JPS63112771A - Fiber processing treatment agent - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is a processing agent for processing fibers, paper, asbestos, and similar substances, which has extremely good heat resistance, solvent resistance, water resistance, and aging resistance. The present invention relates to a processing agent for textile processing.

[Conventional technology and its problems]

Conventionally, when synthetic rubber latex such as SBR latex and NBR latex is added to pulp, asbestos, etc. in the wet part, so-called beater addition, or after papermaking, or when impregnated into fibers and similar substances, elastic solvent-resistant solvents are used. Although a processed product with good properties was obtained, it had the disadvantage of poor heat resistance and aging resistance. On the other hand, an acrylic resin emulsion which does not have these drawbacks is used, but the mold processed using this emulsion has good aging resistance but poor solvent resistance. As a means to improve this, modification using urea resin, melamine resin, etc. has been attempted, but
These films become hard and therefore have poor texture when processed with various resins. Furthermore, the heat resistance and solvent resistance were also insufficient. There is currently a need for a new fiber processing agent that can solve these drawbacks.

c) Means for Solving Problems] As a result of intensive research in order to develop a higher performance treatment agent for fiber processing, the present inventor developed an acrylic resin (A ) and an epoxy resin (Bl) and an acrylated epoxy resin that is chemically bonded to an epoxy resin (Bl) is dispersed in an aqueous medium to obtain a water-dispersible resin composition. I found out.

That is, the present invention relates to an acrylic resin obtained by esterifying an acrylic resin (A) consisting of an ethylenically unsaturated carboxylic acid compound and another copolymerizable unsaturated compound with an epoxy resin (Bl) in the presence of a basic compound. The present invention provides a treatment agent for fiber processing, which is characterized by comprising a water-dispersible resin composition in which a chemically modified epoxy resin is dispersed in an aqueous medium.

The combination of acrylic resin (Al and epoxy resin (Bl) is made by combining an ethylenically unsaturated carboxylic acid compound and other copolymerizable unsaturated compounds with azobisisobutyronitrile and benzoyl peroxide in a hydrophilic organic solvent. Acrylic resin (A) and epoxy resin (B) obtained by copolymerization using a common radical polymerization initiator such as dimethylethanolamine in the presence of a basic compound in a hydrophilic organic solvent It can be obtained by an esterification reaction in the presence of a tertiary amine.A bond of an acrylic resin and an epoxy resin (Bl) can be obtained by reacting an epoxy resin (Bl with a monovalent ethylenically unsaturated cargenic acid). It can also be obtained by polymerizing ethylenically unsaturated calgenic acid and other copolymerizable unsaturated compounds using a radical polymerization initiator in the presence of a composition having a double bond.

Examples of the ethylenically unsaturated carboxylic acid compound include acrylic acid, methacrylic acid, and maleic acid.

One or more types of fumaric acid, itaconic acid, etc. are used. Other copolymerizable unsaturated compounds include methyl (meth)acrylate, ethyl acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, (
Inbutyl meth)acrylate, n-(meth)acrylate
amyl, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethyl-hexyl (meth)acrylate, (meth)
(Meth)acrylic esters such as decyl acrylate and dodecyl (meth)acrylate, styrene monomers such as styrene, vinyltoluene, 2-methylstyrene, t-butylstyrene, and chlorstyrene, hydroxyethyl (meth)acrylate , hydroxyl group-containing monomers such as hydroxypropyl (meth)acrylate, N-methylol (meth)acrylamide, dimethyl in N-butylene (
N-substituted (meth)acrylic monomers such as meth)acrylamide, epoxy group-containing monomers such as glycidyl (meth)acrylate, and 1 such as acrylonitrile.
It can be selected from one species or two or more species.

The amount of the ethylenically unsaturated carboxylic acid compound to be used is at least 12% by weight of the total monomers, and if the amount is less than 12% by weight, the dispersion stability of the resin in an aqueous medium will be poor and the adhesion to fibers will be poor. Deteriorate.

The weight average molecular weight of the acrylic resin (2) produced in advance is preferably 2,000 to 100,000. If the molecular weight is small, emulsification and dispersibility will be hindered, and if the molecular weight is large, gluing tends to occur during reaction with the epoxy resin (B).

Epoxy W fat (Bl is preferably shrimp chlorophyllin/bisphenol type epoxy resin with an average of 1.1 per molecule)
It is preferable to have 2 to 2.0 epoxy groups and a number average molecular weight of 900 or more. Commercially available products include Epicuron 1050, Epicuron 4050, and Epicuron 7050 manufactured by Dainippon Ink and Chemicals Co., Ltd., and Epicuron 1001 and Epicuron 1004 manufactured by Yuka Shell Co., Ltd.
．． Epicor) 1007, Epicor) 1009, Epicor) 1010, etc. Also, the lower molecular weight Evicron 850. Epicote 828 can also be used.

