JPS5957740A - Sheet material for roller - 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 The present invention relates to a sheet material for an erodible roller that has excellent properties for retaining, absorbing and supplying liquid materials, and retains its shape even when used for long periods of time under severe conditions.

Conventionally, felt, synthetic resin foam, paper, non-woven notebook paper, or sheet-like materials with polymeric substances added thereto have been used for the surface of liquid-absorbing rollers. However, many of them have problems with suction and squeezing properties, poor abrasion resistance, lose their shape after long-term use or under harsh conditions, or are severely damaged by solvents and chemicals. was far from sufficient. Regarding these problems, although a considerable improvement can be achieved by adding a polymeric substance to a non-woven notebook, a satisfactory result has not yet been obtained.

For example, a method of imparting a polyurethane elastic body to non-woven fabric is known, but the polyurethane in the upper layer of the notebook may deteriorate, the fibrous layer of the non-woven fabric may not retain its shape sufficiently, or it may not be sufficiently soft and compressible. Problems such as not being able to obtain a product with good thickness recovery properties, insufficient liquid holding properties, and sagging when used at high temperatures severely limit the range of use and lifespan of rollers. It was something like that.

The inventors of the present invention have worked diligently to obtain a material for rollers that overcomes these problems, has extremely high shape retention, has a wide range of uses, is durable, and has excellent workability, and as a result has arrived at the present invention. be.

The gist of the present invention is as follows.

A polymeric polyol, an organic polyisozoane-1, and a chain extender are placed in the voids of a nonwoven fabric in which fibers are six-dimensionally entangled. A car filled with a polyurethane elastomer made of polyneedle-based polyol mustard D) made of polyneedle! An old notebook material for rollers with excellent shape retention.

Soft I constituting the polyurethane elastic body used in the present invention
- The segment component has a hydroxyl group at both ends and a molecular weight of 500 or more, preferably 500 to 4,000. h
Mainly used is a polyether polyol having a melting point of 70 DEG C. or lower and having 6 or more carbon atoms, preferably 5 to 6 carbon atoms.

Of course, we also include polyester polyols, polycarbonate polyols, polybuta/ene polyols, polyacetal polyols, polyethylene oquinodo polyols, etc. that have similar molecular weights and melting points (4
: It is possible to use a mixture of these together, but it is not recommended that the polyether polyol having 6 to 2 carbon atoms be at least 50 parts of the total glycol, and furthermore, at least 70 parts. 1- Suitable for improving shape retention and compressive elasticity. Polyurethanes made from polyether polyols having 2 or less carbon atoms or polynisder polyols are not suitable because they are inferior in shape retention, liquid absorption, compressibility, etc. Typical polyether polyols used include poly(
Mixtures of propylene oquinodo) glycol, poly'(tetramethylene oquinodo) glycol, poly(pentamethylene oxide) glycol, or copolymers thereof, and di-polyols are used.

Of course, other polyethers and/or polyesters may be copolymerized with the above-mentioned polyether-based compound. For example, it is a polymer glycol obtained by graft-polymerizing poly(propylene oxide/de)glycol with ethylene oxide.

Other polyols include polyethylene adihye-1
- glycol, polypropylene adipate glycol,
Polycaprolactone glycol etc. or a mixture thereof.

The ino7anate compound used in the polyurethane elastomer of the present invention is an organic polyinocyanate compound, and is not particularly limited.

Examples include phenylene diisonanate, toluylene diisonone-1, diphenylmethane-a, 4'
-diinoneane-1・, naphthylene diiso/ane-1・
, aromatic diiso7anate such as diphenyl diisocyanate-1, butylene diisocyanate-1, hexamethylene diisocyanate, diiso/anate, zinclohequinylmethane diisocyanate, isophorone diisocyanate, etc. These include aliphatic diisocyanates and mixtures thereof, but the most important are aromatic/ino/anates. Strength of notebook material: +4jjf property 1 Nitrothermic property, particularly preferably toluylene cyone ane = 1~, diphenylmethane 4,4'-cyinoaanate, diphenyldimethylmethane 4,4'-diisocyanate-1., naphthylene zoinocyane-1. , and a mixture thereof is used in an amount of 17 to 6 moles: 1:1, more preferably 1.8 to 5 moles, relative to the polymeric diol.

The chain extender used in the present invention has a functional group that reacts with the commonly used +i polyiso7anate.
Preferred are low-molecular-weight compounds, such as Schiff, glycols, amines, amino alcohols, hydrazine conductors, and water.

