JPS63192407A - Tableware excellent in heat resistance and hydrothermal resistance - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to tableware with excellent heat resistance and hot water resistance.

(Prior Art) Tableware has traditionally been made of ceramics, glassware, various metals, or plastics.

On the other hand, with the modernization of eating habits, containers used not only as conventional household items but also for food packaging and display have become increasingly used as tableware. For example, foods such as frozen foods placed in various containers are heated to about 200 to 300° C. in a microwave oven or microwave oven, and the containers are used as tableware.

Therefore, heavy and easily damaged ceramics and glassware are
This is inconvenient as tableware that needs to be carried around, and metal ones also have the disadvantage that they cannot be used in a microwave oven.

As something that is light, hard to break, and can be used in the microwave,
There are tableware made of plastic snacks, but conventional products have insufficient heat resistance, are easily deformed or discolored when they come into contact with steam or are washed by boiling, and lack hot water resistance. there were.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned problems faced by conventional tableware.

Therefore, an object of the present invention is to provide light and strong tableware that has excellent heat resistance and hot water resistance, and also has a high degree of flame retardancy.

(Means and effects for solving the problem) As a result of various studies by the present inventors, a curable composition obtained by kneading a specific 1M filler with a specific monomer was used as a reinforcing fiber. The present invention was completed based on the discovery that a molded product obtained by impregnating and/or mixing with a polyester resin and then curing the product satisfactorily achieves the object.

That is, the present invention provides a monomer mixture 10 containing an aliphatic polyfunctional (meth)acrylate and an aromatic vinyl compound as essential components.
A reinforcing fiber is impregnated with a curable composition (I) obtained by kneading 250 to 800 parts of an inorganic filler with an average particle size of 5 microns or less and a hardening agent to 0 parts by weight. This invention relates to tableware that has excellent heat and hot water resistance and is obtained by mixing and curing.

The aliphatic polyfunctional (meth)acrylates used in the present invention include ethylene glycol di(meth)acrylate, brobylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. , glycerintri(meth)acrylate, trimedyllolbrobantri(meth)
Acrylate, dipentaerythritol hexa(meth)
Contains acrylate, etc.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, p-methylstyrene, and divinylbenzene.

The ratio of aliphatic group polyfunctional (meth)acrylate and aromatic vinyl compound is 20 to 80% by weight for the former and 80 to 2% for the latter.
The ratio may be 0% by weight, but the former is more preferably 30% to 30% by weight.
The latter is 70 to 30 fffffi%. The above two types are essential components of the monomer mixture in the present invention, but a part of the monomer mixture also contains (meth)acrylic acid, salts thereof, methyl (meth)acrylate, and isobutyl (meth)acrylate.
It is also possible to use various (meth)acrylate monomers such as meth)acrylate, or other monomers and oligomers such as various macromonomers, unsaturated polynisderm oligomers, fumaric acid esters, and maleimides.

However, if these other monomers or oligomers are used too much, it may be difficult to obtain a curable composition with high filler content, or the resulting tableware may have poor heat resistance and hot water resistance. Furthermore, if the other monomers used have low boiling points, they may foam during molding, resulting in poor appearance of the tableware. Further, a thermoplastic polymer may be added to the monomer mixture in order to reduce shrinkage during molding and hardening, prevent cracks in tableware, and improve surface smoothness. Examples of thermoplastic polymers include (meth)acrylic polymers such as polymethyl methacrylate, (meth)acrylic-styrene covalent polymers,
Conventionally known low shrinkage polymers such as polystyrene, polyvinyl acetate, styrene-vinyl acetate copolymer covering, polyvinyl chloride, polybutadiene, polyethylene, polycaprolactam, and saturated polyester can be used alone or in combination. When a thermoplastic polymer for low shrinkage is blended into multiple layers, it increases the viscosity of the monomer mixture, resulting in a highly filler-containing curable composition becoming less than WiM, and decreasing the transparency and heat resistance of tableware. You may end up getting something inferior. Therefore, thermoplastic polymers for low shrinkage are
It is best to use 9 suspensions as much as possible, and 100 weight f of the monomer mixture.
40 parts by weight or less, more preferably 5 to 3 parts by weight based on part fi
It is desirable to use within the range of 0 parts by weight.

The inorganic filler used in the present invention may have an average particle size of 5 microns or less (calcium carbonate, talc, clay, silica, alumina, quartz, calcium silicate, aluminum hydroxide, hydroxide, etc.). Commonly used hydrates of metal oxides such as magnesium and calcium hydroxide can be used.Among such inorganic fillers with an average particle size of 5 microns or less, fillers should be filled as highly as possible.
It is also desirable to have a material that can be dispersed with good stability even at low viscosity, and hydrates of metal oxides are particularly preferred. Furthermore, hydrates of metal oxides are ideal in terms of low elution into water and flame retardancy. If the average particle size of the inorganic filler exceeds 5 microns, tableware with excellent hot water resistance cannot be obtained, and only tableware with poor surface properties such as surface gloss and smoothness can be obtained.

