JP2002173871A - Crosslinked resin aqueous dispersion for textile processing. - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To have excellent physical properties such as lack of flexibility and tackiness, hydrophilicity and wet strength, and have excellent appearance such as no yellowing, and alkylphenyl-based surfactant. Provided is an aqueous dispersion of a crosslinked resin for fiber processing, which can produce an excellent fiber product substantially free of harmful substances such as agents. A specific monomer containing ethyl acrylate as a main component is emulsion-copolymerized in the presence of a specific surfactant substantially free of an alkylphenyl-based surfactant to obtain a specific glass transition point. An aqueous dispersion of a crosslinkable resin for fiber processing, containing an acrylic copolymer having (Tg) and a solubility parameter (SP value).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to resin processing of textile products such as woven fabric, knitted fabric, non-woven fabric, felt made of natural fiber, regenerated fiber, synthetic fiber, etc., and is particularly used mainly for business use in restaurants and the like. More specifically, the present invention relates to an aqueous dispersion of a crosslinked resin used for resin processing of a nonwoven fabric for a disposable wiping material (wiper), specifically, in the presence of a specific surfactant substantially free of an alkylphenyl surfactant. ,
Textile processing containing an acrylic copolymer having a specific glass transition point (Tg) and solubility parameter (SP value) obtained by emulsion copolymerization of a specific monomer containing ethyl acrylate as a main component The present invention relates to an aqueous dispersion of a crosslinked resin for use.

[0002]

2. Description of the Related Art Conventionally, it has been known to impregnate or coat an aqueous resin emulsion on a raw fiber to be processed in order to obtain various resin-processed fiber products. For example, commercial disposable wiping materials ( It is also known that a nonwoven fabric (web) impregnated with an aqueous resin emulsion and processed with a resin is used for the wiper.

[0003] Generally, such a commercial wiper has high hydrophilicity, easily absorbs water, and has excellent water retention. High strength when absorbing water. Have a certain degree of oil absorption. The texture is soft and there is no sticky feeling. Excellent appearance such as no yellowing. It does not substantially contain harmful substances. However, it is difficult to say that conventionally known aqueous resin emulsions necessarily have all of these properties.

For example, when a synthetic rubber latex such as styrene-butadiene rubber, which is widely used for resin processing of textile products, is used, the textile products often turn yellow when dried, and moreover, the water content of the obtained textile products is increased. Problems such as poor absorption and water retention tend to occur.

[0005] An acrylic copolymer emulsion has the advantage of having a high degree of freedom in selecting a copolymer composition, and can provide a product having a desired texture. However, it is not easy to combine the lack of adhesiveness, the hydrophilicity and the wet strength when absorbing water.

To solve these problems, a self-crosslinkable or reactive acrylic copolymer emulsion to which a self-crosslinkable functional group or a reactive functional group is added can be used. The base fabric and the cross-linking agent used in combination may cause discoloration of the base fabric, and there is also a problem that a large amount of harmful substances such as formaldehyde are generated during the cross-linking reaction and remain in the processed fiber product.

[0007] More recently, when a surfactant containing an alkylphenyl group, which is widely used in such an acrylic copolymer emulsion, is contained in wastewater and discharged into a river or the like, an alkylphenol produced by hydrolysis thereof is converted into an alkylphenol. It is known that they are taken up by organisms living in the rivers and the seas into which they flow, especially fish and shellfish, and act as substances that destroy the endocrine function (endocrine) of these organisms (so-called environmental hormones). became. Such alkylphenols, through the consumption of these seafood,
It has also been pointed out that there is a high risk of entering the human body through the water of waterworks directly using water from such rivers.

[0008]

As described above, the present inventors have found that the conventional resin processing using a resin-based aqueous emulsion is still inadequate. Combines physical properties that are hardly compatible with each other, such as strength when wet, has excellent appearance such as no yellowing, and does not substantially contain harmful substances including alkylphenyl surfactants,
Improvement research was carried out to obtain an acrylic copolymer emulsion capable of providing excellent fiber products. As a result, in the presence of a specific surfactant substantially free of an alkylphenyl-based surfactant, a specific monomer containing ethyl acrylate as a main component is emulsion-copolymerized to obtain a specific glass transition point ( Tg) and an aqueous dispersion containing an acrylic copolymer having a solubility parameter (SP value) was prepared, and if necessary, this acrylic copolymer dispersion was
By using an appropriate crosslinking agent such as an oxazoline-based crosslinking agent, it has been found that an excellent aqueous dispersion of a crosslinked resin for fiber processing can be obtained which has solved all of the above problems.

[0009]

The present invention contains substantially no alkylphenyl-based surfactant and contains, as a main component, an aliphatic alcohol polyoxyethylene ether type nonionic surfactant having 10 to 20 carbon atoms. In the presence of a surfactant, the following monomers (a) to (d), (a) ethyl acrylate 25
(B) α, β-unsaturated mono- having 3 to 5 carbon atoms
Or 0.5 to 10% by weight of di-carboxylic acid (hereinafter sometimes simply referred to as unsaturated carboxylic acid), and (c) a monomer having at least one functional group in addition to one radically polymerizable unsaturated group in the molecule. A monomer other than the monomer (b) (hereinafter, sometimes referred to as a functional monomer) 0.5 to 10% by weight, and (d) the monomer (a) to (c) copolymerizable,
A comonomer other than the monomers (a) to (c) (hereinafter, may be simply referred to as a comonomer) 0 to 70% by weight;
(a) to (d) is 100% by weight], and its glass transition point (Tg) is in the range of −40 to 10 ° C. and its solubility parameter (Tg) SP value) is 9.0 to 10.0.
An object of the present invention is to provide an aqueous dispersion of a crosslinked resin for fiber processing, which comprises an acrylic copolymer in the range of 5.

Hereinafter, the present invention will be described in detail.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The acrylic copolymer used in the aqueous dispersion of a crosslinked resin for fiber processing according to the present invention comprises, as essential components, ethyl acrylate (a) and an unsaturated carboxylic acid.
(b) and a functional monomer (c).

The amount of ethyl acrylate which is the essential monomer (a) is 25% with respect to 100% by weight of the total of the monomers (a) to (d) constituting the desired acrylic copolymer. ~ 99% by weight
And preferably 30 to 95% by weight, more preferably 35 to 90% by weight. If the amount of ethyl acrylate is too small, less than the lower limit, the resulting fiber product tends to be insufficient in hydrophilicity and water absorption tends to be insufficient. If it is too much, the unsaturated carboxylic acid (b) and / or the functional monomer (c) relatively decrease, and the strength of the resulting fiber product when wet tends to be insufficient, which is not preferable.

The unsaturated carboxylic acid as the essential monomer (b) includes, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, citraconic acid and the like. Among these, acrylic acid and methacrylic acid are more preferably used.

