JPS5981171A - Manufacture of air permeable composite material - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a breathable composite material, and more particularly, the present invention relates to a method for manufacturing a breathable composite material, and more particularly, a method for producing a breathable composite material, and more particularly, a resin made of a vinyl chloride resin having a large number of small breathable pores on one side of a fabric base material. The present invention relates to an improvement in a method for manufacturing a layered breathable composite material.

Films or sheets made of synthetic resins are widely used as decorative and wear-resistant covers for a wide variety of products. These films or sheets are widely used, for example, for wall, floor and tabletop coverings, book covers, linings, clothing and automotive interior coverings. In many cases, films or sheets of synthetic resin are coated onto a backing of textiles, paper, felt, metal, wood, etc. These agricultural materials have many purposes, the most common being to increase the strength and utility of the product and to accept adhesives to secure the film or sheet.

When a film or sheet made of synthetic resin and a backing material that supports them are bonded together with an adhesive, the characteristics of the backing material are impaired and defects appear during use of the adhesive.

The light part of the book is also a synthetic pattern, fx7 from 5. , Hui 71. picture.

The purpose of this invention is to provide an industrially advantageous manufacturing method that does not significantly sacrifice the breathability, cushioning properties, and feel of the fabric base material that serves as the lining when producing a composite material consisting of a sheet and a fabric base material. As a result of intensive study, the present invention has been completed.

Therefore, the gist of the present invention is to provide a vinyl chloride resin with an average particle size of S-tθ microns obtained by drying a polymer emulsion obtained by an emulsion polymerization method or a fine suspension polymerization method. is dispersed in water together with a plasticizer, this dispersion is applied to one side of a fabric base material to form a coating film, and this coating film is then applied to the following formula (1), that is, Ty + (/j0 - plasticizer). (number of parts added)
... (1) [In the formula (I), T2 means the glass transition point of vinyl chloride-based yuzu butter, and the number of parts added of plasticizer means the number of parts added of the plasticizer relative to ioo parts by weight of the vinyl chloride-based resin. ] The present invention relates to a method for producing a breathable composite material, which comprises heating and melting the resin particles at a temperature equal to or lower than the following to weld the surfaces of the resin particles together and adhering them to a cloth base material, and then cooling the resin particles.

The present invention will be explained in detail below.

In the present invention, the vinyl chloride resin refers to polyvinyl chloride and a copolymer mainly composed of vinyl chloride. Monomers copolymerizable with vinyl chloride include vinyl esters, vinyl ethers, acrylic acid or methacrylic acid and their esters, maleic acid or hafmaric acid and their esters, maleic anhydride, aromatic vinyl compounds, Examples include halogenated vinylidene compounds, acrylonitrile, methacrylonitrile, ethylene, and propylene.

Adding a trace amount of a compound containing a polyfunctional group to these monomers,
It may be partially crosslinked.

The above-mentioned vinyl chloride resin is manufactured by emulsion method or microsuspension polymerization method. The vinyl chloride resins produced by these methods have a small average particle size and are suitable for forming an air-permeable resin layer on a fabric base material.

According to the present invention, the vinyl chloride resin emulsion produced by the above method is dried to form a powder, and this powder is used.

When a resin emulsion obtained by an emulsion polymerization method is dried, for example, by a spray drying method, a large number of microparticles with an average particle size of 2 microns or less aggregate with each other, and porous particles with an average particle size of s microns to 10 microns are formed. is formed. The resin obtained by the fine suspension polymerization method has an average particle size of 2
With a strength of 0 to 4 microns, this resin also aggregates several particles together during drying, but the agglomeration property is not as strong as that produced by the emulsion 1 method.

According to the present invention, the average particle size of the dried vinyl chloride resin powder is ! Use one with a diameter of θ micron or less. If the average particle size is so microns or more, it is difficult to properly adjust the strength and air permeability of the breathable resin layer of the final composite material, and it is difficult to balance these properties and stabilize the resin layer. I can't get it. The air permeability of the resin layer finally obtained varies depending on the vinyl chloride/L used, the system, and the average particle size of the resin particles. Vinyl chloride resins can be selected from those with an average particle size of 100 microns or less, or more than 100 microns, and even if one with a fairly uniform average particle size is used, two types with different average particle sizes can be used The above may be used in combination. The raw material vinyl chloride resin may be one type, a single type, a single resin (homopolymer), or a copolymer depending on the airflow rate, strength, feel, etc. of the final breathable resin layer. You can choose from a variety of materials including resin.

