JPH03227362A - Water-swellable composition and production thereof - Google Patents

Abstract

PURPOSE:To provide the title easy-to-produce composition good in swellability even for ionic water, excellent in swelling stability, comprising polyvinyl chloride and a water-swellable rubber composition comprising an elastomer, a filler and a specific reaction-crosslinked product. CONSTITUTION:The objective composition comprising (A) a water-swellable rubber composition produced by homogeneously mixing (1) an elastomer, (2) a filler and (3) a polyoxyalkylene glycol containing >=25wt.% of oxyethylene unit followed by blending the mixture with (4) diisocyanate and (5) a second isocyanate consisting of a tri or higher functional polyisocyanate at the molar ratio (based on the hydroxyl group of the polyoxyalkylene glycol) NCO/OH =(1:1)-(3:1) and then carrying out a reaction and (B) polyvinyl chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a water-swellable composition and its manufacturability. More specifically, it is made by blending a water-wettable IM composite sole with polyvinyl chloride, has good swelling properties even in ionic water, has excellent swelling stability, and -! In terms of next industry,
This invention relates to a water-swellable composition that can be easily obtained and its manufacturability.

[Conventional technology]

Many water-swellable clean water materials have been proposed in which superabsorbent resins are dispersed in resins or elastomers. but,
Since the superabsorbent resins commonly used in the past are based on polymer electrolytes, they have the disadvantage that their 'IeI11 degrees for ionized water such as seawater is significantly lower than for fresh water.

On the other hand, Kujosui Materials has proposed using nonionic water-swellable polyurethane resin to overcome these drawbacks. For example, a water-swellable material made by mixing rubber with water-swellable urethane resin gold and curing it (t# 1985-2365)
4, JP-A No. 57-11972), and a highly water-absorbing and water-retaining material made by blending a super water-absorbing resin and a water-swellable urethane prepolymer with a soft resin or rubber (JP-A-59-1999).
-120653), etc. have been reported.

The present inventors have developed a water-swellable urethane system that has been added to polyvinyl chloride (hereinafter referred to as PVC), one of the most widely used plastics at present. I have performed the ninth practice to obtain a wet sole. But a water-swellable urethane prepolymer! -PVCcD has poor compatibility and is difficult to mix uniformly, making it difficult to industrially easily obtain water-swellable polyvinyl chloride compositions (hereinafter referred to as water-swellable PVC).

[Problems to be Solved by the Invention] The present invention is intended to improve these drawbacks. That is, the purpose is to provide a water-swellable PVC' which has excellent swelling properties even in ionic water, has excellent lIl water stability properties, and can be produced easily and advantageously industrially, and its manufacturability. That is.

[Ninth means to solve the problem]

As a result of various studies, the present inventors have discovered that a water containing a reaction crosslinked product with an isocyanate consisting of a nidistomer filler and a polyoxydialkyl renge IJ:)-rutho diisocyanate and a trifunctional or higher-functionality polyisocyanate. By first forming a swellable rubber composition and then mixing the obtained composition with PVC, the formed water-swellable polycrethane crosslinked product can be very easily and uniformly dispersed in the nidistomer formulation of the composition. It has been found that water-swellable PVC can be obtained industrially very easily and advantageously. That is, after the filler and polyoxyalkylene glycol are uniformly dispersed in the elastomer, an isocyanate consisting of a diisocyanate and a trifunctional or higher functional polyisocyanate is added and reacted to form the polyoxyalkylene glycol and the polyoxyalkylene glycol in the elastomer compound. The water-swellable PVC obtained by uniformly mixing polyvinyl chloride with the water-swellable rubber composition made of the above-mentioned composition components is prepared by completely producing a water-swellable polyurethane crosslinked product consisting of the above-mentioned composition components. Good Il against
The present invention was completed based on the discovery that it has excellent swelling properties and swelling stability, and that it can be obtained industrially very easily and advantageously. That is, the first invention of the present invention contains an elastomer, a filler, and a reaction crosslinked product with a polyoxyalkylene glycol tocyisocyanate containing 251J1 or more oxyethylene units and an in7anate consisting of a trifunctional or higher functional polyisocyanate. This is a water-swellable composition consisting of a water-swellable rubber composition and PVC. In the first and second inventions, after uniformly mixing an elastomer, a filler, and a polyoxyalkylene glycol containing 25111 or more oxyethylene units, an isocyanate consisting of a diisocyanate and a trifunctional or higher polyisocyanate is added to a polyoxy7alkylene glycol. NCO:OH is added to the hydroxyl group of noglycol in a range of 1:1 to 3:1 and allowed to warp to form a water-swellable polyurethane crosslinked product of the polyoxyalkylene glycol and isocyanate in the elastomer compound. Next, the water-swellable rubber composition obtained from the above composition is blended with PvC.

