JPH04309510A - Conductive backing composition and cloth treated therewith - Google Patents

Abstract

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

Description

Description: [0001] The present invention relates to a conductive backing composition and a fabric backed with the conductive backing composition. More specifically, the present invention provides a backing composition that is excellent in both transparency and conductivity, and is also excellent in fraying prevention properties, thread removal strength, softness of hand, blocking properties, and resin adhesion properties, and a backing composition made from the composition. This relates to cloth that has been subjected to backing treatment. [0002] Conventionally, woven, knitted, or nonwoven fabrics made of natural fibers or synthetic fibers such as wool, rayon, polyacrylonitrile, polyamide, polyester, and polypropylene have properties such as fraying prevention properties, thread removal strength, Backing treatment is performed for the purpose of improving various properties such as softness of texture, blocking properties, and resin adhesion. By the way, in recent years,
Various types of backing-treated fabrics have come to be widely used in houses, vehicles, aircraft, ships, etc. In such applications, in addition to improving the various properties mentioned above, they are particularly effective in preventing accidents caused by static electricity. Therefore, there has been a strong desire to improve conductivity. In response to such demands, a method using a backing composition in which carbon black or graphite is added to rubber latex or resin emulsion has been proposed (Japanese Unexamined Patent Publication No. 2-229267).
. However, such conventional technology is accompanied by a major problem in that the backing treatment surface inevitably becomes black, which impairs the aesthetic appearance, and also improves fraying prevention, dimensional stability, suture removal strength, texture flexibility, blocking performance, etc. This was unsatisfactory from the standpoint of being excellent in all aspects of resin adhesion. [Problems to be Solved by the Invention] In view of the current situation, the main purpose of the present invention is to solve the problems of the conventional technology, to provide a fabric that has excellent properties of both transparency and conductivity, and has excellent fraying prevention and suture removal properties. The object of the present invention is to provide a backing composition that is excellent in strength, softness of hand, blocking property, and resin adhesion, and a cloth that is backed with the composition. [Means for Solving the Problems] The present inventors have arrived at the present invention as a result of intensive studies to achieve the above object. That is, the first invention of the present invention is based on the following general formula (1) (wherein, R1 represents H or CH3, X represents O or NH, and R2 and R3 each independently represent a group having 1 to 4 carbon atoms. an alkyl group, R4 is H or an alkyl group having 1 to 2 carbon atoms,
n represents an integer of 2 to 5, and Y- represents an anion that forms a salt. ) at least one monomer unit (A
) 10 to 50% by weight, and at least one vinyl monomer unit (B) other than the monomer unit (A) that is copolymerizable with the monomer unit (A) 90 to 50% by weight
50 parts by weight, and its glass transition temperature is -15
The present invention relates to a conductive backing composition comprising an emulsion containing a copolymer having a temperature of 0.degree. Moreover, the second invention relates to a cloth that has been backed with the conductive backing composition. [0005] This will be explained in detail below. The monomer unit (A) of the present invention is represented by the general formula (1). Note that R4 in the formula represents H or an alkyl group having 1 to 2 carbon atoms, and from the viewpoint of industrial availability, H or a methyl group is preferable. In addition, Y- represents an anion that forms a salt, specifically, halogen ions (Cl-, Br-,
I-, etc.), CH3 OSO3 −, C2 H5 S
O3 − , HSO4 − , H2 PO4 − , C
Examples include H3 CO2 − , HCO2 − , NO3 − and the like. Among these, halogen ions, CH3
OSO3 − and HSO4 − are preferred. Specific examples of monomer units (A) include inorganic acid salts (hydrochlorides, hydrochlorides, etc.) of dialkylaminoalkyl (meth)acrylates or dialkylaminoalkyl (meth)acrylamides.
Sulfates, nitrates, phosphates, etc.), organic acid salts (acetates, formates, etc.), or quaternary ammonium salts using quaternizing agents (methyl chloride, dimethyl sulfate, benzyl chloride, etc.). The above dialkylaminoalkyl (meth)acrylates include dimethylaminoethyl acrylate,
Dimethylaminopropyl acrylate, dimethylaminobutyl acrylate, diethylaminoethyl acrylate, diethylaminopropyl acrylate, diethylaminobutyl acrylate, di-n-propylaminoethyl acrylate, di-n-propylaminopropyl acrylate, di-n-propylaminobutyl acrylate, -n-butylaminoethyl acrylate, di-n-
Butylaminopropyl acrylate, di-n-butylaminobutyl acrylate, N-(1,1-dimethyl-3
-dimethylaminopropyl)acrylate, N-(2-
