JPH04185748A - Sheet - Google Patents

Abstract

PURPOSE:To obtain sheets by integrated molding, suitable for seats of automobile, having excellent light resistance and durability by using a cloth comprising polyester yarn as the surface yarn and specific polyurethane elastic yarn as the ground yarn. CONSTITUTION:Cloth using polyester yarn having preferably >=0.3 dr fineness of single yarn and 30-140 yarn denier as the surface yarn and polyurethane elastic yarn having >=20% light-resistant strength retention ratio after carbon arc irradiation (fadeometer, 63+ or -3 deg.CX20 hours) as the ground yarn is used as surface cloth and molded in an integrated way to give the objective sheet. The polyurethane constituting the polyurethane elastic yarn is obtained by polymerizing a polymer diol with an organic diisocyanate and a chain extender.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a sheet that is integrally molded.

(Prior Art) A sheet formed by integral molding is produced by laminating an elastic fabric for integral molding onto a plastic sort to form a composite sheet, which is then molded into a desired shape by press molding, thermoforming, vacuum painting, or the like.

For example, Japanese Patent Application Laid-Open No. 63-282
No. 345 proposes a fabric using polyurethane elastic yarn.

(Problems to be Solved by the Invention) Automobiles have a long service life and are required to have excellent light resistance (light resistance, light resistance strength) even when used outdoors. In this respect, integrally molded carnets using polyurethane elastic threads have excellent rationality and appearance quality, but are inferior in light resistance. This is because the polyurethane elastic threads used so far have poor light resistance. For example, when the polyurethane elastic yarn used as the base yarn of a raised fabric made of double raschel used as an integrally molded car seat is photodegraded, cracks in the base, sagging, tweezing, etc. occur, and the appearance quality deteriorates.

On the other hand, regarding light resistance, existing fibers have the highest light resistance when polyester fibers are dyed with disperse dyes, but conventional polyurethane elastic yarns have low hot water resistance, so it is necessary to use polyester fibers with excellent light resistance. (125
High-temperature, high-pressure staining at temperatures above ℃ was not possible.

The present invention solves these drawbacks and has excellent light resistance and sweat resistance! The aim is to provide a notebook made by integrally molding the two.

(Means for Solving the Problems) The present invention uses a fabric and has two sheets, polyester fibers are used for the surface yarn of the fabric, and the ground yarn is irradiated with a carphone arc (Fatemeter, 63±3 This sheet uses polyurethane elastic threads that have a light resistance strength retention rate of 20% or more at temperatures of 200 hours (°C x 200 hours).

This sheet is obtained by integrally molding a fabric using polyester fiber as the face yarn and, preferably, elastic yarn made of polyurethane having the following structural formula as the base yarn.

(In the formula, R1 is an alkylene group having 6 to 10 carbon atoms having one methyl branch, and R2 is a divalent organic group.) Furthermore, in order to achieve high light resistance, at least a disperse dye is used in the fabric. It is dyed at a temperature of ℃ or higher,
Furthermore, there is C1, which processes the fabric to reduce its weight in order to obtain a soft touch and deep dyeing effect.

First, the face yarn of the present invention will be described.

The face yarn is polyester fiber. This is because polyester fibers have excellent mechanical properties and color development, and when dyed with disperse dyes, they have the highest light intensity.

Yarn denier and single yarn fineness may be selected appropriately depending on the desired texture and appearance, or it is better to avoid single yarn fineness of 03dr or less, as the color development and light emission degree will deteriorate. The yarn denier is preferably 30 to 140 denier. Furthermore, the polymer composition of polyester is not particularly stipulated; for example, it is made of polyethylene terephthalate and polybutylene terephthalate, and is obtained by a known polymerization method. In addition, copolymers with other components may also be used within a range that does not impair the object of the present invention.

Next, the polyurethane elastic thread will be described.

The polyurethane elastic yarn used in the present invention is a polyurethane elastic yarn that has a light resistance strength retention rate of 20% or more after carbon arc irradiation (fade meter, 63 = 3°C x 200 hours). You can get it like this.

The polyurethane constituting the polyurethane elastic thread is obtained by polymerizing a polymeric diol, an organic diisocyanate, and a chain extender. The polymer diol used in the present invention has the general formula (wherein R' is an alkylene group having one methyl branch and having 6 to 10 carbon atoms, and R? is a divalent organic group).
3″ Ar Kishi 11 Do...