The present invention will be explained in detail below.

Examples of PvC used in the present invention include homopolymers of vinyl chloride, and copolymers of vinyl acetate, alkyl vinyl ether, edele/progylene, etc. that can be copolymerized with vinyl chloride.

Additionally, mixtures with vinyl chloride and blendable ABS resins can be used. If necessary, stabilizers, plasticizers, etc. may be added as additives. As these additives, 11 of those commonly added to PVC' can be used.

The nidistomer used in the present invention is natural rubber or synthetic rubber, and examples of synthetic rubber include polybutadiene rubber, nitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber, butyl rubber, ethylene chloride rubber, acrylic rubber, hydrin rubber, and chlorinated polyethylene rubber. , ethylene-vinyl acetate copolymer, etc.

These elastomers may be used alone or in combination with
Class 81 or higher may be used in combination.

The basic composition of the water-swellable composition of the present invention is composed of an elastomer, a filler, a polyoxyalkylene glycol containing 25 parts by weight per unit, a diisocyanate, and a trifunctional or higher functional polyisocyanate. It is characterized by being made by blending PVC with a water-swelling unistatic rubber composition containing a reaction crosslinked product with an isocyanate.

Next, each of the above-mentioned compounding components and compounding ratios will be explained.

The filler used in the present invention is blended into the elastomer.
It is sufficient to use fillers that are commonly used, such as silica fillers, calcium carbonate, titanium oxide, talc,
Clay, carbon black, etc. are used. Among these, silica fillers are mainly used. Anti-aging agents, stabilizers, plasticizers, etc. can also be used as part of the filler.

The amount of filler added varies depending on the amount of polyoxyalkylene glycol mixed into the elastomer, but especially for silica-based fillers, it is usually 100% of the elastomer.
10 to 150 parts by weight, preferably 20 to 150 parts by weight
It is desirable to add 100 parts by weight. If it is less than 10 parts by weight, the polyoxyalkylene glycol cannot be uniformly dispersed in the nidistomer, and 150! If the amount exceeds 11 parts, the water-wettable VIM composition becomes too hard and its miscibility with PVC deteriorates. <No.

The polyoxyalkylene glycol used in the present invention is a polymer having hydroxyl groups at both ends obtained by adding and combining alkylene glycol by a conventional method using ethylene glycol as a starting material. This polyoxyalkylene glycol preferably contains 25 or more oxyethylene units, preferably 30 or more oxyethylene units.
Yes. Other oxyethylene units include oxycypterene, oxypropylene, etc., and oxypropylene units are preferably used. If the content of oxyethylene units is less than 25% by weight, the degree of swelling of the water-swellable IM composition will be insufficient, which is not preferable. The molecular weight of the polyoxyalkylene glycol used is 100% due to its moisture content and ease of handling.
A range of 0 to 6,000, preferably 2,000 to 5,000 is desirable.

The amount of polyoxyalkylene glycol used is desirably 50 to 400 parts by weight, preferably 70 to 600 parts by weight, based on 100 parts by weight of the elastomer.

If it is less than 50 parts by weight, the swelling degree of the resulting water-swellable IM composition will be insufficient, and if it is more than 400 parts by weight, it will be difficult to uniformly disperse the polyoxyalkylene glycol in the elastomer, which is not preferred.゛.

