JP2716215B2 - Aqueous binder composition for flocking - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an aqueous binder composition for flocking, and more particularly to a method of applying a binder to a base material such as a fiber (woven fabric), a plastic sheet, or paper to form a pile ( The present invention relates to an aqueous binder composition suitable for use in flocking or the like in which short fibers are implanted by high-voltage static electricity.

[Conventional technology]

In the conventional flocking method (electrostatic flocking method), a binder is applied to various types of base cloths such as woven cloth, nonwoven cloth, and knitted cloth, and a high voltage (for example, about 30,000 V) is applied thereto.
A pile of about 0.3 to 5 mm is implanted, and then the excess pile is collected under high voltage or suction, the binder is pre-dried and heat-treated (crosslinking condensation), and the remaining pile is collected by brushing or suction. It is used as a product, for example, for automobile interiors and clothing.

[Problems to be solved by the invention]

In the above-mentioned flocking, recently, in addition to the base cloth of cotton or nylon, the cloth of polyester fiber is often used as the base cloth, and piles having long hairs of several mm in length are often used. After planting hair, it is also performed to give a feeling similar to animal hair by alkali treatment with caustic soda. On the other hand, conventionally, as a binder for flocking processing, an aqueous emulsion type and a solvent type using an organic solvent are known, but from the viewpoint of workability, mainly an emulsion type is practically used. As the conventional emulsion type binder, for example, acrylic type, vinyl acetate type, synthetic rubber type, urethane type and the like are known. However, such conventional emulsion-type binders cannot withstand alkali treatment for producing animal hair feeling, or have insufficient adhesiveness to polyester fiber cloth which has recently been widely used as a base cloth, or have long hair. There has been a problem that pile retention is insufficient.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problems of the prior art and to provide a binder for flocking processing which is excellent in alkali resistance, adhesion to polyester cloth, and long hair pile retention.

[Means for solving the problem]

According to the present invention, the objects described above are: (A) (A) a general formula CH ₂ CRCR ¹ —COOR ² (wherein R ¹ represents H or CH ₃ , and R ² is a direct bond between C _{1 and} C ₁₂ ) Acrylic acid or methacrylic acid ester monomer represented by the following formula (indicating a chain or a branched alkyl group): 10 to 98.3% by weight, (b) a monomer having a group capable of forming a tertiary or quaternary ammonium-based cationic group 0.5 to 10 wt%, (iii) the general formula CH ₂ = CR ¹ -CONHR ³ (wherein, R ¹ represents H or CH _3, R ³ represents H or ^{_{CH 2 O-R 4, R}} 4 is 0.2 to 10% by weight of a monomer represented by H or a linear or branched alkyl group of C _{1 to} C ₄ ), (d) a general formula CH ₂ 1CR ¹ -COOR ⁵ (wherein R ¹ Represents H or CH ₃ , and R ⁵ represents at least one O
₁ to 20% by weight of a C _{1 to} C ₈ linear or branched alkyl group substituted with an H group), and (e) the monomers (a) to (d) ) Is a monomer copolymerizable with
100 parts by weight of a copolymer composed of 0 to 50% by weight of monomers other than the monomers (a) to (d); and (B) an aqueous epoxy compound having at least one oxirane group in one molecule A cationic aqueous binder composition for flocking comprising 0.3 to 50 parts by weight (as non-volatile content) is provided.

[Specific description of the invention]

 Hereinafter, the present invention will be described in detail.

The copolymer (A) used in the present invention has a general formula CH ₂ = CR ¹ -C
Acrylic acid or methacrylic acid ester monomer represented by OOR ² ; (a) a monomer having a group capable of forming a tertiary or quaternary ammonium-based cationic group (b); general formula CH ₂ ＝ CR ¹
-CONHR ³ (c), a monomer having a hydroxyl group in the side chain (d), and a monomer copolymerizable with these monomers (a) to (d), if necessary. And can be obtained by copolymerizing a monomer (e) other than the monomers (a) to (d).

In the acrylic acid or methacrylic acid ester monomer (a) represented by the above general formula CH ₂ = CR ¹ -COOR ² , specific examples of R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-amyl group, i-amyl group, n-
Examples include a hexyl group, an n-octyl group, an i-octyl group, a 2-ethylhexyl group, an n-nonyl group, an i-nonyl group, an n-decyl group, and an n-dodecyl group. Examples of such a monomer (a) include methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, i-nonyl acrylate, and the like. Acrylic acid ester monomers; for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, n-hexyl methacrylate, n
Methacrylate monomers such as -octyl methacrylate, 2-ethylhexyl methacrylate, i-nonyl methacrylate, n-decyl methacrylate, and n-dodecyl methacrylate;

The amount of the monomer (a) used is from the monomers (a) to (e)
Is required to be 10 to 98.3% by weight, preferably 26 to 97% by weight, particularly preferably 50 to 95.5% by weight, based on the total 100% by weight. If the amount of the turbulence (a) exceeds the upper limit of the range of use, and is too large, at least one of the monomers (b) to (d) described below will necessarily be used in an excessively small amount. The adhesiveness of the binder composition to a base cloth such as a cloth of polyester fiber is reduced, and the crosslinking by heat treatment tends to be insufficient. Therefore, the water fastness of the obtained flocking cloth (a measure of the washing resistance of the flocking cloth), Uses alkali resistance fastness (a measure of the durability of the flocking cloth against alkali treatment), solvent resistance fastness (a measure of the dry cleaning resistance of the flocking cloth), and long hair pile (eg, 5 denier (d), 3 mm long) Unfavorable properties tend to be insufficient, such as the adhesiveness to the base cloth when the hair is placed. On the other hand, if the amount is less than the lower limit and the amount is too small, a desired feeling of a flocking cloth using the obtained binder composition cannot be obtained, or problems such as insufficient weather resistance tend to occur. In addition, the flocking properties such as water fastness are often insufficient, which is not preferable.

