JP3419109B2 - Polymer blend material and method for modifying polymer material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a polymer material such as a thermoplastic resin, a thermosetting resin, or a rubber, in which a low-molecular weight material is uniformly and well-retained, and the characteristics of the polymer material are modified by the low-molecular weight material. The present invention relates to a polymer blend material and a method for modifying a polymer material.

[0002]

2. Description of the Related Art Conventionally, for the purpose of lowering the elastic modulus of a polymeric material such as a thermoplastic resin, a thermosetting resin, or rubber, and improving the impact absorbing ability,
A large amount of low molecular weight material may be mixed with the high molecular weight material.

However, in a polymer material in which a large amount of a low molecular weight material is mixed, it is difficult to uniformly disperse the low molecular weight material, and since the low molecular weight material is poor in retention, the low molecular weight material easily bleeds. For this reason, it was not possible to obtain the desired low elastic modulus.

The present invention has been made in view of the above circumstances and has a low elastic modulus in which a low molecular weight material is uniformly dispersed, and the low molecular weight material is satisfactorily held so that bleeding of the low molecular weight material is minimized. It is an object to provide a polymer blend material and a method for modifying the polymer material to obtain such a polymer blend material.

[0005]

Means and Actions for Solving the Problems The present inventors have
As a result of intensive studies to achieve the above objective, first,
A crystalline olefin-based plastic and a plasticizer are mixed to obtain a polymer network structure in which the plasticizer is held between the three-dimensional continuous network skeletons of the crystalline olefin-based plastic, and the polymer network structure and By mixing with the polymer material, the polymer blend material obtained is such that even if the plasticizer is blended in a high proportion of about 50% by weight of the whole, the plasticizer is uniformly dispersed and hardly bleeds. However, it has been found that this results in an extremely low elastic modulus.

When it is difficult to mix the plasticizer with the polymer material, the plasticizer is made into the polymer network structure, and the polymer material is mixed with the plasticizer that is difficult to mix into the polymer material. If it can be highly blended, or if it is difficult to mix the crystalline olefin-based plastic and the polymer material, the crystalline olefin-based plastic is used as the polymer network structure, and by mixing this with the polymer material,
It is possible to mix crystalline olefin plastics that are difficult to mix with polymeric materials, which makes it possible to use a wide range of polymeric materials, plasticizers, and crystalline olefin plastics, which is extremely useful as a method for modifying polymeric materials. The inventors have found the above facts and completed the present invention.

Therefore, the present invention is (1) obtained by mixing (A) a crystalline olefin plastic and a plasticizer, wherein the plasticizer is present between the three-dimensional continuous network skeletons of the crystalline olefin plastic. A polymer blend material comprising a polymer network structure held and (B) a polymer material, and (2) the plasticizer is a plasticizer other than a fatty acid ester. (1) The polymer blend material according to (1), (3) the plasticizer is a phthalate-based, adipate-based, sebacate-based, phosphate-based, polyether-based or polyester-based plasticizer for NBR, (1) The polymer blend material according to (1), (4) The plasticizer is a phthalate-based plasticizer for NBR, (1) The polymer blend material according to (5) Phthale The polymer blend material according to (4), wherein the NBR plasticizer is diheptyl phthalate (DHP), and (6) the plasticizer is an adipate NBR plasticizer. (1) The polymer blend material according to (1), (7) The plasticizer for NBR of adipate type is diisodecyl adipate (DIDA), (6) The polymer blend material according to (8) The crystalline olefin plastic is one or more selected from polyethylene, polypropylene and polybutylene (1) to (7)
(9) The polymer blend material according to any one of (1) to (7), wherein the crystalline olefin-based plastic is polyethylene. 10) The polymer blend material according to any one of (1) to (7), wherein the crystalline olefin-based plastic is polypropylene, (11) the compounding amount of the plasticizer in the component (A). The polymer blend material according to any one of (1) to (10), wherein the weight ratio is 0.2 to 3 with respect to the polymer material of the component (B),
And (12) a polymer network structure obtained by mixing a crystalline olefin-based plastic and a plasticizer, wherein the plasticizer is retained between three-dimensional continuous network skeletons of the crystalline olefin-based plastic. Provided is a method for modifying a polymer material, which comprises mixing with a polymer material as a modifier material for the molecule material.

