JPH05271366A - Epoxy @(3754/24)meth)acrylate resin emulsion composition - Google Patents

Abstract

PURPOSE:To obtain an emulsion suitable as a binder for glass fiber without containing a low-boiling polymerizable monomer and a combustible solvent by using a self-cross-linkable type resin, especially an epoxy (meth)acrylate resin as a base resin. CONSTITUTION:The objective epoxy (meth)acrylate resin emulsion composition comprises (A) an epoxy (meth)acrylate resin prepared by reacting an epoxy resin having >=2 epoxy groups in one molecule with an unsaturated monobasic acid or, as necessary, an acid pendant type epoxy (meth)acrylate resin obtained by reacting the epoxy (meth)acrylate resin with a polybasic acid anhydride, (B) a high-boiling polymerizable monomer, (C) a nonionic emulsifying agent, (D) an anionic emulsifying agent, (E) a curing agent and (F) water.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a water-dilutable epoxy (meth) acrylate resin emulsion composition suitable for a glass fiber binder.

[0002]

2. Description of the Related Art In recent years, among FRP molding technologies, RTM
(Resin transfer molding) molding has been reviewed and attracted attention because it is less likely to cause styrene monomer to scatter into the environment. In RTM molding and preform matched die molding, in the case of molding of deep drawn products or complicated shaped products, preformed glass chopped strands are often used. Mold by pressure impregnation. At this time, the insoluble preform binder is used so that the glass reinforcing material does not lose its shape and flow.

In general, the preform binder is sprayed on the chopped strands in a point-adhesive manner to insolubilize it. Therefore, in many cases, unsaturated polyester resin emulsions have been widely used in view of workability.

[0004]

However, in the case of the unsaturated polyester resin emulsion, a monomer which is a cross-linking agent such as styrene having a low boiling point is used, and in some cases, B.I. T. X. Flammable solvents such as are also included.

The problem with this type of binder is that after spraying the emulsion on the chopped strands with a spray,
Since it cures at the same time as water and drying at a high temperature of 150 ° C or higher, there is a risk of fire during drying and curing, and as a result, the cost of countermeasure equipment is heavy and the cured binder is attached to the fiber. For this reason, the infused resin and the glass fiber are not well compatible with each other, which may adversely affect the strength and water resistance of the FRP.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that self-crosslinking resins, particularly epoxy (meth) acrylate resins (vinyl ester resins) or this epoxy (meth) resins. An epoxy (meth) acrylate resin emulsion composition using an acid pendant type epoxy (meth) acrylate resin obtained by reacting an acrylate resin with a polybasic acid anhydride as a base resin does not contain a low boiling point monomer and a flammable solvent, and The present invention has been completed by finding that the emulsion is suitable as a glass fiber binder.

That is, the present invention has two epoxy groups in one molecule.
An epoxy (meth) acrylate resin obtained by reacting an epoxy resin having one or more with an unsaturated monobasic acid, or an acid obtained by reacting this epoxy (meth) acrylate resin with a saturated or unsaturated polybasic acid anhydride, if necessary. Pendant type epoxy (meth) acrylate resin (A), high boiling point polymerizable monomer (B), nonionic emulsifier (C), anionic emulsifier (D), curing agent (E), water (F) Epoxy (meth) useful as a glass fiber binder
Acrylate resin emulsion composition.

The constituents of the epoxy (meth) acrylate resin emulsion composition of the present invention will be described below. The epoxy (meth) acrylate resin or acid pendant type epoxy (meth) acrylate resin used in the present invention can be obtained by reacting an epoxy resin having at least two epoxy groups in one molecule with an unsaturated monobasic acid. Epoxy (meth) acrylate resin, and if necessary, an acid value of 4 to 60, preferably an acid value of 9 obtained by reacting this epoxy (meth) acrylate resin with a saturated or unsaturated polybasic acid anhydride. ~ 40.