5≦Total number of carbon atoms/(Number of ester bonds)≦11 (
1) 0015≦number of methine groups/total number of carbon atoms≦013 (
(Here, the total number of carbon atoms is the total number of carbons remaining after excluding the carbon contained in the ester bond in the polymer diol.) The molecular weight of the polymer diol used in the present invention is 1.
A range of 000 to 3500 is ideal. Particularly preferably 1500 to 3000. 1000), elastic recovery, heat resistance, hot water resistance, and cold resistance decrease, and 35
When it is larger than 00, elastic recovery properties, spinning stability, and strength are reduced. As a compound that provides an alkylene group having 6 to 10 carbon atoms and having one methyl branch, for example, 3-methyl-
1,5-bentanediol (MPD) and 2-methyl-1,8-octanediol (MOD),
Suitable diols that provide other alkylene groups that can be used in conjunction with them include 1.6-hexaneol, 1.
8-octanediol, 1,9-nonannool, 1,
Examples include, but are not limited to, straight chain diols such as 10-deca-7-ol.

The use of a diol with one methyl branch improves elastic recovery and heat resistance. When using long tmll M +, f: diols with two or more Mehl branches, such as 1-ni, ninyl, propyl, or butyl groups, the overall performance of heat resistance, elastic recovery, cold resistance, etc. is improved. descend.

If the number of diol 9 carbon atoms is less than 5, the elastic recovery, heat resistance, and track water resistance will decrease.

When it is larger than 10, elastic recovery properties and transparency decrease.

Examples of the compound that provides the organic group (R2) of the polymeric diol include dicarboxylic acids, among which aliphatic dicarboxylic acids having 6 to 12 carbon atoms; aromatic dicarboxylic acids are preferred, and fatty acid dicarboxylic acids are particularly preferred. .

.... In the formula (1), if (total carbon number)/(ester bond number) is less than 5, the water resistance and cold resistance will be reduced, and if it is larger than 11, the elastic recovery property will be reduced. It is preferable that the number of methine groups is 6 to 10.The number of methine groups is 7' and the total number of carbon atoms is 0.
If it is smaller than 015, the elastic recovery property will be reduced, and if it is larger than 013, the heat resistance and elastic recovery property will be reduced. A more preferable range is 0.03-010.

The methine group referred to in the present invention has three different atoms other than hydrogen atoms;
It combines with an atom (which may be the same element) to form f-CH-. Other polymer diols may be used as the polymer diol used in the present invention as long as they do not impair the effects of the present invention.

Among them, the T-polyurethane elastic yarn has excellent elastic recovery even at low temperatures of -10°C, and contains 50 mol% of 3-methyl-1,5-pentanediol as a diol component.
Using diols containing the above, azelaic acid (AZ), sebacic acid (SA), 1 as dicarboxylic acid components
．． , ], ] o-Decanodicarboxylic acid A) is obtained from a polyurethane using a polyester diol obtained by using an aliphatic dicarboxylic acid having a methylene number of 7 to 10.

The polyurethane constituting the present invention is obtained in this manner and has a molecular weight of at least 2 hydrogen atoms capable of reacting with an organic diisonate and an isocyanate having a molecular weight of 500 or less.

The polyurethane used in the present invention may be mixed with other polymers within a range that does not impair the effects of the present invention.

In particular, when producing elastic threads from thermoplastic polyurethane by melt spinning, the organic diisonoanate used to synthesize the thermoplastic polyurethane is 4.4"-diphenylmethaneneusonanate (MD I), and the chain extender is 1.4
By selecting -butanediol (BD) and/or 1,4-his(hydrokinoethokino)henzen (BHEB), excellent performance in heat resistance, elastic recovery, and elongation can be obtained.

Organic diisonoanate (
The ratio (B)/(A) of 15 to 45 in terms of molar ratio is excellent in terms of overall performance such as elastic recovery, heat resistance, and cold resistance.

Furthermore, polymeric diols (^) and organic noisocyanates (B
), the composition ratio of the chain extender (C) is (B)/((A
) + (C) ) molar ratio ranges from 0.9 to 1.2,
Particularly preferred is a range of 095 to 1.15. In this range, a polyurethane elastic yarn with excellent elasticity, elastic recovery, and elongation can be obtained.

In addition, the molar ratio of (B)/((A)(C)'r is controlled during polyurethane polymerization or during spinning.In the case of melt polymerization, the temperature is particularly limited to 5r, or 200°C. It is preferable that the temperature is above 260°C or below.

The polyurethane used in the present invention is essentially a divalent group in which two hydrogen atoms have been removed from the hydroxyl groups at both ends of the A4 polymeric diol molecule (soft semenoto).

b General formula derived from organic noisonoanate (in the formula R3
represents a divalent organic group).

