JPH03290424A - Reactive water-based resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of imparting excellent flame-retardancy to a cushioning material obtained by the treatment of a fibrous material by using a specific blocked polyurethane, a fatty acid ester and water as essential components. CONSTITUTION:The objective composition contains, as essential components, (A) 100 pts.wt. of a blocked polyurethane having polyoxyethylene group and carboxylic acid salt group, (B) 5-20 pts.wt. of a fatty acid ester (preferably a higher fatty acid ester) and (C) water dissolving or dispersing the components A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a reactive aqueous resin composition containing a blocked polyurethane containing a carboxylic acid group.

[Conventional technology] Polyurethane resin has high affinity and adhesive strength to various base materials such as fibers, paper, wood, and plastics, so polyurethane aqueous liquid can be used as a fiber processing agent, paper processing agent, and adhesive for resins and films. It is widely used for such purposes. However, the so-called aqueous polyurethane liquid, whose reaction has been completed during the production of the aqueous liquid, has poor permeability and may not be able to penetrate between (inside) the base materials, or it may have already lost its reactivity, so it cannot be strong due to the formation of covalent bonds. There are many cases where adhesive strength cannot be achieved. On the other hand, reactive polyurethane aqueous liquids containing so-called blocked isocyanates retain their fluidity and adhesiveness even after the water has evaporated, so they can be cast onto relatively hydrophobic substrates. Alternatively, it can be penetrated and bonded. In addition, it is used in several applications because of its characteristics such as the ability to form strong bonds with substrates due to the high reactivity of isocyanate regenerated by heating or the like.

[Problems to be Solved by the Invention] However, when a fibrous base material such as a polyester fiber is impregnated with the above-mentioned blocked isocyanate compound and cured, a so-called cushion body is obtained, but this is not suitable for use in a vehicle, for example, an automobile. If the flame retardant property is extremely poor, causing an inconvenient situation such as ignition and complete burning, flame retardant standards (e.g.
Currently, it cannot be used for applications that require HVSS-302).

The present invention aims to solve this problem of conventional reactive polyurethane aqueous liquids.

[Means for Solving the Problems] The present invention is the following invention made to solve the above-mentioned problems.

A reactive aqueous resin composition containing as essential components a blocked polyurethane having a polyoxyethylene group and a carboxylic acid group, 5 to 20 parts by weight of fatty acid ester based on 100 parts by weight of the blocked polyurethane, and water in which these are dissolved or dispersed. thing.

The fatty acid esters in the present invention include lower fatty acid esters with a boiling point of 150°C or higher such as diethyl malonate, higher fatty acid esters such as methyl stearate and ethyl stearate, or mixtures of higher fatty acid esters such as soybean oil, rapeseed oil, and olive oil. Examples include so-called oils and fats. Oils and fats are preferred in terms of ease of addition, cost, etc., and liquid ones are particularly preferred.

When the compound is in liquid form, it may be added to the blocked polyurethane aqueous solution under strong stirring, or it may be added before the blocked polyurethane is dissolved or dispersed in water.

Further, when the compound is solid, the latter method is preferred in terms of uniform dispersion.

The amount added is preferably 5 to 20 parts by weight per 100 parts by weight of the blocked polyurethane; if the amount is 5 parts by weight, satisfactory flame retardance cannot be obtained. In some cases, the inherent performance of the blocked polyurethane may deteriorate, which is not preferable.

The blocked polyurethane in the present invention is not particularly limited as long as it has a polyoxyethylene group and a carboxylic acid group. However, the polyoxyethylene group and carboxylic acid (salt) group are preferably derived from a polyoxyalkylene polyol containing them. This polyol has a high oxyethylene group content and has -
A carboxylic acid group-containing polyoxyalkylene polyol having a COOX group (x: a hydrogen atom or a cation) is preferred. Blocked polyurethanes obtained using such polyols, raw materials thereof, etc. will be described below.

(1) Polyoxyalkylene polyol before carboxylic acid (salt) group introduction Polyoxyalkylene polyol is a polyoxyalkylene polyol obtained by mixing or sequentially reacting ethylene oxide or ethylene oxide with another alkylene oxide as an initiator. .

It may also be a mixture of two or more types of polyoxyalkylene polyols.
A compound having a hydrogen atom (a hydrogen atom of a hydroxyl group or an amino group) with which an octavalent alkylene oxide reacts, preferably one or more trivalent to tetravalent initiators or a mixture thereof with a divalent or pentavalent or higher valent initiator. be.

Polyhydric alcohols are particularly preferred as initiators. The polyoxyalkylene polyol may be a mixture with other high molecular weight polyols that do not contain oxyethylene groups or have a small proportion of oxyethylene groups. Other high molecular weight polyols include oxyethylene groups. polyoxyalkylene polyols with few groups, polyether ester polyols with a small number of ester groups, polycarbonate polyols,
Examples include polyoxytetramethylene polyol.