The amount of the monomer (b) is from the above-mentioned monomers (a) to
It is necessary to be in the range of 0.5 to 10% by weight based on the total 100% by weight of (d), preferably 1 to 6% by weight, more preferably 1.2 to 4% by weight. The monomer
If the amount of (b) used exceeds the upper limit and is too large, depending on the type of the functional monomer (c), which is a copolymer component, polymerization stability may be impaired during copolymerization, or aqueous dispersion may occur during storage. The liquid may cause gelation, and when a cross-linking agent component is used in combination, the type of the cross-linking agent component may have an adverse effect on the pot life, and furthermore, the wet strength of the resulting textile product may be reduced. It is not preferable because it tends to be insufficient. On the other hand, if the amount is too small as less than the lower limit,
The polymerization stability during copolymerization and the mechanical stability of the resulting aqueous dispersion may be insufficient, and the crosslinking reaction tends to be insufficient and the wet strength tends to be insufficient. Absent.

Further, the functional monomer which is the essential monomer (c), together with the monomer (b), undergoes a cross-linking reaction by heating or the like without being used, and becomes water or a solvent. It is intended to impart a property of becoming insoluble or hardly soluble in the polymer-or a reactivity with another crosslinking agent.

The functional group of such a functional monomer (c) includes, for example, an amide group or a substituted amide group, an amino group or a substituted amino group, a hydroxyl group, a lower alkoxyl group, an epoxy group, a mercapto group or a silicon group. Monomers having a group or the like can be mentioned, and monomers having two or more radically polymerizable unsaturated groups in the molecule can also be used.

Specific examples of these functional monomers (c) include, for example, methylol groups such as N-methylolacrylamide, N-methylolmethacrylamide, Nn-butoxymethylacrylamide and Ni-butoxymethylacrylamide or derivatives thereof. Monomers having; for example, acrylamide, methacrylamide, diacetone acrylamide,
Amide group-containing monomers not containing a methylol group or a derivative thereof, such as N, N-dimethylacrylamide, N-methylacrylamide;

For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, allyl alcohol, methallyl alcohol, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate (preferably 2 Hydroxyl-containing monomers such as -hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate);

For example, 2-methoxyethyl acrylate,
2-ethoxyethyl acrylate, 2-n-butoxyethyl acrylate, 2-methoxyethoxyethyl acrylate,
2-ethoxyethoxyethyl acrylate, 2-n-butoxyethoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-n-butoxyethyl methacrylate, 2-methoxyethoxyethyl methacrylate, 2-ethoxyethoxyethyl methacrylate, 2-n-butoxyethoxyethyl methacrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, (preferably 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxyethyl methacrylate,
Lower alkoxyl group-containing monomers such as 2-ethoxyethyl methacrylate, methoxypolyethylene glycol monoacrylate, and methoxypolyethylene glycol monomethacrylate);

For example, monomers containing an epoxy group such as glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether and glycidyl methallyl ether (preferably glycidyl acrylate and glycidyl methacrylate); monomers containing a mercapto group such as allyl mercaptan;

For example, vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltris (2-methoxy (Ethoxy) silane, vinyltris (2-hydroxymethoxyethoxy) silane, vinyltriacetoxysilane, vinyldiethoxysilanol, vinylethoxysiladiol, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, allyltrimethoxysilane , Allyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltris (2
(Methoxyethoxy) silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 2-acrylamidoethyltriethoxysilane, etc. body;

For example, divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol di (meth) acrylate,
1,2-propylene glycol di (meth) acrylate, 1,3-
Propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di
Monomers having two or more radically polymerizable unsaturated groups such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, and allyl (meth) acrylate; and the like.

Among these functional monomers (c), a monomer having a self-crosslinking property is preferably a monomer having a methylol group or a derivative thereof, and particularly preferably N-methylolacrylamide.

Further, as a monomer for imparting reactivity to another cross-linking agent used in combination as required, a hydroxyl group-containing monomer and a glycidyl group-containing monomer are preferable.

The amount of the functional monomer (c) used is generally required to be 0.5 to 10% by weight based on 100% by weight of the total of the monomers (a) to (d). In particular, when a monomer having a methylol group or a derivative thereof such as N-methylolacrylamide which is a monomer imparting self-crosslinking property is used as the functional monomer (c), the amount used is Monomer (a)
It is necessary that the content be 0.5% by weight or more, and preferably 4% by weight or less, more preferably 0.8 to 3.5% by weight, based on the total 100% by weight of (d). If the amount of the monomer used is too small, less than the lower limit, the obtained fiber product tends to have insufficient wet strength, which is not preferable. On the other hand, if the used amount is equal to or less than the upper limit amount, there is no inconvenience such as impairment of the water absorption and texture of the obtained fiber product, and harmful formaldehyde generated by heating during resin processing of the fiber product is reduced. Can be
The simple post-treatment of the resulting fiber product is preferable because the residual formaldehyde in the fiber product can be suppressed to a negligible extent.

When a monomer other than the above-mentioned monomer having a methylol group or a derivative thereof is used as the functional monomer (c), the amount of the monomer used is as follows: ), Is 0.5 to 10% by weight, preferably 1 to 6% by weight, and more preferably 1.5 to 4% by weight based on 100% by weight of the total. If the amount of the monomer used is too small and less than the lower limit, the progress of the reaction with the crosslinking agent used in combination as necessary is not sufficient, and the wet strength of the obtained fiber product becomes insufficient. Unfavorable because it is prone. On the other hand, if the amount is more than the upper limit, the water absorption of the obtained fiber product may be impaired, or the texture may become too hard to be suitable for a desired use, which is not preferable.

The acrylic copolymer used in the present invention can be copolymerized with the essential monomers (a) to (c) and, if necessary, with the monomers (a) to (c). The monomer (a) ~
Comonomers (d) other than (c) can be copolymerized.

Examples of such a comonomer (d) include acrylic esters other than the above (a). Specific examples of such acrylates include methyl acrylate, n-propyl acrylate, i-
Propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, i-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, i-nonyl acrylate, tridecyl Examples include acrylate, stearyl acrylate, oleyl acrylate, cyclohexyl acrylate, and benzyl acrylate.

Examples of the comonomer (d) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, and 2-ethylhexyl. Methacrylates such as methacrylate, i-decyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate, oleyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate; for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate "
Saturated fatty acid vinyl esters such as (trade name); and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile (preferably acrylonitrile);

The amount of the comonomer (d) used is generally from 0 to 7 based on 100% by weight of the total of the monomers (a) to (d).
0% by weight, preferably 0-50% by weight, more preferably 10%
It is preferably from 50 to 50% by weight, more preferably from 20 to 40% by weight. The amount of the comonomer (d) varies depending on the type thereof, and thus cannot be uniquely determined.However, the amount is within the above range so as not to impair the excellent performance of the obtained aqueous dispersion of the present invention. It can be selected appropriately. It is preferable that the amount of the comonomer (d) used be equal to or less than the upper limit of the above-mentioned range, since the resulting fiber product has sufficient hydrophilicity and finishes with a good texture. Further, by setting the amount to be 10% by weight or more, it is possible to expect the strength at the time of wetness, moderate oil absorbency, suppression of tackiness, etc. while satisfying the hydrophilicity of the obtained fiber product.

