JPS62104846A - Zeolite complex and production thereof - Google Patents

Abstract

PURPOSE:A sheetlike zeolite complex, obtained by applying a compound of a polyurethane urea resin solution with zeolite to a base material, substrate, wet treating the substrate and activating the resultant porous sheet and having improved drying agent characteristic and heat resistance. CONSTITUTION:A sheetlike zeolite complex obtained by preparing a polyurethane urea resin solution from an organic diisocyanate, preferably 4,4'- diphenylmethane diisocyanate and a high polymer diol, preferably polyester diol and an amine based chain extender, preferably 4,4'-diaminodiphenylmethane, incorporating a toner and zeolite, preferably powdery synthetic zeolite or, as necessary, a solvent, mixing and stirring the mixture, applying and/or impregnating the resultant compound into a substrate, wet treating the substrate to produce a porous sheet and activating the resultant sheet while heating or evacuating.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a sheet-shaped zeolite composite and a method for producing the same. [Prior Art] Conventionally, as a sheet-like zeolite composite, a sheet-like zeolite formed by dry film formation and made of polyurethane is being considered in the electronics industry. [Problems to be solved by the invention] However, this product has poor desiccant properties and heat resistance.

[This is inferior. [Means for solving problems]

The inventors of the present invention have conducted extensive research into sheet-shaped zeolite composites with excellent desiccant properties and heat resistance, and as a result, have arrived at the present invention. Specifically, the present invention provides a sheet-like zeolite composite (first invention) characterized by comprising one zeolite supported on a wet process porous polyurethaneurea resin solution, and a blend of the polyurethaneurea resin solution and the zeolite. This is a method for producing a sheet-like zeolite composite (second invention), which comprises activating a porous polyurethane urea sheet obtained by wet processing. In the present invention, the porous polyurethane urea includes:
A porous polyurethane urea obtained by applying a polyurethane urea resin solution consisting of an organic diisocyanate (A), a polymeric diol (B) and an amine chain extender (C) to a substrate, and then wet-processing the polyurethane urea resin solution. The equivalent weight of polymer diol CB) is usually 2fJ (
1-2000. Preferably it is 400-1500. Examples of the polymer diol include polyester diol, polycarbo-4-to diol, polyether diol, and mixtures of two or more of these. Polyester diols include polycaprolactone diols and integrated polyester diols. As polycaprolactone diol, it is substituted with (substituted) caprolactone (substituted) based on an initiator [glycol (ethylene glycol)].
-Methyl-C-cuff. Examples of polyols include polycaprolactone diol, which is obtained by addition polymerizing rolactone, e-methyl-e-caprolactone, etc.) in the presence of a catalyst (organometallic compound, metal chelate compound, fatty acid metal acylated product, etc.). Examples of condensed polyester diols include low molecular diols [ethylene glycol, propylene glycol,
13-butanediol, I4-butanediol, 16-
hexanedio-I, diethylene glycol, dipropylene glycol, openentyl glycol, bis(hydrodimethyl)cyclohexane, bis(hydroquinethyl)benzene, etc., and mixtures of two or more of these] or polyalkylene with a molecule of 1xoooo or less Ether glycols (polytetramethylene ether glycol, polypropylene ether glycol, polyethylene ether glycol, etc., and mixtures of two or more of these), dicarboxylic acids (aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, cepacic acid, etc.), aromatic group dicarboxylic acids (terephthalic acid, isophthalic acid, etc.),
and mixtures of two or more thereof], such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyobentyl adipate, polyethylene propylene adipate, polyethylene butylene adipate, and polybutylene adipate. Examples include lenohexamethylene ambate, polydiethylene adipate, poly(polytetramethylene ether) adipate, polyethylene acelate, polyethylene sepacate, polybutylene azelate, and polybutylene sebacate. ,""'"-1-1 par-t-tv t L "Ci"
-: 0 1 (In the formula, R is a saturated aliphatic di-... residue, . represents the number of repeating units in the □ □ molecule, usually 5
(an integer of 50 to 50). Polycarbonate diol is a saturated aliphatic polyol (1,4-butanediol, I5-bentanediol, 16-hexanediol, polyethylene glycol such as diethylene glycol, polypropylene glycol, oxyethylene, Oxypro 1
pyrene copolymerized diol, etc.) and substituted carbonates (such as pyrene copolymerized diol) and substituted carbonates (
Diethyl carbonate, diphenyl carbonate 1
