JPS58127718A - Unsaturated polyester resin composition and colored molding - Google Patents

Abstract

PURPOSE:The titled composition capable of providing moldings excellent in colorability, low-shrinkage and cracking resistance, comprising a specified unsaturated polyester resin, a particulate polystyrene resin and two kinds of CaCO3 powders with different particle diameters. CONSTITUTION:The titled composition comprising 15-30% unsaturated polyester resin, styrene monomer content of 25-60wt%, prepared by reacting a glycol component containing 15-70mol% neopentyl glycol and 10-30mol% water-containing bisphenol with a dicarboxylic acid component based on alpha,beta-unsaturated dicarboxylic acids, 3-10wt% powdery to particulate polystyrene resin, all particles passing 50 mesh, 15-30wt% CaCO3, particle diameter of 0.5-15mum, and 20-50wt% CaCO3, particle diameter of 40-400mum. This resin composition is excellent in fillability and storage stability; can form moldings excellent in colorability, low-schrinkage and cracking resistance; and is useful in the production of parts of electric and electronic devices and appliances.

Description

[Detailed description of the invention] [Technical field to which the invention pertains] The present invention provides excellent coloring properties, low shrinkage properties, crack resistance, filling properties, The present invention relates to an unsaturated polyester resin composition having storage stability and molded articles thereof.

[Technical background of the invention and its problems]

Generally, when unsaturated polyester resin is cured, 5 to 10%
The curing shrinkage rate is approximately 0.2 to 0.6 even when it is added to a premix molding material. However, molding materials that exhibit a curing shrinkage rate of the same level as levers can be used, for example, for molding medium to large sized no-heat breakers, molding that requires a high degree of dimensional accuracy, and metals such as slip rings for motors. When the premix layer is embedded and molded, there are inconveniences such as cracks occurring in the premix layer due to shrinkage when the premix layer hardens or due to a difference in expansion coefficient between the metal and the premix sheet. Furthermore, when molding embedded objects with complex shapes with holes or grooves of 5 mm or less, or coils of electromagnetic switches with thin enameled wires, especially low-pressure transfer molding (Kada Riki 1 no #tyA111 or less) is required. ), not only were there many restrictions on the filling of holes and grooves, breakage of the enameled wire, layer shorting, etc., but there were also significant restrictions on the use of the wire.

Conventionally, in order to reduce the volume shrinkage due to curing of this unsaturated polyester resin and improve crack resistance, (1) vinyl polymer, (2) vinyl polymer having acid functionality, td, i3, etc. ) It is known to add and blend non-quality linear saturated polyester resins.

By using any of these polymerization methods, the desired effect can be obtained for low-shrinkage grains, but if pigments or dyes are added and used as a colored molding material, uneven coloring will be seen in the molded product obtained by heating and curing. There is a drawback. In other words, considering the aesthetic appearance of the molded product, the coloring properties of the parts added and blended with pigments to the above-mentioned vinyl-based polymers and other compositions intended to reduce the curing shrinkage of unsaturated polyester resins are poor, and the above-mentioned vinyl-based When polymers etc. harden, they become optically non-uniform and become cloudy! In addition, when cured, it may come to the surface of the molded product, causing uneven coloring and impairing the aesthetic appearance. In order to avoid this uneven coloring, attempts have been made to increase the amount of pigments and dyes (1) to the resin content, for example, by increasing the amount of carbon pigment to about 2.0%, which is 5 to 10 times that of ordinary stitching. There are also problems in that the electrical properties and mechanical properties are deteriorated, and furthermore, the storage stability of the resin composition itself and the premix is impaired. In addition, as a measure to prevent uneven coloring, as a third component, (a) other thermoplastic resins may be added or (b) oxides or hydroxides such as magnesium and calcium may be added and chemically modified. It is also known that (C) a pigment whose surface is stabilized by graft polymerization of a vinyl monomer is used. However, a
) is not very effective, and the polymerization of jb)) has the disadvantage that the curing shrinkage rate increases substantially and cracks occur when molded into thick-walled products. In the case of (C), the low shrinkage property is also lost and sufficient effects cannot be obtained.