The acrylic copolymer in the present invention needs to have a glass transition point (Tg) in the range of -40 to 10 ° C., preferably -30 to 0 ° C.
If Tg is too high above the upper limit temperature, the texture of the resulting fiber product is too hard, which is not preferable.If it is too low and lower than the lower limit temperature, the obtained fiber product tends to have a sticky feeling, Further, it is not preferable because sufficient strength cannot be obtained and water absorption tends to decrease.

In the present invention, the glass transition point (Tg) of the acrylic (co) polymer is a value measured and determined as follows.

Glass transition point (Tg): Approximately 10 mg of a sample of an aqueous dispersion of an acrylic copolymer is weighed in a cylindrical cell made of aluminum foil having a thickness of about 0.05 mm and having an inner diameter of about 5 mm and a depth of about 5 mm. The sample is taken and dried at 100 ° C. for 2 hours to obtain a measurement sample.
SSC-5000 type differential scanning calorimeter (Di
fferential Scanning Calorimeter) at a heating rate of 10 ° C / min from -150 ° C.

The solubility parameter (SP value) of the acrylic copolymer in the present invention needs to be in the range of 9.0 to 10.5, and preferably in the range of 9.2 to 10.0. If the SP value is too large beyond the upper limit,
Although the water absorbency of the obtained fiber product is sufficient, a suitable oil absorbency may not be obtained, and the strength when wet tends to be insufficient, which is not preferable. Also, the hydrophilicity of the obtained fiber product tends to be insufficient, and the water absorption tends to decrease, which is not preferable.

In the present invention, the solubility parameter (SP value) of the acrylic copolymer is determined by the method described in “Polymer Handbook Second Edition”.
These values are measured or calculated according to the method described on pages IV-337 to IV-359 of [H. Burrell: (1975)]. The method is outlined below.

The SP value of the homopolymer is calculated by the following SP value calculation formula based on the molecular attraction constant G of the constituent units forming the polymer. SP = dΣG / M where d is the density of the homopolymer (g / l), ΣG is the sum of the molecular attraction constants in the molecules of the structural unit, and M is the molecular weight of the structural unit (g / mol) It is.

According to the above formula, the SP value of the copolymer is calculated based on the homopolymer of each structural unit constituting the copolymer.
The SP value is calculated, and the SP value is multiplied by the mole fraction of each structural unit, and the SP value is added to calculate the SP value.

The acrylic copolymer used in the aqueous dispersion of a crosslinked resin for fiber processing of the present invention comprises the above-mentioned monomer (a)
~ (D) is substantially free of alkylphenyl surfactants, in the presence of a surfactant containing a C10-20 aliphatic alcohol polyoxyethylene ether type nonionic surfactant as a main component It is obtained by emulsion copolymerization.

Here, "substantially free of an alkylphenyl surfactant" means that the alkylphenyl surfactant is not intentionally used in emulsion copolymerization. Even if the surfactant is contained as a contaminant in each raw material, the amount of the alkylphenyl surfactant contained in the aqueous acrylic copolymer dispersion obtained as a result of the emulsion copolymerization is 100 ppm. Or less, preferably 50 ppm or less.

In the emulsion polymerization of the present invention, an aliphatic alcohol polyoxyethylene ether type nonionic surfactant having 10 to 20 carbon atoms represented by the following general formula (1) is required as an essential nonionic surfactant. used.

[0041]

(In the formula, R ¹ represents a linear or branched aliphatic group having 10 to 20 carbon atoms, in which a part of the hydrogen bonded to the carbon chain may be substituted with fluorine or a hydroxyl group.)

The aliphatic group in the general formula (1) is preferably a straight-chain alkyl or alkenyl group in which the hydrogen bonded to the carbon chain is not substituted, and the hydrogen bonded to the carbon chain is substituted. It is particularly preferred that the alkyl group is not a straight-chain alkyl group.

Examples of suitable nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene palmityl ether, polyoxyethylene stearyl ether (preferably polyoxyethylene lauryl ether) and the like. Examples thereof include alkyl ethers and polyoxyethylene alkenyl ethers such as polyoxyethylene oleyl ether.

The length (value of n) of the polyoxyethylene chain in the nonionic surfactant is preferably in the range of 10 to 120, more preferably in the range of 15 to 100, and still more preferably in the range of 17 to 100. It should be in the range of 90. n
Is preferably within the above range, since the occurrence of aggregates during the aqueous emulsion polymerization is small and the mechanical and chemical stability of the obtained aqueous dispersion is good.

The nonionic surfactants represented by the general formula (1) can be used alone or in combination of two or more. The amount of the nonionic surfactant active ingredient is preferably 0.5 to 10 parts by weight, more preferably 1 to 6 parts by weight, based on parts by weight.
When the amount of the nonionic surfactant is equal to or less than the upper limit, the polymerization stability during aqueous emulsion polymerization is good, and the adhesion of the obtained aqueous dispersion to the fiber base material is not impaired. Further, the obtained fiber-processed product is preferable since it has excellent wet strength. On the other hand, if it is not less than the lower limit, it does not cause inconveniences such as generation of agglomerates and destruction of the emulsified state during aqueous emulsion polymerization and reduction in storage stability and mechanical stability of the obtained aqueous dispersion. It is preferred.

In the emulsion polymerization of the acrylic copolymer of the present invention, if necessary, a part of the essential nonionic surfactant is replaced with a nonionic surfactant other than the alkylphenyl surfactant. be able to. Examples of such nonionic surfactants include higher sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, and sorbitan trioleate; and higher polyoxyethylene sorbitan such as polyoxyethylene sorbitan monolaurate. Fatty acid esters; for example, polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monostearate, and polyoxyethylene monooleate; for example, glycerol such as glycerol monooleate and glycerol monostearate Higher fatty acid esters; for example, polyoxyethylene / polyoxypropylene / block copolymer;

In the emulsion polymerization of the acrylic copolymer in the present invention, an anionic surfactant other than an alkylphenyl-based surfactant can be used, if necessary, together with the essential nonionic surfactant.

As such an anionic surfactant, for example, the following general formula (2):

[0050]

(Wherein, R ² represents a linear or branched aliphatic group having 10 to 20 carbon atoms, in which a part of the hydrogen bonded to the carbon chain may be substituted by fluorine or a hydroxyl group; M +
Represents a monovalent counter ion such as Na ⁺ , K ⁺ or NH ₄ ⁺ )

The polyoxyethylene alkyl or alkenyl ether sulfate ester type anionic surfactant represented by the formula (1) is preferably used.

The aliphatic group in the general formula (2) is preferably a straight-chain alkyl or alkenyl group in which the hydrogen bonded to the carbon chain is not substituted, and the hydrogen bonded to the carbon chain is substituted. It is particularly preferred that the alkyl group is not a straight-chain alkyl group.

Examples of such suitable anionic surfactants include, for example, polyoxyethylene lauryl ether sulfate, polyoxyethylene palmityl ether sulfate, polyoxyethylene stearyl ether sulfate and the like. Polyoxyethylene alkenyl ether sulfates such as alkyl ether sulfates and polyoxyethylene oleyl ether sulfates can be exemplified.