The reaction between an epoxy resin and an unsaturated monobasic acid and the acid pendant reaction are already known. Usually, an epoxy (meth) acrylate resin is an epoxy resin having two or more epoxy groups in one molecule, For example, bisphenol type epoxy resin, novolac type epoxy resin, halogenated bisphenol type epoxy resin, halogenated novolac type epoxy resin, cyanurate type epoxy resin, dimer acid modified epoxy resin and the like and unsaturated monobasic acid such as acrylic acid or methacrylic acid. Charge and so that the epoxy group and the carboxyl group are almost equivalent,
As a stabilizer, for example, in the presence of hydroquinone, methylhydroquinone, trimethylhydroquinone, tert-butylhydroquinone, phenothiazine, copper salt, etc., 80
It is synthesized by reacting at ~ 150 ° C until the acid value becomes almost zero. Further, the acid pendant type epoxy (meth) acrylate resin is a saturated or unsaturated polybasic acid anhydride, for example, anhydrous at a ratio of 0.05 to 0.2 equivalent per 1.0 equivalent of hydroxyl group of the above epoxy (meth) acrylate resin. Maleic acid, phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, hettic anhydride, methylnadic acid anhydride, itaconic anhydride, etc. are charged, It is obtained by reacting at 80 to 150 ° C. to form a pendant ester.

The acid value is determined by the epoxy equivalent and the ratio of the polybasic acid anhydride used, but the reaction proceeds quantitatively and can be calculated.

If the acid value is less than 4, stability of the emulsion composition to be obtained is poor (liquid separation, etc.), and if it is more than 60, the properties of the FRP molded product, particularly water resistance, are unfavorable. ..

The high-boiling polymerizable monomer used in the present invention preferably has a boiling point of 200 ° C. or higher at normal pressure, and typified by trimethylolpropane di (meth) acrylate and polyethylenecoldi (meth).
Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate,
Hydroxypivalic acid ester neopentyl glycol diacrylate, bisphenol A di (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate and other (meth) acrylic monomers, diallyl phthalate and other allyl monomers Is mentioned. The addition amount of the high boiling point polymerizable monomer is 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy (meth) acrylate resin or the acid pendant type epoxy (meth) acrylate resin. If the amount of the high-boiling-point polymerizable monomer added is less than 1 part by weight, the stability as an emulsion and the water resistance of the molded article will decrease, while
If the amount is more than the amount by weight, the adhesive strength as a binder and the mechanical strength of the molded product decrease.

Examples of the anionic emulsifiers used in the present invention include higher alcohol sulfuric acid ester salts such as sodium lauryl sulfate, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, polyoxyethylene ether sulfate salts. Etc. Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene sorbitan fatty acid esters,
Examples thereof include sorbitan fatty acid esters, polyoxyethylene acyl esters, oxyethylene-oxypropylene block copolymers and fatty acid monoglycerides. Two or more kinds of these nonionic emulsifiers and anionic emulsifiers may be used in combination.

The amount of the nonionic emulsifier used is 1 to 1 with respect to 100 parts by weight of the epoxy (meth) acrylate resin or the acid pendant type epoxy (meth) acrylate resin.
5 parts by weight, preferably 3 to 10 parts by weight, and the anionic emulsifier is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight. If the amount of the nonionic emulsifier used is less than the above range, the stability of the emulsion composition will be poor, and if it is too large, the properties of the FRP molded product, especially the water resistance, will deteriorate. Further, the amount of the anionic emulsifier to be used must be in the above range from the viewpoint of the liquid stability of the emulsion composition, and the liquid stability will decrease if the amount is more or less than the above range.

The curing agent used in the present invention is generally an organic peroxide used for curing an unsaturated polyester resin or an epoxy (meth) acrylate resin, and the type thereof is not particularly limited, but it is heat curing. The use of mold hardeners is preferred. For example, benzoyl peroxide, dicumyl peroxide, tertiary butyl peroxybenzoate and the like can be mentioned. The addition amount is preferably 1 to 5% by weight based on the total amount of the epoxy (meth) acrylate resin or the acid pendant type epoxy (meth) acrylate resin, the high boiling point polymerizable monomer, the nonionic emulsifier and the anionic emulsifier.