The present invention will be described in more detail below. As described above, the polymer blend material of the present invention is
It is a mixture of (A) polymer network structure and (B) polymer material.

Here, in the polymer network structure of (A), a three-dimensional continuous network skeleton having an internal communication space is composed of a crystalline thermoplastic, and a low molecular weight material is held between the skeletons. Is.

The crystalline thermoplastic resin has a melting point of 100 to 300 ° C. and a number average molecular weight of 5
000 to 700,000, preferably 80,000 to 500
Those in the range of 000 are desirable.

Specific examples of the crystalline thermoplastic include polyethylene (PE) and polypropylene (P
P), ethylene vinyl acetate copolymer (EVA), polybutylene (PB), acrylonitrile resin, polyvinyl chloride resin, polyvinylidene chloride resin, nylon (6, 6-
6, 6-2, 12), polyethylene terephthalate (P
ET), polybutylene terephthalate (PBT), polycarbonate (PC), polyoxymethylene (PO)
M), polyphenylene sulfide (PPS), fluororesin (PTFE etc.), polyether ether ketone (P
Examples thereof include synthetic resins such as EEK), and fibrin-based resins such as ethyl cellulose, cellulose acetate, cellulose nitrate, and cellulose propionate. These can be used alone or in admixture of two or more. You can Among these, polyethylene, polybutylene, polypropylene, nylon, polyethylene terephthalate and polybutylene terephthalate are preferable, and most preferable are crystalline olefin plastics such as crystalline polyethylene, polybutylene and polypropylene.

Further, the crystalline thermoplastic according to the present invention may be modified depending on the intended use by modifying it with a hydrophilic group such as a hydroxyl group or a lipophilic group such as a nitro group.

In the present invention, plastics other than the above crystalline thermoplastics may be used in combination with the above crystalline thermoplastics. Examples of such plastics include polybutadiene and butadiene-styrene random copolymer. Polyethylene and ethylene-styrene random copolymer obtained by hydrogenating a block copolymer with a polymer, obtained by hydrogenating a block copolymer of polybutadiene and polystyrene, or a block copolymer of polybutadiene and polystyrene Block copolymers of polyethylene and polystyrene, etc., which can be used, and are 10 to 9 relative to the above-mentioned crystalline thermoplastics.
It can be used in an amount of 0% by weight, preferably 20 to 80% by weight.

The three-dimensional continuous network skeleton composed of such a crystalline thermoplastic has a microstructure as shown in FIG. In FIG. 1, 1 is a three-dimensional continuous network skeleton made of the above-mentioned crystalline thermoplastic, 2 is an internal communication space, and the internal communication space 2 holds a low-molecular material described later. Here, in FIG. 1, the average diameter d of the skeleton 1 is preferably 10 μm or less, and the average diameter D of the cells is preferably 100 μm or less.