The monomer (b) is a monomer having a group capable of forming a tertiary or quaternary ammonium-based cationic group. Here, the “monomer having a tertiary or quaternary ammonium-based cationic group capable of forming” is a monomer in the form of a salt, which dissociates when dissolved in water to become tertiary or quaternary. Or a monomer having a basic group, which is an aqueous solution of the monomer or an aqueous solution or aqueous solution of the (co) polymer of the monomer. Monomer which forms a tertiary or quaternary ammonium-based cationic group by neutralizing the dispersion with an acid.

 As such a monomer (b), for example, the general formula(Where R¹Is H or CH_ThreeR¹¹, R¹², R¹³Are independent
C which may be substituted with an OH group or a halogen group₁~ C₆Directly
Chain or branched alkyl group, C_Five~ C₈A cycloalkyl group
Or CH₁~ CH₉Substituted with a straight-chain or branched alkyl group
A phenyl group which may be substituted; Y may be substituted with an OH group
C₁~ C₁₈, Preferably C₁~ C_TenLinear or branched al
Kylene group; X Is Cl^-, Br^-, I^-, SO_FourH^-, 1/2 SO_Four ^-, CH_ThreeSO_Four ^-,
C_TwoH_FiveSO_Four ^-And CH_ThreeCOO^-Selected from the group consisting of
And a monomer represented by the following formula:

Examples of the monomer represented by the general formula include, for example, 2-
(Meth) acryloyloxyethyltrimethylammonium chloride, 2- (meth) acryloyloxyethylmethyldiethylammonium chloride, 2- (meth) acryloyloxymethyldi-t-butylammonium bromide, 2- (meth) acryloyloxy Methyldipentylammonium methyl sulfate, 3- (meth) acryloyloxypropyltrimethylammonium chloride, 3- (meth) acryloyloxypropylmethyldiethylammonium bromide, 2-hydroxy-3-
(Meth) acryloyloxypropyltrimethylammonium chloride, 2-hydroxy-3- (meth) acryloyloxypropyltriethylammonium bromide, 2-hydroxy-3- (meth) acryloyloxypropyltributylammonium chloride, 2-hydroxy-3 -(Meth) acryloyloxypropylmethylethylbutylammonium chloride, 2-hydroxy-
3- (meth) acryloyloxypropyldimethylphenylammonium chloride, 2-hydroxy-3- (meth) acryloyloxypropyldimethylclohexylammonium chloride, 4- (meth) acryloyloxybutyltrimethylammonium chloride and the like may be mentioned. For example, dimethylaminoethyl (meth) acrylate / epichlorohydrin adduct, dimethylaminopropyl (meth) acrylate, epichlorohydrin adduct, diethylaminoethyl (meth) acrylate / epichlorohydrin adduct, diethylaminopropyl (meth) acrylate / epichlorohydrin adduct And dihydroxyethylaminopropyl (meth) acrylate / epichlorohydrin adducts.

 As the monomer (b), for example, a compound represented by the general formula(Where R¹, R¹¹, R¹², R¹³, Y, X Is the same as in the general formula
And a monomer represented by the following formula:

Examples of the monomer represented by the general formula include, for example, 2-
(Meth) acrylamidoethyltrimethylammonium chloride, 3- (meth) acrylamidopropyltrimethylammonium bromide, 4- (meth) acrylamidobutyltrimethylammonium methylsulfate, dimethylaminoethyl (meth) acrylamide / epichlorohydrin adduct, diethylaminoethyl (meth) acrylamide -Epichlorohydrin adduct, diethylaminopropyl (meth) acrylamide-epichlorohydrin adduct, dihydroxyethylaminopropyl (meth) acrylamide-epichlorohydrin adduct, etc.

Further, as the monomer (b), for example, a general formula CH ₂ CRCR ¹ -COO-Z-NR ¹⁴ R ¹⁵ ... (wherein R ¹ is the same as the general formula; R ¹⁴ and R ¹⁵ are each A C ₁ -C ₆ linear or branched alkyl group which may be independently substituted with an OH group; Z is a C ₁ -C ₁₈ , preferably a C ₂ -C ₈ linear or branched alkylene group; And the water-soluble salt monomers thereof.

As the monomer represented by the general formula, for example,
Dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, di-t-butylaminopropyl ( Examples thereof include (meth) acrylate, dipentylaminoethyl (meth) acrylate, and water-soluble salts thereof, that is, hydrochloride, bromate, sulfate, bisulfate, methyl sulfate, acetate, and the like.

Furthermore, as the monomer (b), for example, a general formula CH ₂ = CR ¹ -CONH-Z-NR ¹⁴ R ¹⁵ ... (wherein R ¹ , R ¹⁴ , R ¹⁵ , and Z are general formulas And the water-soluble salt monomers thereof.

Examples of the monomer represented by the general formula include dimethylaminomethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, or a water-soluble salt thereof. That is, hydrochloride, bromate, sulfate, bisulfate, methyl sulfate, acetate and the like can be mentioned.

Of these monomers (b), the use of the monomers represented by the above general formula or the like is preferable for reasons such as good copolymerizability, and among them, methacryloxyethyltrimethylammonium chloride, 2-hydroxy-3-meth Preference is given to the use of chloroxypropyltrimethylammonium chloride, dimethylaminoethyl methacrylate hydrochloride and diethylaminoethyl methacrylate hydrochloride, in particular the use of methacryloxyethylmerimethylammonium chloride and 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride. Is preferred.