The glycol chain extenders used in the present invention include ethylene glycol, glopylene glycol, 1.4-
Butanediol, 1,3-butanediol, 1.5-
Hentanediol, neopentyl glycol, hentanediol, nocrohegysandiol, 1,4-bis(β
-Hydroquine ethoxy)benzene, N,N'-bis(β
-hydroxyethyl)aniline, diethylene glycol, triethylene/glycol, etc. or mixtures thereof. Preferred are ethylene glycol, propylene glycol, 1,4-butanediol, 1,4-his(β-hydroxy/ethoxy/)benzene, and the like.

Specific examples of the monovalent amine chain extenders used in the present invention are l)-phenylenediamine/,...-noenylene/amine, l-! J-ren/ami/, naphthylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-cyamino diphenyl ether, 4,4'-diaminodiphenyl thioether, 4,4'-noamino diphenyl sulfone, 4,4' Aromatic organic diamines such as -diamino-ro, 6'-trimethyldiphenylmethane, 4,4'-diamino-2, 3'-dichlorodiphenylmethane, 4,4'-diaminodiphenyldimethylmethane, ethylenediamine, propylenediamine, Menzandiamine, isophoronediamine, /chlorohexylene/amine, 4.4'-diaminonebutalohexflumethane, 4.4'-diamino-ot, ro'-1/methyldicyclohegycylmethane, quinolile/diamine, etc. It is an aliphatic organic/amine, etc. or a mixture thereof. Aromatic organic diamines or alicyclic diamines are preferred, among which 4,4'-/aminodiphenylmethane, tolylene diamine, 4,4'-amino//kurohegi/lunota/, 4,4' -diamino-ro 7
Ro'-Dinotil/Nkuro~\Gizolmek/.

The solvent for the polyurethane of the present invention is not limited to bamboo as long as it dissolves the polyurethane and does not react with ino/anate groups. Dimethylformamide, /ethylformamide, dimethylacetamide, hexamethylphosphoramide, N-methyl-2-pyrido/, dimethylsulfoquinide, tetrahydrofuran, dioxane, etc., and also: those It is a mixture.

When producing the polyurethane elastomer of the present invention, a commonly used monofunctional compound having one amine group or hydroxyl group can be used to adjust the degree of polymerization to a desired degree.

The polyurethane elastomer d5 of the present invention can be obtained by adding a polymeric diol, polyino/anate, a chain extender, and optionally a terminal capping agent to 1tt and stirring as is generally practiced. It is also possible to use the so-called Solebolimer method, in which a so-called prepolymer is synthesized by reacting the polymeric diol and an organic polyinonoanane in advance, and then extended with a chain extender.

When synthesizing the polyurethane of the present invention, in order to accelerate the reaction rate, for example, S, L, R, eegen and I
Gu, (II!, J,'risd1.”Ac1vance
s in Urcthanc 5science
ancl Technology,”i, (197
1) Tcchnomic, .

Of course, it is also possible to add a 6th class amine such as triethylenediamine as listed in 'f'++2 by Plll), On, Inc., or an organometallic compound such as dilauryldibutyltin.

According to the above method, a prepolymer is synthesized, and if necessary, an appropriate emulsifier is used to extend the chain with a chain extender in an aqueous solvent to synthesize a water-based emulsion of polyurethane. The method used for urethane is also adopted. (In terms of skin-mechanical texture, etc., it is not as good as the type 71'j polyurecun, but as described later, a fiber notebook is produced.) This is Jiri.

As already known, the polyurethane shell/surrounding solution of the present invention contains surface additives such as various antioxidants and ultraviolet absorbers, as well as organic and inorganic carbon blanks, Additives such as titanium oxide and coagulation regulators may be added.

Next, the fiber sheet used in the present invention will be explained.

The fiber notebook used in the present invention is a nonwoven fabric in which fibers are six-dimensionally entangled.
Ti species are particularly limited, but include boric esters.

Something made of polyamide or the like would be a good choice.

If the fineness is i, 0 (I or less), the fiber &[1 sheet made of ultrafine fibers #fl is likely to have minute π1■ spaces, so in the case of liquid-absorbing low shee, the liquid-absorbing property becomes large, so it is difficult to use.

Most preferred are microfibers made of 6-nylon, 6.6-nylon, polyethylene terephthalate, copolymers thereof, and mixtures thereof.