In the present invention, isocyanates consisting of diisocyanates and trifunctional or higher functional polyisocyanates are used. Examples of these include triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, crude MDI (approximately 50 parts overlapped with diisocyanate, and trifunctional or higher polyisocyanate t?FJ50). Examples of diisocyanates include those containing superimposed moieties and average NCO groups -F13), and examples of diisocyanates include toluene diisocyanate, naphthylene-1,5-diisocyanate, 0-toluidine diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate.

The isocyanate used in the present invention has safety,
Crude MDI because of its ease of handling! 7t is a combination of crude MDI and diphenylmethane diisocyanate, and if weather resistance and yellowing resistance are important, the combination of hexamethylene diisocyanate and its modified type, non-yellowing polyisocyanate. Suitably used.

The water-swellable rubber composition used in the present invention is composed of polyoxyalkylene glycol and isocyanate.
It contains a wettable cross-linked polyurethane,
This is produced by a one-step reaction of a water-swellable polyurethane crosslinked product in an elastomer compound without using a urethane prepolymer or a curing agent. It consists of branching from parts and crosslinking. The content of trifunctional or higher polyisocyanate in the primary isocyanate is 5 to 50i1 (1
A range of 4 is preferred. If it is less than 5 weight St, the degree of crosslinking of the water-swellable crosslinked polyurethane obtained is too low and the swelling stability is reduced, and if it exceeds 50 weight St, the degree of crosslinking of the water-swellable crosslinked polyurethane is too high and the degree of swelling is reduced. This is not preferable or unfavorable because the moldability deteriorates. For the use of isocyanate,
Although it varies depending on the amount of impurities such as moisture present in the elastomer compound during the urethane reaction, NCO: 0HN1:1 with respect to the hydroxyl group of the polyoxyalkylene glycol
~6:1, preferably 1.2:1~2.5:1. If the amount of NCO: oH is less than 1:1, the reaction will not proceed sufficiently, and unreacted polyoxyalkylene glycol will remain, causing an increase in the amount of eluate; if it exceeds 6:1, water-swellable urethane crosslinking will occur. If the degree of crosslinking of the product becomes too high, the Ne moisture content will be low, which is undesirable.

The water-swellable composition of the present invention is thermoplastic, but when the proportion of the water-swellable rubber composition is large, it may contain a vulcanizing agent such as sulfur, a sulfur compound, a metal oxide, a guazine type, or a sulfene. Vulcanization can be carried out by adding a vulcanization accelerator such as an amide type, thiuram type, thea-tor type, or ditheocarbamate type. 1 liter organic peroxide can also be used as a vulcanizing agent. Examples of organic oxides include dicumyl peroxide, 1,1-bis(t-butylperoxy)3,3
゜5-trimethylcyclohexane, n-butyl-4゜4
-bis(2-butylperoxy)valerate, 2.5-
Examples include dimethyl-2,5-di(t-buteroxy)hexane. These amounts can be the same as those normally used for elastomers.

In the present invention, when manufacturing a water-swellable bim bottom,
A catalyst can also be added to accelerate the urethane reaction. Examples of this catalyst include dibutyltin dilaurate, diptyltin malate, tin chloride, triphenylamine, and the like.

In the present invention, the apparatus for producing the water-swellable dem composite bottom may be any apparatus as long as it is capable of mixing, reacting, heating, and cooling various ingredients. Examples include rolls, Banbury mixer-kneader 1 pressure kneaders, and the like. Among these, a pressure kneader can be most preferably used for reasons such as safety and reaction stability. In addition, the water-swellable BIM set and PVCO blend can also be rolled, Banbury mixer.
Kneader 1 This can be suitably carried out using a pressure kneader or the like, and if the obtained composition is subjected to 7-11 molding or vulcanization molding, a molded product of water-swellable PVC, which is the object of the present invention, can be obtained. It will be done.

