JPH04136278A - Base cloth-treating agent composition and canopy material for paraglider using the same - Google Patents

Abstract

PURPOSE:To obtain the subject composition imparting water repellency, waterproofing property and filling property, etc., having excellent consistency to fiber base cloths, comprising an organosilazane siloxane polymer containing a siloxane unit and a silazane unit in a constant ratio and an organic solvent. CONSTITUTION:An organosilazane siloxane polymer having, in the molecule, the units expressed by formula I and formula II (R<1> to R<3> are H or same or different species of non-substituted or substituted monofunctional hydrocarbon; (a) is 1, 2 or 3; (b) is 1 or 2) in a range of 5-50mol% the former and 50-95mol% the latter is mixed with an organic solvent (e.g. dichloroethane, trichloroethane or methylene chloride) and conditioned, and then applied to a fiber base cloth such as nylon or polyester to afford a base cloth-treating composition, exhibiting excellent water repellency and waterproofing property, etc. Said composition composed of nylon and/or polyester fiber in an amount of 0.05-5g/m<2> per unit area and water repellency and waterproofing property, etc., is especially applied to a canopy material for a paraglider and is comfortably kept for a long period of time.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a treatment composition that can impart properties such as water repellency, waterproofness, sealing properties, and lubricity to a base fabric.
In particular, the present invention relates to a treatment composition suitable for canopy materials for paragliders.

(Prior art) Paragliding is a sky sport with a short history, but it is known for its ``simplicity'', ``safety'', and ``fashionability'', such as the fact that anyone can easily fly it. In a short period of time, it has grown into one of the sky sports with the largest number of enthusiasts. Paragliding Canopy
The properties required of the material are: firstly, for its safety, the base fabric must have sufficient strength such as sewing strength and tearing strength, and do not change over time; secondly, it must have good flight performance and be portable. Third, it should be lightweight to facilitate
Fourthly, it should be water repellent or have low water absorption so that it does not absorb water and increase its weight when wet with rain, and the fourth is surface smoothness.
It has weather resistance, color fastness, etc.

Nylon fibers are often used as the base fabric for paragliders because they have been used for parachute umbrellas (Japanese Patent Laid-Open No. 54-49799), but usually,
In order to improve weather resistance, nylon fibers treated with weather-resistant polyurethane resin are used.

In particular, as a fabric that combines high strength and lightness, which are the basic requirements for a paraglider fabric, a fabric in which polyester fibers are pretreated with a polysiloxane resin with hydroxyl groups at both ends and then coated with a polyurethane resin is suitable. It is widely used as a material that maintains tear strength for a long time, does not easily absorb water, and is lightweight (Japanese Patent Application Laid-Open No. 2-41475).
Publication No.).

However, the nylon material has the disadvantage that it is extremely sensitive to ultraviolet rays, and its initial performance such as water repellency and lubricity deteriorates after about one year of use. Furthermore, paragliders made of polyester material have approximately twice the UV resistance as those made of nylon material, but like nylon material, they have the disadvantage that their initial performance deteriorates over time. In addition, when coating with the above-mentioned double-terminated hydroxyl group polysiloxane resin or polyurethane resin, a catalyst for the condensation reaction and crosslinking and curing at high temperatures are required, so it is easy to reprocess and reduce the It was extremely difficult to restore performance.

However, since paragliders are expensive, everyone wants to make the paraglider they purchase last as long as possible, and it is desirable to have a maintenance agent that can easily restore performance that has deteriorated over time. was.

(Problems to be Solved by the Invention) Under the circumstances described above, there is no known treatment agent that can simultaneously impart sufficient water repellency, sealing properties, lubricity, etc. to the base fabric for paragliders. Not yet.

On the other hand, the present inventors have already proposed that polysilazane polymers are effective as water repellents, layering agents, etc.
JP 60-141758, JP 60-145815 and JP 60-221470).

Therefore, the present invention and others attempted to apply these to base fabrics for paragliders, and found that although the initial objective could not be achieved by simply using a polysilazane polymer, the siloxane units and silazane units were in a constant ratio. The inventors have discovered that extremely good results can be obtained when using organosilazane siloxane polymers, and have thus arrived at the present invention.

Accordingly, a first object of the present invention is to provide a treatment agent that can easily impart all of the properties such as water repellency, waterproofness, sealing properties, and slipperiness to a base fabric.

