JPS6341560A - Unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the title unsaturated polyester resin composition by combin ing with inorganic fillers and maleic half ester, thus being suitable for use as a construction material or for boat construction, because the viscosity becomes so low that the mixing of the resin and the filler is easy. CONSTITUTION:(A) 0.2-10pts.wt. of a maleic acid half ester such as maleic acid monoalkyl ester of the formula (R is 1-18C alkyl) is combined with (B) 10-500pts.wt. of inorganic fillers such as calcium carbonate or kaolin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an unsaturated polyester resin composition, and more particularly to a reinforced polyester resin in which an unsaturated polyester resin is reinforced with an inorganic filler.

The reinforced polyester resin of the present invention is useful for building materials and their ancillary equipment, boats, automobiles, vehicles, containers, aircraft,
It is suitable as a molding material for manufacturing radars, electrical parts, industrial tanks, pipes, safety helmets, etc.

[Conventional technology]

Unsaturated polyester resins are widely used as molding materials It, and are usually used in composite systems containing fillers.

When adding a filler to unsaturated polyester resin, a surface treatment agent such as a titanium coupling agent is added to the resin system in order to uniformly disperse the filler into the resin and improve the physical properties of the molded product and molding workability. be done. For example, for the purpose of improving the bending properties of an unsaturated polyester resin-calcium carbonate composite system, and improving the impact strength, bending strength, etc. of an unsaturated polyester resin-hydrated alumina, calcium carbonate or silica composite system, A reinforced polyester resin containing an unsaturated titanate such as isopropyl triacryl titanate, isopropyl trimethacryl titanate, isopropyl dimethacrylic isostearyl titanate, etc. is disclosed in Japanese Patent Publication No. 18143/1983.

[Problem that the invention seeks to solve]

Molding of unsaturated polyester resin +4 benefits include lowering the shrinkage rate during molding! A low-cost filling that improves physical properties such as mechanical properties, heat resistance, chemical resistance, surface wear, self-extinguishing properties, and electrical properties of the cured product. Fillers are added for the purpose of reducing product costs by adding fillers.

However, unsaturated polyester resin! Even if a filler is added to No. 11, depending on the affinity between the filler and the resin, the amount of filler mixed, etc., Elk defects may occur due to the amount of filler.
Uniformity of product quality cannot be maintained.

In the above-mentioned system of adding a surface treatment agent, the mechanical properties of the molded article are improved, but since the surface treatment agent has an acrylic group or a methacrylic group, the storage stability is extremely poor and it is not practical. Furthermore, the addition of an unsaturated polyester resin, which is a titanate-based coupling agent, does not show any effect on reducing the viscosity of the 1-fat composite, and on the contrary, the viscosity of the unsaturated polyester resin The process of combining the filler and the resin is significantly reduced. Furthermore, the thickening of resin N and (2) acids causes variations in the quality of molded products.

An object of the present invention is to provide a reinforced polyester resin with a high content of inorganic filler.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors found that by adding maleic acid half ester to the unsaturated polyester resin-inorganic filler N111 composition, the viscosity of the composition was significantly reduced. Not only is it easy to mix the filler and resin, but the molded product of this resin & 11 composition has excellent mechanical properties. 1, and completed the present invention.

The present invention provides the following components: Unsaturated polyester resin 100 type cylinder component [3
1,000) Argyl ester of emalic acid. This is an unsaturated polyester resin composition characterized by comprising: 0.2 to 10 parts by weight of L-bis/or monoalkenyl ester; Component C: 10 to 500 parts by weight of an inorganic filler.

In the present invention, the unsaturated polyester resin of component A refers to a polyester obtained by condensation polymerization of dihydrochloric acid and dihydric alcohol, which have an unsaturated bond in the molecule, and a reactive polyester resin such as styrene. When heated in the presence of a curing agent such as peroxide, or in combination with a curing accelerator, it hardens at room temperature to become an insoluble and infusible resin.
It is.

Specifically, manufactured by Narita Pharmaceutical Co., Ltd., product name, Polymer TG21 OL.
, TG3302. YG200゜TH6006, YII6
00], Made by Hitachi Chemical ■Product name: Polyset 565.567, A, 9120, Showa Kobunshi ■Product name: Rigorasoku 1557.5010, 7010.1553 Made by Dainichi Ingi ■Product name: Polylite 8010 .8009.0rl
Commercially available products include R-633°PS-150 and the like.

Component [monoalkyl ester of maleic acid of 3 and +;
r-monoalkenyl ester is represented by the following general formula % formula % (1), in which R is a methyl group, an ethyl group, an n-p1
1-pyl group, i-propyl group, n-butyl group.