The water used in the present invention is epoxy (meth).
40 to 1 with respect to the total amount of acrylate resin or acid pendant type epoxy (meth) acrylate resin, high boiling point polymerizable monomer, nonionic emulsifier, anionic emulsifier
It is preferably 000 parts by weight.

[0017]

EXAMPLES The present invention will be described in more detail with reference to examples (synthesis examples) and comparative examples. The parts in the examples are parts by weight with respect to 100 parts by weight of epoxy (meth) acrylate resin and acid pendant type epoxy (meth) acrylate resin unless otherwise specified. Moreover, the acid value in the synthesis examples indicates the acid value of the epoxy (meth) acrylate resin and the acid pendant type epoxy (meth) acrylate resin.

Synthesis Example 1 In a reaction vessel, 378 g (2.0 equivalents) of bisphenol type epoxy resin (AER331L) manufactured by Asahi Kasei Corporation,
When 172 g (2.0 equivalents) of methacrylic acid, 0.2 g of hydroquinone and 1.5 g of dimethylbenzylamine were charged and reacted at 110 to 120 ° C. for 9 hours while blowing air, the acid value of the ester became almost zero.

Next, 138 g of trimethylolpropane triacrylate was added and dissolved, and 55.0 g of Emulgen 950 (manufactured by Kao, polyoxyethylene alkylphenol ether, nonionic emulsifier) while keeping the temperature down to 80 ° C. (10. 0 part) and Neoperex F-25 (manufactured by Kao, sodium dodecylbenzenesulfonate, anionic emulsifier) 6.9 g (1.25 parts) were added and well stirred and dissolved.

Next, to the dissolved product, ion-exchanged water 75
0 g was added, and stirring was continued for 5 hours while maintaining the temperature at 60 ° C. to obtain an emulsion.

Synthesis Example 2 In a reaction vessel, 475 g of bisphenol type epoxy resin (Epicoat 1001) made of oiled shell epoxy (1.
(0 equivalent), 72 g (1.0 equivalent) of acrylic acid, 0.2 g of hydroquinone, 1.6 g of dimethylbenzylamine, and 137 g of trimethylolpropane triacrylate are charged, and the reaction is carried out at 110 to 120 ° C. for 15 hours while blowing air into the ester. The acid value of was almost zero.

Next, 228 g of trimethylolpropane triacrylate was added and dissolved, and 72.7 g of emulgen 930 (manufactured by Kao, polyoxyethylene alkylphenol ether, nonionic emulsifier) while keeping the temperature down to 80 ° C. (13. 3 parts), and 9.1 g (1.66 parts) of Neoperex F-25 were added and well stirred,
Dissolved.

Next, ion-exchanged water 99 is added to the dissolved product.
4 g was added, and stirring was continued for 5 hours while maintaining the temperature at 60 ° C. to obtain an emulsion.

Synthesis Example 3 In a reaction vessel, the same epoxy methacrylate resin as that obtained in Synthesis Example 1 (550 g) and tetrahydrophthalic anhydride 6 were used.
When 0.8 g (0.2 equivalents per 1.0 equivalent of hydroxyl groups) was charged and reacted at 110 to 120 ° C. for 3 hours while blowing in air, the acid value of the ester became about 37.

Next, 153 g of trimethylolpropane triacrylate was added and dissolved, the temperature was lowered to 80 ° C., and while maintaining the temperature, 38,000 of Emulgen 950 was maintained.
g (6.3 parts), Neoperex F-25 7.6g
(1.24 parts) was added and well stirred and dissolved.

Next, the dissolved product is deionized water 81
0 g was added, and stirring was continued for 5 hours while maintaining the temperature at 60 ° C. to obtain an emulsion.

Synthetic Example 4 To the reaction vessel, 611 g of the same acid pendant type epoxy methacrylate resin and 153 g of isobornyl methacrylate as those obtained in Synthetic Example 3 were added and dissolved, and 38.4 g of Emulgen 950 while maintaining the temperature at 80 ° C. (6.3 parts) and Neoperex F-25 (7.6 g, 1.24 parts) were added and well stirred and dissolved.