C A divalent group from which two hydrogen atoms that can react with the isocyanate of a low-molecular compound (chain extender) molecule are removed.

It is thought to consist of structural units.

Methods for producing polyurethane elastic threads from the polyurethane fibers thus obtained include melt spinning and dry spinning. In the case of the melt spinning method, one wound yarn is heat-treated in a range of -20 to -50°C relative to the glass transition temperature (Tg) of the heart segment under low humidity to cause phase separation of the heart and soft segments. It is preferable to fully implement the following. The fineness of the elastic yarn used in the present invention is preferably 20 to 210 deniers. 20d
If it is less than
If dr is exceeded, the stress is too strong and may cause peeling depending on the note shape. Preferably it is 40 to 100 dr.

The polyester-based polyurethane elastic yarn obtained in this way and the above-mentioned polyester fiber can be made into a fabric for integral molding, for example, by double raschel. At this time, the polyester fiber is used as the pile part (face yarn). Polyurethane elastic yarn is used as the ground yarn, but the strength of the polyurethane elastic yarn is at most 2 g/dr or less, and it is necessary to reinforce it with other fibers. Strong nylon or polyester is suitable as the reinforcing yarn, and polyester is particularly good in terms of its color matching with the surface yarn and its brightness. In terms of usage, the coated yarn is made of polyurethane elastic yarn as the core yarn, and has excellent removability and light resistance. In this case, it is preferable that the cover yarn be a crimped yarn by false twisting etc. from the viewpoint of coverage.
゜As the sheet fabric of the present invention, napped knitted fabric (pile knitted fabric,
In addition to cut pile knitted fabrics and raised knitted fabrics, stretchable fabrics having stretchability in both the warp and weft directions can be used. Among them, it is easy to process knitted fabrics or integral molding because of its high elongation. These knitted fabric structures include pile, velor, motsukuroday,
Examples include punch, etc. (circular knitting), pile, cut pile, half, satin, etc. (referring to gi). When using a cut pile knitted fabric, the pile length is preferably 3 to 10 mm in terms of appearance quality.

The gray fabric obtained in this way is dyed, but it goes without saying that the dyeing step can be omitted if the polyester fiber is yarn-dyed yarn or spun-dyed yarn. Dyeing is carried out using at least a disperse dye at a dyeing temperature of 125°C or higher. This combination results in a dyed product with excellent light fastness. If the dyeing temperature is less than 125° C., it may satisfy the Kenro degree of radiation for general clothing, but it will not meet the above-mentioned evaluation for automobiles.

The polyurethane elastic yarn of the present invention can be dyed at this temperature. Furthermore, it is useful to use an ultraviolet absorber during the dyeing process, including dyeing, because it improves the degree of light emission.

Furthermore, by using caustic soda to reduce the amount of polyester fibers prior to this dyeing, the texture becomes soft and a deep dyeing effect can be obtained. The weight loss rate at this time is preferably 5 to 20%.

If it is less than 5%, the effect will be poor, and if it exceeds 20%, the strength of the fabric will decrease significantly.

Processing conditions vary depending on the processing machine, but for example, in bath processing, the caustic soda concentration is 1 to 6% by weight, the temperature is 80 to 100°C, and the time is 10 to 60 minutes.

A plastic sheet is laminated to the elastic fabric obtained as described above to form a composite sort, and then a sheet of a desired shape is formed by press molding, vacuum forming, etc. using the elastic fabric as the outer material.

The notebook of the present invention can be used as a notebook for automobiles, trains, airplanes, ships, etc.

(Effects of the Invention) The integrally molded notebook of the present invention has excellent light resistance (light resistance strength, light intensity), less discoloration and fading even after long-term light irradiation, excellent perspiration resistance, and appearance quality such as hair loss and sagging. It's a loss.

(Light resistance) Evaluation was carried out at 63°C x 200 hours (carbon arc), which is commonly used in the automobile industry.

(Sweat resistance) Cut the composite sort from the sheet and process it under the following conditions.

Unsaturated fatty acid used Oleic acid concentration: 100% processing time
After treatment for XIO hours at 90°C, it was washed with water and air-dried. After drying, the polyurethane elastic yarn was taken out, and the strength and elongation retention was determined by comparing before and after the oleic acid treatment.

The present invention will be briefly described below with reference to Examples.