In the present invention, it is preferable to use a 41: generation type fiber fa as the ultrafine fiber, for example, a composite fiber from which a bundle of ultrafine fibers consisting of other components can be obtained by removing at least one component. This is an ultrafine fiber bundle obtained by removing the sea component of polymer array fibers as shown in No. 46-6817. In addition, there are also fibers produced by the known mixed Ehito method, fibers of the peeling and splitting type, that is, fibers made of two or more components, which are peeled from the interface by means such as applying an external force to generate ultrafine fibers. Can be used. Depending on the case, ultra-fine 9. 'A fiber can also be used. The thickness of each fiber is 1.0 d or less, preferably 0.5 d or less, or 0.2 d.
The following is good.

The fiber sheet of the present invention can be produced by, for example, making a fiber sheet 1 mainly composed of composite fibers such as IL into such polymer array fibers by needle punching, water punching, etc., and removing the components to be removed with a solvent. This can be achieved by making the composite fiber extremely fine by applying mechanical action or the like.

There are various methods of manufacturing the roller/t-shaped article of the present invention from the fiber #, ff/-1 and the polyurethane elastic body, but a typical manufacturing method is to manufacture the polymer array tjk.
Taking the case of using 1ff- as an example, it is as follows. After forming a web from the above-mentioned polymer arrays KA & fl:, entangling them by a method such as needle punching, extracting the 11σ component with a solvent, and forming a non-woven fabric that also has ultrafine fiber bundles of polyethylene terephthalate. , wet coagulation in water,
Desolute and dry or polymer array fiber! (A nonwoven fabric made of
After binding, the polyurethane solution of the present invention is impregnated, wet coagulation and solvent removal are carried out in water, and the water-soluble polymer is further extracted in warm water and then dried. You may add a slicing or pressing process at an appropriate stage to adjust the thickness. Further, a step such as applying silicone may be added to adjust the piloerection state.

When using a water-based emulsion of polyurethane, for example, a fabric made of the above-mentioned polymer array fibers is impregnated with the water-based emulsion of polyurethane, and after drying, the sea component is removed using percrene to generate ultrafine fibers. It is also possible.

The surface layer of the obtained sheet-like product may or may not be raised, but if a raised product is required, it can be obtained by grinding the sheet obtained as described above by ω1 using a sandpenocoo.

Of course, it is perfectly acceptable to grind and raise the fluff after roller forming.

The roller sheet material bar of the present invention is made of a specific polyurethane elastic body and IBM K, III nonwoven fabric, so it has high performance in absorbing, retaining and supplying liquid materials, and is highly resistant to I'J, such as high-temperature chemicals. It has a small mouth shape that could not be achieved with conventional rollers of this type, +g8r=l, which is said to have extremely excellent shape retention even when used for long periods of time under harsh conditions.

The present invention will be specifically explained below using examples. Of course, the present invention is not limited to these examples in any way.

Note-like! 1. A sample of 20 x 100 ma was prepared and measured using a Ten/Ron UTM-m-100 tensile tester manufactured by Toyo Baldwin.

One-pressure "X" A-L easy method: A 20 m x 20 m sample was tested using a tan-type compressive elasticity tester, and a load of 500 g/an2 t was applied during loading and unloading. The thickness retention rate was measured.

Sheet the surface of the res roller 2 pieces of shidamono The thickness including the test liquid is 1. D 0.1 m, m of cotton wool woven fabric at room temperature Clearance of 1m/min Continuously pass at high speed for 24 hours The thickness of the top sheet is not good. Comparison of liquid absorbent surface smoothness did.

The following abbreviations are used in the examples.

Abbreviation Official name PTM G ・・・・・・ Poly(tetramethylene oxide) glycol PCL ・・・・・・
・・・・・・・・・ Polycaprolactone glycol: P
EBA・・・・・・・・・Song・Polyethylene butylene adipe-1・]”’EC・・・・・・・・・4・Poly(ethylene oquine) glycol MDI・
・・・・・・・・・ Diphenylmethane-4-4′-diisocyanate EG ・・Between songs・・Ethylene glycol M 13 A・・・River・・・・・・・・・
・・4,4'-diphenyldiaminomethane 1) T3
A ・・・・・・・・・・Track G n-Butylamine II'A ・・・Track Isoproper Tool DM
F...... N,N-dimethylpol-11amide M E K...4... 2-sitanone T I-IF......4...Tetrahydrofuran Example 1 Molecular weight is 2050 P T, M (I after reacting j with twice the molar equivalent of MDI to obtain a prepolymer) 5 with MF
Diluted to 0%, M 13 A and o, D I3 A at 96%
DM i' 7+r solution containing at a molar ratio of -7 was added to the remaining Ino/I = 1 group, and after dilution to 25%,
The reaction was carried out at 50° C. for 5 hours to obtain a solution having a viscosity of 250 Po1se.