Then, ion-exchanged water 81 is added to the dissolved product.
0 g was added, and stirring was continued for 5 hours while maintaining the temperature at 60 ° C. to obtain an emulsion.

Synthesis Example 5 In a reaction vessel, 685 g of the same epoxy acrylate resin as that synthesized in Synthesis Example 2 (including 137 g of trimethylolpropane triacrylate), 33.2 g of 4-methyltetrahydrophthalic anhydride (hydroxyl group 1.0 (0.2 equivalents per equivalent) is charged, and while blowing air 110-
When reacted at 120 ° C for 3 hours, the acid value of the ester is about 19
Became.

Further, 250 g of trimethylolpropane triacrylate was added, and the temperature was lowered to 80 ° C. While maintaining the temperature, 48.4 g (8.3) of Emulgen 930 was added.
Part), 9.7 g of Neoperex F-25 (1.67
Part) and well stirred and dissolved.

Next, the dissolved product is deionized water 10
26 g was added, and stirring was continued for 5 hours while maintaining the temperature at 60 ° C. to obtain an emulsion.

Synthesis Example 6 580 g of an acid pendant type epoxy acrylate resin and 388 g of trimethylolpropane triacrylate similar to those used in Synthesis Example 5 were added to a reaction vessel and dissolved, while maintaining at 80 ° C., Tween 60 (manufactured by Kao Corporation). , Polyoxyethylene sorbitan monostearate, nonionic emulsifier) 48.4 g (8.3 parts), Emal 10 (manufactured by Kao, sodium lauryl sulfate, anionic emulsifier)
9.7 g (1.67 parts) was added and well stirred and dissolved.

Next, the dissolved water is added to ion-exchanged water 10
26 g was added, and stirring was continued for 5 hours while maintaining the temperature at 60 ° C. to obtain an emulsion.

Synthesis Example 7 In a reaction vessel, 360 g (2.0 equivalents) of phenol novolac type epoxy resin (DEN438) manufactured by Dow Chemical Co., 144 g of acrylic acid (2.0 equivalents), 0.15 g of hydroquinone and dimethylbenzylamine were used. After charging 1.5 g and 216 g of isobornyl methacrylate and reacting at 110 to 120 ° C. for 15 hours while blowing air, the acid value of the ester became almost zero.

Next, 120 g of isobornyl methacrylate and 60.8 g of tetrahydrophthalic anhydride (0.2 equivalent per 1.0 equivalent of hydroxyl group) were charged, and the reaction was carried out at 110 to 120 ° C. for 3 hours while blowing air into the ester acid. The price became about 39.

Next, while lowering the temperature to 80 ° C. and maintaining the temperature, 42.0 g (7.4%) of Tween 60 was used.
Part) and EMAL 10 (8.4 g, 1.48 parts) were added, and well stirred and dissolved.

Then, ion-exchanged water 89 is added to the dissolved product.
0 g was added and stirring was continued for 5 hours while maintaining the temperature at 60 ° C. to obtain an emulsion.

Synthesis Example 8 The reaction vessel was charged with 550 g of the same epoxy methacrylate resin as that obtained in Synthesis Example 1, and 27.5 g (5.0%) of Emulgen 950 while maintaining the temperature at 80 ° C.
Part) and 5.5 g (1.00) of Neoperex F-25
Part) was added and well stirred and dissolved.

Then, ion-exchanged water 58 is added to the dissolved product.
3 g was added, and stirring was continued for 5 hours while maintaining the temperature at 60 ° C. to obtain an emulsion.

Synthetic Example 9 In a reaction vessel, 550 g of the same epoxy methacrylate resin as used in Synthetic Example 1 and 121.6 g of tetrahydrophthalic anhydride (0.4 equivalent per 1.0 equivalent of hydroxyl group)
, While blowing air at 110-120 ℃ 2
The acid value of the ester was about 67 after the reaction for a time.

Next, 168 g of trimethylolpropane triacrylate was added and dissolved, and while the temperature was lowered to 80 ° C. and the temperature was maintained, 42.3 of Emulgen 950 was added.
g (6.3 parts), Neoperex F-25 8.3g
(1.24 parts) was added and well stirred and dissolved.