The amount of the monomer (b) used is 0.5 to 10% by weight, preferably 1 to 8% by weight, particularly 2 to 6% by weight based on 100% by weight of the total of the monomers (A) to (E). Preferably it is. If the amount of the monomer (b) is too large, exceeding the upper limit of the amount range, for example, when the copolymer is produced by emulsion copolymerization, the viscosity of the polymerization system may increase abnormally during the polymerization. , A film-like or block-like gelled substance may be generated, and the pot life of the obtained aqueous binder composition (abnormal thickening or gelling, or time that can be left without physical property deterioration during use) ) Tend to be short, and further, a flocked cloth using the composition tends to have a rather reduced flocked physical property such as water fastness. On the other hand, if the amount is too small and less than the lower limit, the adhesiveness of the obtained binder composition to a base fabric such as a polyester fiber cloth tends to decrease, and the crosslinking by heat treatment tends to be insufficient. However, the solvent fastness and pile flocking property tend to be insufficient, which is not preferable.

The monomer (C) is represented by the general formula CH ₂ CRCR ¹ -CONHR ³ , R ¹ is H or CH ₃ , R ³ is H or CH ₂ OR ⁴ and R ⁴ is H or a linear or branched alkyl group of C ₁ -C _4. Specific examples of such a monomer (c) include, for example, (meth) acrylamide, N-methylol (meth)
Acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide,
Nn-butoxymethyl (meth) acrylamide, N-
t-butoxymethyl (meth) acrylamide and the like can be mentioned. Of these, (meth) acrylamide or N-
The use of methylol (meth) acrylamide is preferred,
The obtained flocked cloth has low odor and harmlessness when used for clothing (low content of formaldehyde etc.)
The use of (meth) acrylamide is particularly preferred from the viewpoint of the above.

The amount of the monomer (c) used is from the monomers (a) to (e)
Is 0.2 to 10% by weight, preferably 0.5 to 6% by weight, especially 0.5 to 4% by weight based on the total of 100% by weight. If the amount of the monomer (c) used is too large, exceeding the upper limit of the range of use, for example, when the copolymer is produced by emulsion copolymerization, the viscosity of the polymerization system may increase abnormally during the polymerization. In some cases, a gelled product in the form of a film or a block may be generated, and the pot life of the obtained aqueous binder composition tends to be short. Further, a flocking cloth using the composition is also resistant to waterfastness and the like. Is not preferable because the physical properties of hair transplantation tend to decrease. On the other hand, if the lower limit is too small,
The obtained flocking cloth tends to lack solvent fastness and long hair pile adhesion, which is not preferable.

The monomer (d) having a hydroxyl group in the side chain has the general formula CH ₂
= CR ¹ -COOR ⁵ where R ¹ is H or CH ₃ ,
R ⁵ is a straight-chain or branched alkyl group of C ₁ -C ₈ substituted with at least one OH group. Specific examples of such a monomer (d) include, for example, 2-hydroxyethyl (meth)
Acrylate and 2-hydroxypropyl (meth) acrylate can be mentioned. The amount of the monomer (d) is 1 to 100% by weight of the total of the monomers (a) to (e).
-20% by weight, preferably 1.5-15% by weight, especially 2-10% by weight. If the used amount of the monomer (d) exceeds the upper limit of the used amount range and is too large, for example, when the copolymer is produced by emulsion copolymerization, the viscosity of the polymerization system may abnormally increase during the polymerization. In some cases, a film-like or block-like gelled substance may be generated, and the flocking cloth using the obtained binder composition may also have a decreased solvent-fastness, etc. When the amount is too small, the adhesiveness of the obtained binder composition to a base fabric such as a polyester fiber cloth tends to decrease, and the crosslinking by heat treatment tends to be insufficient, and the solvent-fastness of the obtained flocking cloth tends to be insufficient. And long hair pile adhesion tend to be insufficient, which is not preferable.

The above-mentioned monomers (A) to be used as needed
(D) a monomer copolymerizable with the monomer (a)
Examples of the monomer (e) other than (d) include, for example, aromatic vinyl monomers such as styrene, α-ethylstyrene and vinyl toluene; for example, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; For example, saturated fatty acid vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, and vinyl versatate; esters of (meth) acrylic acid such as glycidyl (meth) acrylate and a saturated alcohol having an oxirane group; Two or more radically polymerizable monomers such as divinylbenzene, diallyl phthalate, triallyl cyanurate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol dimethacrylate, allyl methacrylate, etc. Saturated groups It can be mentioned monomers group and the like; monomers.

The amount of these monomers (e) used is from the above-mentioned monomers (a) to
(E) 0 to 50% by weight based on the total 100% by weight,
It is preferably from 0 to 45% by weight, especially from 0 to 30% by weight.
If the amount of the monomer (e) is too large exceeding the upper limit,
The adhesiveness of the obtained binder composition to a base fabric such as a cloth of polyester fibers is reduced, or the crosslinking by heat treatment is insufficient, and the weather resistance and various flocking properties of the obtained flocking cloth tend to be insufficient. Is not preferred.

The copolymer (A) used in the present invention comprises the monomer (A)
To (e) is preferably produced by emulsion copolymerization in an aqueous medium in the presence of a surfactant and / or a protective colloid.

Examples of the surfactant that can be used in the present invention include nonionic surfactants such as polyoxyethylene lauryl ether and polyoxyalkylene alkyl ethers such as polyoxyethylene stearyl ether; for example, polyoxyethylene octyl phenol ether and polyoxyethylene octyl phenol ether; Polyoxyalkylene alkyl phenol ethers such as ethylene nonyl phenol ether; sorbitan aliphatic esters such as sorbitan monolaurate, sorbitan monostearate and sorbitan trioleate; polyoxyalkylene sorbitan such as polyoxyethylene sorbitan monolaurate Fatty acid esters; for example, polyoxyalkylene aliphatic esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate; Ters; for example, glycerin fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride; polyoxyethylene / polypropylene / block copolymer; and the like. As layer ion surfactants, for example, laurylamine acetate; Alkylamine salts such as octadecylamine hydrochloride; quaternary ammonium salts such as lauryltrimethylammonium chloride and alkylbenzyldimethylammonium chloride; and polyoxyethylenealkyl such as polyoxyethylene laurylamine and polyoxyethylene octadecylamine Amine; and the like, and those obtained by substituting a part of hydrogen of the alkyl group of these surfactants with fluorine can also be used.