On the other hand, the low molecular weight material held in the internal communication space may be solid or liquid, and various materials can be used depending on the application. If the low molecular weight material is an organic material, its number average molecular weight is less than 20,000,
It is preferably 10,000 or less, more preferably 5000 or less. The following can be illustrated as a low molecular weight material. Softening agent: Softening agent for various types of rubber such as mineral oil type, vegetable oil type, synthetic type, or resin. As mineral oil type, aromatic type,
Process oils such as naphthene type and paraffin type. Vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, wood wax, pine oil, olive oil and the like. Plasticizer: phthalic acid ester, mixed phthalic acid ester, aliphatic dibasic acid ester, glycol ester, fatty acid ester,
Various ester plasticizers such as phosphoric acid ester and stearic acid ester, epoxy plasticizers, plasticizers for other plastics, or NBR for phthalate, adipate, sebacate, phosphate, polyether, polyester, etc. Plasticizer. Tackifier: Various tackifiers (tackifiers) such as coumarone resin, coumarone-indene resin, phenol terpine resin, petroleum hydrocarbon, and rosin derivative. Oligomer: Crown ether, fluorinated oligomer, polybutene,
Xylene resin, chlorinated rubber, polyethylene wax, petroleum resin, rosin ester rubber, polyalkylene glycol diacrylate, liquid rubber (polybutadiene, styrene-butadiene rubber, butadiene-acrylonitrile rubber, polychloroprene, etc.), silicone oligomer,
Various oligomers such as poly-α-olefins. Lubricants: hydrocarbon lubricants such as paraffin and wax, fatty acid lubricants such as higher fatty acids and oxyfatty acids, fatty acid amide lubricants such as fatty acid amides and alkylenebis fatty acid amides, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty alcohols Various lubricants such as alcohol-based lubricants such as polyhydric alcohols, polyglycols and polyglycerols, metal soaps, mixed lubricants and the like.

In addition, latex, emulsion, liquid crystal, bituminous composition, clay, natural starch, sugar, inorganic silicone oil, phosphazene and the like can be used. In addition, animal oil such as cow oil, pig oil, horse oil, bird oil,
Dairy products such as fish oil, honey, fruit juice, chocolate, yogurt, hydrocarbon type, halogenated hydrocarbon type, alcohol type, phenol type, ether type, acetal type, ketone type fatty acid type, ester type, nitrogen compound type, sulfur compound Organic solvents such as type, or various medicinal components, soil conditioners,
Fertilizers, petroleum, water, aqueous solutions and the like can also be used.

Further, in the present invention, in addition to the above-mentioned materials, the following fillers may be further compounded, if necessary. That is, clay, diatomaceous earth, carbon black, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxides, mica, graphite, scale-like inorganic fillers such as aluminum hydroxide, various metal powders,
Wood chips, glass powder, ceramic powder, granular or powdered solid filler such as granular or powdered polymer, and other various natural or artificial short fibers, long fibers (for example, straw, wool, glass fiber, metal fiber, various other Polymer fibers and the like) can be blended.

The polymer network structure according to the present invention is one in which the low molecular weight material is held between the three-dimensional continuous network skeletons (inside the internal communication space) made of the crystalline thermoplastic as described above. However, in this case, it is desirable to form the three-dimensional continuous network skeleton with as little crystalline thermoplastic as possible.

Here, where A is the amount of the crystalline thermoplastic that constitutes the three-dimensional continuous network skeleton and B is the amount of the low molecular weight material and other components, the weight fraction of the crystalline thermoplastic [{A / ( A + B) × 100}] is 5 to 30
%, Preferably 7 to 25%.

The polymer network structure according to the present invention comprises the above-mentioned predetermined amount of crystalline thermoplastic resin, a low molecular weight material and, if necessary, other components, and the crystalline thermoplastic resin is a three-dimensional continuous network skeleton. It can be obtained by mixing under mixing conditions capable of forming a structure.

Specifically, it is recommended to use a high-speed mixer such as a high-shear mixer and mix at a stirring speed of 300 rpm or more, preferably 500 rpm or more, more preferably 1000 rpm or more. When not stirring at high speed, for example, using a roll or rotor type mixer or a cylinder type mixer and mixing at a low speed, it is difficult to obtain a uniform three-dimensional continuous reticulated skeleton structure of the target crystalline thermoplastic. is there. The mixing temperature is 10
The range of 0 to 350 ° C is desirable, and the mixing time is 5 to 120.
Minutes are good.

Next, the polymeric material as the component (B) is a broad concept in the present invention. For example, a thermoplastic resin,
Any one may be used as long as it includes a thermosetting resin, a thermoplastic elastomer, rubber and the like, and is capable of lowering the elastic modulus and the like by blending the polymer network structure.