This polyoxyalkylene polyol needs to have the following requirements on average.

Average oxyethylene group content: 50% by weight or more is required.
Preferably from 60 to 95% by weight, in particular from 70 to 90% by weight, thus preferably containing small amounts of other oxyalkylene groups in addition to oxyethylene groups, preferably oxypropylene groups, with a low amount of oxyethylene basis. The stability of the inventive composition against pH changes is reduced.

It is preferable that the average number of hydroxyl groups exceeds 2. More preferably 2.3 to 8, especially 2.6 to 4. If the number of hydroxyl groups is small, the curing properties and adhesive properties of polyurethane will decrease.

The average molecular weight per hydroxyl group is preferably 200 to 4,000, preferably 300 to 3,000. If the molecular weight is low, the cured polyurethane will be hard and brittle, resulting in poor toughness. If the molecular weight is high, the permeability of the blocked polyurethane will be poor. Adhesion becomes insufficient.

(2) -CO to the polyoxyalkylene polyol
It is preferable to introduce a COOX group into the polyoxyalkylene polyol by introducing an OX group and esterifying or urethanizing the resulting polyoxyalkylene polyol containing a carboxylic acid (salt) group. Urethane formation is carried out by reacting a reactive polycarboxylic acid derivative having a reactive carboxylic acid group and a -coax group.
A compound having a secondary amino group (such as a secondary amino group) and a -COOX group is reacted with a polyisocyanate (at least one incyanate group of the polyisocyanate is reacted with a hydroxyl group of the polyoxyalkylene polyol, and at least one other
One method is to react the above-mentioned -COOX group-containing compound with an isocyanate group), or by reacting a -COOX group with a compound having an incyanate group.

Examples of these carboxylic acids include maleic acid, fumaric acid, phthalic acid, malonic acid, adipic acid, trimellitic acid, butanetetracarboxylic acid, and reactive derivatives of these polycarboxylic acids such as anhydrides and acid chlorides. .

Examples of incyanate-reactive carboxylic acids include dimethylolbrobionic acid and amino acid.

X in the -COOX group is a hydrogen atom or a cation, and the cations include ammonium, NR, (R:
At least one is a monovalent organic group such as an alkyl group and the others are hydrogen atoms), phosphonium, alkali metal ions, etc.
Particularly preferred is an alkali metal ion, and X in the -COOX group of the blocked polyurethane is ultimately a cation, and the -C00M group can be converted into a salt form at any stage.

-CO introduced into the polyoxyalkylene polyol
The number of OX groups is preferably introduced in an average amount of 0.005 to 0.8 per molecule of polyoxyalkylene polyol, more preferably 0.01 to 0.6,
In particular, it is 0.04 to 064 pieces. Also, per hydroxyl group of polyoxyalkylene polyol is 0,002 to 0.4
, particularly preferably 0.005 to 0.3. This amount is related to the water stability and curing properties of the blocked polyurethane; if it is too small, both the stability and curing properties will be insufficient, and if it is too large, the curing properties will be too high, causing trouble in handling. Therefore, in an introduction method that produces one -COOX group, such as dicarboxylic anhydride,
0.00 per mole of polyoxyalkylene polyol
A compound for introducing 5 to 0.8 mol of -coax groups is used.

In the carboxylic acid (salt) group-containing polyoxyalkylene polyol into which a -coax group has been introduced, the average number of hydroxyl groups is preferably greater than 2, more preferably 2.
．． 1 or more, especially 2.3 or more. The upper limit is 6, preferably 3.5. In addition, on average less than 1 -C per molecule
By having an OOX group, -CO
A polyoxyalkylene polyol with a large number of OX groups is produced and mixed with a polyoxyalkylene polyol without -coax groups to produce the desired carboxylic acid (salt).
It is also possible to produce group-containing polyoxyalkylene polyols.

(3) Blocked polyurethane The blocked polyurethane in the present invention is obtained by reacting the carboxylic acid (salt) group-containing polyoxyalkylene polyol, polyisocyanate, and blocking agent. The blocked polyurethane, which contains about two or more blocked isocyanate groups and is substantially free of free isocyanate groups, can be prepared by conventional methods. That is, it is obtained by reacting an isocyanate-terminated prepolymer obtained by reacting a polyol and a polyisocyanate with a blocking agent, or by reacting a partially blocked polyisocyanate with a polyol. In the former case, the blocking agent may be used in excess, and unreacted blocking agent may remain in the composition.
In the urethanization using a 2.0-fold equivalent excess, the ratio of hydroxyl groups to polyisocyanate groups (NGOloH) of the carboxylic acid (salt) group-containing polyoxyalkylene polyol is suitably 1.2 to 2.5, preferably 1. .5 to 2.0. Therefore, the blocking agent reacts in excess, ie, equivalents of (NGOloH) -1. This equivalent ratio is preferably applied to either of the two methods of producing the blocked polyurethane (an excess may be used in one method as described above). The amount of one COOX group in polyurethane is 0.02 in terms of -COOH group.
It is preferable that the amount is 3%, particularly 0.05 to t, S%.