On the other hand, regarding the filling properties of the resin composition into the insert, if the particle size of the filler is larger than the gap size of the insert, it goes without saying that the filling will not be sufficient. Since the viscosity of the material is high (the particle size of the filler is 5 to 40 μm), it is difficult to perform transfer molding at low pressure (1,000 kg/kg or less).

When molding is carried out at a medium or high pressure of 100/cti/dt or more, the insert such as a coil may be deformed or a layer short may occur.

As mentioned above, BRIMIX molding materials using conventional unsaturated polyester resin and fillers have low shrinkage, colorability,
It has been difficult to achieve all of crack resistance, fillability, and storage stability.

[Purpose of the invention]

The present invention has been made in view of the above points, and it is possible to suppress the shrinkage of unsaturated polyester resin due to heat curing, and easily obtain a molded product without uneven coloring even when colored by adding a pigment or the like. The object of the present invention is to provide an unsaturated polyester resin composition and a molded article having excellent low shrinkage properties, coloring properties, crack resistance, filling properties, and storage stability.

[Summary of the invention]

To explain the present invention in detail below, the present invention comprises (A) a glyfur component containing a total of 15 to 70 mol of neopentyl glycol and 10 to 30 mol of water-added bisphenol;
, made by reacting with a dicarboxylic acid component mainly composed of β-Funawa New Year's rubonic acid, containing a styrene monomer of 25~
6 oat% unsaturated polyester resin 15-30 wt%
(C) Calcium carbonate 15-3 with a particle size of 0.5-15 μm
■) Calcium carbonate with a particle size of 40 to 400 μm 20 to 50
% by weight.

Furthermore, the present invention provides a molding material with improved fillability characterized in that a molding material obtained by adding an initiator for curing 1, a mold release agent, reinforcing fibers, a coloring agent, etc. to the resin composition is heated and press-molded. Concerning shrinkable New Year's day polyester wood 11T&I shaped products.

However, the water-added bisphenol referred to herein is a hydrogenated bisphenol compound, and is a 2,2-bis(4-hydroxycyclohexyl) clopane, which has a weak molecular structure as follows.

Gold and white below.

The unsaturated polyester resin used as one component in the present invention is, for example, α, β, such as maleic anhydride or fumaric acid.
- Obtained by dissolving in styrene monomer the reaction product of a dicarboxylic acid, optionally a dicarboxylic acid component partially substituted with a saturated dicarboxylic acid such as phthalic acid, isophthalic acid, het acid, etc., and a glycol component. It is.

However, the glycol components of the polymerization (dneopentyl glycol 15 ml and 30 ml of water-added bisphenol and pyrene glycol, 3-methylbentanediol, bentanediol, 2-methyl-butanediol, diethylene glycol, dipropylene glycol, Pentyl glycol, glycerin, etc.
9 types using 42 or more types. That is, the glycol component may be composed of only neopentyl glycol (2,2zomethyl-13-propanediol) and water-added bisphenol, but a portion thereof may also be replaced with propylene glycol or the like. However, it is necessary to always contain the cineopentyl glycol component and the water-added bisphenol component within the above range. The reason is that the composition ratio of neopentyl glycol is 1.
If the molar ratio is less than 5 molar ratio, the degree of coloring improvement aimed at by the present invention will be small, and if the molar ratio is 70 molar ratio, crystallization will occur, and storage of the prepared resin composition and premix will be difficult. Stability is impaired, causing problems in workability and quality control. - When the composition ratio of bisphenol added to water is less than 10 molar ratio, crystallization tends to occur in a separately prepared resin composition, resulting in poor storage stability and inconvenience in handling. However, if the amount still exceeds 30 molt, the stability itself will improve, but on the other hand, when prepared as a premix, bisphenol A, which exists as a very small impurity in water-added bisphenol, will act as a polymerization inhibitor. This is because the reaction of the polyester is prolonged and the formability is impaired, and low shrinkage is also hindered, making it impossible to finally obtain a molded product with good aesthetics and dA. In order to improve the mold release property, it is possible to incorporate an internal exfoliating agent such as monozinc stearate, but this is an effective method since it causes oozing to the surface of the molded product and reduces gloss. I can't say it.

