JPH05195437A - Treating agent for synthetic fiber - Google Patents

Abstract

PURPOSE:To obtain the subject treating agent capable of simultaneously imparting excellent feeling and flame-retardancy to a synthetic fiber by compounding a specific reactive organosiloxane with a specific reactive silane compound and aluminum hydroxide surface-coated with a specific siloxane at specific ratios. CONSTITUTION:The objective synthetic fiber treating agent capable of imparting softness and smoothness to synthetic fiber is produced by compounding (A) 100 pts.wt. of an organopolysiloxane containing two or more organic groups consisting of two or more kinds of groups selected from amino group, epoxy group and silanol group, etc., and directly bonded to silicon atom in the molecule, (B) aluminum hydroxide surface-coated with 10-50 pts.wt. of an organopolysiloxane produced by the condensation reaction of a silane compound having two or more silanol groups, etc., and an organic group containing amino group in the molecule and (C) 2-30 pts.wt. of a silane compound having two or more silanol groups, etc., and an organic group containing amino group in the molecule. The treating agent can impart sufficient flame-retardancy as well to the fiber in contrast with conventional treating agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic fiber treating agent (hereinafter simply referred to as a treating agent). Various treating agents containing organopolysiloxane as a main component have been used for the purpose of imparting flexibility and smoothness to synthetic fibers. Particularly in recent years, a treatment agent containing an organopolysiloxane as a main component has been frequently used for the purpose of finishing rough synthetic fibers to have an excellent texture equivalent to that of natural materials such as feathers and animal hair. The present invention relates to improvements in such treating agents.

[0002]

2. Description of the Related Art Conventionally, as a treating agent containing an organopolysiloxane as a main component, a reactive organopolysiloxane is used in combination with another reactive organopolysiloxane or a reactive silane compound, and both are reacted on the fiber surface. Is proposed. For this purpose, for example, an example utilizing the reaction of an amino group and an epoxy group (Japanese Patent Publication No. Sho 48-17514, JP-A No. 52-81197) and an example utilizing the reaction of an amino group, an epoxy group and a silanol group (JP-A No. 59-59). -14468
3, JP-A-63-75184), examples utilizing the reaction of amino group and silanol group (JP-A-50-77700, JP-A-49-133698, JP-A-60-65182),
Example of utilizing reaction of hydrogen directly bonded to amino group, silanol group and silicon (JP-A-61-296183, US Pat.
P-3846506), an example utilizing the reaction of carbon-carbon double bond and hydrogen directly bonded to silicon (JP-A-57-
165069) and so on. However, these conventional treatment agents have the disadvantage that the synthetic fibers treated with the treatment agent have an excellent texture, but on the other hand, they are much more easily burned than those without treatment.

[0003] Therefore, conventionally, as a treating agent for improving the above-mentioned drawback that it becomes easy to burn, there has been proposed a combination of an organopolysiloxane with a flame retardant. For this, for example, an alkylenediamine derivative or the like (JP-A-57-61777), a boron-based compound or the like (JP-A-63-145484), a platinum compound (JP-A-3-161574) or the like is used. There is. However,
These conventional treating agents are not sufficient to make the synthetic fibers both texture-providing and flame-retarding at the same time, or, in reality, the treating agents are insoluble or hardly dispersible in water. It has the drawback of not being applicable.

[0004]

The problem to be solved by the present invention is that the conventional treating agents cannot simultaneously impart texture and flame retardancy and lack practicality. ..

[0005]

However, the present inventors have
As a result of intensive research to solve the above problems, a treatment in which a specific reactive organopolysiloxane is used in combination with aluminum hydroxide particles surface-coated with the specific reactive organopolysiloxane and a specific reactive silane compound in predetermined proportions, respectively It has been found that the agent is correct and suitable.

That is, in the present invention, the following components A, B and C are added to components B10 to B to 100 parts by weight of component A.
The treatment agent is characterized by containing 50 parts by weight and 2 to 30 parts by weight of the component C.