50 parts of polyethylene/terephthalate as island component, 77
Consisting of 50 parts of polystyrene as a component, 16 pieces/filament stretched 2.6 times, thickness 5.4
Denier, length 51ma, number of crimps 15/inch polymer array fiber &
A nonwoven fabric of g/cni' was obtained.

After drying, it was soaked in perchlorethylene to dissolve the polystyrene and obtain a nonwoven fabric in which bundles of ultrafine fibers were entangled.

The nonwoven fabric was immersed in a 16% DMF solution of the polyurethane elastomer and squeezed with a roll to remove excess solution to obtain a sheet-like material.

The obtained notebook-like material was sliced in half to a thickness of 1.8 ms to obtain a sheet-like material of the present invention.

The sliced surface of the notebook was placed on the surface of a stainless steel cylinder with a diameter of 2 cm. After fixing,
The surface was ground and brushed with sandpaper to form a roller.

The evaluation results of the obtained sheet material and the roller using the same are shown in Table 1 and Table 2, respectively. As shown in these results, this plate-like material had excellent shape retention even when exposed to chemicals and high temperatures, and was also excellent in retaining various properties when used as a roller.

Example 2 P'Ll'M()/PCL as a polymeric diol component
A notebook-like material was obtained in the same manner as in Example 1, except that (80/20) was used, and then a roller was used.

The evaluation results are shown in Tables 1 and 2, and good results were obtained in terms of shape retention, performance retention, etc.

Examples: EQ1 terminal Ω as a chain extender: I + as a 1,1 terminator
．． ) A sheet-like product was obtained using A in the same manner as in Example 1, and was further made into a roller. The evaluation results are shown in Tables 1 and 2, and it was found that this sheet-like material had excellent shape retention even when exposed to chemicals and high temperatures, and also had excellent performance retention when used as a roller. .

Comparative Examples 1 and 2 A sheet-like product was obtained in the same manner as in Example 1, except that the polyurethane composition shown in Table 1 was used, and then rolled.

The evaluation results are shown in Tables 1 and 2, and it was found that the plate-like material was inferior in chemical resistance and high temperature resistance, and the rollers were inferior in shape retention and retention of various materials compared to the present invention. It was inferior.

Example 4 7-1 was prepared in the same manner as in Example 1, except that polyester staples with a single yarn fineness of 3.0 CI were used as the fibers λ and fL.
・A similar product was obtained, and a roller was also obtained. The evaluation results are shown in the table below.
As shown in Tables 1 and 2, the rollers exhibited good properties, except for a rather poor liquid absorption performance.

Supplementary procedure J' [S+: 50.5.2 1 Indication of case + r4 JIJ 574IIIf ¥1 Egg No. 168480 2, Title of invention a-Sheet material for sea 5 Person making amendment 4 Date of amendment order Proprietor 5 Amendment The number of inventions increases due to None 6 cuffs χJ
Explanation of the amendments made in Column 7 of the Detailed Description of the Invention in Book 111 of Zou Shii Book K10 (1) Page 1, line 18, "For liquid suction" is changed to "For suction and squeezing liquid."

(2) Page 4, line 6 "Glycol" is referred to as "polyol."

(3) 11th Tei 9th line ``I want to beheaded'' is changed to ``I want to beheaded.''

After that, wet coagulate in water and dry to obtain /-1.
is. ”.

Procedural amendment (formality) Commissioner of the Japan Patent Office 1. Indication of the case Patent Application No. 168480 of 1982 2. Title of the invention Applicant IP, +sr Tokyo Chuo j”-l-],
'1M Sugimuromachi 2-2 Name (3is) Higashishidama Shikikai? ” +Vi February 22, 1958 (Delivery date) 5 Detailed explanation of 1 invention in the specification subject to amendment” column

Claims (1)

[Claims] A polymeric polyol, Okatsuki polyisocyanate, and a chain extender are added to the voids of a nonwoven fabric in which fibers are six-dimensionally entangled, and the main component of the polymeric diol is a polyether whose repeating unit has 6 or more carbon atoms. Made from polyether polyol.