Among these surfactants, nonionic surfactants, in particular, polyoxyalkylene alkyl ethers, poroxyalkylene alkyl phenol ethers and / or polyoxyalkylene alkyl ethers are preferred from the viewpoint of the occurrence of small aggregates during emulsion copolymerization. It is preferable to use an oxyethylene / polyoxypropylene block copolymer, and if necessary, a cationic surfactant such as the above-mentioned quaternary ammonium salt may be used in combination with these nonionic surfactants.

As the amount of the surfactant used, the monomer (a)
Nonionic surfactants are usually used in an amount of 0.5 to 10 parts by weight, and cationic surfactants are usually used in an amount of 0 to 10 parts by weight, based on 100 parts by weight of (e). From the viewpoints of properties and excellent storage stability of the aqueous dispersion of the copolymer (A), about 1 to 5 parts by weight of a nonionic surfactant and about 0.1 to 5 parts of a positive ionic surfactant are polymerized. It is preferred to use about 0.3 to 3 parts by weight, especially about 0.3 to 3 parts by weight.

Examples of protective colloids that can be used in the present invention include, for example, polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; celluloses such as hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose salts. Derivatives; and natural polysaccharides such as guar gum; and the like. The amount of these protective colloids used is, for example, from the above-mentioned monomers (a) to (b).
An amount of about 0 to about 3 parts by weight with respect to the total 100 parts by weight of (e) can be exemplified.

At the time of emulsion copolymerization, as a polymerization initiator, for example,
Azobis compounds such as 2,2'-azobis- (2-amidinopropane) hydrochloride; t-butyl hydroperoxide,
Organic peroxides such as cumene hydroperioside, p-menthane hydroperoxide and t-butylperoxymaleic acid; hydrogen peroxide; and the like can be used alone or in combination. Among these polymerization initiators, 2,2'-azobis- (2-amidinopropane) hydrochloride and hydrogen peroxide are preferable, and 2,2'-azobis- (2-amidinopropane) hydrochloride is particularly preferable. The amount of the polymerization initiator to be used can be appropriately selected. For example, about 0.05 to 1 part by weight, more preferably about 0.1 to 0.7 part by weight, based on 100 parts by weight of the total of the monomers (a) to (e) used. Department,
Particularly preferably, the amount of use such as about 0.1 to 0.5 part by weight can be exemplified.

In the emulsion copolymerization, a reducing agent can be used in combination, 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, the amount of the reducing agent may be about 0.05 to 1 part by weight based on 100 parts by weight of the total of the monomers (a) to (e). it can.

The polymerization temperature can be appropriately selected, and for example, a temperature of about 40 to 90 ° C can be exemplified. At the time of polymerization, the entire amount of a predetermined surfactant can be added to the reaction system in advance.However, a part of the surfactant is added to the reaction system in advance to start the reaction, and the remainder is continuously added or the intervals are increased during the polymerization. And can be added in portions. In addition, the respective monomers can be added as they are, in a lump, dividedly or continuously, but it is preferable to add them continuously from the viewpoint of reaction control.

In addition to the above-mentioned surfactant and / or protective colloid, polymerization initiator and optionally a reducing agent, a pH regulator, a polymerization degree regulator, an antifoaming agent and the like can be appropriately added during emulsion copolymerization.

The aqueous dispersion of the copolymer (A) thus obtained is not particularly limited, but generally has a solid content of about 10 to 10%.
70% by weight, pH 1-10, viscosity 10000 cps or less (B-type rotational viscometer, 25 ° C, 20 RPM). Due to ease of production and good productivity, about 30-65% by weight solids (particularly about 35-55 % By weight), a pH of 2 to 7 (particularly 3 to 6), and a viscosity of about 50 to 5000 cps. Further, the average particle size is preferably 0.01 to 1 μ, preferably 0.02 to 0.5 μ, and particularly preferably 0.05 to 0.3 μ. The glass transition point (hereinafter sometimes abbreviated as Tg) of the copolymer (A) is generally -60 to + 30 ° C, and the obtained flocking cloth is used for clothing requiring relatively soft feeling. In the case of (a), the temperature is preferably -60 to 0 ° C., and in the case of footwear such as book covers, automobile interior materials, hats, sandals, and wallpapers, building materials, and industrial materials, the temperature is preferably about −40 to + 30 ° C.

In the present invention, the average particle diameter of the aqueous dispersion of the copolymer and the Tg of the copolymer are values measured and determined by the following method.

Average particle size: After diluting the aqueous dispersion of the copolymer 50,000 to 150,000 times with distilled water and thoroughly stirring and mixing, about 10 ml was collected into a 21 mmφ glass cell using a Pasteur pipette. It is set at a predetermined position of a dynamic light scattering photometer DLS-700 (manufactured by Otsuka Electronics Co., Ltd.) and measured under the following measurement conditions.

Measurement conditions Measurement temperature 25 ± 1 ℃ Clock rate 10μsec Correlation channel 512 (Core.Channel) Total number of measurement 200 times Light scattering angle 90 ° Obtain the average particle size by computer processing the obtained measurement result .

The above-mentioned method of measuring the average particle diameter (DLS method) is based on the principle described in “New Experimental Chemistry Course Basic Technology 3 Light (II)”, pages 725 to 741 (edited by The Chemical Society of Japan) (1984 edition). Things.