Component A: Organopolysiloxane having two or more one or two or more selected from the organic groups 1) to 3) or silanol groups shown below as an organic group directly bonded to a silicon atom in a molecule. ) Amino group-containing organic group 2) Epoxy group-containing organic group 3) Silanol group or organic group that produces a silanol group by hydrolysis

Component B: Surface-coated with an organopolysiloxane obtained by a condensation reaction of a silane compound having an organic group containing an amino group in the molecule and two or more silanol groups or an organic group which produces a silanol group by hydrolysis. Aluminum hydroxide particles

Component C: a silane compound having an organic group containing an amino group in the molecule and two or more silanol groups or an organic group which produces a silanol group by hydrolysis.

In the component A, as the organic group containing an amino group directly bonded to a silicon atom, 1) 3-aminopropyl group, 3-amino-2-methyl-propyl group, 2-
Primary aminoalkyl group such as aminoethyl group, 2) N-
(2-Aminoethyl) -3-aminopropyl group, N-
Examples thereof include organic groups having primary and secondary amino groups such as (2-aminoethyl) -2-aminoethyl group.

In the component A, the organic group containing an epoxy group directly bonded to a silicon atom includes 1) γ-glycidoxypropyl group, β-glycidoxyethyl group, γ
-Glycidoxyalkyl groups such as glycidoxy-β-methyl-propyl group and 2) glycidoxycarbonylalkyl groups such as 2-glycidoxycarbonyl-ethyl group and 2-glycidoxycarbonyl-propyl group.

Further, in the component A, as the organic group directly bonded to a silicon atom and producing a silanol group by hydrolysis, 1) a methoxy group, an ethoxy group, a butoxy group,
Alkoxy group such as 2-ethylhexyloxy group, 2) Alkoxy-β-ethoxy group such as methoxy-β-ethoxy group, ethoxy-β-ethoxy group, butoxy-β-ethoxy group, 3) Acetoxy group, propoxy group, etc. Acyloxy group, 4) N-alkylamino group such as methylamino group, ethylamino group and butylamino group, 5) N, N-dialkylamino group such as dimethylamino group and diethylamino group, 6) imidazole group and pyrrole group And a nitrogen-containing heterocyclic group.

The component A used in the present invention comprises two or more, preferably 2 to 8, more preferably 2 to 5, one or more selected from the above-mentioned organic groups or silanol groups in the molecule. Organopolysiloxane having a number of the above, and the organopolysiloxane has a structure in which a part of polydimethylsiloxane is substituted with the organic group or silanol group as described above. Among such organopolysiloxanes, the viscosity at 25 ° C. is 50
It is preferable to use a liquid at 0 cst or more and at room temperature.

The organopolysiloxane of component A can be obtained by polycondensation of a mixture of corresponding monomers according to a conventional method, but a commercially available product can be used as it is. Examples of such commercially available products having an organic group containing an amino group include TSF4700, TSF4701,
TSF4702 (all trade names, manufactured by Toshiba Silicone Co., Ltd.), SF8417 (trade name, manufactured by Toray Dow Corning Co., Ltd.), PORON MF-14D, PORON MF-14E (both trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), FZ-3705, FZ-3
38 (all are trade names, manufactured by Nippon Unicar Co., Ltd.) and the like. Further, as an example having an organic group containing an epoxy group,
TSF4730, YF3965 (both trade names, manufactured by Toshiba Silicone Co., Ltd.), SF8411, SF8413 (both trade names, manufactured by Toray Dow Corning Co., Ltd.), Poron MF-
11B, Poron MF-11C, Poron MF-18 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), LE-9300, FZ-
315, TE-24 (all are trade names, manufactured by Nippon Unicar Co., Ltd.) and the like. Furthermore, as examples having a silanol group or an organic group that generates a silanol group by hydrolysis, XF3905, YF3800, YF3807 (all are trade names, manufactured by Toshiba Silicone Co., Ltd.), SF8427,
SF8428 (both are trade names, manufactured by Toray Dow Corning), KF-6001, KF-6003 (both are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Poron MF-17, Poron MF-
32, PORON MF-34 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), FZ-132 (trade name, manufactured by Nippon Unicar Co., Ltd.) and the like.