Examples include methyl-3-dimethylaminopropyl) acrylate, and methacrylate derivatives corresponding thereto. In addition, examples of the dialkylaminoalkyl (meth)acrylamides include dimethylaminoethyl acrylamide, dimethylaminopropylacrylamide, dimethylaminobutylacrylamide, diethylaminoethylacrylamide, diethylaminopropylacrylamide, diethylaminobutylacrylamide, di-n-propylaminoethylacrylamide. ,
Di-n-propylaminopropylacrylamide, di-
n-propylaminobutylacrylamide, di-n-butylaminoethylacrylamide, di-n-butylaminopropylacrylamide, di-n-butylaminobutylamide, N-(1,1-dimethyl-3-dimethylaminopropyl)acrylamide , N-(2-methyl-3-
Examples include dimethylaminopropyl) acrylamide, and methacrylamide derivatives corresponding thereto. Among the above dialkylaminoalkyl (meth)acrylates and dialkylaminoalkyl (meth)acrylamides, particularly preferred are dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and dimethylaminoethyl acrylate. Mention may be made of propyl methacrylate, dimethylaminopropylacrylate, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, diethylaminopropylacrylamide and diethylaminopropylmethacrylamide. The vinyl monomer unit (B) of the present invention is a monomer unit other than the above-mentioned monomer unit (A), and is at least one vinyl monomer unit copolymerizable with the monomer unit (A). Such vinyl monomer units (B
), for example, styrene; vinyltoluene; α-
Methylstyrene; Butadiene; Isoprene; Ethylene;
Vinyl halides such as vinyl chloride and vinylidene chloride; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl laurate, and vinyl versatate; methyl (meth)acrylate, ethyl (meth)acrylate , butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and other ester compounds of (meth)acrylic acid and alkyl alcohol having 1 to 18 carbon atoms. ; (meth)acrylonitrile; glycidyl group, N-methylol group, alkoxymethyl group, amide group, carboxyl group, hydroxyl group, methoxy group,
Vinyl monomers containing a functional group such as a sulfonic acid group; vinyl monomers having two or more polymerizable α, β-illegal saturated bonds, etc. can be exemplified. Specific examples of vinyl monomers containing the above functional groups include N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, Iso-butoxymethyl (meth)acrylamide, acrylic acid, itaconic acid, maleic acid, (meth)acrylamide, 2-hydroxyethyl (meth)acrylamide,
Examples include 2-hydroxyethyl (meth)acrylate, vinylsulfonic acid (or a salt thereof), and the like. In addition, as at least one component of the vinyl monomer unit (B), N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)
When at least one selected from the group consisting of acrylamide and iso-butoxymethyl (meth)acrylamide is used, an advantage is obtained that the effect of improving suture removal strength is particularly remarkable. In addition, the above two or more polymerizable α, β-
Specific examples of vinyl monomers having illegal saturated bonds include ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and trimethylolpropane. Poly(meth)acrylates such as (meth)acrylate and pentaerythritol (meth)acrylate; divinylbenzene, diallyl athalate, diallyl maleate, diallyl adipate, allyl methacrylate, triallyl isocyanurate, triallyl cyanurate, methylene bisacrylamide etc. can be given. The copolymer of the present invention has a monomer unit (A)
10 to 50% by weight, preferably 20 to 40% by weight, and 90 to 50% by weight, preferably 80 to 60% by weight of vinyl monomer unit (B), and has a glass transition temperature of -15°C or lower, preferably -20°C or lower. If the content of the monomer unit (A) is too small, the effect of improving conductivity and blocking property will be poor. On the other hand, if the vinyl monomer unit (B) is too small, the effect of improving fraying prevention properties and suture removal strength will be poor. Furthermore,
If the glass transition temperature exceeds -15°C, the effect of improving the flexibility of the hand and the resin adhesion will be poor. The conductive backing composition of the present invention comprises an emulsion containing the above copolymer. Examples of methods for obtaining the emulsion include the following method. As the polymerization initiator used in polymerization, any compound that generates free radicals can be used, such as 2,2'-
Azobis(2-amidinopropane) hydrochloride, azobisisobutyronitrile, benzoyl peroxide, kyumene hydroperoxide or t-butyl hydroperoxide, or a combination thereof with a reducing agent are preferably used. Furthermore, anionic polymerization initiators such as ammonium persulfate can also be used. Although there is no particular restriction on the amount of the polymerization initiator used, it is preferable to keep the remaining monomer as small as possible, and the appropriate amount of the polymerization initiator used is 0.05 to 5% by weight based on the monomer. As surfactants for polymerization, commonly used water-soluble polymers, cationic or nonionic surfactants are used, but cationic surfactants are stable even in so-called soap-free polymerization, which does not use surfactants. An aqueous dispersion of the polymer is obtained. The polymerization temperature is not particularly limited, but a suitable polymerization temperature is 30 to 100°C, preferably 40 to 80°C. A temperature lower than 30°C is undesirable