and the mold was closed at 2.5 kg / cm ² . Then, the above polymerizable composition and the radical initiator solution shown in Table 3 were separately and quantitatively transferred using a metering pump, and the two solutions were uniformly mixed through a static mixer and injected into a mold. Infusion was stopped when the infusate began to flow out of the clearance opposite the inlet. The mold was removed 30 minutes after the injection was stopped to produce a molded product.

Evaluation of Molded Article The appearance of the molded article produced above was evaluated according to the following criteria. The results are shown in Table 3. ：: Almost colorless ○: Light color ×: Brown XX: Dark brown

[0042]

[Table 3]

Note) In Table 3, the amount used: parts ST: styrene MMA: methyl methacrylate Inorganic powder filler: alumina trihydrate Curing accelerator: cobalt naphthenate Radical initiator: methyl acetoacetate peroxide 25% Solution consisting of 75% dimethyl phthalate (Percure SA, manufactured by NOF Corporation)

As is apparent, the present invention described above includes epoxy (meth) acrylates having good hue,
As a result, there is an effect that a molded product can be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-63821 (JP, A) JP-A-2-251520 (JP, A) JP-A-2-97511 (JP, A) JP-A 64-64 90258 (JP, A) JP-A-62-89719 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/14-59/17 C08F 299/02

Claims (6)

(57) [Claims] 1. The following A, B, and C are separately represented by an epoxy group which is a functional group of A / a carboxyl group which is a functional group of B and C = 0.9 to 1.1 (functional group molar ratio). A method for producing epoxy (meth) acrylates, wherein the reaction is performed without using a catalyst. A: Epoxy resin having at least two epoxy groups in a molecule B: Organic phosphonium sulfonate having a carboxyl group in a molecule C: (meth) acrylic acid 2. The method for producing epoxy (meth) acrylates according to claim 1, wherein A is a bisphenol type epoxy resin and B is a tetraalkylphosphonium sulfoaromatic dicarboxylate. 3. The epoxy (meth) acrylates according to claim 1, wherein A is a novolak-type epoxy resin having an average of more than two epoxy groups in a molecule, and B is a tetraalkylphosphonium sulfoorganomonocarboxylate. Manufacturing method. 4. Epoxy (meth) acrylates obtained by the production method according to claim 1, 2 or 3. 5. A polymerizable composition comprising the epoxy (meth) acrylate according to claim 4 and a vinyl monomer copolymerizable with the epoxy (meth) acrylate. 6. Epoxy (meth) acrylates 30 to
6. The polymerizable composition according to claim 5, comprising 90% by weight and 70 to 10% by weight of a vinyl monomer.