Component B used in the present invention is an organoorganic compound obtained by polycondensation reaction of a silane compound having an organic group containing an amino group in the molecule and two or more silanol groups or an organic group which produces a silanol group by hydrolysis. The aluminum hydroxide particles are surface-coated with polysiloxane.

In Component B, silane compounds for obtaining organopolysiloxane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane and γ-aminopropyltri (β). -Ethoxyethoxy)
Silane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ
Examples thereof include silane compounds having an organic group containing a primary or secondary aliphatic amino group such as aminopropylmethyldimethoxysilane. The aluminum hydroxide surface-coated with the organopolysiloxane obtained by subjecting these silane compounds to condensation reaction is not particularly limited as long as it is in powder form, but preferably has an average particle size of 5 μm or less, and 2 μm.
The following are more preferable. As such aluminum hydroxide, fine aluminum hydroxide C-301 (1.
0), fine aluminum hydroxide C-303 (2.5),
Fine aluminum hydroxide C-3005 (0.5) (all trade names, manufactured by Sumitomo Chemical Co., Ltd., average particle diameter in parentheses, the same in the following parentheses}, Hydilite H-32
Commercially available products such as (3.5), Heidilite H-42 (1.0), Heidilite H-43 (0.6) (all are trade names, manufactured by Showa Light Metal Co., Ltd.) can be used as they are.

Component B is obtained by adding a silane compound to an aqueous dispersion of aluminum hydroxide, and hydrolyzing and polycondensing the silane compound on the surface of the aluminum hydroxide. In this case, the amount of the silane compound used is preferably 0.5 to 10% by weight with respect to the aluminum hydroxide in terms of the stability of the resulting aqueous dispersion of the component B and the like.
More preferably, it is 1 to 8% by weight. For the same reason, a method of using an anionic surfactant as a dispersant or a method of using an anionic surfactant and a nonionic surfactant in combination is useful.

Component C used in the present invention is a silane compound having an organic group containing an amino group in the molecule and two or more silanol groups or an organic group which produces a silanol group by hydrolysis. As the component B, the same silane compounds as described above can be used.

The treating agent of the present invention comprises the component A described above,
Ingredient B and ingredient C are 10 to 50 parts by weight, preferably 15 to 40 parts by weight, with respect to 100 parts by weight of ingredient A.
And component C in an amount of 2 to 30 parts by weight, preferably 5 to 25 parts by weight. The ratio of each component is Component A / Component B / Component C = 100/10 to 50/2 to 30
When the amount is out of the range of (parts by weight), it is impossible to achieve both the desired excellent texture and sufficient flame retardancy.

Examples of the synthetic fibers to which the treatment agent of the present invention is applied include polyester fibers, polyamide fibers, polyacrylonitrile fibers, polypropylene fibers, and composite fibers thereof. Among them, polyester-based synthetic fibers are used. The present invention exerts a remarkable effect. Examples of such polyester synthetic fibers include polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate fiber, polyethylene terephthalate / polyethylene isophthalate fiber, polyethylene terephthalate / polybutylene terephthalate fiber, and various other single units for various purposes. Modified polyester fibers such as basic or acid dyeable polyester fibers obtained by copolymerizing the body, antistatic polyester fibers, flame-retardant polyester fibers and the like can be mentioned.

When the treating agent of the present invention is applied to synthetic fibers, it is preferable to use each component by dispersing or emulsifying it in water. At this time, each component is added so as to have the ratio described above. The application method may be any of a dipping method, a spray method, a roller touch method and the like, and the application time may be either a synthetic fiber manufacturing step or a processing step.