The transesterification method can be carried out by reacting the saturated aliphatic diol with phosgene, or, if necessary, by further reacting the saturated aliphatic diol. Polycarbonate diols are described in US Pat. No. 3,110,686. As polyether diols, alkylene oxides [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide, etc.], heterocyclic ethers (tetrahydrafuran, etc.) are polymerized, or copolymerized (block or random), such as polyethylene ether glycol, polypropylene ether glycol, polyethylene-propylene (block or random) ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether glycol and active hydrogen Containing compounds (low-molecular polyols, amines, polyhydric phenols, alkylene oxide adducts such as polycarboxylic acids (Japanese Patent Publication No. 54-371) 37
Publication No.). Among the polymeric diols, polyester diols are preferred. Amine chain extenders (Lj includes aliphatic diamines (ethylenenonamine, propylenediamine, trinoethylenediamine, butylenediamine, hexamethylenediamine, etc.), alicyclic diamines (isophoronediamine, 1.3-
cyclohexylene diamine, 44'-methylene dicyclohexyl diamine, etc.), aromatic diamine (4,4'-
diaminodiphenylmethane, tolylenediamine, phenyleneduamine, etc.), aromatic aliphatic amines (xylenediamine, etc.), heterocyclic diamines (piperazine, 14-diaminopiperazine, etc.), and mixtures of two or more of these. If necessary, low-molecular diols (ethylene glyfur, propylene gellicol, 1,4-butanediol, 1,6-hexanediol, etc.) may be used in combination. Among these, preferred are aromatic amino acids,
Particularly preferred is 4,4'-diaminodiphenylmethane. Aromatic diisocyanate (44-phenylmethane diisocyanate, tolylene diamine diisocyanate, phenylene diisocyanate, 15-naphthylene diisocyanate) aliphatic diisocyanates (e.g. -t, tetramethylene diisocyanate, hexanoethylene diisocyanate, -t, lysine diisocyanate, etc.), alicyclic diisocyanate, i---) (isophoronodiisocyanate, hydrogenated 44'-sif- Nylmethane diisocyanate,
Examples include isopropylidenecyclohequinyl diisocyate, etc.). Among these, aromatic diisocyanates are preferred, and 44-diphenylmethane diisocyanate is particularly preferred. Note that a trifunctional or higher functional polymer polyol, an organic polyisocyanate, and an amine chain extender may be partially used as long as the performance is not impaired. In the production of polyurethane urea resin, the ratio (equivalent ratio) of organic diisocyanate (A) and polymeric diol CB) and amine chain extender (C3) is usually the isocyanate group: active hydrogen-containing group. If the 0 ratio, which is preferably 095 to 1.2:1, is outside the above normal range, it is better to produce a polyurethane urea resin with a high degree of polymerization.Polymer diol The equivalent ratio of (B) and amine chain extender (C) is usually 1:01 to 5, preferably 1:03 to 3. The method for producing the polyurethane urea resin may be any known method. b) One-shot method, for example (A) and (B)
) and (C) at the same time, (b) Prepolymer method, for example, (A) and CB) are reacted to obtain a terminal NCO prepolymer, and this is chain-extended with (C). and (c) semi-prepolymer method, for example, a method in which (A) and part of (B) are reacted to obtain a terminal NCO semi-prepolymer, and this is extended with the remaining (B) and (C). It will be done. Among these, the prepolymer method is preferred. The above production can be carried out in the presence or absence of a solvent inert to isocyanate groups. Suitable solvents in the presence of a solvent include amide solvents [dimethylformamide (hereinafter abbreviated as DMF), dimethylamide amide, etc.], sulfoxide solvents (dimethyl sulfoxide, etc.), and ether solvents (nioxane, tetrahydrofuran, etc.). ), ketone solvents (cyclohexanone,
Examples include methyl ethyl ketonato), ester solvents (ethyl acetate, etc.), aromatic hydrocarbon solvents (toluene, etc.), and two or more of these solvents. Practically preferred solvents are amide solvents and sulfoxide solvents, and particularly preferred is DMF. The manufacturing number of the polyurethane urea resin is low, and the reaction temperature may be the same as the temperature normally adopted when carrying out the polyurethane urea resin reaction in the relevant industry.If a solvent is used, it is usually 20 to too °C. When not used, it is usually 100 to 22 (IC:, preferably 150 to
2 o. In order to accelerate the reaction at 9 °C, an amine catalyst W (1
-ethylamine, N-ethylmorpholine, triethylenediamine, etc.), tin-based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.), and the like may also be used. Furthermore, polymerization terminators such as monohydric alcohols (methanol, phthanol, cyclohexanol, etc.), amines (methylamine, butylamine, dibutylamine,
Preferably, amines are used, such as cyclohexylamine). The production of polyurethane urea resin can be carried out using production equipment that is normally used in the relevant industry. If no solvent is used, production equipment such as a kneader or extruder can be used. The polyurethane urea resin produced by this process has a solution viscosity of 2 when measured as a 30% by weight (solid content) D i'vf F solution.