The length (value of p) of the polyoxyethylene chain in the anionic surfactant is preferably in the range of 5 to 50, more preferably in the range of 10 to 40.
More preferably, it is in the range of 15 to 30.

The anionic surfactant which can be used in the present invention includes the following general formula (3):

[0057]

(Wherein R ³ is an alkyl group having 10 to 20 carbon atoms;
M ⁺ represents a monovalent counter ion such as Na ⁺ , K ⁺ or NH ₄ ⁺ )

The alkyl aryl sulfonate type anionic surfactant represented by the following formula can be exemplified, and specifically, sodium dodecylbenzene sulfonate and the like can be exemplified.

The anionic surfactant which can be used in the present invention further includes the following general formula (4):

[0061]

(Wherein, R ⁴ represents a hydrocarbon group containing one or more aromatic rings, and M ⁺ represents a monovalent counter ion such as Na ⁺ , K ⁺ or NH ₄ ⁺ )

The polyoxyethylene polycyclic phenyl ether type anionic surfactant represented by the following formula can be exemplified.

R ⁴ in the above general formula (4) is preferably derived from any of distyryl represented by the following three structural formulas or a mixture thereof.

[0065]

The length (value of q) of the polyoxyethylene chain in the anionic surfactant represented by the general formula (4) is generally in the range of 4 to 50, preferably 5 to 50.
It should be in the range of ~ 45. Specific examples of these anionic surfactants include, for example, Hytenol NF-13 and Hytenol NF-17 [trade names; Daiichi Kogyo Seiyaku Co., Ltd.
Manufactured), New Call 707SF, New Call 710SF, New Call 714SF, New Call 723SF, New Call 740SF
[Product name; manufactured by Nippon Emulsifier Co., Ltd.] and the like.

The anionic surfactant which can be used in the present invention further includes, for example, higher fatty acid salts such as sodium oleate and sodium stearate; for example, sodium monooctylsulfosuccinate, sodium dioctylsulfosuccinate, Alkyl sulfosuccinates such as sodium ethylene lauryl sulfosuccinate and derivatives thereof; and the like.

Each of the anionic surfactants can be used alone or in combination of two or more. The amount of the anionic surfactant is based on 100 parts by weight of the obtained acrylic copolymer. The total amount of the active ingredients is preferably 5 parts by weight or less, and particularly preferably 0.1 to 2 parts by weight. When the amount of the anionic surfactant is equal to or less than the upper limit, the obtained aqueous dispersion has good mechanical stability and chemical stability, and the obtained textile has good water absorption and water retention. It is preferred. Further, by using the lower limit or more, it is possible to prevent the occurrence of aggregates and destruction of the emulsified state during aqueous emulsion polymerization, and to improve the storage stability and mechanical stability of the obtained aqueous dispersion. It is preferred.

Further, the proportion of the anionic surfactant used is preferably 40% by weight or less, and more preferably 5 to 30% by weight, based on the total amount of the surfactant used.
Is more preferably within the range. When the use ratio is equal to or less than the upper limit, the obtained aqueous dispersion has excellent chemical stability, and the fiber product obtained using this aqueous dispersion has excellent water absorption and water retention. preferable. The use of the lower limit or more is preferable because the formation of aggregates during emulsion polymerization, the destruction of the emulsified state, and the storage stability and mechanical stability of the obtained aqueous dispersion can be improved.

Further, the total amount of the surfactant used in the polymerization of the acrylic copolymer in the present invention is 1.0 to 100 parts by weight of the acrylic copolymer as an active ingredient.
The range is preferably from 10 to 10 parts by weight, more preferably from 1.5 to 8 parts by weight, and particularly preferably from 2.5 to 7 parts by weight. When the use ratio is equal to or less than the upper limit, emulsion polymerization stability is excellent, and the mechanical stability and chemical stability of the obtained aqueous dispersion are excellent, as well as the base of the aqueous dispersion. It is preferable because a fiber processed product having good water absorption and water retention without inhibiting adhesion can be obtained. The use of the lower limit or more is preferable because the formation of aggregates during emulsion polymerization, the destruction of the emulsified state, and the storage stability and mechanical stability of the obtained aqueous dispersion can be improved.

In the emulsion polymerization of the water-based acrylic copolymer in the present invention, a protective colloid may be used together with the above-mentioned nonionic and anionic surfactants, if necessary and within a range not to impair the excellent effects of the present invention. Can be used together.

Examples of such protective colloids include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; and cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose salts. And natural polysaccharides such as guar gum; and the like.

The amount of these protective colloids used is, for example,
The amount can be, for example, about 0 to 3 parts by weight based on 100 parts by weight of the acrylic copolymer.

In the emulsion polymerization of the acrylic copolymer in the present invention, as a polymerization initiator, for example, persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate; t-butyl hydroperoxide, cumene hydroperoxide, Organic peroxides such as p-menthane hydroperoxide; hydrogen peroxide; and the like can be used alone or in combination of two or more.

The amount of the polymerization initiator can be appropriately selected. For example, about 100 parts by weight of the acrylic copolymer is used.
The amount used may be, for example, 0.05 to 1 part by weight, more preferably about 0.1 to 0.7 part by weight, particularly preferably about 0.1 to 0.5 part by weight.

In the emulsion polymerization, a reducing agent can be used together if desired. Examples of the reducing agent include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, and glucose; and reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. .

The amount of the reducing agent to be used can be appropriately selected. For example, about 0.05 to 1 per 100 parts by weight of the acrylic copolymer is used.
The amount of use such as parts by weight can be exemplified.

In the emulsion polymerization, a chain transfer agent may be used if desired. Examples of such a chain transfer agent include cyanoacetic acid; C1-8 alkyl esters of cyanoacetic acid; bromoacetic acid; C1-8 alkyl esters of bromoacetic acid; for example, anthracene, phenanthrene, fluorene, 9 Aromatic compounds such as -phenylfluorene; aromatic nitro compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol and p-nitrotoluene; 3,5,6-
Benzoquinone derivatives such as tetramethyl-p-benzoquinone; borane derivatives such as tributylborane; for example, carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane,
Halogenated hydrocarbons such as tribromoethylene, trichloroethylene, bromotrichloromethane, tribromomethane, 3-chloro-1-propene; for example, aldehydes such as chloral and furaldehyde; alkylmercaptans having 1 to 18 carbon atoms; , Thiophenols, aromatic mercaptans such as toluene mercaptan; mercaptoacetic acid; alkyl esters of mercaptoacetic acid having 1 to 10 carbon atoms; hydroxyalkyl mercaptans having 1 to 12 carbon atoms; for example, terpenes such as binene and terpinolene; And the like.

When the above chain transfer agent is used, the amount of the chain transfer agent is about 0.005 to 3 with respect to 100 parts by weight of the acrylic copolymer.
It is preferably in parts by weight.