Here, as the thermoplastic resin, in addition to the above-mentioned crystalline thermoplastics, vinyl chloride resin,
Examples include styrene resins, acrylic ester resins, methacrylic acid ester resins, polycarbonate resins, acetal resins, polyamide resins, cellulose resins, alkylene oxide resins, and rubber modified products of these resins. it can.

Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, furan resin, unsaturated polyester resin, alkyd resin, epoxy resin, polyurethane resin and silicon resin.

Further, as the thermoplastic elastomer or rubber, ethylene-propylene rubber (EPR, EPD
M), nitrile rubber (NBR), butyl rubber, halogenated butyl rubber, chloroprene rubber (CR), natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), acrylic rubber, Examples thereof include ethylene-vinyl acetate resin, polyurethane rubber, silicone rubber, fluororubber, ethylene acrylic rubber, polyester elastomer, epichlorohydrin rubber, polysulfide rubber, hypalon and chlorinated polyethylene.

The mixing ratio of these polymer materials and the polymer network structure is such that a value obtained by dividing the weight of the low molecular weight material in the polymer network structure by the weight of the polymer material is 0.2 to. 3,
It is preferably in the range of 0.3 to 2, that is, the low molecular weight material in the polymer blend material is in the range of 17 to 75% by weight, preferably 23 to 67% by weight, and the polymer material and the polymer reticulate. It is desirable to mix with the structure, which allows the elastic modulus to be controlled in a wide range. If the ratio of the polymer network structure of the component (A) is too high, the original function of the polymer material may be impaired,
On the other hand, if it is too low, the intended polymer blend material having a low elastic modulus may not be obtained.

The method of mixing the components (A) and (B) is not particularly limited, and they can be easily blended with, for example, a general roll, kneader, mixer, Banbury mixer or the like. In this case, the mixing temperature may be in the range of 40 to 200 ° C., and the mixing time may be 1 to 60 minutes.

Further, the polymer blend material of the present invention includes
In addition to the components (A) and (B), the following fillers may be further added during mixing, if necessary. That is,
Clay, diatomaceous earth, carbon black, silica, talc,
Scale-like inorganic fillers such as barium sulfate, calcium carbonate, magnesium carbonate, metal oxides, mica, graphite, aluminum hydroxide, various metal powders, wood chips, glass powders, ceramic powders, granules or powders such as granular or powdered polymers Solid fillers, other various natural or artificial short fibers, long fibers (for example, straw, hair, glass fibers, metal fibers, other various polymer fibers, etc.) can be blended.

Since the polymer blend material of the present invention can hold a large amount of low molecular weight material such as liquid, the elastic modulus can be controlled to an extremely low range. Therefore, the polymer blend material can provide products in a wide range of industrial fields, particularly household appliances, sports equipment, industrial equipment, precision equipment, transportation equipment, construction, civil engineering, medical care, leisure, and the like. For example, as the vibration-proof / vibration-damping / cushioning material, a sealing member, a packing, a gasket, a fixing member such as a grommet, a support member such as a mount, a holder, and an insulator, and a buffer member such as a stopper, a cushion, and a bumper can be cited. Furthermore, as shock absorbers, sports goods such as grabs, mitts, golf clubs, and tennis rackets, for insoles of shoes, various toys, audio equipment, electronic
It is preferably used as an electric device, a bed, a chair, especially a medical bed that keeps the same posture for a long time, a barber / beauty bed, a theater chair, and a vehicle material that receives vibration.