．． 000~1, U fJ (J, (100cps/
(Practically preferred is one at 20°C). As the solution of the polyurethane urea resin used in the production of the sheet material, a polyurethane urea resin solution prepared in the presence of a solvent inert to the incyanate group can also be used. It is also possible to use a solution obtained by dissolving the above solvent. The concentration of the solution is usually 5-50% by weight, preferably 4 to IO.
It is 0% by weight. The polyurethaneurea resin solution contains resins other than polyurethaneurea resins, such as polyvinyl chloride, polyacrylic acid ester, polymethacrylic acid ester, polystyrene, polyacrylonitrile, acrylonitrile-vinylidene chloride copolymer, and vinyl chloride-vinyl acetate copolymer. It can also be blended. In addition, if necessary, antioxidant [4
Hinotard phenols such as 4'-butylidene-bis(3-methyl-6-1-butylphenol); organic phosphites such as triphenyl phosphite and trichloroethyl phosphite], ultraviolet absorbers (benzophenone type, benzotriazole type, etc.) ), carboxylic acids, phosphoric acids, ox-7 carboxylic acids, halogenated phenolic acid stabilizers and fillers (calcium carbonate, etc.), plasticizers, antistatic agents, bactericides, and known coagulation regulators 22719), crystalline organic compounds (Japanese Patent Publication No. 56-11652), hydrophobic nonionic surfactants [Japanese Patent Publication No. 45-39634 and Japanese Patent Publication No. 15-
No. 39635, details of each publication, polyoxyalkylene-modified dimethylpolysiloxane (Japanese Patent Publication No. 58-39/151), etc. can be added. In the present invention, zeolite is chemically defined as a crystalline hydrated aluminate containing alkali and alkaline earth metals. It can be expressed by a general formula such as (M, 1, M') O'A/+Qs-nsUOt'mHt
O (1) Carrier M': L+, Na+, K+, Rb+, N
H4-1MeaN+ (TMA), gt, N (TEA
), PY4N+(TPA)+ M':Ca", Ba++, St", Mg to Znl+, etc. Zeolites include naturally occurring ones and synthetic ones.
Synthetic ones are preferred. The main natural zeolites include clinoptilolite, mordenite, and faujasite.
Synthetic zeolites include A type, X type, Y type, L type, etc. Specific products include molecular sieves (Nikka Seiko's 3A, 4A, 5A, 13X, etc.; ring rod s r < -4 (J, SK -11, 5K-5o)
o, etc.), Zeolum (A-3, A-4, A- of Hakka Seiko)
5, F-9, A-48H, etc.). The effective diameter of the zeolite pores is about 20 A or less. The shape of zeolite includes powder, granules, and pellets, and among these, powder is preferable. The particle size of the powder is usually 100μ or less, preferably 20μ
It is as follows. Zeolite is published in Toyo Soda Research Report, Volume 21, No. 2, 4.