because the polymerization rate of the monomer tends to decrease. There is no particular restriction on the method of adding the monomer, and the entire amount may be added at the beginning for polymerization, or may be added in portions or continuously for polymerization. The emulsion of the present invention thus obtained may contain nonionic, cationic or amphoteric dispersants, pigments, thickeners, flame retardants, antifoaming agents, crosslinking agents, anti-foaming agents, etc., depending on the required performance level, coating method, etc. Preservatives, pH adjusters, etc. can be added. [0009] There are no particular restrictions on the method for backing cloth using the conductive backing composition of the present invention, and any conventional method can be used. Furthermore, the base fabric to be subjected to the backing treatment is not particularly limited, and woven fabrics, knitted fabrics, or non-woven fabrics made of various natural fibers or synthetic fibers can be used, but in particular woven fabrics made of polyester, polyamide, polypropylene, etc. , knitted and non-woven fabrics are useful. [Examples] Next, the present invention will be explained with reference to Examples and Comparative Examples. Example 1 A 2-liter separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 660 g of water, 10 g of styrene, 70 g of butyl acrylate, and 25 g of an 80% by weight methacryloyloxyethyl trimethylammonium chloride aqueous solution, and heated to 80°C. After raising the temperature, the inside of the reaction system was replaced with nitrogen gas. Next, 40 g of styrene, 280 g of butyl acrylate, 8
100 g of 0 wt% methacryloyloxyethyl trimethylammonium chloride aqueous solution and 100 g of 10 wt% N-methylol acrylamide aqueous solution were mixed for 4 hours at the same time.
50 g of a wt % 2,2'-azobis(2-amidinopropane) hydrochloride aqueous solution was supplied to the reaction system at a constant rate for 5 hours to react, and the polymerization was completed. After cooling, 100
The polymerization solution was filtered through a stainless steel mesh. The obtained emulsion was a milky white uniform aqueous dispersion with a solid content of 38% by weight and a viscosity of 150 cps (as measured by a BL type rotational viscometer,
(measured at a rotational speed of 6 revolutions/min). 1.5 parts by weight of 2-hydroxyethylcellulose was added to 100 parts by weight of this emulsion to increase the viscosity, thereby obtaining a backing composition of about 20,000 cps. Next, 100% polyester.
Backing treatment was performed by applying the above-mentioned backing composition at 60 g/m2 (solid content) to a base fabric having a weight per unit area of 340 g/m2, and drying it in an oven at 120°C for 10 minutes. The following evaluation results were performed on the obtained backing-treated cloth. (1) Conductivity: Measure the surface resistance value of the backing surface with a resistance meter (H
iresta (manufactured by Mitsubishi Yuka Co., Ltd.), an applied voltage of 10 V,
Measurements were made at a temperature of 20°C, humidity of 30%, and 60% RH. (2) Transparency: Visually observe the transparency of the backing surface,
Evaluation was made with 〇 (excellent) and × (poor). (3) Anti-fraying property: A Scott rubbing abrasion tester (manufactured by Toyo Seiki Co., Ltd.) was used. The test piece is 25mm wide and 120mm long.
The distance between the grips was 30 mm, the load was 1 kg, the kneading operation was 1000 times, the kneading cycle was 120 times/min, and the kneading stroke was 50 mm. Evaluation was made by visually observing the degree of fraying and damage on the backing surface, and grading it as 〇 (excellent) or × (poor). (4) Suture removal strength: Performed based on JIS-L1201. (5) Texture: Flexibility was evaluated by touch. The result is 〇(
Excellent) and × (poor). (6) Blocking property: Evaluated by touch. The results were expressed as 〇 (excellent) and × (poor). (7) Resin adhesion: Visually observed, and the results were expressed as ○ (no abnormality) and × (poor resin permeability or film formation, causing powder to fall off). The evaluation results are shown in Table 1. Examples 2 to 6 and Comparative Examples 1 to 3 The same procedure as Example 1 was carried out except that the conditions shown in Tables 1 and 2 were used. In addition, in Example 2 and Comparative Example 1, the surfactants lauryl trimethylammonium chloride 2% by weight (based on monomer weight) (Example 2) and sodium lauryl sulfate 3% by weight (Comparative Example 1) were added. . The evaluation results are shown in Tables 1 and 2. Examples 1 to 6 according to the present invention show satisfactory results in all evaluation items. On the other hand, in Comparative Example 1 in which the monomer unit (A) was not used, the conductivity and blocking property were poor. Furthermore, in Comparative Example 2 in which the proportion of the vinyl monomer unit (B) is too low, the fraying prevention property and suture removal strength are poor. Moreover, in Comparative Example 3, which has a high glass transition temperature, the softness of the hand and the resin adhesion are poor. Table 1
implementation
example
1 2 3
4 5 Structure of copolymer (wt%)

