JPS61213082A - Polymer resin material for toy capable of being processed bywarm water - 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] Cmlm Industrial Field) The present invention provides a hot water processable polymer for toys that can be softened at a relatively low temperature and freely deformed, and that can be hardened and retains its shape by cooling to room temperature. This is a book about resin materials.

(Prior art) In recent years, the materials for toys have been polyethylene, and the polyps have been pyrene, polystyrene, AB8. acrylic resin.

Plastics such as polyvinyl chloride resin are often used. These plastics are clean and easy to handle, but are generally molded at temperatures above 100°C.

On the other hand, natural or synthetic trans-isoprene polymers have crystals that melt at relatively low temperatures.

The feature of the j! 1. Taking advantage of this feature, its use as a toy material that can be processed in hot water is being considered.

(Problems to be Solved by the Invention) Although the polymer resin material using the above-mentioned transisoprene polymer has the characteristic that it can be molded using hot water, etc., on the other hand, it has a slow curing speed and is not suitable for 4I. Since the curing speed is slow when reworked, it is necessary to maintain the shape while cooling and hardening the product for several minutes to several tens of minutes during molding.

t, or may not harden at all depending on the work conditions. It had one problem, such as poor molding operation due to its high tackiness.

(Means and effects for solving the problems) The present inventors have arrived at the present invention as a result of intensive studies to improve the drawbacks of the above-mentioned trans-inoprene polymer.

That is, the present invention has a trans bond content of 75 to 95%,
Weight average molecular weight (c) 3 ooo to 56 oo.

and a butadiene polymer having a structure with a molecular weight distribution (My/Mn) of 1.2 to 5.0.
It is a polymer resin material for toys that can be molded at low temperature.

That is, the polymer resin material of the present invention is (1) a material having appropriate hardness, impact strength, and rebound resilience.

(2) When soaked in warm water, it immediately becomes flexible, and can be cut freely with scissors or a knife, and can be shaped into any desired shape.

(3) When removed from hot water, it quickly hardens and can be easily shaped.

(4) It can be colored freely by mixing dyes and pigments, and it is also possible to apply paint.

It contains the characteristics of nishiki, and the toys made with it are
Children can express their creativity even more.

The trans-butadiene polymer constituting the polymer component of the polymer resin material of the present invention must have the following structure. First, the trans bond content measured by the Morley method using an infrared spectrophotometer is 95-95-, gel permeability! ! / The weight average molecular weight (Mw) measured by Chromatogoku 7 is no, o o o ~ 50 to 000, and the molecular weight distribution (My/MI &) indicated by the ratio of 1 weight average molecular weight to number average molecular weight is 1.2 ~5.0. If the transformer bonding wheel is lower than this range, a polymer resin material for toys with sufficient rigidity and strength cannot be obtained.
On the other hand, if the temperature is too high, the softening temperature becomes high, making it difficult to perform molding using hot water or the like at a relatively low temperature. If the weight average molecular weight (Mw) is lower than this range, a polymer resin material for toys with sufficient strength cannot be obtained.

If it is higher than this, the operability at the time of forming 9 will be significantly reduced. If the molecular weight distribution is wider than this range, moldability and rigidity will deteriorate, which is undesirable. On the other hand, polymers with a narrow molecular weight distribution are difficult to manufacture.

No advantages in terms of physical properties are observed.

The polymer resin material for toys of the present invention is usually preferably a trans-butadiene polymer alone.

Depending on the application, it may be preferable to use a mixture with other polymer resins in order to further improve the softening temperature, rigidity, strength, impact resilience, moldability, etc. of the resin material. however,
Even in this case, the desired effect of the present invention cannot be sufficiently achieved unless the transbutadiene polymer is contained in an amount of at least 30% by weight.As other polymer resin components to be mixed, particularly preferred are Examples include trans isoprene polymer, trans polyoctenamer, and caproctone polymer.

In the present invention, the butadiene polymer and expanded butadiene monomer are combined with a homogeneous composite catalyst (specially Kaisho 55-3
No. 8827, JP-A @Hl%, No. 111916), in a hydrocarbon solvent in the presence of a homogeneous composite catalyst consisting of a transition metal compound such as lubrication or 2 tanthane and an organometallic compound such as organomagnesium. It can be obtained into a container by solution polymerization.

Examples of the trans-isoprene polymer mentioned in the present invention include 1, for example, Clareizoprene Chemical I&l@Ii
Kuraray TP-301 manufactured by Kuraray Corp. can be used. Also, as a transpolyoctenamer.

For example, Vestenamer 8012 and Pestenamer 9 manufactured by Hiels can be used. Furthermore, as the capro2chton polymer, for example, Plaxel H-7, Zuccel H-4゜Plaxel H%, manufactured by Daicel Chemical Industries, Ltd.
can be used. In the hot-water processable polymer resin material for toys of the present invention, in addition to the above-mentioned polymer resin components, it is necessary to adjust the hardness, flexibility, etc. By this, inorganic fillers and possifiers can be added. Further, stabilizers, pigments, etc., which are general additives added to monopolymer resin materials, can be appropriately added in the case of the present invention as well as in conventional resin materials.