As a preferred embodiment of the emulsion copolymerization, the above-mentioned monomers (a) to (d) are added to an aqueous medium containing or not containing the above-mentioned surfactant and / or protective colloid.
(d), an embodiment in which a surfactant and / or a protective colloid, a polymerization initiator, and a reducing agent to be used, if necessary, are sequentially added. The copolymerization temperature is about 40 ~
The temperature is 100 ° C., preferably about 50-90 ° C.

The aqueous dispersion of the acrylic copolymer thus obtained may be added with ammonia water or the like, if necessary.
H may be adjusted. Such a dispersion generally has a solid content of 30 to 55% by weight, a viscosity of 10 to 3000 cps (BH type rotational viscometer, 25 ° C., 20 rpm; the same applies to the viscosity measurement conditions and below), and a pH of 2 to 9.
And the average particle diameter of the acrylic copolymer particles in the aqueous medium is preferably 0.05 to 0.5 μm.

The aqueous dispersion of a crosslinked resin for fiber processing according to the present invention is further required in the aqueous dispersion of an acrylic copolymer in order to improve the strength of the obtained fiber product, particularly, the strength when wet. May contain a crosslinking agent component.

The above-mentioned cross-linking agent component needs to be reactive with the above-mentioned monomer (b) and / or monomer (c). Depending on the type of the monomer (c), it can be appropriately selected from those having no inconvenience such as yellowing of the obtained fiber product.
As such a crosslinking agent component, it is preferable to use an oxazoline-based crosslinking agent, a blocked isocyanate-based crosslinking agent (non-yellowing type) or an epoxy-based crosslinking agent.

The oxazoline-based cross-linking agent described above is characterized in that the acrylic copolymer has a functional group having an active hydrogen capable of causing a ring-opening addition reaction of the oxazoline group, such as a carboxyl group, a carboxyl anhydride group, a mercapto group, It can be suitably used when it contains a group or the like.

As such an oxazoline-based crosslinking agent, an oxazoline group-containing monomer represented by the following general formula (5) and, if necessary, at least one of other monomers copolymerizable therewith. Is preferably a water-soluble or water-dispersible polymer compound that is easily compounded with the acrylic copolymer aqueous dispersion.

[0086]

(Wherein R ^{5 to} R ⁷ are each independently
R ^{8 to} R ¹¹ are each independently hydrogen, a halogen, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group; X is a single bond, -A ¹ -OCO -, - A ² -NHCO- or -A
³ -O- and represents, A ¹ to A ³ each independently represents a single bond or an alkylene group having 1 to 3 carbon atoms)

R ⁵ in the above oxazoline group-containing monomer is, for example, vinyl group, allyl group, propenyl group, i-propenyl group, α-butenyl group, β-butenyl group, γ-butenyl group, i- An alkenyl group having 2 to 4 carbon atoms such as a butenyl group; for example, a (meth) acryloyloxy group,
(Meth) acryloyl group-containing group such as (meth) acrylamide group; for example, having 2 carbon atoms such as vinyloxy group and allyloxy group
Examples of such oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, and 2-vinyl. Examples thereof include -5-methyl-2-oxazoline, 2-i-propenyl-2-oxazoline, 2-i-propenyl-4-methyl-2-oxazoline, and 2-i-propenyl-5-ethyl-2-oxazoline. The use of 2-vinyl-2-oxazoline is preferred for reasons such as easy availability.

If necessary, the monomers used together with the oxazoline group-containing monomer include the monomers exemplified as monomers (a) and (d) in the acrylic copolymer; For example, (meth) acrylic acid ester monomers other than the monomers (a) and (d) such as methoxy (poly) ethylene glycol (meth) acrylate; and the monomer exemplified as the functional group-containing monomer (c) Examples of the monomer include an amide group-containing monomer and a hydroxyl group-containing monomer that do not contain a methylol group or a derivative thereof.

The details of such an oxazoline group-containing polymer compound that can be used as the oxazoline-based crosslinking agent in the present invention are disclosed in, for example, JP-A-5-295275, which is disclosed in the publication. It can be manufactured and used according to the method described above.

The amount of oxazoline groups in the oxazoline-based crosslinking agent that can be used in the present invention is determined based on 100 g of the crosslinking agent.
It is preferably 0.1 to 1 equivalent, more preferably 0.2 to 0.6 equivalent. When the amount of the oxazoline group is equal to or more than the lower limit, the reactivity with the acrylic copolymer used in the present invention is good, and a sufficient cross-linked structure can be formed in the formed film, which is obtained. It is preferable because appropriate water resistance and oil resistance can be imparted to the fiber-processed product. On the other hand, the water-absorbing property and the flexibility of the obtained fiber-processed product are preferably not less than the upper limits.

The weight average molecular weight of the oxazoline group-containing polymer compound which is an oxazoline crosslinking agent is generally 50
It is preferably from 0 to 10,000, more preferably from 1,000 to 7,000. Further, the aqueous liquid of the oxazoline-based crosslinking agent generally has a solid content of about 10 to 50% by weight, a viscosity of 10,000 cps or less, and a pH of 7 to 9.

As the aqueous liquid of such an oxazoline-based crosslinking agent, for example, those commercially available as "Epocross WS-500" (manufactured by Nippon Shokubai Co., Ltd.) can be suitably used.

The oxazoline-based crosslinking agent is a functional group 1 having a reactivity with the oxazoline group in the acrylic copolymer.
The oxazoline group in the crosslinking agent is generally
It is good to use 0.1 to 3 equivalents, preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.5 equivalents. When the amount of the oxazoline group in the used crosslinking agent is equal to or more than the lower limit, the crosslinked structure of the formed film is sufficiently formed, and it is possible to impart appropriate water resistance and oil resistance to the obtained fiber processed product. . On the other hand, when the content is equal to or less than the upper limit, the water absorption and flexibility of the obtained fiber-processed product are not impaired, which is preferable.

In the present invention, a blocked isocyanate-based crosslinking agent can be used as a crosslinking agent component.
The blocked isocyanate-based crosslinking agent is a functional group having an active hydrogen capable of undergoing an addition reaction with the isocyanate group regenerated by heating, such as a carboxyl group, an anhydrous carboxyl group, a hydroxyl group, and a mercapto group. It can be suitably used when it contains a group or the like. As such a blocked isocyanate-based cross-linking agent, it is preferable to use a non-yellowing type blocked isocyanate compound from the viewpoint of preventing discoloration of the obtained fiber processed product.

The above-mentioned blocked isocyanate compound is generally obtained by adding a volatile low-molecular-weight active hydrogen compound (blocking agent) which is released and volatilized by heating to a polyisocyanate compound.

The polyisocyanate compounds which can be suitably used in the present invention include, for example, hexamethylene diisocyanate, isophorone diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 1-methylcyclohexane-isocyanate.
2,4-diisocyanate, 1-methylcyclohexane-2,6-
Aliphatic or alicyclic diisocyanate compounds such as diisocyanate, 1,3-diisocyanatomethylcyclohexane, 1,4-diisocyanatomethylcyclohexane, dicyclohexylmethane-4,4'-diisocyanate and dimer acid diisocyanate; Mers or 3
And adducts of these isocyanates with, for example, divalent or trivalent polyols such as ethylene glycol and trimethylolpropane. Among these polyisocyanate compounds, a dimer or trimer of an aliphatic diisocyanate such as hexamethylene diisocyanate is particularly preferable from the viewpoint of good reactivity and easy availability.

