JPH0446917A - Liquid thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition which has a high curing rate and little emits black smoke upon being burnt by mixing a liquid resin comprising a specified vinyl ester/(meth)acrylic ester copolymer with a powdery inorganic filler containing water of crystallization in a specified mixing ratio. CONSTITUTION:A liquid resin is produced by copolymerizing 80-20wt.% vinyl ester of formula I or II (wherein X and Y are each a bivalent organic group; A is formula III; B is formula IV; R<1> and R<3> are each H or methyl; R<2> is alkylene or formula V; (m) is 0 or 1 or greater; and (n) is 1 or greater) with 20-80wt.% alkyl (meth)acrylate (e.g. methyl methacrylate). This liquid resin is mixed with a powdery inorganic filler containing water of crystallization (e.g. alumina trihydrate) in such a manner that the amount of the powdery inorganic filler is 50wt.% or above based on the vinyl ester to produce a liquid thermosetting resin composition desirable for automobile outside sheets, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a thermosetting liquid resin composition-acid (hereinafter simply referred to as a composition).

Compositions containing a thermosetting liquid resin (hereinafter simply referred to as liquid resin) and various fillers, reinforcing fibers, etc. are widely used. For example, in a typical composition, unsaturated polyester is used as the liquid resin. There are compositions using resins, and molded products of these compositions are used for bathtubs, water tank panels, wash basins, automobile exterior panels, and the like.

The present invention relates to a composition using a liquid resin comprising a vinyl ester and an alkyl (meth)acrylate.

<Prior art and its problems> Conventionally, typical compositions include compositions using unsaturated polyester resins, such as vinyl ester unsaturated polyester resins, as liquid resins.

However, this composition has a problem of slow curing speed. A slow curing speed is contrary to the demand for improved productivity by shortening the molding cycle, and is a major constraint in fields that require mass production, such as automobile exterior panels. Furthermore, since the composition has a high content of aromatic hydrocarbon groups, there is a problem in that black smoke is often generated when a molded article obtained from the composition is exposed to flame. It is well known that the generation of a large amount of black smoke makes evacuation and guidance difficult, and is considered the number one cause of fatalities in fires.

In order to improve the flame retardancy of the resulting molded products, we have developed compositions using unsaturated polyesters containing halogen in the molecule as the polymer of unsaturated polyester resins, and halogenated aromatic vinyl as the solvent for unsaturated polyester resins. Compositions using halogen-containing flame retardants are known, and compositions in which an unsaturated polyester resin contains an inorganic powder filler having water of crystallization in the molecule are also known. There is.

However, in compositions using halogen, although it is possible to prevent the resulting molded product from flaming by increasing the amount of halogen, black smoke is still often generated when the molded product is exposed to flame. There is a problem. In addition, in a composition containing an inorganic powder filler having water of crystallization in the molecule, the viscosity of the unsaturated polyester resin is originally high, and a large amount of inorganic powder filler is added to the composition to avoid the generation of black smoke. The inclusion of fillers significantly increases the viscosity of the prepared composition, making it difficult to mold the composition and, in practice, resulting in resin transfer molding (RTM), reaction injection molding (RIM), There is a problem that pultrusion molding etc. cannot be performed.

<Problems to be Solved by the Invention and Means for Solving the Problems> The present invention provides a composition that solves the conventional problems as described above.

Therefore, the present inventors have developed a vinyl ester composition in order to obtain a composition that has a fast curing speed, significantly reduces the generation of black smoke when the resulting molded product is exposed to flame, and does not cause difficulties in the molding operation. As a result of research on combinations of vinyl intermediates, vinyl intermediates, and inorganic powder fillers, it was found that an inorganic powder filler containing water of crystallization in the molecule was added to a liquid resin consisting of a predetermined proportion of vinyl ester and alkyl (meth)acrylate, respectively. It was discovered that a substance containing a predetermined amount is suitable for the purpose, and the present invention was completed.

That is, the present invention provides a liquid resin consisting of 80 to 20% by weight of a vinyl ester represented by the following general formula (1) or (II) and 20 to 80% by weight of an alkyl (meth)acrylate, and a liquid resin containing crystal water in the molecule. The present invention relates to a composition characterized in that it contains an inorganic powder filler having the following properties and an amount of 50i [1% or more] of the vinyl ester.