Monomer unit (A)

DMC *
20 20
30 20
-DMA *
− − −
-20 vinyl monomer unit (B)

ST *
10 10 5
-10
MMA *-
- - 10
- BA *
68 68
63 68
68 N-MAM *
2 2
2 2 2
Glass transition temperature ℃ -34
-35 -33 -35
-30 Evaluation results


Conductivity Ω 30%RH 4.1×
107 5.0×107 1.2×107 3.
8×107 8.2×107
60%RH 3.2×106 3.4
×106 8.5×105 3.0×106 4
．． 0x106 transparency
○ ○ ○
○ ○ Anti-fray property ○ ○
○ ○
○ Stitch removal strength kg/pile 3.5
3.4 3.2
3.4 3.3 Texture
○ ○
○ ○
○ Blocking property ○
○ ○
○ ○ Resin adhesion
○ ○
○ ○ ○ *
See below for marks.Table 2
Example ratio
comparison example
6
1 2 3 Structure of copolymer (wt%)

Monomer unit (A)

DMC *
20
-68
20 DMA *
−
− − −
Vinyl monomer unit (B)

ST *
10
20 5 48
MMA *
− −
- - B.A.
*70
78 25
30 N-MAM *
0
2 2
2 Glass transition temperature ℃
-35 -35
-30 +20 Evaluation results


Conductivity Ω 30%RH
4.0×107 2.8×10
12 6.8×106 7.2×107
60%RH 3
．． 1×106 1.4×1011 2.4×
105 3.9×106 Transparency
○
○ ○ ○
Anti-fray property
○ ○ ×
○ Suture removal strength kg/pile
2.6 3
．． 3 1.4 2.8
Texture
○ ○
○ × Blocking property
○
× ○ ○ Resin adhesion ○
○ ○
× See below for * marks. *DMC: In general formula (1),
R1 = CH3, X=O, n=2, R2 ~ R4 =
CH3, Y- = Cl- compound * DMA: In general formula (1), R1 = H,
X=NH, n=3, R2 ~ R4 = CH3, Y-
=Cl- compound* ST: Styrene* MMA: Methyl methacrylate* BA: Butyl acrylate* N-MAM: N-methylolacrylamide [
[0016] As explained above, the present invention has excellent properties of both transparency and conductivity, and also has excellent fraying prevention properties, thread removal strength, flexibility of texture, blocking properties, and resin adhesion properties. It was possible to provide a backing composition and a fabric backed with the composition.

Claims (3)

[Claims] Claim 1: The following general formula (1) (wherein, R1 represents H or CH3, X represents O or NH, R2 and R3 each independently represents an alkyl group having 1 to 4 carbon atoms, and R4 represents H or An alkyl group having 1 to 2 carbon atoms,
n represents an integer of 2 to 5, and Y- represents an anion that forms a salt. ) at least one monomer unit (A
) 10 to 50% by weight, and at least one vinyl monomer unit (B) other than the monomer unit (A) that is copolymerizable with the monomer unit (A) 90 to 50% by weight
50 parts by weight, and its glass transition temperature is -15
A conductive backing composition comprising an emulsion containing a copolymer having a temperature of 0.degree. 2. At least one component of the vinyl monomer unit (B) is N-methylol (meth)acrylamide, N-
Methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (
The conductive backing composition according to claim 1, which is at least one selected from the group consisting of meth)acrylamide and iso-butoxymethyl(meth)acrylamide. 3. A cloth backed with the conductive backing composition according to claim 1 or claim 2.