Examples of the volatile low-molecular active hydrogen compound include methyl alcohol, ethyl alcohol, n-
Aliphatic, alicyclic or aromatic alcohols such as butyl alcohol, cyclohexyl alcohol, benzyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, phenol;
Hydroxy tertiary amines such as dimethylaminoethanol, diethylaminoethanol; for example, acetoxime,
Examples include ketoximes such as methyl ethyl ketoxime; active methylene compounds such as acetylacetone, acetoacetate, and malonate; lactams such as ε-caprolactam;

The blocked isocyanate-based crosslinking agent that can be used in the present invention is preferably water-dispersible. In addition, since the acrylic copolymer aqueous dispersion, which is a main component in the present invention, usually has a weak anionic property, from the viewpoint of miscibility with this, the blocked isocyanate is a nonionic or anionic dispersion. It is particularly preferable that the liquid is a liquid and does not contain an alkylphenyl-based surfactant.

Examples of the aqueous liquid of such a blocked isocyanate-based crosslinking agent include, for example, Elastron BN-5, Elastron BN-8, Elastron BN-11 (produced by Dai-ichi Kogyo Seiyaku Co., Ltd.), and Prominate XC-915 , Prominate B830
W, Prominate XC-939 (manufactured by Takeda Pharmaceutical Co., Ltd.),
Those commercially available as Coronate 2507, Coronate 2513, and Coronate 2515 (all manufactured by Nippon Polyurethane Industry Co., Ltd.) can be suitably used.

The blocked isocyanate-based crosslinking agent is generally used in an amount of 0.2 equivalent of the blocked isocyanate group in the acrylic copolymer per 1 equivalent of a functional group reactive with the isocyanate group. It is good to use it so that it may become -2 equivalent, Preferably it is 0.3-1.2 equivalent, More preferably, it becomes 0.5-1 equivalent. When the amount of the blocked isocyanate group in the used crosslinking agent is equal to or more than the lower limit, formation of the crosslinked structure of the formed film is sufficient, and appropriate water resistance and oil resistance can be imparted to the obtained fiber processed product. It is preferred. On the other hand, when the content is not more than the upper limit, the water absorbency and flexibility of the obtained fiber-processed product are not impaired, which is preferable.

In the present invention, an epoxy crosslinking agent can be used as a crosslinking agent component. The epoxy-based crosslinking agent can be suitably used when the acrylic copolymer contains a functional group having an active hydrogen capable of undergoing an addition reaction with an epoxy group, for example, a hydroxyl group, a mercapto group, or the like. . When the epoxy-based crosslinking agent has a hydroxyl group in its molecule, it can be used when the acrylic copolymer contains a carboxyl group, an anhydrous carboxyl group, or the like.

The epoxy-based crosslinking agent that can be suitably used in the present invention is preferably water-soluble or water-dispersible and does not contain an alkylphenyl-based surfactant.

As such an epoxy-based crosslinking agent, for example, a polyol polyglycidyl ether compound, a polyacid polyglycidyl ester compound and the like can be preferably used.
As the above polyol, for example, ethylene glycol, diethylene glycol, polyethylene glycol,
Aliphatic or alicyclic polyols such as propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, glycerol, diglycerol, polyglycerol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and sorbitan can be mentioned. Examples of the polyacid include adipic acid.

Among the epoxy crosslinking agents that can be used in the present invention, specific examples of polyol polyglycidyl ether compounds include, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol (n ≒ 4, 9,
13, 22) diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol (n （
3, 11) diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, polyglycerol (n （4, 6, etc.) polyglycidyl ether, trimethylolpropane poly Examples thereof include glycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, and sorbitan polyglycidyl ether. Specific examples of the polyacid polyglycidyl ester compound include, for example, diglycidyl adipate and the like. . Particularly preferred among these epoxy-based crosslinking agents are ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, glycerol diglycidyl ether,
Glycerol triglycidyl ether, diglycerol triglycidyl ether, sorbitol polyglycidyl ether, and sorbitan polyglycidyl ether.

The aqueous liquid of such an epoxy crosslinking agent is, for example, Nagase Kasei Kogyo under the trade name of “Denacol”.
Various epoxy-based cross-linking agents sold by Co., Ltd. can be suitably used, for example, Denacol EX-313, Denacol EX
-314, Denacol EX-611, Denacol EX-614 and Denacol EX-810 can be particularly preferably used.

The epoxy-based crosslinking agent is generally used in an amount of from 0.3 to about 1 equivalent of a functional group reactive with an epoxy group (and a hydroxyl group) in the acrylic copolymer. 2 equivalents, preferably 0.3-1.5 equivalents,
More preferably, it is used in an amount of 0.5 to 1.2 equivalents. When the amount of the epoxy group in the cross-linking agent to be used is not less than the lower limit value, the cross-linking structure of the formed film is sufficiently formed, and it is possible to impart appropriate water resistance and oil resistance to the obtained fiber processed product. . On the other hand, when the content is not more than the upper limit, the water absorbency and flexibility of the obtained fiber-processed product are not impaired, which is preferable.

The aqueous dispersion of a crosslinkable resin for fiber processing according to the present invention may further contain various additives, if necessary, in addition to the above-mentioned crosslinker component which can be used if necessary. Can be.

Examples of these additives include thickeners and viscosity improvers such as polyvinyl alcohol, cellulose derivatives, polycarboxylic acid resins, and surfactants other than alkylphenyl resins; Sodium hexametaphosphate, sodium tripolyphosphate, etc.),
Dispersants such as organic dispersants [Nopcosperse 44C (trade name), polycarboxylic acid type; manufactured by San Nopco Co., Ltd.]; defoamers such as silicone type; for example, terpene ethylene glycol, butyl cellosolve, butyl carbitol, butyl Organic solvents such as carbitol acetate; antioxidants; preservatives and fungicides; ultraviolet absorbers;
And the like.

The above-mentioned aqueous dispersion of a crosslinked resin for fiber processing according to the present invention is suitably used for resin processing of textile products such as woven fabric, knitted fabric, nonwoven fabric, felt made of natural fiber, regenerated fiber, synthetic fiber and the like. In particular, it is useful for resin processing of non-woven fabrics for disposable wiping materials (wipers) mainly used for business use in restaurants and the like.

[0111]

The present invention will be described in more detail with reference to the following examples. The test method and evaluation method in this example are as follows.

(1) Preparation of Test Sheet The aqueous resin dispersion was diluted with water so that the solid content was about 10% by weight, and No. 2 filter paper (manufactured by Toyo Roshi Kaisha, Ltd.) was immersed therein. It was squeezed using a mangle so that the basis weight became about 10 g / m ^2, and immediately heat-treated at 150 ° C. for 4 minutes to obtain a test sheet.