Therefore, the above unsaturated r% IJ ester resin is considered to be a styrene monomer and its content is in the range of 25 to 60%.Styrene is an unsaturated polyester 144%.
1] It is a substantially inexpensive monomer that exhibits copolymerizability with Ff. If its content is outside the above range, desired effects may not be achieved in terms of mixability, low shrinkage, coloring properties, filling properties, etc. of the molding material. This is because it cannot be obtained. In addition, the reason why the unsaturated polyester resin is used in the range of 15 to 30 times is because the desired effects cannot be obtained in terms of molding material mixability, low shrinkage, coloring property, filling property, etc. It is.

Examples of the polystyrene resin constituting another component in the present invention include general polystyrene and butadiene-modified polystyrene. However, this polystyrene resin must be in the form of powder or particles with a particle size that can pass through all 50 meshes! It is. That is, in the case of powder or particles with a coarser particle size than the above (C has insufficient solubility in the mixing process for the unsaturated monomer used in combination, polystyrene protrudes on the surface of the molded product and damages the outer shell).

Further, when mixed with powders such as fillers and additives using a kneader, it is difficult to mix uniformly.

However, if the composition ratio of this polystyrene resin is 3 to 10%, it may cause a decrease in thermal properties, and furthermore, it may cause a decrease in colorability, and if it is less than 3% by weight, effects such as low shrinkage cannot be obtained substantially. That's because there isn't.

The reason why polystyrene resin was specifically selected here is as follows. That is, instead of this polystyrene resin component, 50
If, for example, 1D saturated polyester resin particles are used, the acrylic resin components will come out or the coloring will be uneven, which will defeat the purpose of the present invention.

In the present invention, since calcium carbonate, which is another component, is selected for filling, it is possible to use a trowel as an inexpensive filler when kneading molding materials. This is because there is less wear on the 1/- blade, and the molded product has excellent characteristics such as crack resistance. However, the particle size of this calcium carbonate and the compound stitch are 0.5~
15. am, 4f)~400umTh and 15~30j
tj 91%, 20 to 50 wt. It's because I can't get it. That is, if the ratio of cal/lam carbonate of 0.5 to 15 μm is less than 15 it, the filling properties for holes and grooves will deteriorate, and cavities, weld lines, etc. will occur, and if it exceeds 30←1, it will be difficult to The flow of the material decreases significantly, making low-pressure molding difficult. In addition, 20% of Cal/Rum carbonate with a particle size of 40 to 400 μm is added.
If the coulometric amount is less than 1, the flow of material during molding will decrease significantly,
This is because if it exceeds 50 tons, the kneading properties and molding workability will be significantly reduced, and further problems will occur, such as a reduction in the 1tlWf impact resistance of the molded product.

Granular form of calcium carbonate l#i used in the present invention: Although not particularly limited, spherical form is more preferable in terms of crack resistance and impact resistance. Also, regarding the particle size, ld,
Coarse particles of 400 tt or more, 15-40. Even if the total content of umO particles is less than 5%, the effect of the present invention is not inferred.

In addition to the above-mentioned photonic agents, aluminum hydroxide, talc, glass powder, silica powder, berylum sulfate, asbestos, and the like may be added to the extent that the object of the present invention is not impaired.

Inorganic fibers such as glass fibers and asbestos fibers, organic fibers such as vinylon fibers and polyamide fibers are used as reinforcing agents, and carnauba wax, zinc stearate, other pigments, anti-aging agents, etc. are used as mold release agents. Known materials are also added and blended.

As the curing initiator used in this invention, tert-butyl perbenzoate dicumyl peroxide, 1,1 di-tert-butyl peroxy 3°3.5) IJ methylcyclohexane, etc. are preferable, and as a mold release agent, Idl Steer 1 Zinc phosphate, carnauba wax, etc. are preferable; as reinforcing fibers, glass fibers, synthetic fibers, etc. are preferable; as coloring agents, carbon black, red iron oxide, etc. may be added in the amounts usually used.

The above materials are blended and kneaded using a kneader, ruder kneader, etc., then shaped into desired shapes such as bulk, flakes, and granules to obtain an unsaturated polyester molding material. A colored molded article made of an improved low shrinkage unsaturated polyester resin is obtained.

〔Effect of the invention〕

According to the present invention, it is possible to simultaneously improve the colorability, low shrinkage, crack resistance, fillability, and storage stability of an unsaturated polyester resin composition, and it is possible to provide a practically excellent molding material. .