pp. 5-62; R9285 Chemical Products'', (pp. 88-89, published by Kagaku Nipposha, January 1985), Tokuko Showa 6 (J-
No. 23129 and "Chemistry Dictionary 5" published by Kyoritsu Shuppan in April 1963 (this is described). A pigment can be used if necessary.The pigment may be either an inorganic pigment or an organic pigment.Inorganic pigments include gunjo, cadmium yellow, red iron, chrome yellow, lead white, titanium white, carbon black, etc.; organic pigments include azo Examples include triphenylmethane, quinoline, anotraquinone, and phthalonanine. Among these, carbon black is preferable for use in the electronics industry, such as EL panels, in order to enhance contrast. Pigments can be used as they are. However, it is preferable to use it as a toner.The amount of toner added is usually 2 to 1 + 3 parts by weight, preferably 4 to 1 + 3 parts by weight in total of polyurethaneurea resin (solid content) and zeolite. In the formulation, the amount of polyurethaneurea resin and zeolite is determined by the total weight of both (based on which the polyurethaneurea resin (solid content) is usually 5 to 50%, preferably 10 to 50%).
30%, zeolite usually 50-95%, preferably 7
( ] to 90%. The formulation consists of a polyurethane resin solution, toner and zeolite, and if necessary, a solvent (same as the solvent described in the above section on polyurethane urea production (herein 11112)). It can be obtained by mixing and agitating the mixture using G. When wet-processing the mixture, this mixture is applied to a substrate.Substrates include non-woven fabrics, knitted fabrics, woven fabrics, raised fabrics, paper (release paper, etc.). ), plastic films, glass plates, etc.Furthermore, substrates that have been resin-treated with a polymeric substance in advance may also be used. The substrate is resin-processed with a material (polyurethane urea or polyurethane, such as the polyurethane urea resin according to the invention and conventional polyurethane resins from polyether polyols and/or polyester polyols, chain extenders and organic diisocyanates. Resin processing methods include impregnating the substrate with a solution or dispersion of a polymeric substance, or subsequent wet treatment.Methods for applying the compound to the substrate include coating. and/ma1
An example of this method is impregnation. Next, a wet treatment is performed. Examples of the liquid (nonsolvent) used in the wet treatment include water, ethylene glycol, glycerin, ethylene glycol monoethyl ether, hydroxyethyl acetate, and mixtures thereof. Alternatively, a mixture of the above-mentioned non-solvent and the above-mentioned solvent inert to isocyanate groups (mixture ratio: 90:10 to 3)
U: 7 t3) can also be used. Preferred among these are mixtures of water and solvents and water. The wet processing method is the usual method 1, i.e., applying the compound and immersing the substrate in a coagulation bath, coagulating it with water vapor, partially solidifying it with water vapor, and then placing it in a hot bath. Immersion method There is a method of applying a polyurethane urea resin solution (a non-solvent is added to the substrate as a colloidal dispersant and immersing it in a coagulation bath).The usual wet processing method is as described in U.S. Pat. No. 3,284,274, No. 10. -1
(a), (b3, (cl), described in column 1 (also described as the old method). After the wet treatment, the solvent is removed, washed (with water, methanol, etc.) and dried in the usual manner. Solvent promotion (anionic, nonionic or cationic/or amphoteric surfactants may also be used).
The crosslinking treatment can also be carried out by the method of No. 2 il&. The obtained sheet may be used as it is or after being peeled off from the substrate (in the case of using a plastic film, release paper, glass plate, etc.). The zeolite supported on the wet-processed porous polyurethane urea sheet of the present invention is coated with (a) the base composition and subjected to wet processing, and then the base is peeled off. (b) A substrate containing a porous polyurethane urea layer supporting a zeolite: (b) A base layer and a porous polyurethane urea coating supporting a base layer and a zeolite obtained by coating the mixture and wet-processing the mixture. (c) A substrate is impregnated with a polyurethane urea solution supporting zeolite, and a zeolite obtained by wet processing is supported. Consisting of a base layer having a porous polyurethane impregnated layer; (d) Prepare a base layer that has been impregnated with the compound in advance and wet-treated if necessary; I) Apply the compound thereon and then perform wet treatment? or il) A resin-processed zeolite-supported substrate layer obtained by laminating a wet-processed polyurethaneurea film coated with a zeolite-supported polyurethane urea film on top of another substrate. Among these, preferred are (a) and (b).The resulting polyurethaneurea sheet is then subjected to activation treatment, which is performed by heating or vacuum. The conditions are usually 100-300°C, preferably 150-250°C, and the degree of vacuum is usually 10°C.