Glass transition point (Tg): Approximately 10 mg of a sample of the aqueous copolymer dispersion is weighed into 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 dried for 2 hours is used as a measurement sample. Using a SSC-5000 Differential Scanning Calorimeter (manufactured by Seiko Electronics Co., Ltd.), the measurement is determined at a heating rate of 10 ° C./min from −150 ° C.

However, when the binder composition for flocking processing of the present invention contains an organic or inorganic filler, a coloring agent, and the like described below, in addition to the (A) copolymer and the (B) aqueous epoxy compound, After the binder composition is appropriately diluted with ion-exchanged water or the like to reduce the viscosity (for example, about 50 cps or less), and then centrifuged, the filler having a relatively large specific gravity is obtained.
It is possible to separate the copolymer component from the water-soluble component by separating the colorant and the like, and further performing centrifugation.

As described above, the aqueous binder composition for flocking processing of the present invention comprises a copolymer (A) composed of monomers (a) to (e), and an aqueous epoxy resin having at least one oxirane group in one molecule. It comprises the compound (B).

The aqueous epoxy compound (B) is not particularly limited, and does not cause troubles such as poor dispersion and generation of scum when blended with the copolymer (A) to form an aqueous binder composition. Any of these can be used. Examples of such an aqueous epoxy compound include a water-soluble or water-dispersible epoxy compound, and an aqueous solution or dispersion of an epoxy compound. Of these aqueous epoxy compounds, the use of a water-soluble or water-dispersible epoxy compound is preferred. In addition, "water-soluble or water-dispersible" as used herein means that when 5 parts by weight are added to 100 parts by weight of water and stirred and mixed, they do not separate as oil droplets or generate solid matter, This refers to the case where the aqueous solution or the aqueous dispersion is uniform in appearance.

Examples of the water-soluble or water-dispersible epoxy compound suitable for the present invention include, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, Mono-polyalkylene glycol diglycidyl ethers such as dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether; di- or triglycidyl ether of glycerol or a mixture thereof;
Di-, tri- or tetraglycidyl ethers of diglycerol or mixtures thereof, mono-polyglycerol di-polyglycidyl ethers such as polyglycerol polyglycidyl ether; di- or triglycidyl ether of trimethylolpropane or mixtures thereof; For example, di, tri or tetra glycidyl ether of pentaerythritol or a mixture thereof; for example, di, tri, tetra or penta glycidyl ether of sorbitol or a mixture thereof; for example, a di or triglycidyl ester of isocyanuric acid or a mixture thereof For example, diglycidyl adipate; and the like.

These suitable epoxy compounds can be selected from those commercially available under the trade name of Denacol (manufactured by Nagase Kasei Co., Ltd.).

The amount of the aqueous epoxy compound (B) used depends on the amount of the copolymer
The nonvolatile content of the epoxy compound is 0.3 to 50 with respect to 100 parts by weight.
Parts by weight, preferably 0.5 to 20 parts by weight, particularly preferably 1 to
~ 10 parts by weight. Even if the used amount of the aqueous epoxy compound (B) exceeds the upper limit of the used amount range and is too large, the water resistance, alkali resistance, solvent resistance fastness, etc. of the flocking cloth are rather lowered by using the obtained binder composition. On the other hand, if the amount is less than the lower limit, the crosslinking by heat treatment of the obtained binder composition becomes insufficient, and the water resistance, alkali resistance, and solvent fastness of the obtained flocking cloth and However, the adhesive property when using a long hair pile tends to be insufficient, which is not preferable.

The nonvolatile content of the aqueous epoxy compound is JISK-6839
It is measured by the method according to 4.2.

The aqueous binder composition for flocking processing of the present invention is produced by adding and mixing an aqueous epoxy compound (B) to an aqueous dispersion of the copolymer (A), mixing the mixture by an appropriate means, and uniformly dispersing the mixture. Can be.

The timing of the above-mentioned addition and blending is not necessarily limited, and should be appropriately determined according to the type and amount of the functional group in the copolymer (A) and the effect of the water-soluble salt described later. Since the oxirane group of (B) is hydrolyzed in an aqueous solvent and its activity may be reduced,
Usually, it is better to be within 24 hours from the time of using the binder composition.

In order to suppress the decrease in the activity of the aqueous epoxy compound (B) in the aqueous solvent and improve the stability of the aqueous epoxy compound, it is preferable to add a water-soluble salt whose aqueous solution is weakly acidic. It is valid.

Examples of the above water-soluble salts include strong acid weak base salts such as ammonium sulfate, ammonium chloride, and ammonium nitrate; sodium hydrogen sulfate, potassium hydrogen sulfate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, potassium monohydrogen phosphate, phosphorus Strong base hydrogen salts of inorganic acids such as potassium dihydrogen acid; for example, ammonium dihydrogen citrate, sodium dihydrogen citrate, potassium dihydrogen citrate, sodium hydrogen tartrate, potassium hydrogen tartrate, sodium hydrogen phthalate, hydrogen phthalate Strong base hydrogen salts of organic acids such as potassium; zinc acetate; and the like. These salts may be used alone or in combination of two or more.If necessary, for example, a base such as sodium hydroxide, potassium hydroxide, ammonium water, or, for example, hydrochloric acid, sulfuric acid , Phosphoric acid, acetic acid, tartaric acid, citric acid, etc., to adjust the pH of the aqueous binder composition to 2
To 7, preferably 3 to 6.

The amount of the water-soluble salt to be used is generally 0 to 5 parts by weight based on 100 parts by weight of the copolymer, and is preferably 0.
It is preferably from 05 to 2 parts by weight, especially from 0.4 to 1.5 parts by weight.