It is preferable to use a silane coupling agent when kneading the monomer mixture and the inorganic filler because it improves the water resistance of tableware obtained by curing the resulting curable composition. Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriethoxysilane, and vinyldriahydroxysilane.

The ratio ω of the inorganic filler used is in the range of 250 to 800 parts by weight per 100 parts by weight of the monomer mixture. 250
If the amount is less than 1 ffi part, the molded product is likely to crack during curing, and tableware with excellent heat resistance, hot water resistance, and flame retardancy cannot be obtained. In addition, if the suspension exceeds 800 parts by weight, the viscosity of the curable composition obtained by kneading becomes too high.
The reinforcing fibers are not sufficiently impregnated or mixed, and tableware with excellent hot water resistance and mechanical strength cannot be obtained.

By blending a hardening agent when kneading the single W (4 mixture) and the inorganic filler, the hardened fi composition (I
) is obtained.

As the curing agent used in the present invention, benzoylper A
Organic peroxides commonly used in heat-pressure molding such as dicumyl peroxide, t-butyl peroxyoctoate, t-butyl peroxybenzoate, and dicumyl peroxide, and organic peroxides that are accelerators used in combination with them. There are amines and polyvalent salts. The curing agent is flff, a monomer mixture.
It is customary to use a value corresponding to 0.5 to 3.0% based on l.

In addition, when obtaining the curable composition (I), the average particle size is 5.
In addition to inorganic fillers and hardeners of micron size or less, if necessary, various fillers within a range that does not adversely affect the effects of the present invention, mold release agents such as zinc stearate, thixotropic agents, plasticizers, flame retardants, and flame retardants. Agents, coloring agents, etc. may also be added.

The tableware of the present invention is obtained by impregnating and/or mixing reinforcing fibers with the curable composition (I) and then curing the reinforcing fibers. For example, after preparing the curable composition (I), the reinforcing IN is impregnated and cured, specifically by R-R1M molding, resin injection molding, preform matte die molding, or the like. In addition, reinforcing fibers are added when kneading inorganic fillers and curing agents into the single omega substance mixture, and mixing, impregnation, and mixing are performed at the same time to create a premix molding material, which can be used for press molding, transfer molding, and injection molding. Tableware can also be obtained by molding and curing using methods such as molding.

Among these, it is preferable to use a heating/pressure molding method for curing, since it allows the production of tableware with excellent surface properties such as surface gloss and smoothness, and no distortion or cracks with good dimensional accuracy.

The reinforcing mH used in the present invention includes glass fiber, carbon! ! There are organic and inorganic materials such as fiber, polyamide Jllff, and various whiskers.

There are no particular restrictions on the amount of reinforcing fiber used, but it is preferably 5 to 5 parts per 100 parts of the curable composition (I).
This is the ratio of the range of 30-fold ω part.

In order to carry out the present invention specifically, for example, first, 80 to 20% by weight of aliphatic polyfunctional (meth)acrylate, preferably 70 to 30% by weight, and 20 to 80% by weight of aromatic vinyl compound.
A weight mixture of 5% by weight, preferably 30 to 70% by weight is prepared, and 250 to 800 parts by weight of an inorganic filler and a curing agent with an average particle size of 5 microns or less are kneaded for 100 m of this mixture. A curable composition (I) is prepared. At this time, the inorganic filler may be treated with a silane coupling agent in advance, or the silane coupling agent may be added in an amount of 0.1 to 2.0% based on the m of the inorganic filler used. No need to worry about dissolving or dispersing the monomer mixture! By using the A-grade filler, the hot water resistance of the resulting tableware can be improved. As a kneading method, for example, a low-speed mixer such as a double-arm kneader, a high-speed stirrer such as a disper, a pigment dispersion machine for manufacturing paints, or a kneading roll may be used, but the curable composition has a high filler content. In order to obtain this, a low-speed crosstalk machine with strong crosstalk force is preferable.

(Effects of the Invention) The tableware of the present invention has a high degree of flame retardancy and high heat distortion temperature because it is highly filled with a specific inorganic material, and also has high temperature and high humidity during cooking and washing. It does not deform or change color even under environmental conditions (and has excellent heat resistance and hot water resistance.

Furthermore, the tableware of the present invention hardly generates volatile substances even at high temperatures of about 250° C., and does not change the taste of the food on which it is served or add odor to it.

Further, the tableware of the present invention can be made to have a natural stone-like appearance or be colored by selectively using an inorganic filler, and is excellent in color and design.

(Examples) Examples will be described in more detail below, but these do not represent the entirety of the present invention.