[Embodiments of the invention]

Next, examples of the present invention will be described.

Example 6 moles of neopentyl glycol, 1 mole of water-added bisphenol, 3.3 moles of propylene glycol, and 10 moles of maleic anhydride were used as reaction components, and 1 mole of water was added under an N2 gas atmosphere.
First, an unsaturated polyester resin having an acid value of 28 was synthesized by carrying out an esterification reaction at 20 to 200'C. Next, this unsaturated polyester resin is dissolved and dissolved in styrene monomer,
While preparing a solution having a resin content of 70% by weight, 300 ppm of hydroquinone was added (unsaturated polyester resin #7.A).

An esterification reaction was carried out under the same conditions as above using 10.2 moles of propylene glycol and 10 moles of maleic anhydride as reaction components to synthesize an unsaturated polyester resin having an acid value of 26. Next, 300 ppm of hydroquinone was added while styrene monomer was added and dissolved, resulting in a resin content of 70 t-t%.
An unsaturated polyester resin solution B (for comparison) was prepared.

Unsaturated polyester resin (N.

), granular polyroll resin, calcium carbonate, organic peroxide, glass fiber, etc. in the composition ratio (parts by weight) shown in Table 1.
Ten tubs of unsaturated polyester resin compositions (premix molding materials), including a comparative example, were prepared by selecting and blending K.

Using the premix molding materials thus obtained, the shrinkage rate measurement disk was heated to 150°0, 80 to 100, and cd pressure for 3 minutes, still by transfer molding method, i 55 '(,'), 30 kg/*, 4 minutes, 1ri+m groove, 1o with magnetic coil insert.

Xl, ('1OX50/7) Yunosugi/tax f cedar product has been completed. Table 1 shows the molding shrinkage rate (according to the JIS-6911 method), the ability to fill grooves (visually), the unevenness of color on the surface (colorability, visually), and the occurrence of cracks (visually). Each shows.

As is clear from the table, Example 1 according to the present invention? ,3
All of these roses exhibit good undergrowth in terms of low shrinkage, coloring, filling, and crack resistance. On the other hand, in Comparative Examples 1 and 3, which are not based on the present invention, the unsaturated polyester resin (B) that does not contain an alcohol component according to the present invention is used, and in Comparative Example 2. Since granular polystyrene resin was used, it did not dissolve sufficiently during crosstalk, resulting in extremely poor surface smoothness. In comparison examples using calcium carbonate with a particle size distribution not according to the present invention, high viscosity; no W, insufficient filling at 39 kg/lyl (Comparative Example 4), molding material too soft, frequent cracking,
Due to molding pressure escaping, the surface loses its luster, and cracks occur (
Problems such as Comparative Examples 5 and 6) occurred.

Representative patent attorney Kensuke Norichika (and one other person)

Claims (1)

[Scope of Claims] [A glycol component containing 15 to 70 moles of neopentyl glycol and 10 to 30 moles of water-added bisphenol is reacted with a dicarboxylic acid component mainly composed of α,β-unsaturated dicarboxylic acid. (B) Powdered or particulate polysteel resin with a particle size of 50 mesh and 3 to 10 weight parts.
and (q calcium carbonate 15 to 15 μm in particle size)
An unsaturated polyester dendritic composition comprising: 30 elms and 20 to 50% by weight of calcium carbonate each having a grain size of 40 to 400 μm. [21 A styrene monomer-containing product made by reacting a glycol component containing 15 to 70 moles of neopentyl glycol and 10 to 30 moles of water-added bisphenol with a dicarboxylic acid component mainly composed of α,β-Funawa New Year Rubonic Acid. Powder or particulate polystyrene powder that passes through a mesh of unsaturated polyester resin 15 to 30 weight 11 with a particle size of 25 to 60'1iHit% and a particle size of 3 to 10 weight,
Calcium carbonate 15-30% by weight with a particle size of 0.5-15 μIn and calcium carbonate 2 with a particle size of 40-400 μm.
A curing initiator, a mold release agent, a curing initiator, a mold release agent,
This is a colored molded product of ester resin with improved fillability, low shrinkage, and a molded material made from a molding material containing reinforcing fibers and a coloring agent.