~10"Tuz, preferably l U-3~I O-'T
It is urr. The composite of the present invention (where the density of the composite is usually 0.3~
0.9, preferably L<ha 0.4 to 0.8. Thickness is usually 0.01 to 5 mm, preferably 0.057%
It is 1111N. The strength is usually 1-5o1. Preferably it is 3-2°1. [Example] The present invention will be further described below with reference to Examples, but the present invention is not limited thereto. Example 1 (Synthesis of polyurethaneurea resin solution) 500-re
Add polyethylene adipate diol (molecular weight = 2000) 1007 and 25 g of 4,4'-diphenylmethane diisocyanate and react in a nitrogen stream for 5 hours at 6 (J°C) to form a urethane prepolymer having terminal NCO groups. The actual NGO content was 3.
, 35%. Next, add DMF3osy and stir until homogeneous, then add 44'-diaminodiphenylmethane 8) and DMF185.
Add a solution of ' and polymerize at 35°C for 3 hours, then add 2 g of dibutylamine to terminate the polymerization. This resin solution had a solid content of 45.00 Ucp at 30.1%.
The viscosity was s/2oC. (Blending prescription of the compound) Polyurethane urea resin solution 2551 synthesized above
1 Ko Nikka Seiko Molecular Sieves 3A Powder 2 t
J51', carbon fiber toner 5Li, and DMF'5U9 were added and mixed and stirred in a beaker until uniform. (Preparation of sheet-shaped zeolite composite) The above-mentioned formulation was applied onto a glass plate (using a bar coater), and then immersed in a water tank prepared in advance for about 3 minutes. Remove the formed sheet from the glass plate, and
After pre-drying for 30 minutes in a dryer at 0℃, 180℃, 1f
Activation treatment was performed for 2 hours under J'Tu++ high vacuum to obtain a sheet of the present invention. The density of the sheet was 0.649/cd, the thickness of the sheet was 0.15 m, and the strength of the sheet was 67η. Ratio Example 1 (Synthesis of polyurethane resin solution) Urethane prepolymer 125yG having the same terminal NCO group as in Example 1' was mixed with DMF 298P, stirred until homogeneous, and then 25 g of ethylene glycol was added and heated at 90°C. The polymerization was carried out for 12 hours, and 1 part of methanol was added to terminate the polymerization. This resin solution had a solid content of 30.3% and 12. (JOOcp
The viscosity was s/2oC. (Blending recipe of the compound) A compound was obtained under the same conditions as in Example 1 using the polyurethane resin solution synthesized above in place of the polyurethane urea resin iNI of Example 1. (Preparation of sheet-like zeolite composite) After applying the above composition on a glass plate using Vertu 9-'r, pre-drying it in a 91J'C dryer for about 2 hours,
8 (1'c, 10' Turr. Activation treatment was performed for 2 hours under high vacuum, but some sheets were deteriorated. Test example) The desiccant properties and heat resistance of one sheet obtained above were evaluated. A test was conducted and the results are shown in Table 1. Table 1 Notes (Test method) Desiccant properties; Humidity sensor (with adhesive)
f) Xo, 151111.1 and relative humidity 6
The time required to change from 0% to 5% was measured. Heat resistance: Changes in the appearance of the sheet after activation treatment (18 (1'c x 2 hours) were observed. [Effects of the Invention] Composite of the present invention The body has the following effects: (1) It has excellent desiccant properties and heat resistance compared to conventional dry deformed polyurethane. (2) It is notebook-shaped, so it is easy to process and is relatively durable. In other words, it can be applied to electronic parts and is easy to handle.''The uninvented composite can be used as a drying agent for electronic parts (such as EL panels of EL display devices) because it achieves the effects described in 1. It can also be used as a desiccant in other fields such as food and petrochemicals.

Claims (1)

[Claims] 1. A sheet-like zeolite composite comprising zeolite supported on a wet-processed porous polyurethane urea sheet. 2. A method for producing a sheet-like zeolite composite, which comprises activating a porous polyurethaneurea sheet obtained by wet-processing a blend of a polyurethaneurea resin solution and zeolite.