The solid content ratio of the acrylic resin (A) and the epoxy resin (B) is selected from the range of 2:1 to 1:10 by weight.

In the present invention, the water-dispersible resin composition is prepared using the above-mentioned Cal. A basic compound, preferably ammonia or amine, in an amount such that - in the final composition is 4 to 11, is added to the xyl group-containing acrylated epoxy resin and dispersed in an aqueous medium.

The above-mentioned amines include, for example, alkylaminos such as trimethylamine, triethylamine, and butylamine, alkanolamines such as dimethylethanolamine, jetanolamine, triethanolamine, and aminomethylglopanol, morpholine, etc., ethylene diamine,
Polyvalent amines such as diethylenetriamine can also be used.

These basic compounds may be added simultaneously as esterification catalysts during the esterification of acrylic resin (Al and epoxy resin (Bl), or may be added as esterification catalysts and neutralizing agents before and after esterification, respectively. They may be added separately to the system; in short, it is sufficient as long as they can prevent the product from gluing during the esterification reaction and that the product can be stably dispersed in the aqueous medium.

In the present invention, the aqueous medium means water alone or a mixture of water and a hydrophilic organic solvent, and examples of hydrophilic organic solvents include methanol, ethanol, n-propanol, impropatol, n-butanol, and especially butanol. Alkyl alcohols such as tart-butanol and isobutanol,
Methyl cellosolve.

Ether alcohols such as ethyl cellosolve, propyl cellosolve, butyl cellosolve, methyl calpitol, ethyl calpitol, ether esters such as methyl selonlupus acetate, ethyl cellosolve acetate, and other dioxane, dimethyl formamide, and diaheptone alcohols are used. .

Furthermore, water-based aminosilast resin, phenosilast resin, etc. can be added as a curing agent to the above-mentioned water-dispersible resin composition as needed, and used as a treatment agent for fiber processing.

〔Effect of the invention〕

The fiber processing agent of the present invention can be used to treat natural fibers, recycled, semi-synthetic and
Application to substrates such as synthetic fibers, such as fiber paper, asbestos, and other similar substrates, can be accomplished in a variety of ways. For example, there is a method in which the substrate is immersed in a liquid bath containing a treatment agent for fiber processing, or a method in which the substrate is applied by spraying, roller coating, knife coating, or the like. When the fiber processing agent is applied in the required amount to a fiber material as a specific base material, it is usually done by drying at a temperature of 150°C or less, which cannot be achieved by any conventional resin processing method. A fibrous material having the above-mentioned characteristics can be obtained.

The treatment agent for fiber processing of the present invention is for natural fibers, recycled, semi-synthetic and
It can be applied to various base materials such as synthetic fibers, and the base material to be processed is, for example, I's fiber.

Examples include so-called monofilaments, woven fabrics, non-woven materials; asbestos; paper; foams, ie, foams of natural or synthetic polymers.

〔Example〕

The present invention will be explained below with reference to Examples. In addition, in the example "part",
"CH" indicates "part by weight" and "% by weight", respectively.

Example 1 Condenser, thermometer, dropping funnel, nitrogen gas introduction pipe,
After purging the flask equipped with a stirrer with nitrogen, 100 parts of n-butanol was charged, the temperature was raised to 105°C, and 42 parts of methacrylic acid, 32 parts of styrene, and 26 parts of ethyl acrylate were added.
parts, 2.5 parts of benzoyl peroxide, 47 parts of n-butanol.
5 parts of the mixed solution was added dropwise over 2 hours, and then heated to 105°C.
The mixture was held for 3 hours to obtain an acrylic resin.

48 parts of n-butanol was charged into a flask equipped with a condenser, a thermometer, a nitrogen gas inlet tube, and a stirrer, and the temperature was raised to the reflux temperature.
After dissolving 100 parts of the acrylic resin and 10.7 parts of dimethylethanolamine at 105°C, the mixture was maintained at 105°C for 1 hour. After cooling at 90C1, 781.3 parts of ion-exchanged water was added and mixed with stirring to obtain a water-dispersible resin composition. To the obtained water-dispersible resin composition, 3.8 parts of Beckamine APM (Water-soluble melamine resin manufactured by Dainippon Ink Chemical Industry Co., Ltd.) was added.

Examples 2 to 4 In the same manner as in Example 1, blended compositions as shown in Table 1 were obtained.

Table-1 Note 1) Ebikuron 850 (Dainippon Ink Chemical Co., Ltd.)
liquid epoxy resin) 48.1 parts, bisphenol A2
A product obtained by reacting 5.9 parts of butyl celonol, 18.1 parts of butyl celonol, and 0.15 parts of tri-n-butylamine at 130°C to 150°C.