The amount of inorganic filler used is not more than 13,100 parts by weight per 100 parts by weight of acid content of one polymer resin. Examples of inorganic fillers include titanium oxide, calcium carbonate, clay-talc, mica-bentonite, and the like. The use of more than 100 parts by weight of an inorganic filler is undesirable because it lowers the zero impact strength IILt of the resulting polymer resin material.

The amount of plasticizer used usually ranges from 0 to 30 parts by weight per 100 parts by weight of polymer resin component.

Examples of hardening agents include diptylphthalate, di(2-
ethylhexyl) 7 tallate, di(2-ethylhexyl) adipate, diethylene glycol dibenzoate, butyl stearate), butyl epoxy stearate) 1
) 9-(2-ethylhexyl) phosphate and the like.

The polymeric resin material of the present invention can be easily mixed using an extruder, kneader roll, or the like.

The set temperature of these devices can be freely selected within the range of go-too degrees Celsius, but it is preferably set at 80% or 80 degrees Celsius. Alternatively, they can be dissolved in a suitable solvent and mixed in solution.

The polymer resin material of the present invention can also be vulcanized, if necessary, by any conventional vulcanization method used for conjugated diene polymer compositions.

For example, chemical vulcanization methods such as an iodine compound vulcanizing agent system, a tium compound vulcanizing agent system, and a peroxide compound vulcanizing agent system can be used, and physical vulcanization methods such as electron beam irradiation can be used. It can also be used. If such vulcanization is carried out appropriately, the polymer resin material for toys of the present invention will not lose its fluidity, and will retain its shape when it is melted and deformed and then cooled and hardened, but if the temperature is raised again. It is also possible to obtain a one-component memory resin that returns to its original shape when melted.

(Effects of the Invention) The hot water processable polymer resin material for toys provided by the present invention can be softened at relatively low temperatures and freely molded,
It is characterized by an excellent balance between hardness and flexibility, rebound resilience, impact resistance, formability, and workpiece properties during processing.

(Example) In order to explain the present invention in more detail, Examples are shown below.

Example 1%, 1% Comparative Examples 1 to 8 A total of 100 f of trans-butadiene polymer, trans-isoprene polymer, tokunespolyoctenamer, and cablocton polymer were weighed out in the following percentages and stirred well. After that, put it into a pressure point plus mill (specially manufactured by Toyo Seiki Seisakusho) set at 140℃.

The mixture was kneaded for S minutes at a screw speed of 5 Orpm to obtain a polymer resin material. The obtained polymer resin material was press-molded at 120°C, and its deformation temperature, hardness, rebound resilience, impact strength,
Deaf moldability was tested. Also.

The rework characteristics were evaluated by repeating the process of kneading and press molding five times under the same conditions as above, and then evaluating the fineness of the molded resin after cooling it at room temperature for 30 minutes.

Although its physical properties vary depending on the structure of the trans-butadiene polymer, the resulting resin material has a hardness of 85-98, which is an excellent balance between hardness and flexibility, and has an impact strength of 60% or more, and an impact strength of 30 Kf. /csi or more.

Polymer resin materials with excellent moldability and a hardness of 8 times or higher after reworking have a trans bond content of 75 to 95 cm as a polymer resin acid content and a weight average molecular weight (My) of 1.
ao, ooo ~ soo, ooo and molecular weight distribution (M
w/Mn) having a structure of 1.2 to 5.0,
It can be seen from the table % that it contains an ene polymer.

*L Measured by Morello method using an infrared spectrophotometer.

*2 Gel permeation measurement was performed using chromatograph.

*λ Clan TP-301 (manufactured by Klarets Brefu Kenkar).

*Also Pestenamer aoxz (manufactured by Hiels).

*1 Bookcell H-7 (manufactured by Daicel Chemical Industries, Ltd.).

*a Raise the temperature from room temperature at a rate of 5°C/min (JI8-A
The temperature at which l becomes 40.

*7. Measured by JI8 K-6301.

*& Measured at room temperature using a Dunlop trip meter.

*Zhang A DuPont impact tester was used, a 2w x 10mm notch was used, and the value was expressed as the value at which a cut occurred.

*1 αO is good, Δ is slightly good, and × is bad.

Claims (1)

[Claims] 1. Trans bond content 75-95%, weight average molecular weight (
A low-temperature moldable product containing at least 30% by weight of a butadiene polymer having a structure of @M@w) 30,000 to 50,000 and molecular weight distribution (@M@w/@M@n) 1.2 to 5.0. A polymeric resin material 3 for toys according to claim 1, comprising 30 to 90% by weight of a high trans butadiene polymer and 70 to 10% by weight of a trans isoprene polymer. Polymeric resin material 4 for toys according to claim 1, comprising 30-90% by weight of a butadiene polymer and 70-10% by weight of trans-polyoctenamer, 30-90% by weight of a high-trans-butadiene polymer and 70-10% by weight of trans-polyoctenamer. Polymer resin material for toys according to claim 1, comprising 70 to 10% by weight of the polymer resin material.