The treatment agent of the present invention is
It is preferable that the total amount of the component, the component B, and the component C be 0.05 to 1% by weight, and 0.1 to 0.
It is more preferable to add 7% by weight. It is also useful to heat treat the synthetic fibers after application. The heat treatment can be performed using a drying process. The heat treatment condition is usually 110 to 170 ° C. for 5 to 30 minutes, preferably 120 to 150 ° C. for 5 to 20 minutes.

When the treating agent of the present invention is applied to synthetic fibers, other agents can be used in combination within the range where the effect of the present invention is not impaired. Examples of such other agents include antistatic agents, water absorption imparting agents, water repellents, antioxidants, ultraviolet absorbers, preservatives and the like.

[0024]

【Example】

Test Category 1-Preparation of component B-1 and its evaluation Aluminum hydroxide (fine aluminum hydroxide C-30
05, average particle diameter 0.5 μm, manufactured by Sumitomo Chemical Co., Ltd.) 70
g, potassium lauryl phosphate salt as a dispersant 1
7.5 g and 180 g of water were charged into a stainless steel container, 300 g of glass beads having a diameter of 0.8 mm was added thereto, and a wet dispersion machine (sand grinder manufactured by IMEX Co., Ltd., 4T) was added.
SG-1 / 4 type) at room temperature for 12 hours, 150
Dispersed at 0 rpm. The contents were taken out and the glass beads were removed with a 60-mesh wire net to obtain an aqueous dispersion of aluminum hydroxide. The stability of this aluminum hydroxide aqueous dispersion was evaluated as follows.

200 g of the aqueous dispersion of aluminum hydroxide obtained above and 1.3 g of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane were charged in a reaction vessel and reacted at 60 ° C. for 2 hours while stirring. Thus, an aqueous dispersion of the component B-1 in which the surface of aluminum hydroxide was coated with the organopolysiloxane was obtained. The stability of the aqueous dispersion of this component B-1 was evaluated as follows.

Evaluation of stability 100 ml of the aqueous dispersion was placed in a 100 ml glass cylinder and allowed to stand, and the state after 7 days was visually observed and evaluated according to the following criteria. ⊚: No sediment is observed ○: Slight sediment is observed Δ: Separation of the aqueous layer in the sediment and / or the upper layer ×: Remarkable sedimentation and / or separation of the aqueous layer in the upper layer Is recognized

Components B-2 to B-9 and components R-1 and R
-2 and its evaluation, components B-2 to B-9
And an aqueous dispersion of components R-1 and R-2 were obtained. Component B-1
-B-9 and the contents of the aqueous dispersions of components R-1 and R-2, the stability thereof, and the stability of the aqueous dispersions of the aluminum hydroxides obtained in the intermediate are summarized in Table 1.

[0028]

[Table 1]

In Table 1, numerical values in parentheses in the column of aluminum hydroxide: average particle size (μm) SA-1: potassium lauryl phosphate salt SA-2: calcium dodecylbenzenesulfonate salt SA-3: polyoxyethylene (6 mol) Nonylphenyl ether Si-1: N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane Si-2: γ-aminopropylmethyldimethoxysilane Si-3: γ-aminopropyltrimethoxysilane * 1: Stability of an aqueous dispersion of aluminum hydroxide obtained in the middle * 2: Stability of an aqueous dispersion of components B-1 to B-9, R-1 and R-2

Test Category 2 ・ Examples 1 to 13 and Comparative Examples 1 to 10 Using the treating agents having the compositions shown in Tables 2 and 3, the total concentration of components A to D was adjusted to 1% by weight. The treatment liquid was adjusted. This treatment liquid was applied to polyester cotton (6 denier,
64 mm) 20 g was sprayed with oil so that the total amount of the components A to D deposited was 0.3% by weight. Then, using a hot air drier, after drying at 80 ° C. for 90 minutes, heat treatment was further performed at 150 ° C. for 30 minutes to obtain sample cotton. The sample cotton obtained here was evaluated for flame retardancy and texture as follows. The results are summarized in Tables 2 and 3.