Example 1 Semi-dull polynystyl l00dr/48 as cover yarn
Using f, the core thread was made of polyester and BD with a total carbon number of MPD and AZ/number of ester bonds of 693, number of methine groups/total number of carbons of 0.0825, and a number average molecular weight of 1900 at 30°C. mixture heated to 50℃
Polyester/MDr/
A twin screw extruder was charged with a molar ratio of BD of 1/3.15/2 to carry out melt polymerization. The produced polyurethane (PU) is continuously extruded into water in the form of a strand, and then formed into pellets using a pelletizer. This pellet was vacuum-dried at 80°C for 10 hours, and spun using a single-screw extruder spinning machine at a spinning temperature of 230°C and a spinning speed of 500 m/min (using a straight oil agent).
To obtain 70dr-2f polyurethane elastic yarn. This yarn has a strength of 1.2 g/dr and an elongation of 510%, and after carbon arc irradiation (fade meter, surface temperature 63°C,
Irradiation time: 200 hours) The light resistance strength retention rate is 50%.
two.

This yarn was subjected to non-dull covering with a draft of 35 times and a twist number of 600 T/m to obtain a ground yarn. On the other hand, semi-dull polyester 100dr/48f false twisted yarn was used as the face yarn, and knitted using a 28 gauge double raschel machine. The knitting conditions are: Ground thread draft = 150% On-machine course = 50/inch run Length: Pile part 880cm Ground thread part 120c
m Needle bed spacing: 6 mm Next, the knitted double knitted fabric was center cut to obtain two pieces of raised stretch fabric. Next, brush this fabric 110 times
After presetting at 180°C for 45 seconds, dyeing was carried out under the following conditions.

Dye: Autocolor Blue M (manufactured by Moriroku Co., Ltd.) 20% owr Dispersion aid: Disper TL (manufactured by Meiho Kagaku Kogyo Co., Ltd.)
...Ig/ (1 PH regulator, ammonium sulfate...Ig/ Q Acetic acid...Ig/ (1 bath ratio)
, 30 Temperature Increase the temperature from 40℃ to 130℃ over 30 minutes,
Hold at ℃ for an additional 60 minutes.

Reduction cleaning hydrosulfide 2g/Q Soda ash 2g/(1 Amirazine (Dai Pharmaceutical) Ig/ρ Bath ratio 130 Temperature 80°C x 20 minutes Final set = 160°C x 40 seconds, finishing with UV absorber This finished fabric was bonded to a PVC resin film with a thickness of 0.45n+m for 20 seconds at 110°C to form a composite notebook, and then a car sheet was formed by vacuum forming.

The light resistance of this car seat was 4th to 5th grade.

Moreover, the composite sort after irradiation showed almost the same elasticity as before irradiation. Pilling of the composite sort after irradiation (IcI method for 5 hours) was good at grade 5, with no shedding or loosening of the fabric. Furthermore, the perspiration durability strength retention rate was 90%, and the perspiration durability elongation retention rate was 90%.

In addition, the staining color fastness by JIS L-0848A method and the rubbing fastness by JIS L-0849Il type were as follows.

Alkaline sweat dyeing fastness: 4th to 5th grade Acidic sweat dyeing fastness: 4th to 5th grade Dry abrasion fastness, 4th to 5th grade Wet abrasion fastness, 4th to 5th grade Comparative example 1 Commercially available ether-based polyurethane The light resistance strength retention rate of the elastic yarn could not be measured due to severe photodeterioration.

Comparative Example 2 The light resistance strength retention rate of a commercially available ester-based polyurethane elastic yarn was 14%. In the fabric using this polyurethane elastic thread in Example 1, the polyurethane elastic thread was fused and cut during dyeing.

Example 2 Prior to the dyeing of Example 1, the gray fabric was subjected to weight reduction processing under the following conditions.

Caustic soda concentration: 40g/(1 Treatment temperature: lOO'C Treatment time: 60 minutes The weight loss rate at this time was about 15% and f2. The light resistance of this car sort was 4 to 5, and the pilling of the composite sheet after irradiation (ICI method 5 hours) was 5, which was good, and there was no hair loss or fabric damage. There was no bow wrapping, and the sweat durability strength retention rate was 88%, and the sweat durability elongation retention rate was 89%.

Further, the alkaline sweat dyeing fastness was 4th to 5th grade, the acidic sweat dyeing fastness was 4th to 5th grade, the dry rub fastness was 4th to 5th grade, and the wet rub fastness was 4th to 5th grade.

Patent applicant RiRashi Co., Ltd.

Claims (1)

[Claims] (1) A sheet using a fabric, in which polyester fiber is used as the surface thread of the fabric, and the ground thread is irradiated with carbon arc (fade meter, 63±3°C x 200 hours)
1. A sheet comprising polyurethane elastic yarn having a light resistance strength retention rate of 20% or more.