Then, deionized water 84 is added to the dissolved product.
0 g was added, and stirring was continued for 5 hours while maintaining the temperature at 60 ° C. to obtain an emulsion.

Synthesis Example 10 550 g of the same epoxy methacrylate resin as used in Synthesis Example 1 and 60.8 g of tetrahydrophthalic anhydride (0.2 equivalent per 1.0 equivalent of hydroxyl group) were charged into a reaction vessel, and air was blown into the reaction vessel. However, when the reaction was carried out at 110 to 120 ° C. for 2 hours, the acid value of the ester became about 37.

Next, 153 g of trimethylolpropane triacrylate was added and dissolved, and the temperature was lowered to 80 ° C. and Emulgen 950 was added at 109.9 while maintaining the temperature.
g (18.0 parts), Neoperex F-25 7.6g
(1.24 parts) was added and well stirred and dissolved.

Then, deionized water 86 is added to the dissolved product.
3 g was added, and stirring was continued for 5 hours while maintaining the temperature at 60 ° C. to obtain an emulsion.

Synthesis Example 11 A reaction vessel was charged with 550 g of the same epoxy methacrylate resin as used in Synthesis Example 1 and 60.8 g of tetrahydrophthalic anhydride (0.2 equivalent per 1.0 equivalent of hydroxyl group), and air was blown into the reaction vessel. However, when the reaction was carried out at 110 to 120 ° C. for 2 hours, the acid value of the ester became about 37.

Next, 153 g of trimethylolpropane triacrylate was added and dissolved, and the temperature was lowered to 80 ° C. and 38.4 g of Emulgen 950 while maintaining the temperature.
(6.3 parts), 0.4 g of NeoPerex F-25
(0.07 parts) was added and well stirred and dissolved.

Next, 80% of ion-exchanged water was added to the dissolved product.
3 g was added, and stirring was continued for 5 hours while maintaining the temperature at 60 ° C. to obtain an emulsion.

Synthetic Example 12 A reaction vessel was charged with 550 g of the same epoxy methacrylate resin as used in Synthetic Example 1 and 60.8 g of tetrahydrophthalic anhydride (0.2 equivalent per 1.0 equivalent of hydroxyl group), and air was blown into the container. However, when the reaction was carried out at 110 to 120 ° C. for 2 hours, the acid value of the ester became about 37.

Next, 153 g of trimethylolpropane triacrylate was added and dissolved, and the temperature was lowered to 80 ° C. and 38.4 g of Emulgen 950 while maintaining the temperature.
(6.3 parts), Neoperex F-25 42.7g
(7.0 parts) was added and well stirred and dissolved.

Then, ion-exchanged water 82 is added to the dissolved product.
4 g was added, and stirring was continued for 5 hours while maintaining the temperature at 60 ° C. to obtain an emulsion.

Table 1 shows the formulations of the emulsions obtained in Synthesis Examples 1 to 12. Further, Table 2 shows the liquid stability of these and a typical commercial product A (unsaturated polyester emulsion) as an emulsion.

[0053]

[Table 1]

Example 1 100 g of the emulsion obtained in Synthesis Example 1 was further diluted with ion-exchanged water so that the non-volatile content (water-removed product) became 5% by weight, and then liquid benzoylper was used as a curing agent. Oxide [(Nippon Yushi, Niper BMT-40
(Effective ingredient 40%)] 3.75 g (3% by weight based on the nonvolatile content) was added to obtain an epoxy methacrylate resin composition.

Then, 1 kg of this emulsion composition
And roving glass (Nitto Boseki RS240F-1
14AS) 1 kg was cut into a length of 5 cm and simultaneously sprayed onto the screen using a preformer. The amount of solid matter adhered to the glass fiber was 5% by weight.

Further, the sprayed product was left in an oven at 200 ° C. for about 10 minutes to be dried and cured at the same time to prepare a preformed mat.