General formula (■) 2 General formula (II) 13 [Q -ri] -Y-ζ) -00H20HC82 Dimension Q - (] -Y-ζ) -〇BH [However, X, Y, divalent organic group A; CH2=C C-0-R2- (herein)71. R3 is hydrogen or a methyl group; R2 is an alkylene group having 2 to 4 carbon atoms; n is an integer of 0 or 1 or more; -3 divalent organic groups such as alkylene group, impropylidene group, sulfone group or 1,000-onythyl group,
As the vinyl ester represented by the above general formula used in the present invention, known vinyl esters can be used. That is, when m is 0, the vinyl ester of formula (I) is bisphenol-di(meth)acryloyloxy-2-hydroxypropyl ether or bisphenol-di(meth)acryloyloxyalkyl ether. be. Specifically, bisphenol-di(meth)acryloyloxy-2-hydroxypropyl ethers such as methylene bisphenol-diacryloyloxy-2-hydroxypropyl ether and impropylidene bisphenol-dimethacryloyloxy-2-hydroxypropyl ether; or bisphenol di(meth) such as methylene bisphenol-dimethacryloyloxyethyl ether isopropylidene bisphenol-diacryloyloxypropyl ether;
Examples include acryloyloxyalkyl ethers.

Furthermore, when m is an integer of 1 or more, the vinyl ester of the general formula (I) is a poly(meth)acryloyloxy-
2-hydroxypropyl ethers. in this case.

In terms of the viscosity of the liquid resin, m is preferably 0, 1 and/or 2 alone or as a mixture.Furthermore, the vinyl ester of the general formula (II) is prepared by reacting a bisphenol type epoxy resin with (meth)acrylic acid. This is what you get. Specifically, examples include a reaction product between a methylene bisphenol type epoxy resin and acrylic acid, a reaction product between an impropylidene bisphenol type epoxy resin and methacrylic acid, and the like.

In this case, from the viewpoint of the viscosity of the liquid resin, vinyl esters where n is 2 or less, particularly vinyl esters where n is 1, are preferred.

These vinyl esters can be obtained by conventionally known methods.
For example, dissolving bisphenol glycidyl ether, polyphenol polyglycidyl ether, or bisphenol type epoxy resin in a solvent that does not have active hydrogen groups,
It is obtained by adding methacrylic acid or acrylic acid to this and reacting it in the presence of a catalyst such as a quaternary ammonium salt or lithium halide. In this case, it is advantageous to use an alkyl (meth)acrylate as the solvent since there is no need to remove the solvent after the reaction.

The alkyl (meth)acrylate used in the present invention includes alkyl acrylate and alkyl methacrylate. Specifically, the alkyl group includes a methyl group, an ethyl group, a propyl group, an inpropyl group, and the like. Among these, methyl methacrylate is preferred for the purpose.

The liquid resin in the present invention is composed of vinyl ester and alkyl (meth)acrylate as described above, and the ratio of both is vinyl ester/alkyl (meth)acrylate = 20/80 to 80/20 (weight ratio). ), preferably 35/65 to 75/25 (weight ratio); if the ratio of both is less than 20/80 (weight ratio), the physical properties of the resulting molded product will be poor; If the ratio exceeds the above ratio, the viscosity of the liquid resin becomes too high, which is inconvenient in any case.

The inorganic powder filler used in the present invention has crystal water in its molecules. Specifically, alumina 3-kiwamono (^12
03.3HzO), calcium sulfate dihydrate (Ca5O
a・2H20), etc. The inorganic powder filler is preferably one whose crystal water release temperature is about 50 to 300°C higher than the maximum temperature during molding, although it depends on the composition of the liquid resin containing it and the molding method of the composition. ,
Particularly preferred is alumina trihydrate.