A second object of the present invention is to provide a canopy material for a paraglider that can maintain water repellency, waterproofness, sealing properties, sliding properties, etc. for a long period of time.

(Means for Solving the Problems) The above features of the present invention include: ■ 72 units of R'a S10 (4□) in the molecule, and R''bSi (
NR3) <, a-b+ /Z unit (here R', R
8 and R2 are hydrogen atoms or groups selected from the same or different unsubstituted or substituted monovalent hydrocarbon groups, a is an integer selected from 1.2 and 3, and b is 1 or 2)
An organosilazane siloxane polymer containing
') A base fabric treatment agent composition comprising an organosilazane siloxane polymer characterized in that the content of syt units is within the range of 50 to 95 mol% and (1) an organic solvent, and a canopy for a paraglider using the same. achieved by the material.

Above - R1 in shipyard. R1 and R3 are a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group or a tolyl group, or a cycloalkyl group such as a cyclohexyl group. , the same or different unsubstituted or substituted monovalent hydrocarbon groups (e.g. chloromethyl group, 3,3.3-
trifluoropropyl group, cyanomethyl group, etc.).

The organosilazane siloxane polymer described above can be synthesized using known methods, such as those described in U.S. Pat.
No. 41758, No. 60-145815, No. 60-22
It is disclosed in Japanese Patent No. 1470.

As a method for producing such an organosilazane siloxane polymer, for example, the formula % is the same as the formula %, where X is a halogen atom, O<c<4;0<d<
4;O<c+d<4) and one or more organopolysiloxanes represented by -Ship R"a Si
with one or more organohalosilanes represented by It can be obtained by reacting the mixture with ammonia or primary amines.

The above-mentioned one shipyard R'cX 4 SiO<a-<c+a>
, 7t, C is preferably 1.8 to 2.2 from the viewpoint of the properties of the resulting organosilazane siloxane polymer, and d is preferably 1.5 to 2.2 from the viewpoint of curing speed. It is preferable to set it to 3.5. Examples of such organopolysiloxanes include (m is an average positive number of 5 or more). Such chlorine-containing linear polysiloxanes can be prepared by known methods such as cyclic organopolysiloxane and dimethyldichlorosilane,
It can be easily obtained by equilibration reaction with dichloroorganosilane such as ethyldichlorosilane using #I Asahi medium.

In addition, the organosilane represented by the above-mentioned Ichifunazo R'', SiX (4-111) is one in which R2 is a hydrogen atom or the above-mentioned R
is selected from unsubstituted or substituted monovalent hydrocarbons that are the same as 1, the same kind, or different, and e is 1 or 2. Such organosilanes include methyltrichlorosilane, dimethyldichlorosilane, ethyltrichlorosilane, diethyldichlorosilane, propyltrichlorosilane, propylmethyldichlorosilane, vinyltrichlorosilane, allyltrichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and trichlorosilane. Examples include fluoropropyltrichlorosilane.

The reaction between the above organopolysiloxane and organosilane proceeds easily by dissolving them in a suitable organic solvent and then contacting them with ammonia or a primary amine. The primary amine in this case is denoted by NR3,
R3 is selected from the same or different unsubstituted or substituted monovalent hydrocarbons as R1 described above. Examples of such primary amines include methylamine, ethyleneamine, butylamine, etc., but it is particularly preferable to use ammonia from the viewpoint of ease of synthesis.
In addition, the above-mentioned organic solvent is preferably one that is inert to ammonia gas and primary amines and also dissolves well the organosilazane siloxane polymer produced. Examples of such organic solvents include dichloroethane, Examples include trichloroethane, methylene chloride, tetrahydrofuran, benzene, toluene, xylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and dibutyl ether.

Although the reaction between the organopolysiloxane and organosilane is an exothermic reaction, it is usually carried out at 0 to 50° C. while controlling the reaction temperature. In addition, the blending ratio of the organopolysiloxane and organosilane described above is such that the content of siloxane units in the organosilazane siloxane polymer obtained by this reaction is 5 to 50 mol% and R"Si (N
It is necessary that the content of sit units (R") is within the range of 50 to 95 mol%.