It is a maleic acid half ester which is an alkyl group having 1 to 1B carbon atoms such as a tert-butyl group, pentyl%, n-hexyl group, heptyl group, or octyl group, or an alkenyl group such as an allyl group. As component B, one type of the above maleic acid half esters can be used alone or a mixture of two or more types having different LR (substituted) types can be used. Maleic acid half ester is prepared by adding 1 mol of monohydric alcohol to 1 mol of maleic anhydride in the presence or absence of a reaction solvent,
It can be easily synthesized by stirring and maintaining the reaction at a temperature of 0 to 80°C for 2 to 6 hours.

The inorganic filler of component 0 is added to the unsaturated polyester resin of component A to improve the moldability and processability of the composition,
It is an inorganic solid substance that is relatively inert to the resin component and is used for the purpose of improving the physical properties of molded products and reducing the cost.

For example, calcium carbonate, kaolin, clay, mica, talc, calcium oxide J2, titanium oxide, alumina, calcium sulfate, halium sulfate 11, silica, carbon blank, glass fiber, iron powder, aluminum powder, copper powder, iron oxide, Examples include cobalt oxide, and inexpensive calcium carbonate, talc, clay, etc. are preferably used.

The unsaturated polyester resin composition of the present invention comprises the component A
Component B to 100 parts by weight of unsaturated polyester resin
This composition contains 0.2 to 10 parts by weight of a maleic acid half ester of Component C and 10 to 500 parts by weight of an inorganic filler of component C.

If the blending ratio of component C to component A is too small, the above-mentioned effects due to the blending of component C cannot be achieved, and if it is too large, the moldability and mechanical properties of the molded article will deteriorate.

The blending amount of component B is determined based on component C, and is preferably 0.1 to 10 parts by weight of the maleic acid half ester of component B to 100 parts by weight of the inorganic filler of component C. is blended in an amount of 0.5 to 2 parts by weight. Component C of component B
If the blending ratio is too small, the dispersion of component 0 into component A will be poor, making it impossible to obtain a uniform composite system, and if it is too large, the mechanical, electrical and electrical properties of the molded product will deteriorate etc. will decrease.

The unsaturated polyester resin composition of the present invention contains resin curing catalysts such as organic peroxides such as henzoyl peroxide, methyl ethyl ketone peroxy F+ dicumyl peroxy F, and t-butyl peroxide; ′
Cobalt phthenate, manganese octylate, metal soaps such as iron naphthenate, curing accelerators such as tertiary amines such as dimethylaniline, stabilizers such as hyalyl:I quinone, t-butylcatechol, stearin. Release agents such as acid zinc and higher alcohol phosphate esters, thickeners, glass fiber, glass cloth, glass mat, vinylon fiber 2 asbestos.

Additives such as fiber reinforcing agents such as carbon fibers, aramid fibers, nylon fibers, and polyester fibers, coloring agents, and retardants may be added as desired.

The unsaturated polyester resin composition of the present invention can be prepared by adding and dissolving the maleic acid half ester of component B into the unsaturated polyester resin of component A, and then adding and kneading the inorganic filler of component C; A method of adding and kneading an inorganic filler of component C that has been surface-treated with an acid half ester to an unsaturated polyester resin of component A, and
It can be prepared by adding the three components at the same time and kneading them. In particular, it is preferable to employ the first two methods, and it is preferable to use a Henschel mixer, type 2 mixer, all-purpose mixer, etc. to mix and purify the composition.

The unsaturated polyester resin composition of the present invention can be used for general unsaturated polyester resins 3, [1] matte die molding, cold press molding, transfer molding,
It can be molded by injection molding or the like. In addition, B-stage prepreg formed by impregnating mat, cloth, nonwoven fabric, etc. as a fiber reinforcing agent with the unsaturated polyester resin composition of the present invention can also be formed by pressure molding under normal heating. .

[For production]

As described above, the unsaturated polyester resin composition of the present invention is characterized by the addition and blending of maleic acid half ester.

In the present invention, the maleic acid half ester reduces the viscosity of the unsaturated polyester resin-inorganic filler composite system. As a result, the inorganic filler can be uniformly dispersed in the unsaturated polyester resin, and the physical properties of the molded article are improved. Furthermore, it becomes possible to fill the molded article with a high amount of inorganic filler, and it becomes possible to manufacture a molded article having the characteristics due to the high filling of the inorganic filler.

That is, in the present invention, the maleic acid half ester acts as a surface treatment agent for the inorganic filler. Although its mechanism of action is not clear, the carboxyl group of the maleic acid half ester reacts and bonds with the 1011 group present on the surface of the inorganic filler as a reactive substituent, and the remaining alkyl ester W or alkenyl ester It is presumed that the group acts as a group having an affinity for the unsaturated polyester resin. In particular, the molecular structure of maleic acid half ester is similar to that of the molecular chain of unsaturated polyester resin.
In addition, during curing, the bond between the unsaturated polyester resin and the inorganic filler is Make it stronger,
As a result, a molded article with excellent properties can be obtained.

〔Example〕

The present invention will be explained in more detail with reference to Examples and Comparative Examples.

However, the scope of the present invention is not limited in any way by the following examples.