The reaction is usually carried out without a solvent or in the presence of a non-reactive solvent. This temperature is usually room temperature -160℃, especially 60 to 120℃.
It is carried out at ℃. Although a catalyst can be used in this reaction, it is preferred that the catalyst is not an organometallic compound, since organometallic compounds reduce the stability of the blocked polyurethane in the final aqueous composition and may reduce the stability of the blocked polyurethane in the final aqueous composition. Dispersion problems are likely to occur. If a catalyst is used, it is preferably an amine catalyst, particularly a tertiary amine catalyst.

When the blocked polyurethane is finally dispersed or dissolved in water, its -C00X group is a carboxylic acid group (
That is, it is necessary that X is a cation). -COOX group of polyoxyalkylene polyol is -COOH
In the case of a group, it is necessary to change the hydrogen atom of X to a cation midway through. This conversion can be carried out while the blocked polyurethane is dispersed or dissolved in water, or it can be carried out at any previous stage.

Blocked polyurethane can be dispersed or dissolved in water at any ratio. Preferably, the amount of blocked polyurethane is 5 to 70% by weight, especially 10 to 50% by weight, based on the total of both. The composition may contain other ingredients such as various resins and coloring agents.

(4) The raw material polyisocyanate and the blocking agent polyisocyanate are preferably polyisocyanates with an average number of functional groups per molecule of 1.8 or more, especially 2 to 4, and an isocyanate group content of 10% or more, especially 2
The polyisocyanate, which is preferably 0% or more, can be either a so-called yellowing polyisocyanate or a non-yellowing polyisocyanate, or they can be used in combination. Preferably, a highly reactive yellowing polyisocyanate is used. Specific polyisocyanates include, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), methylene bis(cyclohexyl isocyanate) (H,, MDI), and hexamethylene diisocyanate. (HDrl, isophorone diisocyanate (IPDIl), modified products thereof (nurate modified products, prepolymer modified products, carbodiimide modified products, etc.).

As the blocking agent, various kinds of agents used as blocking agents for incyanate groups can be used. Examples include phenols, mercaptans, oximes, malonic acid diesters, acetylacetone, acetoacetic acid esters, lactams, and the like.

Blocked products using the above-mentioned partially carboxylated polyols have a catalyst in the form of a carboxylic acid salt in the molecule, which is necessary to dissociate the blocking agent and improve the subsequent curing properties. Since the groups can interact efficiently on a molecular order, curing can be performed using the minimum necessary amount of catalyst and mild curing conditions. In contrast, conventional catalysts are present in the aqueous phase if they are water-soluble. In the case of an oil-soluble catalyst, the catalyst is liquefied into an aqueous liquid by means such as emulsification and added, but the catalyst is present as particles separate from the blocked product. Another method is to forcibly stir and disperse the oil-soluble catalyst in the aqueous liquid of the blocked product, but the compatibility with the hydrophilic blocked product of the present invention is poor. In the method of adding, the catalyst efficiency is low and an excessive amount of catalyst is required, and this excess amount significantly reduces the thermal stability and long-term stability of the polyurethane resin after curing. Therefore, in the present invention, the aqueous composition It is preferable that substantially no organometallic catalyst be blended into the product.

Various additives other than the catalyst can be added to the composition of the present invention. Examples of additives include antioxidants,
Not only can UV absorbers and other additives commonly used in polyurethane resins be used, but also known flame retardants, such as halogen-containing phosphate esters, may be used in combination as necessary, and the performance of blocked polyurethane can also be improved. When a fibrous base material, such as polyester fiber, is impregnated with a conventional aqueous polyurethane liquid, which may be used in combination with other resins as long as it does not impair the properties, and is heated (120 to 130°C),
A cushion body is obtained in which the polyurethane uniformly covers the entire fibers. When this cushion body was subjected to a combustion test, the polyurethane quickly ignited, and due to the above-mentioned covering condition, the fire easily spread and the cushion body was completely burnt out.

On the other hand, when a fatty acid ester coexists, its effect is not necessarily clear, but the fluidity and surface properties of the resin at high temperatures are significantly improved, resulting in a coated state in which the polyester fiber is partially "naked". is obtained. When ignited, the polyester fiber melts at high temperatures, so the fire cannot propagate through the resin as described above, and it can be assumed that the polyester fiber has extremely excellent self-extinguishing properties.