Next, to specifically explain the method for producing the uninvented water-swellable composition, first, the elastomer is placed in the device and kneaded, then a filler and polyoxyalkylene glycol are added, and a uniform Mix with

Next, a urethane reaction catalyst is added as needed, and after cooling, an isocyanate consisting of a diisocyanate and a trifunctional or higher polyisocyanate is added and the reaction is carried out at a temperature of 40 to 110°C for 10 to 30 minutes to form a polyoxyalkylene glycol. A water-swellable urethane crosslinked product consisting of a reaction product of
A water-wettable rubber composition comprising the above composition components is prepared. Next, the obtained water-swellable rubber composition and PVC to which a plasticizer, stabilizer, etc. have been added as necessary are uniformly blended using the above-mentioned apparatus, and then the final product is formed by molding or vulcanization molding. A water-swellable composition, which is the object of the invention, can be obtained.

The invention is based on the composition of Nidistomer, water-swellable urethane resin and p
The present invention relates to a water-swellable composition comprising VC. The water-swellable composition obtained according to the present invention is water-swelled by uniformly mixing the elastomer, filler, and polyoxyalkylene glycol, and then adding and reacting isocyanate consisting of diisocyanate and trifunctional or higher functional polyisocyanate. It is obtained by forming a polyurethane crosslinked product into a nidistomer compound, adding a swellable rubber composition to it, and then blending the obtained next group acid product with PVC. 1. also has good swelling properties. Water-swelling Volicleta with excellent stability and poor mixing properties.
Since the resin and P'vc can be easily mixed, it can be easily and advantageously produced industrially. In addition, the processability is excellent as injection molding, extrusion molding, injection molding, calender bottom shape, etc. can be performed, and a wide variety of molded products can be manufactured.

〔Example〕

Next, the present invention will be explained in detail with reference to Examples.
The present invention is not limited in any way by these examples. Furthermore, all numerical values shown in Examples, Comparative Examples, Table 1 and Table 2 are parts by weight. The degree of swelling was determined by cutting a 20×20 dragon angle sample piece from the press-molded body and measuring it after immersing it in tap water or each electrolyte aqueous solution at 23° C. for 14 days, and using the following formula.

19. The extraction rate is determined by immersing the above sample in water at 26°C for 60 days, drying it at 100°C with the gear open for 24 hours, calculating the dry mass at 9 o'clock, and calculating it using the following formula: 90 Water-swellable BIM composition Production of Product> Mixing and reaction are carried out using a 20 liter pressure kneader (Moriyama Urasakusho A, D20-40 type) with the formulation shown in Table 1. Note that the raw materials and operations used in all formulations were the same. First, the elastomer was put into a kneader and kneaded for 5 minutes, and then a filler and poly(oxyethylene-oxypropylene) glycol [ethylene glycol was mixed with ethylene oxide and propylene oxide in a weight ratio of 90% by a conventional method. Random copolymer containing hydroxyl groups at both ends obtained by addition polymerization with :10, molecular weight 300
0. OH=2) was added and mixed uniformly. After adding dibutyltin dilaurate as a urethane forming catalyst, the polyisocyanate mixture (MDI-CR200XMDI
-LT Mixed polyisocyanate ffi (both manufactured by Mitsui Toatsu Chemical Co., Ltd.) or Coronate 2049, Coronat) EFi (both mixed polyisocyanate manufactured by Nippon Polyurethane (a)) was added and reacted at 60°C for 15 minutes. Then, the water-swellable rubber composition was expanded with water.Hereafter, the obtained water-swellable rubber composition will be indicated by the samples shown in Table-1.

<Example 1> P impregnated in advance with a compound such as a plasticizer shown in Table 2
vC compound 300m and the water-swellable rubber composition 4
1.90 parts were uniformly blended using a roll at 170°C. Next, the nine swellable PVC obtained was press-molded to create a plate-shaped press sheet.

Table 3 shows the degree of swelling, physical properties, etc. of the water-swellable PVC obtained.

<Example 2> P impregnated in advance with a compound such as a plasticizer shown in Table 2
125 parts of the vC compound and 41,210 parts of the water-wettable rubber composition were uniformly blended using a roll at 170°C. Next, TMDT was added to the obtained water-swellable PVC as a vulcanization accelerator.
lfide) 2nd part and MBTS (di-2-be
After adding 1 part of nzothiazyl disulfide and 4 parts of sulfur, press molding was performed to create a plate-shaped press sheet. The obtained water swelling property P
The swelling degree, physical properties, etc. of VC are shown in Table 3.
250 parts of Hpvc compound and 42,120 parts of the water-swellable rubber composition! It was uniformly blended using a roll at +-170°C. Next, the obtained A7'j water-swellable PVC was press-molded to create a plate-shaped press sheet. Table 6 shows the degree of swelling, physical properties, etc. of the obtained Kusui+II wettable PVC.

