JP2527417B2 - Self-crosslinking low temperature processable composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a self-crosslinking low-temperature processable composition which has undergone a crosslinking reaction at a temperature of 150 ° C. or lower and around room temperature to improve shape stability and surface properties.

[0002]

2. Description of the Related Art A plastic molded product processed at a low temperature, that is, at a temperature of 100 ° C. or lower and around room temperature is liable to be cold-flowed as it is, is easily deformed, has a low surface hardness, and is easily contaminated, so that it has a low commercial value as a product. Conventionally, in order to eliminate this drawback, silicon compounds or isocyanate compounds, which react with moisture in the air and two components to form a three-dimensional structure, are used as binders, unsaturated polyester resins, diene-based polymers or acrylic oligomers, etc. Styrene monomer, sulfur, reactive crosslinking agents such as acrylic monomers, organic peroxides, accelerators, sensitizers, etc.
Active energy such as radiation and electron beam irradiation was applied to carry out a cross-linking polymerization reaction to form a three-dimensional structure and improve the shape stability and surface characteristics, thus giving practical value as a product. In the conventional techniques, the means by chemical reaction near humidity or room temperature has a problem of pot life, and scrap cannot be recycled. Also, when the activation energy is given from the outside,
When heated, deformation is likely to occur, and it is necessary to add an organic peroxide which is expensive as a catalyst and requires careful handling, and it is necessary to prevent deformation by pressurization. on the other hand,
With ultraviolet rays, radiation, electron beams, etc., there is no problem of deformation because pressure is not applied, but equipment costs are high. Further, when sulfur or nitrogen compounds are added to the composition as a cross-linking agent or an accelerator, there is a problem of environmental pollution when incinerating waste.

[0003]

[Purpose] The present invention is an ultraviolet ray which requires special equipment for a plastic material processed and molded at room temperature or a low temperature of 100 ° C or lower,
It does not use expensive and dangerous active energy sources such as radiation and electron beams, requires careful handling, does not add expensive organic peroxides, and has a pot life time constraint. In addition, in the air without using reactive compounds such as expensive silicon compounds and isocyanate compounds that have difficulty in pot life and recycling, and without using sulfur or nitrogen compounds that may cause environmental pollution. The purpose of the present invention is to provide a self-crosslinking low-temperature processable composition that has undergone a crosslinking reaction under heating conditions of 150 ° C. or lower, or near room temperature, and has improved shape stability and surface properties.

[0004]

The present invention is characterized by containing (a) a polymerizable oil and / or a processing oil having an iodine value of 100 or more, (b) a dryer, (c) a diene polymer, and (d) a reactive crosslinking agent. The present invention relates to a self-crosslinking low temperature processable composition. The composition is various molded products (eg, flooring materials, resin terrazotile),
It is useful as a sealing material and coating material.

The composition of the present invention usually contains an inorganic and / or organic filler. Of course, a colorant, various processing aids, a plasticizer, a dispersant, a fungicide, and the like may be added depending on the needs of the application.
Various additives such as an antistatic agent and a conductive agent can be blended. However, the addition of antioxidants, antioxidants, and ultraviolet absorbers is not preferable because it inhibits the self-crosslinking reaction. In the composition of the present invention, the component (b) is usually added to the component (a), and the component (c), the component (d) and various additives are added thereto and kneaded at room temperature or at a low temperature of 100 ° C. or lower. It can be obtained by And the composition of the present invention is 1
Molding or processing at a temperature of 00 ° C or less, near room temperature,
Alternatively, by leaving it in a heated air of 150 ° C. or less, self-crosslinking proceeds without using any polymerization initiation means such as peroxide, light or active energy, and a product having a stable shape and surface state is obtained. It presents the surprising phenomenon of becoming. To do this,
It is indispensable that the component (a) has an iodine value of 100 or more and the component (b) contains a dryer. Such a self-crosslinking reaction at room temperature produces a lipid peroxyl radical by the autoxidation of the polymerizable oil or the processing oil containing the dryer, which is one of the compositions, which is the metal soap, by the oxygen in the air. It reacts with the hydrogen of the methylene group sandwiched between the double bonds in highly active lipids and changes into hydroperoxylipids, which are metal soaps (Co, M
n), that is, decomposes with a drier as an accelerator to generate free radicals like organic peroxides and becomes a polymerization initiator, and not only oxidative polymerization of oil itself but also crosslinking of a diene polymer and a reactive crosslinking agent. It is presumed that the polymerization causes the increase of gel fraction and physical properties.