The binder composition of the present invention comprises the component (A),
(B) In addition to the component and the water-soluble salt, if necessary, for example,
Thickeners such as polyvinyl alcohol type, cellulose derivative type, polyacrylic acid type and surfactant type; for example, inorganic fillers such as clay, talc, calcium carbonate, aluminum hydroxide, glass powder, asbestos; titanium oxide, carbon Organic or inorganic colorants such as black and phthalocyanine blue; antioxidants, preservatives, ultraviolet absorbers and the like can be added.

The thus obtained aqueous binder composition for flocking processing of the present invention is thickened if necessary, for example, roll coating, kiss coating, doctor blade coating, gravure coating, fiber coating or the like by an appropriate coating direction such as spray coating. It is applied on the base cloth. Next, the base fabric coated with the binder composition is immediately planted with a pile of about 0.5 to 80 d and a length of about 0.3 to 10 mm under an electrostatic voltage of about 1 to 100,000 volts, and a drying oven of about 80 to 180 ° C. After drying and curing, the excess pile is removed to form a flocked cloth. The obtained flocking cloth becomes a product after post-treatment such as alkali treatment as necessary.

Examples of the base fabric include natural fibers such as cotton, pulp, wool, and silk; regenerated or semi-synthetic fibers such as viscose rayon, cuprammonium rayon, and saponified acetate rayon; polyamides and polyesters (Polyester terephthalate), polyurethane, polyurea, polyolefin, polystyrene,
A woven fabric, a knitted fabric, a nonwoven fabric, a felt, a natural or synthetic paper, and the like comprising one or more kinds of synthetic fibers such as polyvinyl chloride, polyacrylonitrile, and polyvinyl alcohol can be given. Further, the aqueous binder composition of the present invention, in addition to the base fabric, for example, natural rubber, butadiene / styrene rubber, butadiene / acrylonitrile rubber, butadiene / methyl methacrylate rubber, isoprene rubber, acrylic rubber, silicone rubber, fluorine rubber, etc. Films, sheets, plates and molded articles of rubbers such as cellulose acetate, polyamide, polyester (polyester terephthalate), polyolefin, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, and poly Films, sheets, plates and molded products of thermoplastic resins such as (meth) acrylates and polyvinyl acetates; for example, thermosetting of phenolic resins, urea resins, melamine resins, unsaturated polyester resins, epoxy resins, silicone resins, etc. Resin DOO, plate, composition; for example, iron, copper, metal or alloy plate, such as aluminum extrusions; can be used as the flocking binders to substrates such.

As the pile, those produced from the above natural, regenerated, semi-synthetic or synthetic fibers can be used, for example,
Cotton, rayon (viscose rayon), polyamide,
Acrylic (polyacrylonitrile) and polyester fibers can be suitably used.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Reference Examples. In addition, the test method in an Example and a comparative example is as follows.

(1) Film test (1-1) Preparation of film The aqueous binder composition was applied to a release paper held horizontally by a doctor blade to a thickness of about 200 µm when wet using a doctor blade, and allowed to stand at 25 ° C for about 30 minutes. After being placed and semi-dried, it is dried in a hot air drier at 100 ° C. for 1 minute, and then cured by heating at 140 ° C. for 10 minutes.

(1-2) Breaking strength, elongation at break and 100% modulus A cellophane tape is attached to the surface of the film prepared in (1-1) in parallel with two rows at intervals of 10 mm to reinforce the film, The cellophane tape is cut at 10 mm intervals in a direction perpendicular to the longitudinal direction to obtain a test piece. The tensile test is performed in a constant temperature and humidity room at 20 ° C. and 65% RH using a self-recording tensile tester [Tensilon UTM-4: Toyo Baldwin Co., Ltd.].

Fix the test piece with the cellophane tape sticking reinforcement part with the knob jig of the tensile tester, attach it with no stress in the vertical direction with a space of 10 mm for the film part to be subjected to the tensile test, pulling speed 100 mm / min And pull until film cutting.
The stress at 100% elongation, the stress at break, and the elongation at break of the film are read from the automatic recording paper, and the breaking strength, the elongation at break, and the 100% modulus are determined according to the following formulas.
The numerical value is the average value of the results of five test pieces.

(1-3) Film swelling ratio The film prepared in (1-1) was cut into a size of 30 × 30 mm to prepare a test piece, immersed in each liquid at room temperature of 25 ° C. for a predetermined time, and the area swelling ratio Ask for.

(2) Polyester film adhesion test The aqueous binder composition was applied on a 25 µm thick polyethylene terephthalate (PET) film to a thickness of about 500 µm when wet, and immediately with a cotton cloth (cotton broad # 40). And pre-dried in a dryer at 100 ° C. for 10 minutes. Next, the pre-dried product is subjected to a thermal crosslinking treatment at 140 ° C. for 10 minutes.

Five strips each having a width of 25 mm and a length of 13 cm are sampled from the laminate of the PET film thus obtained and the cotton cloth, and the strips are used as test pieces.

The above five test pieces were subjected to constant temperature and humidity conditions of 20 ° C and 65% RH.
After holding for 16 hours and adjusting the condition, a 180 ° peel test was performed on five test pieces using a tensile tester under the conditions of constant temperature and humidity and a tensile speed of 300 mm / min. Force (g / 25mm).

(3) Test for flocking physical properties (3-1) Preparation of flocking cloth Approximately 5000 to 10000 cps (Type B rotational viscometer, 25 ° C, 20 RPM)
The thickened aqueous binder composition is applied to a base cloth fixed horizontally on a stainless steel plate to a thickness of about 200 μm when wet.

On the other hand, on the horizontal iron electrode plate of the up type flocking tester,
A predetermined pile is scattered, and a stainless steel plate on which the base material coated with the above adhesive is fixed is placed horizontally on the insulators placed at the four corners with the adhesive coated side down, and the cotton on the stainless steel plate is removed. Ground. Next, the pressure was increased by the high static voltage generator.
A static voltage of 30 KV is applied between the stainless steel plate and the iron electrode plate, and the hair is implanted for 15 seconds.