In the composition of the present invention, the above-mentioned inorganic powder filler is added to the above-mentioned liquid resin, and 5% of the vinyl ester in the liquid resin is added to the above-mentioned liquid resin.
The content is 0% by weight or more. With a lower limit of 50% by weight of vinyl ester, the content can be changed as appropriate depending on the composition of the liquid resin, the particle size of the inorganic powder filler, the method of molding the composition, the desired physical properties of the resulting molded product, etc. Examples of the content of the inorganic powder filler in relation to the molding method of the resulting zero composition and the particle size of the inorganic powder filler include:
Per 100 parts by weight of liquid resin, it is usually 0.2 to 3 # in the case of premix methods such as sheet molding (SMC).
180 to 230 parts by weight of Lm, resin transfer molding method (
RTM) or reaction injection molding (RIM) from 10 to
The amount is 30 to 100 parts by weight for 20 μm, and 100 to 200 parts by weight for 8 to 20 pm in the case of pultrusion. In any case, by containing at least 50% by weight of the vinyl ester an inorganic powder filler having water of crystallization in its molecules, it is possible to avoid the generation of black smoke when the molded product obtained is exposed to flame. In addition, by containing at least the same weight as the liquid resin, it is possible to not only avoid the generation of black smoke but also to prevent flaming, and furthermore, the content of the inorganic powder filler can be increased within the range that is possible for molding operations. The oxygen index (L, 0
．． 1. ) can be improved.

Various formulations developed for unsaturated polyester resins can be applied to the preparation of the composition of the present invention, and methods for obtaining molded articles from the composition can also be applied to methods developed for unsaturated polyester resins. Various molding methods can be used in succession.

In order to make the configuration and effects of the present invention more specific,
Examples are given below.

<Examples, etc.> Reference test category 1 (production of liquid resin) - Bisphenol A diglycidyl ether 34 in the reaction vessel for production of liquid resin A
0 g (1, o mol), methyl methacrylate) 322.
7g of acrylic acid and 3g of tetrabutylammonium bromide were charged, and kept at 60°C to prepare 146.9g of acrylic acid (
2.04 mol) was added. At this time, reaction heat was generated, but the temperature inside one reaction vessel was maintained at 60 to 70°C. Continued 60
The reaction was carried out at ~65°C for 2 hours to obtain vinyl ester a.
A reaction mixture containing . Oxirane oxygen based on bisphenol A diglycidyl ether was not detected in this reaction mixture. This reaction mixture is a liquid resin A consisting of 60% by weight of vinyl ester and 40% by weight of methyl methacrylate, and this liquid resin A is the liquid resin in the present invention.

... Production of liquid resin B Polymethylene polyphenyl polyglycidyl ether (average glycidyl ether functional group a3,5 (1'1/1 molecule) 324.6 g (0.6 mol), methyl methacrylate 513.8 g, methacrylic acid 189 .2g (2,2
A reaction mixture containing vinyl ester b was obtained in the same manner as in the case of liquid resin A using 5 g of tetramethyl chloride (mol) and 5 g of tetramethyl chloride. This reaction mixture contains vinyl ester b5
03i amount% and methyl methacrylate 50ffiit%
This liquid resin B is the liquid resin in the present invention.

...Bisphenol A diglycidyl ether 34 is added to the reaction vessel for producing liquid resin R-1.
0 g (1.0 mol), 3227 g of styrene, and 3 g of tetrabutylammonium bromide were charged, the temperature was kept at 60° C., and 146.9 g (2.04 mol) of acrylic acid was added. Thereafter, in the same manner as in the case of liquid resin A, a reaction mixture containing vinyl ester a was obtained. The reaction mixture consisted of 1% vinyl ester a60ii and styrene 403.
3(ii%) of liquid resin R-1, this liquid resin R
-1 is a conventional vinyl ester type unsaturated polyester resin.

...Production of liquid resin R-2 Polymethylene polyphenyl polyglycidyl ether (average number of glycidyl ether functional groups: 3.5, 71 molecules) 32
Vinyl ester b was prepared in the same manner as in the case of liquid resin R-1 using 4.6 g (0.6 mol), 513.8 g of styrene, 189.2 g (2.2 mol) of methacrylic acid, and 5 g of tetramethyl chloride. A reaction mixture was obtained containing: This reaction mixture is a liquid resin R-2 consisting of 50% by weight of vinyl ester B and 50% by weight of styrene, and this liquid resin R-2 is a conventional vinyl ester type unsaturated polyester resin.