According to the present invention, the vinyl chloride resin powder is dispersed in water together with a plasticizer, and the plasticizer is absorbed into the vinyl chloride resin powder.

Plasticizers that can be used include phthalate esters such as dioctyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, dibenzyl phthalate, diisodecyl phthalate, didodecyl phthalate, and diisodecyl phthalate; dioctyl adipate, di-adipate, etc. Aliphatic dibasic acid esters such as n-butyl and dibutyl sebacate; pentaerythritol ester,
Glycol esters such as diethylene glycol dibenzoate; Fatty acid esters such as methyl acetyl ricinoleate; Phosphate esters such as tricresyl phosphate and triphenyl phosphate; Epoxidized oils such as epoxidized soybean oil and epoxidized linseed oil; Acetyl Citric acid esters such as tributyl citrate, acetyl trioctyl citrate, and tri-n-butyl citrate; various plasticizers such as trialkyl trimellitate, tetra-n-octyl pyromellitate, polypropylene adipate, and other polyester-based plasticizers can be given. These plasticizers may be used alone or in combination of two or more. The amount of plasticizer is based on 700 parts by weight of vinyl chloride resin.
It can be selected within the range of -0 to 20 parts by weight.

A dispersant is used to disperse the vinyl chloride resin powder and plasticizer in water. Dispersants that can be used include those commonly known as surfactants. For example, a-on surfactants such as fatty acid esters, alkyl sulfate salts, and alkyl sulfonate salts; cationic surfactants such as 7th-class amine salts, secondary amine salts, and tertiary amine salts; Examples include amphoteric surfactants such as alkyl betaines; nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl amines.

The amount of the above dispersant is 0.7~! based on the total amount of vinyl chloride resin and plasticizer! , if used within the range of θN amount %, it will be more than 0. To disperse the vinyl chloride resin powder and plasticizer in water, these two components are added to water in which the dispersant is dissolved and mixed by stirring. At this time, the ratio of water and solid content (sum of vinyl chloride resin and plasticizer) is such that the concentration of solid content is within the range of 2O-rO weight% of the dispersion liquid (sum of water and solid content). . If the solid content concentration is lower or higher than this range,
It is difficult to control the thickness of the resulting breathable resin layer, which is not preferred. The solid content concentration is particularly preferably in the range of 70 to 60% by weight within the above range.

The dispersion is stirred and mixed in order to absorb the plasticizer into the vinyl chloride resin powder. The temperature before stirring and mixing is J
'θ~? It is preferable to set the temperature to θ°C. If the entire amount of the blended plasticizer is absorbed by the vinyl chloride resin powder,
Cracks occur on the surface of the finally obtained breathable resin layer. Therefore, the amount of plasticizer absorbed into the vinyl chloride resin powder is
It is preferable to use a portion of the plasticizer blended, preferably about half, and the rest to be in a state where it is not absorbed but is dispersed in water. To do this, add the entire amount of plasticizer to water and change the stirring intensity, stirring time, etc. to adjust the amount absorbed into the vinyl chloride resin powder.First, add about half of the plasticizer and then A method may be used in which most of the plasticizer is absorbed into the vinyl chloride resin powder, and the remaining plasticizer is added to water and dispersed.

The stirring mixer that can be used to disperse the vinyl chloride resin and plasticizer in water may be a stirring mixer conventionally used for the purpose of dispersing solids in liquids.

When preparing the dispersion, small amounts of resin stabilizers, ultraviolet absorbers, fillers, dyes, pigments, flame retardants, fungicides, fragrances, etc. can be added and mixed.

When preparing the above dispersion using a stirring mixer, the dispersion contains
Since air bubbles, gels, and lumps may be included, it is preferable to remove these using a vacuum defoamer, a Hobart mixer, a roll mill, or a filter.

According to the present invention, the dispersion prepared by the above method is applied to one side of a fabric substrate. Fabric substrates refer to felt-like sheets, woven sheets, and knitted textile products. The weave may be plain weave, twill weave, satin weave, twill weave, gauze weave, fine weave, or the like.

The knitting method may be stockinette knitting, lace knitting, etc. In addition to vegetable fibers, the raw materials for the fibers may be animal fibers, synthetic fibers, and mixtures thereof. It may also be a mineral fiber such as asbestos. Particularly preferred are those woven with threads having a small diameter in a plain weave, twill weave, satin weave, or the like.

To form a coating film by applying a dispersion liquid to a fabric base material, spray coating method, roll coating method, gravure coating method,
Any of various coating methods known per se, such as a reverse coating method, may be used.