Next, the planted base cloth is placed on cardboard and placed in a dryer.
After preliminary drying at 80 ° C. for 10 minutes, a thermal crosslinking treatment is carried out at 140 ° C. for 10 minutes, and further, this is brushed under suction to remove excess pile to obtain a test flocking cloth.

(3-2) Dry fastness test A strip of 20 mm in width and 50 mm in length is cut out from the flocking cloth obtained in the above section (3-1) to obtain a test piece. The five test pieces were maintained in a constant temperature and humidity condition of 20 ° C. and 65% RH for 16 hours to adjust the condition, and then subjected to a JIS L-10 using a Gakushin-type dyeing fastness tester.
84 [Flocking strength, A method A-1 (edge method) (b) (45)
R method)]. The test was performed using the 45R edge method, and the residual hair ratio of the test piece after 500 times of vibration was measured by visual observation. (Percentage of remaining hair 100%) is evaluated.

(3-3) Water fastness test Using the same tester as in the above section (3-2),
Perform according to the test method described in 2). However, the wet test is performed after immersing the five test pieces in tap water at approximately 25 ° C. for 15 minutes.

(3-4) Alkali resistance fastness test Using the same tester as in the above section (3-2),
Perform according to the test method described in 2). However, five test pieces
After immersion in a 20% by weight aqueous sodium hydroxide solution at about 25 ° C for 15 minutes, a wet test is performed.

(3-5) Solvent fastness test Using the same tester as in the above section (3-2),
Perform according to the test method described in 2). However, five test pieces
After immersion in perclene at about 25 ° C for 15 minutes, the wet test is performed.

(3-6) Scratch test of alkali resistance The flocking cloth obtained in the above (3-1) was immersed in a 20% by weight aqueous sodium hydroxide solution at about 25 ° C for 15 minutes, washed with water, and moistened the flocking cotton. Scratch with a nail and evaluate from that state.

Evaluation:…: The pile and the binder layer hardly peel off.

Δ: peeling of pile only ×: peeling from binder layer (3-7) Pile adhesion test (short hair) Two-pack epoxy adhesive on flocking cotton of flocking cloth obtained in (3-1) [ R-990: Dainippon Shikizai Kogyo Co., Ltd.], then apply the same cotton cloth as used in the previous item (2), roll-press it, cure for 24 hours, cut out to 20 mm width, Using a tensile tester similar to that used in 1-2), the 180 ° peel strength is measured at a peel speed of 300 mm / min.

(3-8) Pile Adhesion Test (Long Hair) The pile is picked up with a finger from a flocking cloth on which a long pile is planted, and the pile is evaluated based on the resistance at that time.

Normal: The flocking is tested dry.

Water resistance: Test after immersing the flocking cloth in deionized water at about 25 ° C for 15 minutes.

Evaluation: ○: Strong resistance and difficult to pull out pile.

 Δ: There is resistance, but the pile is pulled out.

×: The pile is pulled out without resistance. The binder layer is also easily peeled.

Reference Example 1 520 ml of deionized water was placed in a 2-liter separable flask equipped with a stirrer, a temperature controller, a nitrogen inlet tube, and a metered addition device.
Was added, the internal temperature was controlled at 78 ° C., and the atmosphere was sufficiently replaced with nitrogen.

Next, 200 ml of deionized water was placed in one flask, and alkylbenzyldimethylammonium chloride was used as an emulsifier.
50% by weight aqueous solution [Sanisol B-50: Kao Soap Co., Ltd.] 7.2
g, polyoxyethylene nonylphenol ether [H-3
305: Daiichi Kogyo Seiyaku Co., Ltd.] 12 g, 80% by weight aqueous solution of methacryloyloxyethyltrimethylammonium chloride as monomer (b) [Acryester DMC: Mitsubishi Rayon Co., Ltd.] 30 g and monomer (c) Acrylamide (A
AM) was added, and mixed with stirring to dissolve to obtain an aqueous solution. A mixture of 426 g of butyl acrylate (BA), 108 g of methyl methacrylate (MMA) [monomer (a)] and 30 g of 2-hydroxyethyl methacrylate (2HEMA) [monomer (d)] was added to this aqueous solution, followed by stirring and emulsification. Then, a monomer premix was obtained. As the polymerization initiator aqueous solution, a 3% by weight aqueous solution of 2,2'-azobis- (2-amidinopropane) hydrochloride was used. The emulsion copolymerization reaction was performed by sequentially adding the monomer premix and the aqueous solution of the polymerization initiator while maintaining the internal temperature at 78 ° C. The obtained aqueous dispersion of the copolymer had a solid content of about 42% by weight, a pH of 4.7, a viscosity of 290 cps (B-type rotational viscometer, 25 ° C., 20 RPM) and an average particle diameter of about 0.21 μm. The Tg of the copolymer was -24 ° C.

Reference Examples 2-3 and Comparative Reference Example 1 In Reference Example 1, the amount of methacryloyloxyethyltrimethylammonium chloride was changed, or
Without using this, and the Tg of the resulting copolymer is −24 to −
An aqueous dispersion of the copolymer was obtained in the same manner except that the amounts of BA and MMA used were adjusted to 25 ° C. Table 1 shows the composition of the monomers used and various physical properties of the obtained aqueous dispersion.

Reference Examples 4 to 5 and Comparative Reference Example 2 In Reference Example 1, the amount of AAM used was changed or not used, and the Tg of the obtained copolymer was −24 to −25.
An aqueous dispersion of a copolymer was obtained in the same manner except that the amounts of BA and MMA used were adjusted so that the temperature became ° C. Table 1 shows the composition of the monomers used and various physical properties of the obtained aqueous dispersion.