The number of siloxane units in the silazane siloxane polymer is 5
If the siloxane unit content is less than 50 mol%, the silicone coating film formed will become hard, resulting in poor texture of the treated fabric and poor water repellency, which is undesirable.On the other hand, if the siloxane unit content exceeds 50 mol%, the curing speed will be slow, This is not preferable because the sealability deteriorates.

Also, 17”si (
NR3)! If the content of the /□ unit is less than 50 mol%, the curing speed will be slow, resulting in poor silicone coating formation, and if it is more than 95 mol%, the formed silicone coating will become hard (which may result in poor texture). , water repellency also deteriorates, which is not preferable.

The organosilazane siloxane polymer thus obtained is concentrated or diluted with a solvent or the like to obtain the composition of the present invention, depending on the type of object to be treated and its use.
Dichloroethane, trichloroethane,
It may be appropriately adjusted with a chlorine-based solvent such as methylene chloride, or a solvent such as toluene, xylene, ether, hexane, etc.

The treatment composition of the present invention is applied to the substrate surface of a paraglider canopy material such as nylon or polyester by brush coating, roll coating, spraying, dipping, etc., and then the solvent is evaporated at room temperature or by slight heating. As a result, the surface hardens within 10 minutes even at room temperature to form a thin, uniform coating, giving the canopy material excellent properties such as water repellency, waterproofing, sealing, and slipperiness over a long period of time. can.

In this case, the characteristics can be exhibited by surface curing at room temperature within 10 minutes, but complete curing requires 3 hours or more at room temperature, and by curing for 3 hours or more, the above performance can be fully exhibited. can be done.

One application is usually sufficient, but the effect will be further improved if it is applied two or three times.

In order to impart the above-mentioned properties, the organosilazane siloxane polymer of the present invention must be added in an amount of 0.00% per unit area of the object to be treated.
It is necessary to adhere within the range of 0.05 to 5.0 g/r+f. If it is less than 0.05 g/rrf, the characteristics will not be sufficiently imparted, and 5. Even if it is deposited in an amount of Og/% or more, it is not preferable because the characteristics cannot be further improved.

The treatment liquid composition of the present invention can be applied to a canopy for a bala glider.
Water repellency and waterproofness due to deterioration of the material over time due to UV rays, etc.
It is effective for preventing and restoring loss of smoothness, but it can also be used for the same purpose when treating fabrics used in assembled canoes, hang gliders, stand kites, windsurfing, sailboats, etc. , can be used similarly.

(Effects of the Invention) After applying the treatment composition of the present invention to a base fabric by spraying or dipping, it can easily become water repellent, waterproof, sealable, and slippery just by drying at room temperature for several minutes to several hours. These characteristics can be imparted to the base fabric, and the effects last for a long time.

Therefore, the treatment composition of the present invention is effective not only for imparting initial properties but also as a maintenance agent and performance improving agent for base fabrics that have deteriorated over time due to the influence of ultraviolet rays and the like. Moreover, a canopy for a bala glider coated with the treatment composition of the present invention
The material is lightweight and has long-term water repellency, waterproofness,
Since it can maintain sealing properties, sliding properties, etc., it is superior to any conventional material as a canopy material for paragliders.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Terminal chlorine-containing dimethylpolysiloxane 51.
A reactor was charged with 448 g of methyltrichlorosilane and 9,050 g of methylene chloride, cooled to 5''C, and while cooling was continued, ammonia gas was blown in at a temperature below 20°C to react for 4 hours.

Next, the reaction system was heated to 40 to 50°C and refluxed for about 30 minutes to remove excess dissolved ammonia, cooled, and the resulting ammonium chloride was filtered off, resulting in a colorless and transparent solution 9. 360 g was obtained. This product contains 3.0% by weight of active ingredients, 0.66% by mole of units and [CH
iSi (NH)! /□] unit was confirmed to contain methylsilazane siloxane polymer A consisting of 99.34 mol%.

The above polymer contains 18 mol% of C(CHs)zsiO) units and 82 mol% of (CH3Si(NH)sz□) units.
It was confirmed that it consists of

Next, Composition A was prepared by diluting the thus obtained methylsilazane siloxane polymer A with dibutyl ether so that the concentration in the solution was 1% by weight.