(2) Strength of resin-impregnated filter paper The test sheet prepared in the section (1) was subjected to a temperature of 23 ° C. and a humidity of 65% R
After leaving for 3 hours or more under the constant temperature and humidity condition of H, the normal-state breaking strength was measured under the same conditions. Tensilon UYM-41 for measurement
Using 00 [manufactured by Toyo Baldwin Co., Ltd.], the measurement test piece was 25 mm in width, the grip distance was 100 mm, and the tensile speed was 300 mm / min.

After immersing the test sheet in water for 1 minute, the wet rupture strength was measured in the same manner as above, and the dry-wet strength ratio was determined by the following formula.

[0115]

(3) Water Absorption Test The test sheet prepared in the previous section (1) was subjected to a temperature of 23 ° C. and a humidity of 65% RH.
After standing for 3 hours or more under constant temperature and humidity conditions, water was spotted on the test sheet using a 10-ml polyethylene Komagome pipette under the same conditions, and the time until water droplets penetrated into the test sheet was measured. .

(4) Hand The hand of the test sheet prepared in the section (1) was evaluated by touch. The evaluation criteria are as follows. ○ ・ ・ ・ ・ ・ ・ Very flexible △ ・ ・ ・ ・ ・ ・ Slightly hard x ・ ・ ・ ・ ・ ・ Hard

(5) Adhesion The two test sheets prepared in the previous section (1) were pressed together, and 200 g /
left for 16 hours at 25 ° C. under a load of cm ^2, the temperature further 23
After leaving it for 30 minutes under a constant temperature and humidity condition of 65 ° C. and a humidity of 65% RH, it was peeled off, and the stickiness was evaluated from the peeling resistance. The evaluation criteria are as follows. ○ ・ ・ ・ ・ ・ ・ Almost no resistance at peeling (no stickiness) △ ・ ・ ・ ・ ・ ・ Some resistance at peeling (slightly sticky) x ・ ・ ・ ・ ・ ・ Resistance at peeling (very sticky) Big)

Preparation of Aqueous Acrylic Copolymer Dispersion Example 1 In a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 301 g of ion-exchanged water was charged, and the internal temperature was raised to 60 ° C. I let it. Meanwhile, 140 g of ion-exchanged water in another container, and
“DKS NL-250” [polyoxyethylene (n = 25) lauryl ether type nonionic surfactant (active ingredient concentration: 100% by weight) as a surfactant for emulsion polymerization (hereinafter sometimes simply referred to as an emulsifier); Daiichi Kogyo Seiyaku Co., Ltd.) (N
L-250) 15 g and "HITENOL-18E" [polyoxyethylene (n = 18) lauryl ether sulfate ammonium salt type anionic surfactant (active ingredient concentration: 95% by weight); manufactured by Daiichi Kogyo Seiyaku Co., Ltd. ] (H-18E) 2.63 g, and N-methylolacrylamide (NMA) which is a functional monomer (c)
M) was charged and stirred and dissolved.
(a) 325 g of ethyl acrylate (EA), comonomer (d)
Of butyl acrylate (BA), 50 g of methyl methacrylate (MMA), and 10 g of acrylic acid (AA), which is monomer (b), and stirred to obtain a monomer emulsion. Was.

The contents of the reactor were heated while stirring under a nitrogen stream. When the water temperature in the reactor reached 60 ° C., ammonium persulfate (APS) and sodium metabisulfite (APS) were used as a polymerization initiator and a reducing agent. After adding 0.5 g of each of SMBS), 60 g of a monomer emulsion, an aqueous solution of 2.5% by weight ammonium persulfate, and sodium metabisulfite of 2.5% by weight are sequentially added, and a polymerization reaction is carried out at 60 ° C. for about 3 hours. Was. After the completion of the polymerization reaction, stirring was continued at the same temperature for about 1 hour, followed by cooling to obtain an aqueous dispersion of an acrylic copolymer.

This aqueous dispersion had a solid content of 49.8% by weight and a pH of
2.3, viscosity 80 mPa · s (25 ° C., BH-type rotational viscometer 20 rpm), Tg of the copolymer was −19 ° C., and SP value was 9.2.

The monomer composition of the acrylic copolymer and
Type and amount of emulsifier used (acrylic copolymer 100
The amount of the active ingredient per part by weight) is shown in Table 1, and the characteristic values of the aqueous acrylic copolymer dispersion are shown in Table 2. The same applies to the following Examples 2 to 12 and Comparative Examples 1 to 9.

Examples 2 to 9 and Comparative Examples 1 to 8 In Example 1, ethyl acrylate as monomer (a), unsaturated carboxylic acid as monomer (b), and functional monomer
Acrylic copolymer aqueous dispersion was obtained in the same manner as in Example 1 except that (c) and comonomer (d), and the type and amount of the emulsifier were changed as shown in Table 1. .

Among these, the aqueous acrylic copolymer dispersion of Comparative Example 7 in which the unsaturated carboxylic acid (b) was not copolymerized had many aggregates, and the emulsion was easily broken only by rubbing with a finger. , The mechanical stability was poor.

The abbreviations of the monomers and surfactants used in Table 1 are as follows. MAA: methacrylic acid IA: itaconic acid HEMA: 2-hydroxyethyl methacrylate GMA: glycidyl methacrylate MA: methyl acrylate AN: acrylonitrile EHA: 2-ethylhexyl acrylate EHMA: 2-ethylhexyl methacrylate

NL-600: "DKS NL-600"; Daiichi Kogyo Pharmaceutical
Polyoxyethylene (n = 60) lauryl ether type nonionic surfactant (active ingredient concentration: 100% by weight) NL-850: "DKS NL-850"; Daiichi Kogyo Pharmaceutical Co., Ltd .; Poly Oxyethylene (n = 85) lauryl ether type nonionic surfactant (active ingredient concentration: 100% by weight) Ono.109: "Neugen Ono.109"; manufactured by Daiichi Kogyo Seiyaku Co., Ltd .;
Polyoxyethylene (n = 27) oleyl ether type nonionic surfactant (active ingredient concentration: 100% by weight) ET-189: "Neugen ET-189"; manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; polyoxyethylene (n = 18.5) Oleyl ether type nonionic surfactant (active ingredient concentration: 95% by weight) NF-17: "HITENOL NF-17"; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .;
Polyoxyethylene (n = 17.5) distyryl phenyl ether sulfate ammonium salt type anionic surfactant (active ingredient concentration: 95% by weight) No. 6: “Neoperex No. 6”; manufactured by Kao Corporation; dodecylbenzene Sulfonate sodium salt type anionic surfactant (active ingredient concentration 60% by weight)

[0127]

[Table 1]

[0128]

[Table 2]

Preparation of Crosslinkable Aqueous Resin Dispersion for Fiber Processing and
Physical property test Examples 11 to 18 and Comparative Examples 11 to 19 Using the acrylic copolymer aqueous dispersions prepared in Examples 1 to 8 and Comparative Examples 1 to 9 as they were, a crosslinked resin aqueous dispersion for fiber processing was used. did. Using these, a performance test was performed according to the test method described above. Table 3 shows the obtained results.