Reference Examples 6 to 7 and Comparative Reference Example 3 In Reference Example 1, the amount of 2HEMA used was changed, or
Without using this, and the Tg of the resulting copolymer is −24 to −
An aqueous dispersion of the copolymer was obtained in the same manner except that the amounts of BA and MMA used were adjusted to 25 ° C. Table 1 shows the composition of the monomers used and various physical properties of the obtained aqueous dispersion.

Reference Examples 8 to 10 An aqueous dispersion of a copolymer was obtained in the same manner as in Reference Example 1, except that the Tg of the obtained copolymer was changed by changing the use ratio of BA and MMA. Table 1 shows the composition of the monomers used and various physical properties of the obtained aqueous dispersion.

Reference Examples 11 to 14 In Reference Example 1, EA was used instead of BA, or glycidyl methacrylate (GMA) was used as the monomer (e).
Using styrene (St) or acrylonitrile (AN),
In addition, an aqueous dispersion of the copolymer was obtained in the same manner except that the amount of the angular monomer was adjusted so that the Tg of the obtained copolymer was about 0 ° C. Table 1 shows the composition of the monomers used and various physical properties of the obtained aqueous dispersion.

Comparative Reference Example 4 In the same apparatus as in Reference Example 1, 520 ml of deionized water was added, the internal temperature was controlled at 78 ° C., and the atmosphere was sufficiently replaced with nitrogen.

Next, 290 ml of deionized water per flask, 7.6 g of polyoxyethylene nonylphenol ether sulfate ammonium salt [Hytenol No. 8: Daiichi Kogyo Seiyaku Co., Ltd.] as an emulsifier, 23 g of polyoxyethylene nonyl phenol ether [H-3305], 12 g of itaconic acid, 12 g of N-methylolacrylamide and 12 g of AAM were added, mixed with stirring and dissolved to obtain an aqueous solution. A mixture of 444 g of BA, 102 g of MMA and 18 g of acrylic acid was added to this aqueous solution, and the mixture was emulsified with stirring to obtain a monomer premix. In addition, a 3% by weight aqueous solution of ammonium persulfate was used as the polymerization initiator aqueous solution. Thereafter, an emulsion copolymerization reaction was carried out in the same manner as in Reference Example 1, and the solid content was about 42% by weight.
An aqueous anionic copolymer dispersion having a pH of 2.2, a viscosity of 70 cps, and an average particle diameter of about 0.15 μ was obtained. The Tg of the copolymer was −24 ° C.

Example 1 2.1 parts by weight of sorbitol polyglycidyl ether [Denacol EX-614: Nagase Kasei Co., Ltd.] as a water-soluble epoxy compound per 100 parts by weight of the aqueous dispersion of the copolymer obtained in Reference Example 1 About 5 parts by weight per 100 parts by weight of the union was added, and a uniform aqueous binder composition for flocking was obtained by using this composition. A force test was performed, and the test results are shown in Table 2.

Next, the above composition was thickened to about 8000 cps (B-type rotational viscometer, 25 ° C., 20 RPM) with a surfactant-based thickener [Bissurf S: Kao Soap Co., Ltd.] The test was performed according to the test method. The pile used was rayon short hair 1.
Polyamide taffeta was used for the base cloth, which was 5d, 0.7 mm and had a long hair of 1.5 d of polyamide and 3 mm long. The test results are shown in Table 2.

Examples 2-3 and Comparative Example 1 An aqueous binder composition was prepared in the same manner as in Example 1, except that the amount of the water-soluble epoxy compound used was changed or not used. Thereafter, a film test and a polyester film adhesion test were performed in the same manner as in Example 1.
In addition, this composition was prepared in the same manner as in Example 1 at about 5000 to 10000 cps.
And a flocking property test was performed. Table 2 shows the amount of the water-soluble epoxy compound used and the results of the various tests obtained.

Examples 4 to 16 and Comparative Examples 2 to 5 In Example 1, instead of using the aqueous dispersion of the copolymer of Reference Example 1, Reference Examples 2 to 10 or Comparative Reference Examples 1 to 4
An aqueous binder composition was prepared in the same manner as in Example 1 except that any one of the above was used, and a film test, a polyester film adhesion test, and a flocking test were performed in the same manner. Table 2 shows the types of copolymers used and the results of the various tests obtained.

Claims (1)

(57) [Claims] (A) (A) General formula CH ₂ CRCR ¹ —COOR ² (wherein R ¹ represents H or CH ₃ , R ² is a C ₁ -C ₁₂ linear or branched alkyl group) Acrylic acid or methacrylic acid ester monomer represented by 10 to 98.3% by weight, (b) a tertiary or quaternary ammonium-based monomer having a group capable of forming a cationic group, 0.5 to 10% by weight, (iii) the general formula CH ₂ = CR ¹ -CONHR ³ (wherein, R ¹ represents H or CH _3, R ³ represents H or ^{_{CH 2 O-R 4, R}} 4 is H or C ₁ -C 0.2 to 10% by weight of a monomer represented by the formula ( ₄ ) representing a linear or branched alkyl group: (d) a general formula CH ₂ = CR ¹ -CONHR ⁵ (wherein R ¹ is H or CH ₃ ) Where R ⁵ is at least one O
₁ to 20% by weight of a C _{1 to} C ₈ linear or branched alkyl group substituted with an H group), and (e) the monomers (a) to (d) ) Is a monomer copolymerizable with
100 parts by weight of a copolymer composed of 0 to 50% by weight of monomers other than the monomers (a) to (d); and (B) an aqueous epoxy compound having at least one oxirane group in one molecule A cationic aqueous binder composition for flocking comprising 0.3 to 50 parts by weight (as a non-volatile content).