It can also be used in medical devices such as artificial limbs, artificial hands, robots, electrode materials for measuring electrocardiograms, electrode materials for low-frequency therapeutic devices, and the like. Furthermore, it can be used as an ultra-low hardness rubber for OA equipment, seismic isolation rubber, anti-vibration rubber, and even racing tires. In addition, it can be used as a low hardness plastic for various molding materials. Furthermore,
Since it is possible to control the release of the low molecular weight material to the outside, it is also used for various sustained release materials that utilize the release characteristics of fragrances, medical agents, functional materials and the like. In particular, paper (including thin-leaf materials other than paper) feed rubber rolls, for example, copiers, printers, and other OA equipment and automated teller machines (ATM),
It is suitable for various feeding rolls such as money changers, counters, vending machines, and cash dispensers (CDs).

[0031]

INDUSTRIAL APPLICABILITY The polymer blend material of the present invention can be mixed with a large amount of low molecular weight material and has good retention of the low molecular weight material, so that the elastic modulus can be controlled to an extremely low range, It can be applied to various fields utilizing low elastic modulus.

Further, according to the method for modifying a polymer material of the present invention, it is possible to effectively and surely reduce the elasticity of various polymer materials.

[0033]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to the following examples.

[Example] Polypropylene (melting point 169 ° C), polyethylene (melting point 125 ° C) as a crystalline thermoplastic, diheptyl phthalate (DHP), diisodecyl adipate (DID) as a low molecular weight material
Using A), these were stirred by a high shear mixer under the mixing ratio and stirring conditions shown in Table 1 to obtain a polymer network structure.

With respect to the obtained polymer network structure, the average diameter d of the skeleton and the average diameter D of the cells were determined. The results are also shown in Table 1.

[0036]

[Table 1]

Next, these polymer network structures and the polymer materials shown in Table 2 were mixed at the ratio shown in the same table to obtain a polymer blend material.

[0038]

[Table 2]

[Brief description of drawings]

FIG. 1 is a schematic diagram showing the structure of a polymer network structure according to the present invention.

[Explanation of symbols]

1 three-dimensional continuous network structure 2 Internal communication space

Continuation of the front page (56) Reference JP-A-51-148761 (JP, A) JP-A-5-239256 (JP, A) JP-A-5-194763 (JP, A) JP-A-7-233280 (JP , A) JP-A-8-73681 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (12)

(57) [Claims] 1. A polymer network obtained by mixing (A) a crystalline olefin plastic and a plasticizer, wherein the plasticizer is held between three-dimensional continuous network skeletons of the crystalline olefin plastic. A polymer blend material comprising a structure and (B) a polymer material. 2. The polymer blend material according to claim 1, wherein the plasticizer is a plasticizer other than a fatty acid ester. 3. The polymer blend material according to claim 1, wherein the plasticizer is a phthalate-based, adipate-based, sebacate-based, phosphate-based, polyether-based or polyester-based NBR plasticizer. 4. The polymer blend material according to claim 1, wherein the plasticizer is a phthalate-based plasticizer for NBR. 5. The polymer blend material according to claim 4, wherein the phthalate-based plasticizer for NBR is diheptyl phthalate (DHP). 6. The polymer blend material according to claim 1, wherein the plasticizer is an adipate NBR plasticizer. 7. The polymer blend material according to claim 6, wherein the adipate-based NBR plasticizer is diisodecyl adipate (DIDA). 8. The crystalline olefin plastic is one or more selected from polyethylene, polypropylene and polybutylene.
8. The polymer blend material according to any one of items 1 to 7. 9. The polymer blend material according to claim 1, wherein the crystalline olefin-based plastic is polyethylene. 10. A crystalline olefin-based plastic,
8. A polypropylene, characterized in that it is polypropylene.
The polymer blend material according to any one of 1. 11. The blending amount of the plasticizer in the component (A) is 0.2 to 3 in weight ratio with respect to the polymer material of the component (B). Polymer blend material. 12. A polymer network structure obtained by mixing a crystalline olefin plastic and a plasticizer, wherein the plasticizer is held between three-dimensional continuous network skeletons of the crystalline olefin plastic. A method for modifying a polymer material, which comprises mixing the polymer material as a modifier material for the polymer material.