In preparing the test sheet, the aqueous solution of the crosslinked resin for fiber processing of Comparative Example 17 was prepared using the aqueous acrylic copolymer dispersion of Comparative Example 7 in which the unsaturated carboxylic acid (b) was not copolymerized. In the dispersion, a large amount of agglomerates adhered to the mangle roll due to the emulsion breaking of the dispersion, which also adhered to the test sheet, resulting in poor appearance.

Example 20 0.2 parts by weight of 25% aqueous ammonia was added to 100 parts by weight of the aqueous resin dispersion obtained in Example 3, and 3.0 parts by weight of a blocked isocyanate crosslinking agent [Elastron BN-08; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] With stirring, pH 7.0, viscosity 250 mPas, solid content 4
A 9.6% by weight aqueous crosslinked resin dispersion for fiber processing was obtained.
Using this, a performance test was performed according to the test method described above. Table 3 shows the obtained results.

Example 21 To 100 parts by weight of the aqueous resin dispersion obtained in Example 6, 0.4 part by weight of 25% aqueous ammonia and an epoxy-based crosslinking agent [Denacol EX-
614; Nagase Kasei Kogyo Co., Ltd.] 3.0 parts by weight were added with stirring to obtain a crosslinked resin aqueous dispersion for fiber processing having a pH of 6.5, a viscosity of 250 mPa · s, and a solid content of 49.7% by weight. Using this,
A performance test was performed according to the test method described above. Table 3 shows the obtained results.

Example 22 To 100 parts by weight of the aqueous acrylic copolymer dispersion obtained in Example 8, 0.4 parts by weight of 25% aqueous ammonia, and an oxazoline-based crosslinking agent (Epocross WS-500, manufactured by Nippon Shokubai Co., Ltd.) 3.0 Parts by weight, with stirring, pH 7.9, viscosity 350 mPas, solid content 4
A 9.7% by weight aqueous solution of a crosslinked resin for fiber processing was obtained.
Using this, a performance test was performed according to the test method described above. Table 3 shows the obtained results.

[0134]

[Table 3]

[0135]

According to the present invention, the aqueous dispersion of a crosslinked resin for fiber processing according to the present invention comprises a specific surfactant containing ethyl acrylate as a main component in the presence of a specific surfactant substantially free of an alkylphenyl surfactant. An aqueous dispersion of an acrylic copolymer having a specific glass transition point (Tg) and solubility parameter (SP value) obtained by emulsion copolymerization of a monomer is contained as an essential component. . The aqueous dispersion of a crosslinkable resin for fiber processing of the present invention may further contain, if necessary, a crosslinker such as an oxazoline crosslinker, a blocked isocyanate crosslinker (non-yellowing type), or an epoxy crosslinker. it can.

Thus, the aqueous dispersion of a crosslinked resin for fiber processing of the present invention can be used for resin processing of textile products such as woven fabric, knitted fabric, nonwoven fabric, felt made of natural fiber, regenerated fiber, synthetic fiber, etc. It can be suitably used for resin processing of non-woven fabrics for disposable wiping materials (wipers) used for business use in restaurants and the like, and resin processing using a conventional resin aqueous emulsion was still insufficient. Textile products are soft and non-sticky, have excellent hydrophilicity and high wet strength, have excellent appearance such as no yellowing, and harmful substances including alkylphenyl surfactants To provide an excellent fiber product having various properties such as substantially not containing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G59 / 40 C08G59 / 40 4L033 C08L 33/08 C08L 33/08 // (C08F 220/18 (C08F 220 / 18 220: 04) 220: 04) (C08F 220/18 (C08F 220/18 222: 02) 222: 02) F-term (reference) 4J002 BG041 BQ004 CD014 CD084 CH052 CH053 EG027 ER006 EU216 EV187 EV237 FD144 FD146 FD310 FD312 FD313 FD317 GK02 HA07 4J011 KA02 KA04 KA15 KA23 KB14 KB29 4J034 BA03 DA01 DA02 DA03 DA05 DA07 DA08 DB03 DB08 DD11 DP03 DP18 DP20 HA01 HA07 HB07 HC03 HC17 HC22 HC34 HC35 HC46 HC52 HC61 HC64 HC67 HC71 HC73 HD03 4 AK12 AK14 DC27 DC38 FB01 FB03 FB04 4J100 AB16R AD01R AD03R AE18R AE26R AG03S AG04S AG05S AG70R AJ01Q AJ02Q AJ08Q AJ09Q AL03P AL03S AL04S AL05S AL08 R AL08S AL09R AL10R AL62R AL63R AL75R AM02S AM15R AM17R AM19R AM21R AP01R AQ19R AQ21R BA03R BA04R BA05R BA06R BA08R BA14R BA52R BA75R BA77R BA78R BA85R BC04S BC43S BC54R CA05 CA03 DA25 DA39 EA3

Claims (8)

[Claims] (1) In the presence of a surfactant substantially free of an alkylphenyl surfactant and containing a C10-20 aliphatic alcohol polyoxyethylene ether type nonionic surfactant as a main component, The following monomers (a) to (d), (a) 25 to 99% by weight of ethyl acrylate, (b) 0.5 to 10% by weight of α, β-unsaturated mono- or di-carboxylic acid having 3 to 5 carbon atoms (C) a monomer having at least one functional group in addition to one radically polymerizable unsaturated group in the molecule, wherein the monomer other than the monomer (b) is 0.5 to 10% by weight. %, And (d) the monomer (a) copolymerizable with the monomers (a) to (c).
0 to 70% by weight of a comonomer other than to (c), provided that the total amount of monomers (a) to (d) used is 100% by weight), Glass transition point (Tg)
Is in the range of −40 to 10 ° C. and its solubility parameter (SP
Value) in the range of 9.0 to 10.5. An aqueous dispersion of a crosslinked resin for fiber processing, comprising an acrylic copolymer having a value of from 9.0 to 10.5. 2. The aqueous dispersion according to claim 1, wherein the ethylene oxide addition mole number (n) of the aliphatic alcohol polyoxyethylene ether type nonionic surfactant having 10 to 20 carbon atoms is in the range of 10 to 120. 3. The aqueous dispersion according to claim 1, further comprising an anionic surfactant other than the alkylphenyl surfactant as the surfactant. 4. The aqueous dispersion according to claim 3, wherein the amount of the anionic surfactant used is 40% by weight or less of the total amount of the surfactant used as an active ingredient. 5. The aqueous dispersion according to claim 1, wherein the total amount of the surfactant used ranges from 1.0 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer as an active ingredient. 6. The monomer (c) selected from the group consisting of a monomer having a methylol group or a derivative thereof, a hydroxyl group-containing monomer, and a glycidyl group-containing monomer.
2. The aqueous dispersion according to item 1. 7. The aqueous dispersion according to claim 1, further comprising a crosslinking agent component. 8. The aqueous dispersion according to claim 7, wherein the crosslinking agent component is selected from an oxazoline-based crosslinking agent, a blocked isocyanate-based crosslinking agent (non-yellowing type), and an epoxy-based crosslinking agent.