Test Category 2 (Measurement of High Temperature Curing Properties of Liquid Resin) Using the liquid resin obtained in Test Category 1, the high temperature curing properties were measured by the following method.

...Measurement of high temperature curing properties It was carried out according to JIS-6901, but the measurement conditions were changed as follows in consideration of the actual RTM method or RIM method. That is, benzoyl peroxide 2
Weight % and N,N-dimethyl-paratoluidine 0.07
A sample mixed with 5% by weight was left at a bath temperature of 60°C, and the time required for the liquid temperature to reach 65°C from 45°C was the gelation time (G, T, seconds in the table), 65°C. Minimum curing time (C, T, seconds in the table)
It was measured as This measurement operation was performed three times, and the average was taken as the test result. In addition, to read the temperature, a desktop recorder (IIIA) manufactured by Okura Riken Co., Ltd.
IO type) was used.

The measurement results are summarized in Table 1.

Table 1 Test Category 3 (Measurement of viscosity of composition and evaluation of black smoke generation status of molded product) Liquid resin obtained in Test Category 1 or its diluted liquid resin 100
A composition was prepared by containing alumina trihydrate having a particle size of 17 m per part by weight as shown in Table 2, and its viscosity was measured by the following method. Then, 10% of the liquid resin is added to the composition.
0 parts by weight, 1 part by weight of benzoyl peroxide as a catalyst,
N,N-dimethyl-paratoluidine 0 as curing accelerator
．． 008 parts by weight and 0.5 parts by weight of INT-EQ6 (manufactured by Accel Plastics Co., Ltd., trade name) as a mold release agent, and poured this into a glass casting mold with a clearance of 3 inches using a 250 x 250 inch shoe. Cured at 60℃, thickness 3cm
A molded product was produced.The produced molded product was cut into a length of 70 cm and a width of 6.5H to prepare a sample for evaluating the black smoke generation status described below.

...Measurement of viscosity of composition Brookfield viscometer (model HTB, Spind t
Use TA), ioorpm, 50rpm20rp
(2) Each sample was measured twice at 25°C), and the average value was taken as the binding.

...Evaluation of black smoke generation The sample was placed in a lighter fire for 30 seconds, and the black smoke generation was visually observed and evaluated based on the following criteria.

0: No flame ignition, no black smoke generation O; Flame ignition, but no black smoke generation Δ: No flame ignition, but black smoke generation is observed ×: ★ flaming, black smoke generation often The measurement or evaluation results are summarized in Table 2, and the results in Table 2 also show that the composition of the present invention has a relatively low viscosity compared to conventional compositions, and therefore can be easily molded. It has been found that black smoke is not generated if the alumina trihydrate is contained in an amount of 50% by weight or more of the vinyl ester. The compositions of Comparative Examples 6 and 1O had high viscosities, so it was difficult to inject them into casting molds, and the surfaces of molded products produced by forced injection were significantly rough.

Table 2 Note) In Table 2.

Liquid resin C: Liquid resin B diluted with methyl methacrylate Liquid resin R-3: Liquid resin R-2 diluted with styrene <Effects of the invention> As is already clear, the present invention described above includes the following: It has excellent effects such as a fast curing speed, extremely low black smoke generation when the resulting molded product is exposed to flame, and easy molding operations.

Claims (1)

[Scope of Claims] 1. A liquid resin consisting of 80 to 20% by weight of vinyl ester represented by the following general formula (I) or (II) and 20 to 80% by weight of alkyl (meth)acrylate; 1. A thermosetting liquid resin composition comprising an inorganic powder filler having water of crystallization and an amount of the inorganic powder filler that is 50% by weight or more of the vinyl ester. General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, X, Y; divalent organic group A; ▲mathematical formula, chemical formula , tables, etc. ▼ B; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R^1, R^3 are hydrogen or methyl groups, R^2
is an alkylene group having 2 to 4 carbon atoms, or ▲ has a numerical formula, chemical formula, table, etc. ▼) m: an integer of 0 or 1 or more n: an integer of 1 or more] 2. The alkyl (meth)acrylate is methyl methacrylate The thermosetting liquid resin composition according to claim 1. 3. Claim 1, wherein the inorganic powder filler is alumina trihydrate.
or the thermosetting liquid resin composition according to 2.