The thickness of the coating film formed on one side of the fabric base material is determined by the following heating,
It is preferable to adjust the air permeability so as not to sacrifice the air permeability of the breathable composite material after the melting process is completed.

According to the present invention, the coating film formed by the above method is heated to volatilize the water contained in the coating film, and then the surface of the resin particles is melted to weld the particles to each other, and at the same time, the coating film is also applied to the cloth base material. Make it adhere. If water in the coating film evaporates rapidly and resin particles adhere to the surface, many small cracks often occur on the surface of the breathable resin layer of the final composite material. In order to prevent the formation of these small cracks, before heating the surface of the resin particles to melt them, a
It is preferable to perform preliminary drying by heating within a temperature range of 100° C. for 1 minute or less to volatilize a considerable proportion of the water in the coating film.

The coating film can be prepared with or without the above pre-drying.
The resin particles are heated to almost completely volatilize the moisture, melt the surface of the resin particles, weld adjacent particles to each other, and also adhere to the fabric base material.

If the heating temperature at this time is too low, the surface of the resin particles will not melt even if heated for a long time, and a breathable resin layer with excellent strength will not be obtained, which is not preferable.

According to experiments conducted by the present inventors, it has been found that the optimum temperature for heating and melting varies depending on the secondary transition point of the resin and the amount of plasticizer added to the resin.

That is, the temperature during heating and melting is determined by the following equation (1), Ty -1-(/60-number of parts of plasticizer added)...
...(1) [In formula (I), Ty means the glass transition point of the vinyl chloride resin, and the number of parts added of the plasticizer means the number of parts added of the plasticizer relative to the part by weight of the vinyl chloride resin/θθ. ] It was found that it is best to keep the temperature below the following. Note that if the heating temperature is too low, the surfaces of the resin particles will not melt even if heated for a long time, and a breathable resin layer with excellent strength will not be obtained. The lower limit temperature during heating and melting is about -tθ°C lower than the temperature expressed by the above formula (1).

The heating and melting operations should be performed at a temperature slightly lower than the upper limit temperature expressed by equation (1) above for a short time of about 2 to 3 minutes, but if heating is performed rapidly at high temperatures, the final Many small cracks often occur in the resulting breathable resin layer. In order to prevent the formation of small cracks, before heating and melting operations, it is necessary to
At a temperature of! It is preferable to carry out a pre-drying operation in which the coating film is heated for up to 30 minutes to volatilize a portion of the water contained in the coating film, and then to carry out the heating and melting operations.

According to the present invention, the permeable composite material obtained by the above method is cooled in a trench at around room temperature, and then wound into a roll.

In addition, if a water repellent substance such as silicone oil or silicone emulsion is applied to one or both sides of the composite material during or after cooling the composite material, water repellency will be imparted to the breathable composite material. can do.

The resin layer of the breathable composite material obtained by the method of the present invention is printed using various printing methods known per se, such as gravure printing, screen printing, flexible printing, foam printing, and valley dyeing printing, in the same way as ordinary soft plastic films. is possible. The breathable composite material obtained by the method of the present invention is suitable for use in, for example, tabletop covers, book covers, linings for storage boxes, chair upholstery cloths, automobile interior cloths, diaper covers, rain gear, and the like.

The present invention has particularly remarkable effects as described below, and its industrial utility value is extremely large.

(1) When using the method of the present invention, 0.0/~0.
Composites with an air-permeable vinyl chloride stalk fat layer of thickness in the range of 6 mm can be easily produced.

(2) The composite material obtained by the present invention is easy to manufacture because the breathable resin layer is integrally attached to the fabric base material without using an adhesive.

(3) In the composite material obtained by the method of the present invention, the resin layer is soft, and the resin particles constituting the resin layer form voids between adjacent particles, and these voids form one side of the resin layer. The side communicates with the fabric base material side. Therefore, even if it is used as it is as a diaper cover, rain gear, etc., moisture will be easily dispersed and it will not get stuffy.

Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example: 50% by weight of polyvinyl chloride powder (average degree of polymerization // θ0, glass transition temperature 0°C, average particle size 70 microns) produced by emulsion polymerization method and dried by spray drying method.
, 92% by weight of water, and 3% by weight of sodium dodecylbenzenesulfonate (DBS) were mixed to prepare a mixed solution A.

On the other hand, dioctyl phthalate 6! Mixed liquid B was prepared by mixing three components consisting of 3.2% by weight of water and 3% by weight of DBS'.

Mixed liquid A and mixed liquid B were mixed at a weight ratio of 2.6 to 1 to obtain a dispersion liquid. The solid content of this dispersion is ss, tr
The weight percent, the number of parts of plasticizer added to 100 parts by weight of polyvinyl chloride, is jO parts.