..Evaluation of flame retardance A test piece measuring 14 cm × 3 cm and weighing 1.5 g was taken from the cotton sample, and the test piece was placed vertically in a room in which air was kept quiet. , Held its top. Then, a flame having a height of 3 cm was exposed to the test piece for 3 seconds from a fire source arranged 1 cm below the lower end of the test piece. The state of the test piece at the time when the flame burned out was visually observed and evaluated according to the following criteria. ⊚: Only melted but not ignited ○: 1/4 or less of the test piece burned △: 1/4 to 2/3 of the test piece burned ×: 2/3 or more of the test piece burned, Some unburned parts remained XX; the test piece was completely burned

.. Evaluation of texture The sample cotton was subjected to a sensory test by touch by five judges and evaluated according to the following criteria. ⊚: Very good softness smoothness ○: Good softness smoothness △: Slightly poor softness smoothness ×: Remarkably poor softness smoothness

[0033]

[Table 2]

[0034]

[Table 3]

In Tables 2 and 3, numerical values in the columns of components A to D; parts by weight A-1; having an average of 2.7 γ-aminopropyl groups in the molecule and having a viscosity of 850 cst at 25 ° C. Polydimethylsiloxane derivative A-2; having an average of 1.8 γ-aminopropyl groups and 2.0 methoxy groups in the molecule and having a viscosity of 120 at 25 ° C.
0 cst polydimethylsiloxane derivative A-3; polydimethylsiloxane derivative A-4 having an average of 3.1 γ-glycidoxypropyl groups in the molecule and a viscosity of 7500 cst at 25 ° C. A-4; Polydimethylsiloxane derivative A-5 having 5 γ-glycidoxypropyl groups and 2.0 methoxy groups and having a viscosity of 13000 cst at 25 ° C .; an average of 2.1 silanol groups in the molecule. Have,
Polydimethylsiloxane derivatives having a viscosity of 13000 cst at 25 ° C B-1 to B-9; those prepared in Test Category C-1; N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane C-2; γ-aminopropyltrimethoxysilane D-1; having an average of 3.4 vinyl groups in the molecule, 25
Polydimethylsiloxane derivative having a viscosity at 15000 cst of 15000 c-2; R-1 obtained in test category 1 D-3; R-2 D-4 obtained in test category 1; γ-glycidoxypropyltrimethoxysilane B / A; parts by weight of component B with respect to 100 parts by weight of component A C / A; parts by weight of component C with respect to 100 parts by weight of component A

[0036]

As is apparent from the above, the present invention described above has an effect that both excellent texture and sufficient flame retardancy can be imparted to the synthetic fiber at the same time, and that the synthetic fiber has practical utility. ..

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 83/00 LRU 8319-4J D06M 11/45 15/643 D06M 15/643

Claims (1)

[Claims] 1. A composition comprising the following components A, B and C in a proportion of 10 to 50 parts by weight of component B and 2 to 30 parts by weight of component C relative to 100 parts by weight of component A. Textile treatment agent. Component A: Organopolysiloxane having 2 or more of one or two or more selected from organic groups of 1) to 3) or silanol groups as organic groups directly bonded to silicon atoms in a molecule 1) amino group An organic group containing 2) an organic group containing an epoxy group 3) a silanol group or an organic group that produces a silanol group by hydrolysis Component B: an organic group containing an amino group in the molecule and two or more silanol groups or by hydrolysis Aluminum hydroxide particles surface-coated with an organopolysiloxane obtained by a condensation reaction of a silane compound having an organic group that forms a silanol group Component C: An organic group containing an amino group in the molecule and two or more silanol groups or water Silane compounds having organic groups that generate silanol groups by decomposition