Example 1 Trimethylolpropane trimethacrylate 2Sffi
ffi part and 75 parts by weight of styrene and 1 part by weight of styrene, 3 parts by weight of zinc stearate, and a curing agent of t-butyl peroxyoctoate [Barbutyl 0, NOF H! J)
0.8 parts by weight and silane coupling agent (KBM-50
3. Mix 1 part of 0.5ffifi manufactured by Shin-Etsu Chemical @, and add aluminum hydroxide [Hisilite H-32] to this mixture.
0, average particle size 3.5 microns, manufactured by Showa Light Metal ■ 300
Parts by weight were added while stirring with a high-speed stirrer to obtain a liquid curable composition.

Next, the mold set in the press molding machine (product size: 2
00φ shoes, 10# depth dish shape) was humidified to 120℃, chopped glass mat #450 (l/m2 to 450)
Three sheets were placed in the mold. The above-mentioned curable composition 150Q was poured onto this glass mat, and 30K per medium area of the product was applied.
Pressure was applied for 3 minutes at a pressure of g/m2 to obtain plate-shaped tableware with a thickness of 3 shoes.

The resulting tableware had a beautiful milky white color, and as shown in Table 1, had excellent heat resistance and hot water resistance, and a high degree of flame retardancy. Furthermore, as a result of conducting a test in accordance with the Quality Sanitation Law, it was found that the obtained tableware had physical properties that passed the test.

Example 2 Trimethylolpropane trimethacrylate 1afNi
Polymethyl methacrylate (Acryvet MDOO 1, manufactured by Mitsubishi Rayon ■), 3 parts by weight of zinc stearate, and a curing agent t-butyl peroxyoctoate [Barbutyl 01 NOF ■] (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.5 parts of a silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed together, and this mixed solution was charged into a double-arm kneader.Next, the kneader - Aluminum hydroxide [Hisilite H]
-320, average particle size 3.5 microns, manufactured by Showa Light Metal ■]
300 parts by weight were added with stirring to obtain a highly viscous curable composition. Subsequently, 45 parts by weight of glass IAM chops cut to a length of 6 m were added and kneaded with Fl for 5 minutes to obtain a bulk molding compound (BMC). Cut this BMG with a knife and total ff1L, 18
When 0Q was put into the same mold used in Example 1 set in a press molding machine and press molded in the same manner as in Example 1, it was found to have a milky white translucent color with excellent surface gloss and no cracks or distortion. Beautiful plate-shaped tableware was obtained. The physical properties of this tableware are as shown in Table 1, and it was excellent in heat resistance, hot water resistance, and flame resistance.

Examples 3 and 4 BMG was prepared in the same manner as in Example 2 except for using the formulation shown in Table 1. When each of the obtained BMCs was press-molded in the same manner as in Example 2, beautiful milky-white translucent plate-shaped tableware with excellent surface gloss was obtained. The physical properties of this tableware were as shown in Table 1.

Comparative Example 1 0.3 mol of isophthalic acid, maleic anhydride i'l! 0.7
mol, neopentyl glycol 0.3 mol, propylene glycol 0.6 mol and hydrogenated bisphenol A0
．． Unsaturated polyester 47 obtained by condensing 15 moles
．． 5 parts by weight of styrene 47.5 fl! Dissolves in the fan,
An unsaturated polyester resin liquid was prepared by adding 0.005 fflff 1 part of hydroquinone as a stabilizer.

5 parts by weight of polymethyl methacrylate [Acrivet MDOOI, manufactured by Mitsubishi Shion Co., Ltd.] was dissolved in this resin liquid, and then 0.5 parts by weight of a silane coupling agent [KBM-503, manufactured by Shin-Etsu Chemical] and internal mold release were added. 3 parts by weight of zinc stearate as a curing agent, 0.81 m part of t-butyl peroxyoctoate as a hardening agent, and aluminum hydroxide [Hisilite H-3201 average particle size 3.5 microns, Showa Light Metal ■
130 parts (M) was added and mixed using a high-speed stirrer to obtain a highly viscous curable composition. Using this curable composition, molding and curing were performed in the same manner as in Example 1 to obtain comparative tableware.

The resulting tableware was a beautiful white product, but as shown in Table 1, it had shortcomings in heat resistance, hot water resistance, and flame retardancy.

Claims (1)

[Claims] 1. 250 parts by weight of an inorganic filler with an average particle size of 5 microns or less per 100 parts by weight of a monomer mixture containing an aliphatic polyfunctional (meth)acrylate and an aromatic vinyl compound as essential components.
A tableware with excellent heat resistance and hot water resistance obtained by impregnating and/or mixing reinforcing fibers with a curable composition (I) obtained by kneading ~800 parts by weight and a curing agent, and then curing the curable composition (I). 2. The tableware according to claim 1, wherein the inorganic filler is a hydrate of a metal oxide.