In addition, "1 part" and [%-] in the following examples are overlapping standards unless otherwise specified.

(11 maleic acid half esters (B-1 to B-4)
60 parts (1 mole) of isopropanol was added to a reaction flask equipped with a stirrer, a thermometer, a heating device, and a reflux condenser.
was charged, 98 parts (1 mol) of maleic anhydride was added under stirring, and the temperature was raised to 60°C, followed by 3 hour intervals t'l! Retain maleic acid monoisopropyl ester (B-1) 1
100cm11C=Cll-COOC31h was synthesized.

In the synthesis of 1''3-1, 60 parts of isopropanol (
270 parts (1 mol) of stearyl alcohol instead of 270 parts (1 mol)
The reaction was carried out under the same conditions as in the synthesis of B-1, except that 130 parts (1 mol) of 2-ethylhexanol and 58 parts (1 mol) of allyl alcohol were used, and each alcohol residue was maleic acid half ester (n 2 ) l100c lIC-Cl
1 C00C+ell:++, (l(-3) 110(
lC-11c=cH-C00CI-IZCll(C21
1S) C, l+9 and (r3-4) +100cm11C=C11-COO
C31h(+1) C=C1l□ was synthesized.

(2) Titanium coupling agent As a comparison of the maleic acid half ester of component B, the following titanium coupling agent was used as a semi-ωh.

(CB1) (1-C31170). , Ji
(OCOC171135) 3.1 (CB 2 )
t-CJ70Ti(OCO(CIL+)C”4:II
□) 3(CB-3) 1-Cil170Ti(OC
OIIC=CII2)3(3) Preparation of unsaturated polyester resin composition Maleic acid half esters B-1 to B-4 synthesized in the above (1) and titanium coupling cut CR- prepared in the above (2) A predetermined amount of calcium carbonate (product name: Whiten SB, manufactured by Shiraishi Kogyo ■), which has been surface-treated in advance using a predetermined amount of each of CB-1 to CB-3, is added to an orthophthalic acid-based unsaturated polyester resin for general lamination (product name: Whiten SB). Name: Polymer YG300B, manufactured by Narita Pharmaceutical Co., Ltd.) 1
00 parts and kneaded for 30 minutes using an Ishikawa crusher.

In addition, for comparison, calcium carbonate without surface treatment was added to the unsaturated polyester resin, and kneaded under the same conditions as in "-".

The viscosity of the kneaded material at 25°C was measured using a rotational viscometer (BSR type).
Measurements were made using a Tokyo Keiki Co., Ltd.).

Table 1 shows the blending ratio of maleic acid half ester and calcium carbonate to 100 parts of unsaturated polyester resin and the results of viscosity measurements.

(4) Molding of unsaturated polyester resin To 300 parts of the unsaturated polyester resin composition prepared in the above (3), 1 part of t-butyl perhendoate, 7 parts of zinc stearate, 1 part of magnesium hydroxide, 174 parts. °°Chopped grass 15% (based on the blend) was added and kneaded using a kneader.

The obtained kneaded material was molded at a temperature of 130°C and a molding pressure of 20 kg.
Compression molding was performed under the conditions of /cIA.

Regarding the obtained molded product, JIS-6911 (p
- Various physical properties were measured based on the results.

The measurement results are shown in Table 1.

〔Effect of the invention〕

As is clear from the above Table 1 showing the results of the examples, the unsaturated polyester resin-inorganic filler composite system of the present invention containing maleic acid half ester, the substitute (2) is the system containing a titanium coupling agent. And the viscosity is significantly lower than that of the system containing nothing. That is, the addition and blending of maleic acid half ester has a large viscosity-reducing effect, which not only enables uniform dispersion of the inorganic filler in the unsaturated polyester resin, but also facilitates the workability of kneading. Furthermore, since it has a large viscosity-reducing effect, it is possible to incorporate a high amount of inorganic filler into the unsaturated polyester resin.

On the other hand, compared to the system containing a titanium coupling agent and the system containing no titanium coupling agent, the molded product of the unsaturated polyester resin-inorganic filler composite composition of the present invention blended with maleic acid half ester showed If the blending amount of the filler is about the same, mechanical properties such as tensile strength, bending strength, and impact strength are excellent. Systems with high inorganic filler content also have excellent mechanical and electrical properties. This shows that the maleic acid half ester acts as a coupling agent that chemically bonds the unsaturated polyester + Δ1 fat and the inorganic filler.

The present invention provides an unsaturated polyester resin-inorganic filler system with excellent physical properties, particularly a system with a high content of inorganic filler, and its industrial significance is extremely large.

Claims (1)

[Claims] (1) Component A: 100 parts by weight of unsaturated polyester resin Component B: 0.2 to 10 parts by weight of monoalkyl ester and/or monoalkenyl ester of maleic acid Component C: 10 to 500 parts by weight of inorganic filler The above component A, Unsaturated polyester resin composition characterized by consisting of B and C