48 g of dimethylpolysiloxane containing terminal chlorine shown in Example 2°
287 g of 1-methyltrichlorosilane, 160 g of dimethyldichlorosilane, and 9.050 g of methylene chloride were charged into a reactor, cooled to 5°C, and heated to 20°C while continuing cooling.
Next, the mixture was heated to 40-50°C and refluxed for about 30 minutes to remove the excess dissolved ammonia, and after cooling, the resulting ammonium chloride was removed. When filtered, 9,410 g of a colorless and transparent solution was obtained. It was confirmed that this product contained 3.2% by weight of methylsilazane siloxane polymer B as an active ingredient. The above polymer is ((CHs
)tsio) units was 17 mol%, (CHiSi(NH
) x/z ) unit is 50 mol% and ((CL) zs
It was confirmed that the composition consisted of 33 mol% of iNH) units.

Next, composition B was prepared by diluting the thus obtained methylsilazane siloxane polymer B with dibutyl ether so that the concentration in the solution was 1% by weight.

Example 3 Composition C was prepared by diluting siloxane polymer C with dibutyl ether so that the concentration in the solution was 1% by weight.

Example 4 84g of dimethylpolysiloxane containing terminal chlorine represented by the average structural formula
, 416 g of methyltrichlorosilane and 9 g of methylene chloride
, 050g were charged into a reactor and reacted in the same manner as in Example 1, followed by filtration to obtain 9,290g of a colorless and transparent solution.
I got it. It was confirmed that this product contained 2.9% by weight of methylsilazane siloxane polymer C as an active ingredient. This polymer has 24 ((CH3)zsiO) units.
Mol% and (CH3Si (NO) s7□) units are 7
It was confirmed that it consisted of 6 mol%.

Next, 81.5 g of chlorine-containing dimethylpolysiloxane represented by methylsilazane thus obtained, 418.5 g of methyltrichlorosilane, and 9.0 g of methylene chloride.
50g of the solution was charged into a reactor and reacted in the same manner as in Example 1, followed by filtration to obtain 9,330g of a colorless and transparent solution. It was confirmed that this product contained 3.1% by weight of methylsilazane siloxane polymer D as an active ingredient. This polymer contains 24 mol% ((CH3)zsio) units.
It was confirmed that the composition consisted of 76 mol% of (CH3Si(NH)sz□) and (CH3Si(NH)sz□) units.

Next, the thus obtained methylsilazane siloxane polymer D was diluted with dibutyl ether so that the concentration in the solution was 1% by weight to prepare a composition.

Example 5 38 g of the terminal chlorine-containing dimethylpolysiloxane used in Example 1 was prepared by formula C, F, , CHz SiCl.

462 g of perfluoroalkyl group-containing trichlorosilane and 9.05 g of trichlorotrifluoroethane
0g was charged into a reactor and reacted in the same manner as in Example 1, followed by filtration to obtain 9,450g of a colorless and transparent solution.

It was confirmed that the active ingredient contained perfluoroalkyl group-containing silazane siloxane polymer E in an amount of 3.4 wt. 1%. This polymer is ((CTo)zsio
) units are 37 mol% and (CHzSi (NH) 3/
2) It was confirmed that the unit consisted of 63 mol%.

Next, the concentration of the thus obtained perfluoroalkyl group-containing silazane siloxane polymer E in the solution was 1.
Composition E was prepared by diluting with trichlorotrifluoroethane to give a weight percent.

Comparative Example 1 450 g of methyltrichlorosilane and 9 g of methylene chloride,
050 g was charged into a reactor and reacted in the same manner as in Example 1, followed by filtration to obtain 9,450 g of a colorless and transparent solution. This product contains 3.5% by weight of methylpolysilazane polymer F as an active ingredient, (CI(3Si(N)l)
It was confirmed that it consisted of 100 mol% of s7z) units.

Next, Composition F was prepared by diluting the thus obtained Polymer F with dibutyl ether so that the concentration in the solution was 1%.

Comparative Example 2 317 g of methyltrichlorosilane, 183 g of dimethylchlorosilane and 9,050 g of methylene chloride were charged into a reactor and reacted in the same manner as in Example 1, followed by filtration to obtain 9,450 g of a colorless and transparent solution. This product has an active ingredient of 3.3% (CLSi (NH) 3i□) and a unit of 6
0 mol% and ((CL)zSiNH) units are 40 mol%
It was confirmed that it contained methylpolysilazane polymer G consisting of.