<Example 4> F was pre-impregnated with the formulations such as plasticizers shown in Table 2.
250 parts of VC co/pound and the water-swellable rubber composition 4
3,120 parts were uniformly blended using a roll at 170°C. Next, the obtained water-swellable PvC was press-molded to create a plate-shaped press sheet. Table 3 shows the degree of swelling, physical properties, etc. of the resulting water-swellable FVC.

<Example 5> Zea H pre-impregnated with a formulation such as a plasticizer shown in Table 2
250 parts of the PVC compound and 44,120 parts of the water-swellable rubber composition were uniformly blended using a roll at 170°C. Next, the obtained fLfi water-swellable PvC was press-molded to create a plate-shaped press sheet. Obtained water 1III
Table 3 shows the degree of swelling, physical properties, etc. of Type II P'VC.

Comparative example> F that was pre-impregnated with the compound such as plasticizer shown in 夛-2
300 parts of a VC compound was mixed with a paste-like polyurethane prepolymer [404 parts of a urethane prepolymer obtained by reacting 1 mole of the poly(oxyethylene-oxypropylene 7)/IJ cole and 3 moles of MDI with 300 parts of a VC compound.
5 000 obtained by reacting 5 parts of MOCA solution
cps (35°C) pasty urethane prepolymer was blended with a roll at 170°C. Next, the obtained water-swellable PVC was press-molded to form a plate-shaped press sheet. We moisture degree of the obtained nine-swellable PVC,
The physical properties are shown in Table 6, but the miscibility of the water-swellable urethane prepolymer and polyvinyl chloride was poor, and the condition of the water-swellable PVC was poor, making it impossible to obtain a product that could withstand practical use.

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Table 2 of 0 - ~ PVC Compound PVC: Product name ss-110 (Denki Kagaku Kogyo (I)) Stabilizer A: Product name MARK AC-183 (Adeka Argus Chemical Co., Ltd. Exhibition) Stabilizer B: Product Name: MARK BT-31 (Dyeed by Adeka Argus Chemical Co., Ltd.) Stabilizing aid: Product name: ADK CIZER0-130F (
(Manufactured by Adeka Argus Chemical Co., Ltd.) [Effects of the Invention] The water-swellable PvC of the present invention has good swelling properties even in ionic water such as seawater, has excellent swelling stability, and is suitable for industrial use. It is an extremely useful water-swellable composition that can be produced easily and advantageously. First, the water of the present invention! Water-resistant PVC ('
1. FC, which has thermoplasticity or vulcanizability and has excellent moldability (injection molding, extrusion molding, injection molding, and calendar molding is possible), can manufacture a variety of molded products such as films, foams, and molded products. It is possible. The water-swellable PvC thus obtained is suitably used for sealing materials, packing materials, water stop plates, agricultural films, packaging materials, wall covering materials, interior materials, etc.

Claims (2)

[Claims] (1) A water-swellable rubber composition containing an elastomer, a filler, and a reactive crosslinked product consisting of a polyoxyalkylene glycol containing 25% by weight or more of oxyethylene units, a diisocyanate, and a trifunctional or higher-functionality polyisocyanate, and polyvinyl chloride. A water-swellable composition comprising: (2) After uniformly mixing the elastomer, filler, and polyoxyalkylene glycol containing 25% by weight or more of oxyethylene units, an isocyanate consisting of diisocyanate and trifunctional or higher-functionality polyisocyanate is added to the hydroxyl group of the polyoxyalkylene glycol. TeNCO
:OH=1:1 to 3:1 and react to form a water-swellable polyurethane crosslinked product of the polyoxyalkylene glycol and isocyanate in the elastomer formulation, and then from the resulting composition components. A method for producing a water-swellable composition comprising blending a water-swellable rubber composition with polyvinyl chloride.