Using this preformed mat, an isophthalic acid type unsaturated polyester resin (manufactured by Showa High Polymer, Rigolac G-35) having good water resistance is used as a gel coat resin.
7), Modified isophthalic acid type unsaturated polyester resin for backing resin (Showa High Polymer, Rigolac RI-201)
Using a 30 cm square gel coated FRP plate with RTM
Molded.

A test piece was cut out from this FRP plate and subjected to a bending strength test, a tensile strength test and a water resistance test. In the water resistance test, one side of the gel-coated surface was boiled and evaluated on the basis of blisters on the gel-coated surface, embossing of crack fibers and the like.

Examples 2 to 7 Using the emulsions obtained in Synthesis Examples 2 to 7, Example 1
An FRP with a gel coat was prepared with the same formulation as above, and strength and water resistance tests were conducted.

Comparative Examples 1 to 5 Synthesis Examples 8 to 12 Using the obtained emulsions, Example 1
An FRP with a gel coat was prepared with the same formulation as above, and strength and water resistance tests were conducted.

Comparative Example 6 Representative commercial product A (unsaturated polyester type, containing styrene monomer and toluene, resin content 40% by weight, nonvolatile content 2
3% by weight) was used to prepare a gel-coated FRP with the same formulation as in Example 1, and the strength and water resistance tests were conducted.

In this case, the type and amount of the curing agent are the same as those of the commercially available product A
A predetermined amount of the product specified by the manufacturer (benzoyl peroxide type) was used. Further, the amount of the solid content attached to the glass fiber was adjusted to be 5% by weight.

Table 2 shows the mechanical strength and water resistance test results of the test pieces cut out from the FRP plates obtained in Examples 1 to 7 and Comparative Examples 1 to 6.

[0064]

[Table 2]

Liquid stability High-temperature stability and ◎ No change Freeze-thaw stability 〇 There is a change, but it returns to the original when stirred at high temperature △ Changes and does not return even when stirred at high temperature Single-sided boiling test ◎ No change (appearance ) Slight blistering △ Blistering × Large blistering and cracking FRP molding conditions FRP composition: gel coat + surface mat + preformed mat Resin: gel coat → iso type unsaturated polyester (Showa Polymer, Rigolac G- 357) Lining → modified iso type unsaturated polyester (Showa High Polymer, Rigolac RI-357) Curing system: Acetylacetone peroxide / cobalt naphthenate, after cure 80 ° C x 2 hours Molding product: Gel coat layer 0.3 mm, Lining layer 3.0
mm (Glass content 29%) Injection pressure: 1 kg / cm ² High temperature stability and freeze-thaw stability conform to JIS K 6828. The bending test and the tensile test conform to JIS K 6919. The one-sided boiling test is an observation of the surface after one-hour boiling for 300 hours.

[0066]

The water-dilutable epoxy (meth) acrylate resin emulsion composition of the present invention has excellent liquid stability as an emulsion. Furthermore, since a low-boiling polymerizable monomer and flammable solvents are not included during preparation of a preformed mat used for RTM molding and preform matched die molding, there is little risk of fire or the like. Also, RTM
The FRP molded product obtained by molding has high mechanical strength,
Since it exhibits water resistance, its use as a glass fiber binder is effective.

Claims (2)

[Claims] 1. Epoxy (meth) acrylate resin (A) 100 parts by weight High boiling point polymerizable monomer (B) 1 to 100 parts by weight Nonionic emulsifier (C) 1 to 15 parts by weight Anionic emulsifier (D) 0.1 -5 parts by weight Curing agent (E) Water (F) Epoxy (meth) acrylate resin emulsion composition for glass fiber binder used in FRP, characterized in that: 2. An acid pendant type epoxy (meth) acrylate resin (A) having an acid value of 4 to 60 obtained by reacting an epoxy (meth) acrylate resin with a saturated or unsaturated polybasic acid anhydride. Boiling point polymerizable monomer (B) 1 to 100 parts by weight Nonionic emulsifier (C) 1 to 15 parts by weight Anionic emulsifier (D) 0.1 to 5 parts by weight Curing agent (E) Water (F) And an epoxy (meth) acrylate resin emulsion composition.