Test Example 1 A pigment-printed taffeta fabric was impregnated with the treatment agents of Examples 1 to 4,
The resin-treated cloth was squeezed to a squeezing rate of 40% with a mangle, pre-dried at 90℃ for 3 minutes, and then cured with a hot air pin tenter at 130℃ for 2 minutes. il head.

A dyeing rub fastness test was conducted using Kanakin No. 2003.

For comparison, the same procedure was carried out using an acrylic emulsion and using Beckamine APM as a hardening agent (5%/solid content). The results are summarized in Table-2. The acrylic emulsion used was synthesized as follows.

A stainless steel kettle reactor with a stirrer and a condenser.

The following raw materials were added to a container equipped with a thermometer and a dropping funnel and purged with nitrogen.

Deionized water 1,120 partsFact
s” 6H200-5% aqueous solution 2 parts sodium formaldehyde sulfoxylate
5.Next, the temperature inside the reaction vessel was adjusted to 60°C, and the monomer mixture (sodium lacryl sulfate; Kao Atlas Co., Ltd.)
Butyl acrylate 550 parts, methyl methacrylate 420 parts
parts, 20 parts of Dia7ton acrylamide, 1 part of acrylic acid
0 parts) and a polymerization catalyst solution (3 parts of potassium persulfate dissolved in 100 parts of deionized water) were added dropwise over 180 minutes to effect polymerization. During this time, the temperature inside the container was adjusted to 60°C and 2°C. After the dropwise addition was completed, the mixture was stirred at the same temperature for 1 hour.

Thereafter, the contents were cooled to 30°C, adjusted to -7 to 8 with 28% ammonia water, and further adjusted with deionized water to a solid content concentration of 45%, with a solid content concentration of 45 cm and a viscosity of 52 cp.
8, an acrylic emulsion with a pH of 7.5 was obtained.

7'/'' Test Example 2 A polyester web with a basis weight of 4011/m'' was impregnated with the treatment agents of Examples 1 to 4, dried at 100°C for 5 minutes, and then heated at 150°C.
, by baking for 1 minute, resin solids/fiber = 2
A nonwoven fabric having a weight ratio of 5/100 was obtained.

Next, nonwoven fabric stain test method (JIS L-1085
), the dry cleaning strength, washing strength, and morphological changes of the nonwoven fabric during the test were evaluated. The results are shown in Table-3.

For comparison, results obtained using a similar method using latex are shown. The latex was synthesized as follows.

1 part of dodecylbenzenesulfonic acid sorter ("Neodan R" manufactured by Dai-Kogyo Nohaku Co., Ltd.) and 120 parts of ion-exchanged water were placed in a nitrogen-substituted autoclave equipped with a stirrer.

50 parts of butadiene, 10 parts of methyl methacrylate, 40 parts of acrylonitrile, and 0.5 parts of potassium persulfate were charged, and polymerization was carried out at 60°C with stirring until the polymerization rate reached 98% or more.

Next, ammonia water was added to adjust the pH to 8.0, and unreacted monomers were removed and concentrated by steam distillation, and ammonia water was added again to adjust the pH to 8.3 and solid content to 50. A latex with a viscosity of 500 cP was obtained.

Table 3 Test Example 3 The blended compositions of Examples 1 to 4 were further diluted with methanol, impregnated with F paper (Mu65 manufactured by Toyo Paper Co., Ltd.) K as a treatment agent with a solid content concentration of 7, and squeezed with a mangle. 15 at 150℃
It was fired during the hot air open for a minute. Using the resin-treated paper thus obtained, the normal strength and strength after immersion in heat oil were measured, and the results are shown in Table 4 below. For comparison, a general commercially available phenol resin (Pryophen J-325J; manufactured by Dainippon Ink and Chemicals) was treated in the same manner and tested.

7/'/''//''//'' Test method> Tensile Crab Measured at a tensile rate of 200 ta/min using a Tensilon autograph in a constant temperature and humidity room at 23°C and 65% RH. (N/15.) Bursting strength:
Bursting strength was measured using a Mielen low-pressure tester in accordance with JIS P-8112. (,9/ctn") Air permeability: Air permeability was measured according to JIS P-8117.

(See) Oil resistance test: Mobil oil #30 at 180℃±2℃
After soaking for a period of time, tensile strength and bursting strength were measured under the above conditions.

Claims (1)

[Claims] (1) Acrylic resin obtained by esterifying an acrylic resin (A) consisting of an ethylenically unsaturated carboxylic acid compound and other copolymerizable unsaturated compounds with an epoxy resin (B) in the presence of a basic compound. 1. A treatment agent for fiber processing, comprising a water-dispersible resin composition in which a chemically modified epoxy resin is dispersed in an aqueous medium.