JPH04185772A - Resin-finished fabric - Google Patents

Abstract

PURPOSE:To provide the subject fabric having a bending resistance at room temperature and a bending resistance at the washing water-temperature satisfying a specific relationship, exhibiting high bending resistance in normal use and easily washable with a washing machine. CONSTITUTION:A textile fabric is immersed in a shape-memory resin solution containing a block copolymer of a high-melting crystalline segment composed mainly of a crystalline aromatic polyester unit (e.g. polybutylene terephthalate) and a low-melting segment composed mainly of an aliphatic polylactone [e.g. poly(alpha-caprolactone)]. The immersed fabric is dried and heat-treated to obtain a shape-memory resin-finished fabric having the memory of e.g. a flat shape and having a bending resistance at 20 deg.C (Ga) and a bending resistance at 6O deg.C (Gb) satisfying the formula. The fabric is flexible in washing and restored to the original moderate hardness after washing to keep the preferable quality of the fabric.

Description

[Detailed Description of the Invention] [Field of Industrial Application] This invention provides a resin-treated fabric (Fuha<), which has high bending resistance during normal use at room temperature and is easily washable in a washing machine. [Prior art and problems related to resin-treated fabrics] Fabrics used for connecting materials and industrial materials are often required to have high bending resistance due to the form of use. For this reason, stiff resin-treated fabrics that have been given a hard finish with resin adhesion to give them a certain level of bending resistance are widely used in a variety of applications, including blinds, tents, sails, and flexible containers. There is.

Hereinafter, a case for blind use will be specifically explained as an example.

Resin-treated fabrics for blinds are usually non-woven fabrics or woven or knitted fabrics treated with resin. In particular, for roll blinds, a hard finish by resin processing is desired in order to make them suitable for winding.

Roller blinds are being adopted in ordinary homes as interiors become more luxurious in recent years. The resin-treated fabric gets dirty while the blinds are in use, so
Sometimes they need to be washed. However, resin-treated fabrics for blinds are difficult to wash at home.

This is because general resin-treated fabrics with a hard finish have high bending resistance and cannot be gathered up compactly, making them difficult to fit into household washing machines. Forcibly folding, pushing, and washing can cause damage to the resin film, cracks, and chalk-like wrinkles (
Chalk marks) etc. will appear on the product, making it unsuitable for use.

Reducing the amount of resin adhesion improves washability, but this leads to inconveniences such as not being able to provide a sufficiently hard finish and lack of bending resistance, resulting in loss of winding suitability, so reducing the amount of resin adhesion is an appropriate solution. I can't say it's a strategy.

[Problem to be solved by the invention]

In view of the above circumstances, it is an object of the present invention to provide a resin-treated fabric that has both appropriate bending resistance and good washability.

[Means to solve the problem]

In order to solve the above problems, in the resin-treated fabric according to the present invention, the relationship between the bending resistance Ga at 20°C and the bending resistance cb at 60°C is as follows: C(Ga -Gb)/Ga]x 100≧15 -(1)
A configuration is adopted that satisfies the formula fi+.

In addition, in this invention, r C (Ga Gb) /Ga)
For convenience, X100J is referred to as the bending resistance change rate.

This invention will be explained in more detail below.

In the case of the resin-treated fabric of this invention, the bending resistance change rate is 20 to
It is more preferable if it is in the range of 70. If the bending resistance change rate is less than 15, appropriate hardness and good washability cannot be achieved at the same time. The bending resistance at 20°C indicates the hardness during use, but from the perspective of maintaining appropriate hardness during use, it varies depending on the application, but in the case of the resin-treated fabric of this invention, Usually, the numerical value of the bending resistance Ga is preferably about 0, 3 to 13, more preferably about 1 to 10.The meaning of the other bending resistance cb being the value at a temperature of 60°C is as follows. It is. The temperature of 60℃ not only creates a temperature difference between room temperature and room temperature that is sufficient to cause the necessary change in hardness, but also allows for appropriate washing (the temperature of the hot water used for washing is within the appropriate range and stains are removed well). This is because this is the temperature at which results can be obtained.

The resin-treated fabric of the present invention becomes soft and can be washed smoothly with suitable warm water at 60 to 70°C, and returns to appropriate hardness when returned to room temperature (about 20°C).

Next, the measurement of bending resistance according to the present invention will be explained. The bending resistance referred to in this invention is JIS L 1096.6.1
9. Values measured by a method similar to the IA method (45° cantilever method).

As shown in FIG. 1, from the resin-treated fabric obtained, a longitudinal sample 3a and a transverse sample sb orthogonal to the longitudinal direction are obtained.
Collect 5 pieces of each. Sample size is 2C[llX
15CI11. M amount W (g/cut) of each temple
), and as shown in Figure 2, the moving path ml (fi) was measured using a measuring device, and the average value (for 5 vertical samples and 5 horizontal samples) was calculated. put.

The method of measuring the moving path Ml is as follows. That is, the sample is placed on a horizontal plane H with one short side aligned with the base line P at the end. Then, slide the sample on the left slope B side until one short side touches slope B. The distance that the other short side moves until the − side short side reaches the slope B is the moving distance l.

Here, when measuring the moving distance l, use the table of each sample.
The back was measured in two conditions at 20°C and 60°C (4 measured values). The ten moving distance l data of the sample Sa at 20° C. are averaged and substituted into the following formula (2) to calculate the stiffness Ga in the shrinkage direction. In addition, 60℃ of sample Sa
The 10 moving distance l data in the state are averaged and the following formula (
2) to calculate the stiffness Gb in the contraction direction. Similarly, the bending resistance Ga and the bending resistance Gb in the lateral direction are calculated.

G=WX (0,5(!X O,I)'...
(2) However, G: Bending resistance (g-cm) l: Travel distance (average value, m) W: Sample weight (average value, g/c++) As the base fabric used in the resin-treated fabric of Riko's invention, , nonwoven fabric, woven fabric, knitted fabric, etc. From commercially available base fabrics, basis weight, texture,
It can be selected and used as appropriate by considering the color, pattern, etc.

In addition to synthetic fiber base fabrics and natural fiber base fabrics, there are also base fabrics that use a combination of synthetic and natural fibers. This base fabric may be subjected to flame retardant treatment, antistatic treatment, water repellency treatment, etc., or may be previously treated with resin for other purposes.

The resin adhered to the base fabric is a resin whose hardness changes significantly between the room temperature state (hard) and the 60° C. temperature state (soft). Resins that undergo this type of change are usually heated at room temperature to 60°C.
It is a resin that has a glass transition point or crystalline melting point between . In particular, shape memory resin is a material that tends to have a very large degree of change in hardness. In addition, in the case of shape memory resin, if it is deformed at a temperature below the molding temperature after molding,
In order to remove the deformation caused by heating to a temperature above the glass transition point or crystal melting point of the resin and below the molding temperature, it has a function of restoring the original shape. Shape memory provides excellent shape retention and good quality can be maintained for a long time. In the case of resin-treated fabrics that have been processed to have shape memory using shape memory resin, there are advantages such as the ability to erase wrinkles that form during washing.

In this invention, suitable shape memory resins include: ■Polyester/Polyester Brosoxy Polymer (hereinafter referred to as
(referred to as "resin■" as appropriate), or ■polyester.
Polyether Brosoxco Polymer C Below, “resin ■” as appropriate
J), etc.

A specific example of the resin (2) is a block copolymer of a high melting point crystalline segment mainly composed of a crystalline aromatic polyester unit and a low melting point segment mainly composed of an aliphatic polylactone. Can be mentioned. In the case of this block copolymer, when the content of the aliphatic polylactone component is from 60-1% to 99-t% of the copolymer, it is easy to ensure appropriate shape memory and bending properties. moreover,
This block copolymer has a heat of fusion peak of 0.5 c a 1.5 c a 1. / g or more, especially 2.0 c
A of 78 or more is preferred.

The crystalline aromatic polyester used in resin ■ is as follows:
Examples include polybutylene terephthalate and polycyclohexine dimethylene terephthalate, which can be used alone or as a copolymer. In particular, as in claim 3, polybutylene terephthalate is preferred because it is easy to obtain one with excellent shape memory performance.

The aliphatic polylactone used for resin has a carbon number of 4.
-11 lactone homopolymers or copolymers of two or more types, etc. are mentioned. In particular, as claimed in claim 3,
(ε-caprolactone) is preferable because it is easy to obtain one with excellent shape memory performance.

A specific example of the resin (2) is a block copolymer of a high melting point crystalline segment mainly composed of a crystalline aromatic polyester unit and a low melting point segment mainly composed of polyethylene glycol, as described in claim 4. It will be done. In the case of this block copolymer, the content of the polyethylene glycol component is usually 60-t% or more to 95 wt% of the copolymer.
% or less. This is because it is easy to ensure appropriate shape memory and bending properties. Furthermore, this block copolymer has a 0 to 6
The heat of fusion peak that appears in the temperature range of 5℃ is 0.5ca#/
g or more is preferable.

The above-mentioned crystalline aromatic polyester used in resin ■ is
Examples include polybutylene terephthalate and polycyclohexine dimethylene terephthalate, which can be used alone or as a copolymer. In particular, polybutylene lenticulate resin having excellent shape memory performance is easily obtainable, as described in claim 5.

The low melting point segment used in resin■ is mainly polyethylene glycol, but compared to polyethylene glycol,
Other polyalkylene glycols may be used in combination within 0 wt% to constitute a low melting point segment.

In addition to the above resins ■ and ■, shape memory urethane polymers,
Shape memory crystalline diene polymers (such as trans polyisoprene), shape memory styrene-butadiene polymers, shape memory polynorbornene polymers, shape memory polyester polyolefin polymers, etc. can also be used. In addition to this, any resin that has a glass transition point or crystal melting point between room temperature and 60° C. and whose hardness changes significantly can be used, even if it is not a shape memory resin. For example, as in claim 6, the number of carbon atoms is 3 to 20
Examples include flexible epoxy resins prepared by blending and curing polyacid anhydrides obtained from aliphatic dicarboxylic acids. In the case of this flexible epoxy resin, the blending amount of polyacid anhydride is preferably 20 to 70 iy based on the total amount of the compound before curing.
t%, more preferably about 30-60-t%.

In addition, the above resin contains commonly used flame retardants and coloring 1j.
It goes without saying that 'J (carbon black, pigments, dyes), reinforcing agents, nucleating agents, hydrolysis resistance improvers, antistatic agents, heat stabilizers, light stabilizers, etc. may be added.

Next, a method of attaching the resin to the base fabric will be explained.

Examples of attachment methods include the following.

■ A method in which the molten resin itself is directly coated on the base fabric.

■ Create a solution by dissolving or dispersing the resin in a solvent.
A method in which the solvent is removed after coating the base fabric with this solution or dipping the base fabric in the solution.

■ Create a solution by dissolving or dispersing the resin in a solvent.
A method of coating this on release paper and evaporating the solvent to form a film, which is then laminated to a base fabric.

■ A method in which a film made by melting and extruding the resin itself is laminated onto a base fabric.

■ A method in which fibers made by melt-spinning resin are laminated onto a base fabric.

■ A method of laminating a resin nonwoven fabric made by melt-blowing resin onto a base fabric.

The amount of resin deposited varies depending on the type of base fabric and its use, but is preferably about 5 to 150 g, more preferably about 10 to 100 g per unit area (♂). If it is less than 5g, it is difficult to ensure the necessary bending resistance and wrinkle resistance during washing;
If it exceeds g, the characteristics of the base fabric itself will be lost, and the weight and thickness will increase so much that it will not be a practical resin-treated fabric.

The resin-treated fabric of the present invention has a single-layer structure in which resin is attached to one base fabric, and a laminated structure in which resin is attached to two base fabrics. For example, a laminated and integrated product in a Santoi/chi form in which a resin film or a base fabric to which resin is attached rather than the resin itself is sandwiched between two base fabrics is claimed in claim 7.
As such, it is suitable for blinds. The resin-treated fabric of the present invention may have a structure in which another base fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric, and a sheet-like material other than these, such as a film or synthetic paper, are bonded together.

Of course, it goes without saying that even when these base fabrics and sheet materials are bonded together, the bending resistance change rate is 15 or more.

The resin-treated fabric of the present invention can be used not only for blinds but also for tents, sails, bags, flexible containers, hats, footwear, various interlinings, and the like.

C Example] Example 1 - A shape memory resin consisting of polybutylene terephthalate/polycaprolactone copolymer [blending ratio (weight ratio) = 25 near 5] was dissolved in chloroform under conditions of normal pressure and boiling point. A solution with a resin content of 8 ivt% was prepared.

A polyester flat fI6 fabric (base fabric) was immersed in this solution, taken out, and dried at a temperature of about 80° C. to evaporate the chloroform. Next, use a setter and set 180
The fabric was heat-treated at a temperature of 0.degree. C. so as to have a flat shape, thereby obtaining a resin-treated fabric with a resin adhesion amount of 15 g/rd.

Example 2 - Example 1 except that the resin coverage was 50 g/rd.
A resin-treated fabric was obtained in the same manner as above.

Example 3 - A shape memory resin consisting of polybutylene terephthalate/polyethylene glycol (average molecular weight 30.00) copolymer [blending ratio (weight ratio) = 35 + 65] was mixed with 6 volumes of chloroform at normal pressure and boiling point. Decomposed resin content 1
A 0←t% solution was prepared.

A polyester plain weave fabric (base fabric) was immersed in this solution, taken out, and dried at a temperature of about 80° C. to evaporate the chloroform. Then, use cef, tar, 180℃
The fabric was heat-treated to have a flat shape at a temperature of 20 g/rr, and a resin-treated fabric with a resin adhesion amount of 20 g/rrr was obtained.

Example 4 - The resin-containing solution was an emulsion solution of a commercially available polyurethane shape memory resin [1 diary JMM2500J manufactured by Mitsubishi Heavy Industries, Ltd.]. A resin-treated fabric was obtained in the same manner as in Example 1 except for the above.

-Comparative example 1- A commercially available resin-treated fabric for blinds was prepared.

The bending resistance Ga (20'C) and bending resistance Gb (60°C) of the resin-treated fabrics of Examples 1 to 4 and the comparative example above were measured in the longitudinal direction and
In addition to measuring each in the lateral direction, the bending resistance change rate was calculated. The results are shown in Table 1.

In addition, the washability and other properties of the resin-treated fabrics of Examples and Comparative Examples were investigated.

Example] 180CIIIX from the resin-treated fabric of ~4]0
When a 0 cm test piece was cut out and washed in a washing machine with warm water at 70°C, the test piece softened sufficiently in the warm water.
I was able to wash it easily and easily. I didn't get many chalk marks after washing.

On the other hand, the resin-treated fabric of Comparative Example 1 did not soften and had high bending resistance, so it could only be stored in a washing machine in a folded state, and many chalk marks appeared on the fabric after washing.

Example 5 - A shape memory resin consisting of polybutylene terephthalate/polycaprolactone copolymer [blending ratio (weight ratio) ~15:85] was dissolved in chloroform in the same manner as in Example 1, and the resin content was 12 iut%. A solution was prepared.

This solution was applied onto release paper and dried to obtain a film with a thickness of 40 nm.

This film was made into a polyester plain weave fabric [No. 40 single yarn (vertical 50
60 pieces/inch)] Sandwiched between two sheets, laminated and laminated, then heated to 180°C.
After 1 minute of tension heat treatment, the shape memory resin adhesion amount was 40.
A flat resin-treated fabric of g/m was obtained.

Example 6 - A resin-treated fabric was obtained in the same manner as in Example 4, except that one of the polyester plain-woven fabrics was replaced with a commercially available polyester non-woven fabric (basis weight: 50 g/m).

Example 7 - A shape memory resin consisting of polybutylene terephthalate/polycaprolactone copolymer [blending ratio (weight ratio) = I5:85] was dissolved in chloroform in the same manner as in Example 1, and the resin content was 84%. A solution was prepared.

A polyester plain-woven fabric [No. 10 double yarn (46 vertical threads/inch, 36 horizontal threads/inch)] was immersed in this solution, pulled up, chloroform was evaporated, and then heated at 180°C using a setter. A resin-treated fabric for a leisure tent with a resin adhesion amount of 55 g/rd was obtained by heat treatment to obtain a flat shape.

Bending resistance Ga, Gb of the resin-treated fabrics of Examples 5 to 7
, the bending resistance change rate was investigated. The results are shown in Table 1.

180cm (length) from the resin-treated fabric of Example 5.6
A 90 cm (width) test piece was cut out to produce a roll blind. Repeated lifting and lowering tests were conducted, and it was extremely smooth and showed good winding suitability. Then, when the resin-treated fabric was removed from the blind and washed in a washing machine with warm water at 70°C, the test piece was sufficiently softened in the warm water and could be washed easily and smoothly. After washing, it was cooled to room temperature under tension and air-dried. As a result, the shape was comparable to that before washing, and it was confirmed that the effect of the shape-memory resin was well exhibited.

A test piece of 200cm x 200cm was cut out from the resin-treated fabric of Example 7 and washed with warm water at 70°C using a washing machine.The test piece softened sufficiently in the warm water and could be washed easily and smoothly. did it.

Example 8 - 100 parts of epoxy resin (Epicote 828), 68 parts of polydodecanedioic anhydride with average degree of polymerization n = 3.2 (40 wt% of the total formulation), curing accelerator (BDMA: benzyldimethylamine) Mix 1 part of the viscous liquid well with polyester flat l1ir6 [No. 10 twin thread (vertical 46
After coating the surface of the paper (viscosity liquid adhesion amount: 60 g/m), the whole body was placed in a hot air oven at 140°C for 1 hour, then heated to 160°C.
A hardening treatment was performed by heating for 7 hours.

The resin-treated fabric of Example 8 was examined for bending resistance Ga, Gb, and bending resistance change rate. The results are shown in Table 1.

A test piece of 59 cm x 3 Q cm was cut out from the resin-treated fabric of the example day and washed in warm water at 65° C. using a washing machine. The test piece was sufficiently softened in the warm water and could be washed easily and smoothly.

〔Effect of the invention〕

As mentioned above, the resin-treated fabric of the present invention has a
Since the bending resistance change rate between ℃ and 60℃ is 15 or more,
It becomes soft when washed and returns to its original hardness after washing, and has both appropriate bending resistance and good washability.

In addition, when a shape memory resin is used as the resin, by processing it at a temperature that allows it to memorize the shape, it is possible to create a resin-treated fabric that memorizes the desired shape of the fabric, such as a flat shape or a pleated shape. be able to. Resin-treated fabrics with shape memory have excellent shape retention and can maintain good quality for a long time. - For example, in the case of a resin-treated fabric for roll blinds that has a flat shape memorized, the fabric is taken out of the hot water bath after washing, kept flat, and cooled to room temperature. Wrinkles, bends, chalk marks, etc. on the fabric disappear, the fabric returns to its pre-memorized flat shape, and desirable product quality can be maintained.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing how a sample for bending resistance measurement is cut out, and FIG. 2 is an explanatory diagram showing the principle of measuring the moving distance β for calculating bending resistance. Sa...Vertical sample sb...Horizontal sample Agent Patent attorney Takehiko Matsumoto Figure 1 Figure 2

Claims (1)

[Scope of Claims] 1. A fabric to which a resin is attached, and the relationship between the bending resistance Ga at 20°C and the bending resistance Gb at 60°C is expressed by the following formula in both the longitudinal and lateral directions of the resin-treated fabric. A resin-treated fabric that satisfies the following. [(Ga-Gb)/Ga]×100≧15 2 The attached resin has a high melting point crystalline segment mainly composed of crystalline aromatic polyester units and a low melting point segment mainly composed of aliphatic polylactone. The resin-treated fabric according to claim 1, which is a shape memory resin made of a block copolymer. 3. The resin-treated fabric according to claim 2, wherein the crystalline aromatic polyester is polybutylene terephthalate and the aliphatic polylactone is poly(ε-caprolactone). 4. A claim that the attached resin is a shape memory resin consisting of a block copolymer of a high melting point crystalline segment whose main component is a crystalline aromatic polyester unit and a low melting point segment whose main component is polyethylene glycol. Item 1. The resin-treated fabric according to item 1. 5. The resin-treated fabric according to claim 4, wherein the crystalline aromatic polyester is polybutylene terephthalate. 6. The resin-treated fabric according to claim 1, wherein the attached resin is a flexible epoxy resin prepared by blending and curing a polyacid anhydride obtained from an aliphatic dicarboxylic acid having 3 to 20 carbon atoms. 7. The resin-treated fabric according to any one of claims 1 to 6, which is a resin-treated fabric for blinds.