The polymerizable oil in the present invention usually means a drying oil or a semi-drying oil, such as tung oil having an iodine value of 100 or more, flaxseed oil, safflower oil, soybean oil, cottonseed oil, eno oil, edible waste oil and the like. The mixed oil of can be mentioned. Further, as the processing oil, a drying oil, a semi-drying oil, a respective boil oil, a heat-polymerized oil, a vinylated oil such as a styrenized oil, a cyclopentadiene oil, a maleated oil, a sorbinized oil,
Examples thereof include dehydrated castor oil, urethane oil, and the like (Nippon Kogyo Shimbun, Inc., November 29, 1965, "Paint Handbook" P143-149). As the dryer (drying agent), all metal soap type dryers used in the paint field can be used. Examples of acid roots of metal soaps include rosin (abietic acid), linseed oil fatty acid, soybean oil fatty acid, naphthenic acid, diethylhexanoic acid, tall oil, and the like. Metals include Co, Mn, Cu, Fe, and Z.
r, rare earth metals, and the like (the above-mentioned “Handbook of Paints” P425-433). As the auxiliary desiccant, lead,
Linoleic acid or naphthenic acid soap such as zinc, calcium, aluminum, etc., 0.0005-0.0 as metal
1% by weight can be added to the oil. In addition, for natural oils and fats in which an antioxidant enzyme is present in the polymerizable oil itself, be sure to keep it at a temperature of 130 ° C. or higher for 1 to 2 hours or heat it to bring it into contact with air before use. It is necessary to decompose and shorten the oxidation induction period. It is necessary to use so-called boil oil. The diene polymer must be compatible with the polymerizable oil, and specifically, styrene butadiene block copolymer (SBS), styrene isoprene block copolymer (SIS), styrene ethylene butylene block copolymer. (SEBS), styrene-butadiene rubber, acrylonitrile butadiene rubber, butadiene rubber, 1,
A thermoplastic elastomer such as a 2-syndiotactic polybutadiene polymer or a liquid diene-based polymer such as a 1,2-atactic polybutadiene liquid polymer and a polyisoprene liquid polymer may be used. When an antioxidant or an antiaging agent is included, the effect can be removed by heating and kneading in air and contacting with oxygen. Although the reactive cross-linking agent is selected according to the corresponding polymer and the required physical properties, there are monofunctional, difunctional or trifunctional acrylic compounds and styrene monomers. Specifically, trimethylolpropane triacrylate (TMPT
A), trimethylolproban trimethacrylate (TMPT), ethylene glycol dimethacrylate,
Propylene glycol diacrylate, polyethylene glycol dimethacrylate, styrene, etc., preferably P.I. I. I. It is preferable to use a highly safe product having a value of 1 or less. Examples of the filler include inorganic materials such as calcium carbonate, clay, wollastonite, and talc, and organic materials include cork powder, wood powder, walnut powder, and fiber materials such as nylon and tetron (P.I.I. Is the primary stimulation index of the primary stimulation index, which is a 9-step display from 0 to 8 and is 2
It's pretty safe, and 5 is a rank that requires a lot of attention. ). Further, as a processing aid is a kneading property and a surfactant that improves the adhesion between the binder and the filler and a processing aid that improves the processability during kneading and processing, a petroleum resin that can be mixed well with a polymerizable oil, Examples thereof include ester gum and phenol-formalin modified resin.

The blending ratio in the composition of the present invention is (a)
Polymerizable oil or its processing oil 5 to 40% by weight, preferably 10 to 20% by weight (b) Dryer [ratio to component (a)] 0.0005 to 0.01% by weight as a metal,
Preferably 0.001 to 0.005% by weight (c) 45 to 85% by weight of diene polymer, preferably 70 to 80% by weight (d) 5 to 20% by weight of reactive crosslinking agent, preferably 5 to
It is 10% by weight. The amount of the filler added is not particularly limited, but usually, the total amount of the above (a), (c), and (d) is 15 to
4 to 60 parts by weight, preferably 20 to 30 parts by weight
0 to 85 parts by weight, preferably 70 to 80 parts by weight are used.

The composition of the present invention is mixed at a temperature of 100 ° C. or lower with a kneading machine such as a Banbury mixer, a German mixer, a Werner kneader, and molded into a mold, a thin material, a thick material or the like with an extruder or a calender machine. Alternatively, the granular material is pressure-bonded, the block is sliced if necessary, and die-cutting is performed to obtain a molded product. On the other hand, scrap in the molding process is recycled. These pattern forming methods are useful for manufacturing floor materials and wall materials made of celluloid, linoleum, rubber and synthetic resin. This molded product is left at room temperature or in an air atmosphere heated to 150 ° C. or lower to carry out a crosslinking reaction to obtain a product. The longer the standing period is, the shorter the iodine value of the polymerizable oil and the processed oil thereof, the larger the functional number and the amount of addition of the reactive crosslinking agent, the thinner the thickness, and the higher the standing temperature, the shorter the standing period. The time required to reach the required physical properties by crosslinking is preferably adjusted to about 4 hours to 24 hours. If it has a thickness of 2 mm or more, an electron beam may be used together to promote crosslinking. Further, the time can be further shortened by adding the organic peroxide. The amount used is 0.5 to the total amount of the above (a) (c) (d).
1% by weight is preferred. When the heating temperature at the time of crosslinking is 100 ° C. or higher, the effect of an inhibitor that inhibits the crosslinking reaction such as an antioxidant can be reduced.

[0009]

Example 1 Example 1 (manufacture of a molded product such as a floor tile)
(A) 5.0 parts by weight of boiled soybean oil (b) 0.005 parts by weight of 5% cobalt naphthenate solution (c) 1,2-syndiotactic polybutadiene * 17.5 parts by weight (d)
TMPT 2.5 parts by weight (e) 100 mesh wood powder 35 parts by weight (f) Titanium white 1 part by weight (g) 150 mesh pass calcium carbonate powder 39 parts by weight * Japan Synthetic Rubber RB805
After kneading each component consisting of the antioxidant and the antiaging agent by heating and kneading and removing with a mixing roll at 80 to 85 ° C.,
It is rolled with a calendar roll at 60 ° C. to form a tile having a pressure of 3 mm, and the scrap is recycled. The formed product is left to stand in a greenhouse at 50 to 60 ° C. for 48 hours to be hardened to obtain a product.

Example 2 (Sealant) (a) 50 parts by weight of boiled flaxseed oil (b) 0.05 part by weight of 5% cobalt naphthenate solution (c) 50 parts by weight of 1,2-atactic polybutadiene (Nisso # 3000) (d) Crosslinking agent TM
To 100 parts by weight of a binder composed of 10 parts by weight of PT, 300 parts of calcium carbonate (200 mesh pass), 95 parts of wollastonite and 5 parts of titanium white rutile type were added and kneaded to obtain a sealing material. When it was used for the scilly ring of the gap of the building, the surface was hardened in one week and the sealing effect was exhibited.

Example 3 (Wallpaper) (a) Boiled soybean oil or 2 parts by weight Boiled flaxseed oil (b) 0.002 parts by weight of a 5% solution of cobalt naphthenate (c) 1,2-Synthium used in Example 3 20 parts by weight of tactic polybutadiene (d) 2 parts by weight of ethylene glycol dimethacrylate (e) 20 parts by weight of aluminum hydroxide (f) 10 parts by weight of 60 mesh cork powder (g) 200 meshes 36 parts by weight of calcium carbonate (h) A mixture consisting of 10 parts by weight of antimony oxide was kneaded at 80 ° C., cooled and crushed to give 5
Rolled on kraft paper to 0.5-1mm thickness at 0 ℃ 30
Leave for 24 hours at -40 ° C to obtain a product.

Example 4 (Manufacture of moldings such as floor tiles)
(A) 4.0 parts by weight of boiled soybean oil (b) 0.004 parts by weight of 5% cobalt naphthenate solution (c) 1,2-syndiotactic polybutadiene * 112.0 parts by weight (d) butadiene rubber * 22. 0 parts by weight (e) TMP
T2.0 parts by weight (f) Reinforcing material * 35 parts by weight (g) Titanium white 2 parts by weight (h) 150 mesh pass Calcium carbonate powder 73 parts by weight * 1 Japanese synthetic rubber RB810 * 2 Japanese synthetic rubber BR01 * 3 Wollast After kneading each component consisting of ait or organic short fibers with a mixing roll at 85 to 95 ° C., rolling with a calendar roll at 60 to 70 ° C., 3 mm
Formed into pressure tiles and the scrap is recycled. The formed product is left in a greenhouse at 100 to 110 ° C. for 24 hours without being pressed to be cured, and is then made into a product.

[0013]

The composition of the present invention can be molded and processed at a low temperature, for example, 100 ° C. or lower, and after molding or coating, the composition is left unpressurized in a heated atmosphere near room temperature or 150 ° C. Self-crosslinking without addition of polymerization initiator such as peroxide gives a stable product in shape and surface state, so it is easy to handle and use of polymerization initiator or active energy ray which is dangerous to handle. Is unnecessary. Further, even if these are used supplementarily, the addition amount and the irradiation amount are small, so that it is a very energy-saving composition.

Claims (4)

(57) [Claims] 1. Self-crosslinking, which comprises (a) a polymerizable oil having an iodine value of 100 or more and / or a processed oil thereof (b) a dryer (c) a diene polymer (d) a reactive crosslinking agent. Mold low temperature processable composition. 2. A molded body made of the composition according to claim 1. 3. A sealing material comprising the composition according to claim 1. 4. A coating material comprising the composition according to claim 1.