The above dispersion was applied to a commercially available nylon woven fabric (diameter 20
Plain woven with micron thread. The hole size is 200 microns. ) was coated by knife coating method to form a coating film.

What about the nylon woven fabric that formed this coating film? The coated film was pre-dried by leaving it in a hot air oven adjusted to θ°C for 3 minutes. Read the nylon paper cloth with this coating film at 72θ℃.
After leaving it for 7 minutes in a hot air oven adjusted to 100% to completely volatilize the moisture, the surface of the polyvinyl chloride powder particles is melted, adhering adjacent particle surfaces to each other, and at the same time becoming integrated with the surface of the nylon woven fabric. It was attached to.

It refers to the thickness of the resin layer formed on the base material, ignoring the portion that has permeated into the pores of the cloth base material after cooling after the above heating and melting operations have been completed. ) A breathable composite material having a breathable resin layer of approximately θ,/mm was obtained.

Regarding the obtained breathable composite material, the average pore diameter of the resin layer, the average air permeability of the composite material, the moisture permeability of the composite material, etc. were measured according to the following method. The measurement results are shown in Table 7.

The average pore diameter and curvature of the resin layer were measured using an electron microscope.

Average ventilation rate of the composite material...Nitrogen gas was sent from one side of the composite material at a pressure of 'kg/cr/N, and the ventilation rate per square centimeter for 7 minutes was calculated. In the width direction for a composite material with a width of 3θomm! Measured by force and averaged.

Moisture permeability of composite materials...JIS ZO2θL!
? Compliant with.

Example The polyvinyl chloride in the example described in Example/ was produced by an emulsion polymerization method and dried by a spray drying method. A dispersion liquid was prepared in the same manner as described on the same side, except that the amount of rB (% rB, glass transition temperature of 20° C., average particle diameter, xs microns) was changed.

The resulting dispersion was applied to the same type of nylon fabric used in Example/as described on the same side.

1. The coating film was pre-dried. Next, place this coated nylon paper cloth on a metal plate, and!
The coated film was pre-dried by leaving it in a hot air oven adjusted to θ°C for 3 minutes. Next, this coated nylon woven fabric was placed on a metal plate and kept in a hot air oven adjusted to 10°C for 7 minutes to almost completely volatilize the moisture.
The particle surfaces of the polyvinyl chloride powder were melted to adhere adjacent particle surfaces to each other and at the same time to integrally adhere to the surface of the nylon fabric.

After the above heating and melting operations were completed, it was cooled to obtain a breathable composite material having a breathable resin layer formed on one side with a thickness of about θ, tmm (same definition as in Examples).

Various properties of the obtained breathable composite material were measured by the methods described in Examples. The results are shown in Table 1.

Comparative Example/Example/Composite material was prepared using the same procedure as described in the same example, except that the operating conditions for heating and melting the coating film were set to a temperature of 1.200°C. was manufactured.

Various properties of the obtained composite material were measured by the methods described in Examples. The results are shown in Table 1.

Comparative Example 2 A composite material was manufactured using the same procedure as that described in Example λ, except that the operating conditions for heating and melting the coating film were set to 0°C. .

Various properties of the obtained composite material were measured using the methods described in Examples. The results are shown in Table 7.

Table 1 According to Table 1, the composite material obtained by the method of the present invention exhibits large values for both air permeability and moisture permeability, but the operating conditions for heating and melting are set at or above the upper limit temperature expressed by equation (1) above. It is clear that the resulting composite material exhibits small values for both air permeability and moisture permeability.

Applicant Mitsubishi Monsanto Chemicals Co., Ltd. Representative
Person Patent Attorney Hase - (7 others)

Claims (1)

[Claims] (1) The average particle size obtained by drying a polymer emulsion obtained by the emulsification chamber method or the fine suspension polymerization method is 5~!
1. Disperse θ micron vinyl chloride resin in water together with a plasticizer. This dispersion is spread on one side of a cloth base material to form a coating film, and then this coating film is expressed by the following formula (1), that is, Tf + (/!θ-number of parts of plasticizer added)...・(
I) [In formula (I), Tf is the glass transition point of vinyl chloride resin, and the number of plasticizer added is vinyl chloride resin/θ
Each refers to the number of parts of plasticizer added to parts by weight of O. ] A method for producing an air-permeable composite material, which comprises heating and melting the resin particles at a temperature below the temperature expressed by the formula to weld the surfaces of the resin particles to each other, adhering the resin particles to a fabric base material, and then cooling the resin particles.