Next, a composition G was prepared by diluting the thus obtained polymer G with dibutyl ether so that the effective content in the solution was 1%.

Comparative Example 3 381 g of methyltrichlorosilane, 119 g of tetramethyldichlorodisilane represented by the formula and 9,050 g of methylene chloride were charged into a reactor, and Example 1
After reacting in the same manner as above, the mixture was filtered to obtain 9,450 g of a colorless and transparent solution. The active ingredient in this product is 3.4% by weight, and the (CIIffSi (NH): l/2) unit is 80
It was confirmed that it contained methylpolysilazane polymer H consisting of 20 mol% of units.

Next, a composition H was prepared by diluting the thus obtained polymer H with dibutyl ether so that the concentration in the solution was 1%.

Comparative Example 4 Example 1 was prepared by charging 222 g of the terminal chlorine-containing dimethylpolysiloxane used in Example 2, 299 g of methyltrichlorosilane, and 9,050 g of methylene chloride into a reactor.
When the mixture was reacted in the same manner as above and filtered, 9.410 g of a colorless and transparent solution was obtained. This product has 3 active ingredients.
3% by weight, 61 mol% of ((CH3)zsiO) units and 39 mol% of (CHsSi(NTI)*/z'J units).

Next, Composition K was prepared by diluting the polymer thus obtained with dibutyl ether so that the concentration in the solution was 1% by weight.

Example 6゜400Id of the composition A- obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was transferred to a handy spray can, and sprayed onto a polyester fiber mW canopy material for a ballast glider.
After coating, it was dried for 15 minutes at room temperature. Further, the spray coating was repeated twice in the same manner and then left for 2 hours to form a uniform amount of silicone adhesion on the polyester fiber substrate. Paraglider canopy treated in this way
The materials were checked for water-based properties and sealing properties using the following methods.

The amount of silicone deposited per unit area of the object to be treated was determined by measuring the weight of the polyester fiber 1i substrate before and after treatment.

Spray Test After spraying 250 cc of water onto the canopy material from a height of 20 CI in a shower-like manner, the shape of the water droplets remaining on the back surface of the TA fiber and the ability of the water droplets to penetrate (filling property) were evaluated according to the following criteria.

O: The water droplets are completely monodispersed and independent, and do not leak to the back surface.

Δ: Water droplets are partially agglomerated, and some droplets are seen on the back surface.

×: The water droplets are completely aggregated and are completely shed on one surface.

Using a micropipette, 6 μl of water was dropped onto the canopy material (3 points), and the contact angle (A) was determined as the average value of the 3 points from the shape of the generated water droplet. The larger the contact angle, the better the water repellency.

Pour 100μ of water into the canopy using a micropipette.
Water droplets were created by dropping the canopy onto the material, one side of the canopy material was gradually lifted to an angle, and the angle at which the water droplets rolled down was measured. It has a small falling angle and has good water repellency and lubricity.

The evaluation results are shown in Table 1.

Table 1 The results in Table 1 show that the treatment agent of the present invention is significantly superior to the case where polysilazane is used as a treatment agent, and that the results depend on the composition ratio of siloxane units and silazane units. It is something that proves that

Claims (1)

[Claims] 1) (1) R^1_aSiO_(_4_-_a
_)_/_2 units and R^2_bSi(NR^3)_(
＿４＿−＿b＿)＿／＿２units (here R^1, R^2
and R^3 is a hydrogen atom or a group selected from the same or different unsubstituted or substituted monovalent hydrocarbon groups, a is an integer selected from 1, 2 and 3, and b is 1 or 2)
An organosilazane siloxane polymer containing R^1_aSiO_(_4_-_a)_ in the molecule.
The content of /_2 units is 5 to 50 mol%, and R
^2Si (NR^3)_3_/_2 unit content is 50
A base fabric treatment agent composition comprising an organosilazane siloxane polymer and (2) an organic solvent, characterized in that the amount thereof is within the range of 95 mol %. 2) Attach the organosilazane siloxane polymer according to claim 1 to a paragliding canopy material made of nylon and/or polyester fibers in an amount of 0.05 to 5.0 g/m^2 per unit area of the object to be treated. A canopy material for paragliding that is characterized by: