JP3457771B2 - Composition for separating specific gravity difference - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a specific gravity separation composition containing cyclopentadiene-based petroleum resin, which is used for separation by utilizing the difference in specific gravity of each component of a substance, and more particularly to separation of blood. To the composition useful for.

[0002]

2. Description of the Related Art Conventionally, in order to separate each component in a substance such as blood containing components having different specific gravities, a method utilizing a difference in specific gravities, in which a separating agent is added and centrifugal separation is used. Came. As such a separating agent that has been used for separating blood, for example, a composition containing silicone and silica (JP-A-51-83654) is known. However, since blood separation agents using silicone have problems such as marked phase separation, they have not been used much recently. Therefore, various separating agents that replace silicone have been developed. As a main component of such a separating agent, for example, a polyester polymer (JP-A-61-233368) and an acrylic polymer (JP-A-53-42283) are known. However, since these polymers have polar groups, the measured value may be affected depending on the type of drug when monitoring the drug concentration in blood.

On the other hand, a composition for separating blood using a cyclopentadiene resin is known (Japanese Patent Laid-Open No. 1-295163). However, since the cyclopentadiene resin has a large temperature dependence of viscosity, it is centrifuged with a refrigerator. When a separator is used, there is a problem that the fluidity deteriorates. As a solution to such problems of cyclopentadiene resin, 0.8 to 25 parts by weight of a viscosity modifier and an organic gelling agent are added to 100 parts by weight of cyclopentadiene resin which is liquid at room temperature.
Composition containing 0.03 to 0.9 parts by weight (JP-A-6-3356)
Is also known.

The present invention has an excellent specific gravity difference separation performance,
An object of the present invention is to provide a composition for separating specific gravity difference which is stable and whose specific gravity value can be easily set.

[0005]

The present invention provides (A) a softening point.
70 to 140 ℃, specific gravity at 25 ℃ 1.00 to 1.10, and 180 ℃
A specific gravity difference composition containing 100 parts by weight of a hydrogenated cyclopentadiene-based petroleum resin having a melt viscosity of 30 to 500 centipoise (cps) and (B) 40 to 100 parts by weight of a phthalic acid ester having 17 to 30 carbon atoms. is there.

The present invention is characterized in that a relatively large amount of phthalic acid ester having a carbon number within a specific range is added to a hydrogenated cyclopentadiene-based petroleum resin which is solid at room temperature and has specific characteristics.

The hydrogenated cyclopentadiene-based petroleum resin used in the present invention is a known hydrogenated cyclopentadiene-based petroleum resin having specific characteristics. That is, the softening point is 70 to 140 ° C, preferably 80 to 110.
C., specific gravity at 25 ℃ 1.00 to 1.10, preferably 1.02 to 1.
08 and melt viscosity at 180 ℃ 30-500 centipoise
(cps), preferably 50-150 cps. If the softening point is too low, the handling will be poor, and if it is too high, it will be difficult to melt. If the specific gravity is too high or too low, it becomes difficult to set the specific gravity of the composition to the target value. If the melt viscosity is too high, the viscosity will increase significantly at low temperatures, making it difficult to use.

Cyclopentadiene petroleum resin is a polymer of cyclopentadiene monomer. Examples of the cyclopentadiene-based monomer include cyclopentadiene, dicyclopentadiene, and alkyl-substituted cyclopentadiene (eg, methylcyclopentadiene). It may be a homopolymer of these or a copolymer obtained by combining two or more thereof. Alternatively, there may be aromatic olefins. Further, it may be a mixture of such polymers or copolymers.

The hydrogenated cyclopentadiene type petroleum resin used in the present invention can be produced, for example, as follows. That is, the monomer or mixture of monomers is thermally polymerized at a temperature of usually 160 to 320 ° C., preferably 200 to 300 ° C. for 10 to 500 minutes, preferably 30 to 300 minutes. At that time, a non-reactive polymerization diluent (solvent) such as toluene may be used. The resin solution obtained from thermal polymerization has a temperature of 150-300 ° C, with or without flow injection.
The solvent and the unreacted monomer can be removed by heating the above.

[0010] The thus-obtained resin and then the obtained resin is hydrogenated to a level of 6.0 (g Br ₂ / 100g) or less bromine number. That is, 100 parts by weight of the above resin and 100 to 400 parts by weight of solvent diluent (preferably 100 to 300 parts by weight).
In a hydrogenation reactor at a reaction temperature of 100-
Reaction time 10 to 15 at 350 ℃, preferably 200 to 320 ℃
Hydrogenation is carried out for 0 minutes, preferably 20-100 minutes.

The solvent diluent may be any saturated hydrocarbon solvent, with substantially aliphatic or alicyclic hydrocarbons being preferred.

The solution resulting from the hydrogenation process can be heated to temperatures of 150 to 300 ° C., with or without jetting of streams, to remove solvent and oligomeric materials.

The hydrogenation can be carried out in the presence of known catalysts usually used for hydrogenating petroleum resins. Such catalysts include, for example, Group VIII metals (eg Ni, P
d, Ru, Rh, Co, Pt, etc.), Group VIA metals (eg, W, Cr, Mo, etc.), Group VIIA metals (eg, Re,
Mn, etc.) and Group IB metals (eg Cu) are included. These metals can be used alone or in combination of two or more in a metal form or an activated form, and can be used directly or supported on a solid support such as alumina or silica-alumina.

Hydrogenation is 20 to 300 atm, preferably 50 to
It is carried out at a hydrogen pressure of 250 atm.

By thus hydrogenating, a cyclopentadiene-based petroleum resin having excellent heat resistance and weather resistance can be obtained.

Next, the (B) phthalic acid ester used in the present invention will be described. Phthalates have 17 carbon atoms
Or more, preferably 22 or more, and 30 or less, preferably 28 or less. Phthalates having too few carbon atoms have poor compatibility with cyclopentadiene-based petroleum resins, and too many carbon atoms make it difficult to adjust the specific gravity of the composition. The corresponding alcohols are preferably alkyl alcohols and arylalkyl alcohols. In addition, the alkyl group is preferably an alkyl group having a high linearity, since it has good compatibility with cyclopentadiene-based petroleum resin and phase separation hardly occurs. Preferred phthalates include, for example, butylpentyl phthalate, dipentyl phthalate, butylhexyl phthalate, butylheptyl phthalate, dihexyl phthalate, pentylheptyl phthalate, butylnonyl phthalate, pentyloctyl phthalate, hexylheptyl phthalate, Diheptyl phthalate,
Heptyl octyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, octyl nonyl phthalate,
Examples thereof include diisononyl phthalate, octyldecyl phthalate, diisodecyl phthalate, decyl undecyl phthalate, diundecyl phthalate, and butylbenzyl phthalate. These phthalic acid esters can be used alone or in admixture of two or more. Preferably 22 carbons
Selected from ~ 28 phthalates.

The above-mentioned phthalic acid ester is 40 parts by weight per 100 parts by weight of (A) hydrogenated cyclopentadiene-based petroleum resin.
The amount is not less than 60 parts by weight, preferably not less than 60 parts by weight and not more than 100 parts by weight, preferably not more than 80 parts by weight. If the amount of the phthalate ester is too small or too large, it becomes difficult to set the viscosity and the specific gravity of the resulting composition to the target values.

The composition of the present invention can be produced by mixing the above-mentioned components using a means such as a heating tank with a stirring device.

The composition of the present invention has a viscosity of 100 to 50 ° C.
It is preferably 100,000 cps, more preferably 1,00
0 to 5,000 cps and 10,000 to 500,000 cp at 25 ° C
It is preferably s. The specific gravity of the composition may vary depending on its use, but preferably 1.00 to 1.10 at 25 ° C,
More preferably, it is 1.02 to 1.08. The composition of the present invention is
For example, when used as a blood separating agent, when the specific gravity of the composition is in the range of 1.02 to 1.08 at 25 ° C, the composition is located between the serum (or plasma) layer and the blood clot (or blood cell) layer. This is preferable because it serves as a partition wall of both and facilitates separation.

The composition of the present invention may further contain various additives depending on its use. As such an additive, for example, an organic gelling agent (for example, JP-A-4-039
Condensates of sorbitol and aromatic aldehydes described in Japanese Patent Publication No. 65, for example, dibenzylidene sorbitol, tribenzylidene sorbitol, etc.), specific gravity adjusting agent (inorganic fine powder such as silica, alumina, glass, talc, kaolin, bentonite, titania, zirconium , Asbestos; fine powder of organic polymer such as polystyrene, polyurethane, etc., having an average particle size of 500 μm or less), antioxidant, light stabilizer, anticoagulant (heparin etc.)
Etc. can be mentioned.

The composition of the present invention is used as a separating agent utilizing the difference in specific gravity between substances containing two or more components having different specific gravities. Such a substance is not particularly limited, but it can be used, for example, for separation of physiological fluids of organisms such as blood, tissue fluid (such as lymph fluid), secretory fluid (such as pancreatic fluid), spinal fluid, and exudate. Alternatively, it is also possible to use it for separating a mixture of organic liquids; waste liquid of a factory and the like. A particularly preferred application is blood separation.

[0022]

In the composition of the present invention, a hydrogenated cyclopentadiene petroleum resin having specific characteristics is selected. This is necessary in order to satisfy the required properties of the final composition, that is, the stability and the property that the viscosity does not increase remarkably even at low temperatures. By combining such a hydrogenated cyclopentadiene-based petroleum resin with a specific phthalate ester, a stable composition having good compatibility can be obtained, and a target specific gravity value can be easily set. .

[0023]

The present invention will be further described by the following examples.