The composition of the present invention is used as an adhesive or a binder, for example, for fibers, paper, wood, plastics, and other substrates. It is particularly useful as a binder to be used by coating or impregnating fibers such as polyester fibers and fibrous bodies such as polyester cotton as described above.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. Moreover, "1 part" in the following represents parts by weight.

[Example] <Reference Example 1) Synthesis of partially carboxylated polyol 2500 parts of polyether triol (oxyethylene group content 80% by weight) with an average molecular weight of 2500, 17.7 parts of anhydrous phthale and N,N'-benzyldimethyl 3.0 parts of amine was added and the mixture was reacted at 120° C. for 6 hours under a nitrogen stream to obtain a partially carboxylated polyol.

<Reference Example 2> Synthesis of blocked polyurethane aqueous composition l Partially carboxylated polyol 2520 obtained in Reference Example 1
．． Tolylene diisocyanate (tolylene diisocyanate) 43L (5 parts) was added to 7 parts, and the reaction was carried out at 80°C for 3 hours under a nitrogen stream to obtain a urethane prepolymer having 3.07% of free incyanate groups. After cooling to ℃,
Add 187.9 parts of methyl ethyl ketoxime to 30 parts with stirring.
The reaction mixture was added dropwise within minutes, and the reaction was further carried out at 60° C. for 60 minutes.

0% free isocyanate groups in urethane prepolymer
After confirming that 295.9 parts of olive oil was added and stirred for an additional 30 minutes, an aqueous solution of 4.8 g of sodium hydroxide dissolved in 7068 parts of water was added with a stirrer and heated at 30°C. Mixing was carried out for 30 minutes to prepare a slightly cloudy, low-viscosity blocked polyurethane aqueous solution with a resin content of 31%.

(Reference Example 3) A blocked polyurethane aqueous liquid was prepared in the same manner as in Reference Example 2 except that coconut oil was used instead of olive oil.

<Reference Example 4> A blocked polyurethane aqueous liquid was prepared in the same manner as in Reference Example 2 except that olive oil was not used.

<Example 1> Polyester fiber cotton is impregnated with the aqueous blocked polyurethane solution prepared in Reference Example 2 so that the adhesion amount is 30%, and heat-treated at 130° C. for 5 minutes using a hot air generator. Further, drying in an oven at 120"CX for 20 minutes yields a foam-like cushion body. This cushion body is
Table 1 shows the results of a combustion test conducted in accordance with S-302.

<Example 2> Same as Example 1 except that Reference Example 3 was used, the results are shown in Table-
Shown in 1.

<Comparative Example 1) Same as Example 1 except that Reference Example 4 was used, the results are shown in Table-
Shown in 1.

(Table 1) [Effects of the Invention] The reactive aqueous resin composition of the present invention significantly improves the fluidity and surface properties of the resin at high temperatures, resulting in extremely excellent cushioning bodies especially obtained by treating fibrous base materials. The present invention provides a reactive aqueous resin composition that imparts flame retardancy.

Claims (1)

[Claims] (1) Blocked polyurethane having a polyoxyethylene group and a carboxylic acid group, the blocked polyurethane 1
A reactive aqueous resin composition containing as essential components 5 to 20 parts by weight of fatty acid esters and water in which they are dissolved or dispersed. (2) The composition according to claim 1, wherein the fatty acid ester is a higher fatty acid ester alone or a mixture of two or more thereof, or an oil or fat. (3) The blocked polyurethane contains 50% by weight or more of oxyethylene groups and has a -COOX group (X
: A polyoxyalkylene polyol containing a carboxylic acid (salt) group having a hydrogen atom or cation), a polyisocyanate having an excess equivalent of isocyanate groups relative to the hydroxyl group of the polyol, and an equivalent of the excess equivalent of the polyisocyanate. 1. A blocked polyurethane containing a carboxylic acid group, which is a reaction product of a blocking agent in an amount of 100% and is a blocked polyurethane obtained by converting X into a cation at any stage when X is a hydrogen atom. Compositions as described. (4) The carboxylic acid (salt) group-containing polyoxyalkylene polyol contains on average more than two hydroxyl groups and 0.005 to 0.8 -COOX groups per molecule. is an oxyalkylene polyol,
The composition according to claim 3. (5) The polyoxyalkylene polyol has an oxyethylene group content of 70 to 90% by weight and a molecular weight per hydroxyl group of 3
00 to 3000, with an average number of hydroxyl groups of 2.3 to 3.5, and a carboxylic acid (salt) group-containing polyoxyalkylene polyol derived from the polyoxyalkylene polyol has an average number of hydroxyl groups of 2.3 to 3,000. ~3.5, average -COOX base 0.04~0.4
The composition according to claim 4, which is.