Component (A) The following resins were used as the hydrogenated cyclopentadiene-based petroleum resin: Resin A has a softening point of 85 ° C., a specific gravity of 1.073 (25 ° C.) and a melt viscosity of 72 cps at 180 ° C. Prepared as follows: Cyclopentadiene monomer was thermally polymerized at 270 ° C. for 90 minutes and then hydrogenated. Hydrogenation was carried out by adding 250 parts by weight of a solvent diluent (alicyclic hydrocarbon) to 100 parts by weight of the obtained resin, and then in a hydrogenation reactor at a reaction temperature of 250 ° C, a reaction time of 20 minutes, and a hydrogen pressure. It was carried out at 120 atm using nickel tungsten sulphide as catalyst. Resin B has a softening point of 106 ° C., a specific gravity of 1.070 (25 ° C.), and a melt viscosity at 180 ° C. of 320 cps. A cyclopentadiene monomer was produced according to the production method of Resin A except that it was thermally polymerized at 270 ° C. for 120 minutes.

The following phthalates were used as component (B): DOP: di-2-ethylhexyl phthalate (24 carbons, specific gravity (25 ° C) 0.986, viscosity (50 ° C) 16.6 cps) DINP: phthalate Diisononyl acid (C26, specific gravity (20
(° C) 0.977, viscosity (50 ° C) 17.6 cps) DIDP: diisodecyl phthalate (carbon number 28, specific gravity (25
(° C) 0.965, viscosity (50 ° C) 23.2 cps) The following phthalates were used for comparison: DBP: dibutyl phthalate (16 carbons, specific gravity (25 ° C) 1.
Viscosity (50 ° C.) 6.8 cps) Examples 1 to 5 Resin A was used as component (A), and DOP was used as component (B) phthalate ester. Ingredient (A) and ingredient (B)
Were mixed at various blending ratios shown in Table 1 at 80 ° C. using a vessel equipped with a stirrer to obtain compositions having various specific gravities. The compatibility of the obtained composition was observed, and the specific gravity and the viscosity were measured. The compatibility was evaluated as "good", "somewhat cloudy" and "poor" (cloudy). The viscosity is a value measured at 50 ° C. using a B type rotational viscometer. Specific gravity is 25 ℃
It was determined by the float-sink method using a copper sulfate standard specific gravity liquid in. The results are shown in Table 1.

[0026]

[Table 1]

Examples 6 to 8 Resin B was used as component (A) and DOP was used as component (B) phthalate ester. Ingredient (A) and ingredient (B)
Was mixed in various proportions shown in Table 2, and a composition was produced in the same manner as in Examples 1 to 5, and the composition was evaluated. The results are shown in Table 2.

[0028]

[Table 2]

Examples 9 to 11 Resin A was used as component (A), and DOP, DIDP and DINP were used as component (B) phthalic acid ester, respectively. The component (A) and the component (B) were mixed in a weight ratio of 100: 60, a composition was produced in the same manner as in Examples 1 to 5, and the composition was evaluated. The results are shown in Table 3.

Comparative Example 1 100 parts by weight of Resin A and 60 parts by weight of DBP were blended,
Compositions were prepared and evaluated as in Examples 1-5. The results are also shown in Table 3.

[0031]

[Table 3]

[0032]

INDUSTRIAL APPLICABILITY The composition of the present invention has good compatibility of each component and is less likely to undergo phase separation. Further, by appropriately selecting and blending both components, a fine specific gravity value can be set and the separation performance as a specific gravity difference separating agent is excellent. further,
No alteration due to chemical changes or moisture absorption is observed. Moreover, even if the centrifugation operation is performed at a low temperature (for example, 4 ° C.), the fluidity is not relatively lowered, and a good separated image can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chiaki Tochiuchi 7-1 Ukishima-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Tonex Co., Ltd. (56) Reference JP 6-3356 (JP, A) JP H7 -260775 (JP, A) JP-A-6-222056 (JP, A) JP-A-4-203965 (JP, A) JP-A-1-295163 (JP, A) JP-A-6-324034 (JP, A) ) JP-A-8-101189 (JP, A) JP-A-5-10945 (JP, A) JP-A-51-83654 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G01N 33/48-33/98 A61K 35/14 G01N 9/36

Claims (5)

(57) [Claims] 1. (A) Softening point 70 to 140 ° C., specific gravity at 25 ° C. 1.00 to 1.10, and melt viscosity at 180 ° C. 30 to 500
A specific gravity difference separating composition comprising 100 parts by weight of a hydrogenated cyclopentadiene-based petroleum resin having a centipoise and (B) 40 to 100 parts by weight of a phthalic acid ester having 17 to 30 carbon atoms. 2. The composition according to claim 1, wherein the phthalate ester is selected from phthalate esters having 22 to 28 carbon atoms. 3. The composition has a viscosity of 100 to 100,000 at 50 ° C.
The composition according to claim 1, which is centipoise. 4. The composition according to claim 1, wherein the specific gravity of the composition is 1.00 to 1.10 at 25 ° C. 5. A blood separating agent containing the composition according to any one of claims 1 to 4.