JPS6166641A - Thermoformable laminated structure - 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 thermoformable laminates, monolithic articles made of thermoplastic materials, particularly foamed thermoplastic sheets that are formed into complex shapes. Furthermore, the present invention provides a thermoformable laminate i':! The present invention relates to a method for producing an 8J artifact and such an 8J artifact.

Laminated thermoplastic products have been used for many years.

These laminates are often formed as a sandwich construction in which a foamed thermoplastic material is wrapped between a linerboard overlay. An example of this construction is a polystyrene foam sheet with a liner board of kraft paper on each side. Such products have been formed by die-cutting +fH or cutting, and by pressing the board and applying resin and fixing the pressed shape. However, this kraft paper liner overlay was not formed into a G product, and
This is a material that tends to wrinkle during the molding of structural artifacts.

Other efforts have been made to provide laminated structures that are more easily formed. A plastic laminate is made from 11 of foamed styrene-anhydride maleic 1-cell composite to which a Jukumachi plastic composite film is adhered.

This laminate can be molded without the problems encountered with previously developed Giage linings.

More recent efforts have provided a material that is formed from a foamed thermoplastic sheet that is coated with a shield-impregnated fabric. . For example, the fabric may be impregnated with a highly softened acrylic composite.

Such damage...skin 4 pickles are, for example, cloth χ polymer r
8: It is formed by immersing it in +ffi and pouring the combined solution into 1 onto the cloth. solvent? Provide a cloth impregnated with a grass-grown polymer. This is impregnated with polymer χ. f5χ
・A bow is formed by attaching it to a sheet of plastic foam.

This kn':5 molding method is not without drawbacks (
・.

For example, the product; 5! In order to make pickles, an excessive amount of polymer is used in the unit area regulation. Similarly, polymer 1
4 medium from cloth impregnated with liquid? , :5 It takes an excessive amount of time to cool down.

The method of the present invention provides a mature formable laminate (4) structure having a polymeric impregnated fabric adhered to at least one side of a thermoplastic foam sheet without the disadvantages of prior art methods.

The present invention is characterized by the following:
A thermoformable structure 11 comprising a jointed plastic sheet is provided. Desirably, the fabric is comprised of synthetic 1R material and stretches easily in any direction on its surface. This fabric is impregnated with a polymer that has a softening temperature above 75°C.

The present invention similarly applies a polymer emulsion film to the surface of a sheet of plastic film, dries it to an emulsion film by evaporation of the liquid, and turns the dry emulsion film into a cloth? C. by applying 1% and pressure to the surface of the fabric to impregnate the fabric with a film of polymer, and removing the heat and pressure from the surface of the fabric, allowing the polymer to cool and solidify. , provides a method comprising adhering this fabric to a sheet of Konocho plastic foam. On the other hand, this cloth is damp
4 Applicable to emulsion film. Ripe and pressure? By adding, moisture is removed and the fabric is laminated to the hot fvtheta foam.

Another method of the present invention is to apply the polymer emulsion film to the surface of the plastic foam sheet, apply the emulsion to the plastic foam sheet, and impregnate it into the plastic foam sheet. The emulsion is dried by 14 shots, and the solid content of the emulsion is made plastic by the addition of iron and pressure, which is then applied to a sheet to cool and solidify the polymer under heat and pressure. It has become.

In one method of the present invention, the agglomerate-containing fabric is heated to
f may be adhered to a plastic foam sheet.

The aged formable laminate of the present invention, consisting of a foamed thermoplastic sheet with a polymer-impregnated fabric adhered to one side, is preferably made using a polymer having a softening temperature of at least 75C.

The foamed thermoplastic sheet may be made of various foamed thermoplastics, such as 2-styrene, styrene-anhydride copolymers and styrene-acrylonitrile copolymers, and the like. It may be made of porcelain. The foamed thermoplastic sheet may also be comprised of other foamed thermoplastics 1 that are substantially rigid at moderate temperatures, such as monoolefins such as polyethylene.

However, adhesion to polyethylene is only marginal without surface treatment such as flame treatment. Foamed thermoplastic notebook suitable for the method of the present invention? A preferred material to provide is comprised of polyethylene and is thermoformable at temperatures up to about 1 ao-c.

The foamed thermoplastic sheet can be provided in any desired thickness. Foamed thermoplastic sheets, which are particularly suitable for gastric use in the laminates of the present invention, generally have a thickness of 33 am or less. The preferred thickness of the foamed thermoplastic sheet used to make the composite laminate is from 2 to 20 mm.

The thermoformable laminate of the present invention has a composite impregnated fabric adhered to one side of the foamed thermoplastic sheet. The method of the present invention includes
A polymer-impregnated fabric is provided temporarily attached to at least the -[411] side of a foamed thermoplastic sheet. This )k-coalesced impregnated cloth is 1
Stability of pickles that have been aged into complex shapes at a ripening temperature ranging from 30°C to 18D'C (17), such as composite products? give. The temperature range for ripening is 1+Q°C, which is the temperature at which the foamed thermoplastic sheet can be easily ripened.
limited to low temperatures.

This category is based on the decomposition of foamed thermoplastic sheet material (I8
! 0chi, foaming failure) is limited to high temperatures around 1 degree.

The upper level of thermoformable laminate 1 therefore varies depending on the foamed thermoplastic used. Temperatures up to about 180'C are satisfactory for molding with styrene-maleic anhydride/acid copolymer foams. However, the ocular humidity for thermoformable laminates using polystyrene foams is approximately 1 so-c.

For the purposes of the present invention, the term "softening@degree J" is defined as
PerkinElmer f1% draft (') r TADS T
MSSTD TEVO1,Q 4 PCN Q5.
06 B 01.01.04'' as determined by thermal mechanical analysis using a program named 01.01.04. The analysis parameters were: decoude load: 10,9, @fc@[:25℃, maximum temperature: 200G, heating rate 5'C/min, cooling rate: 20℃/
Minutes, the intrusion was made with two rounded tips. The polymer sample was approximately 1/4 inch x 11 inches x 1716 inches (6,
55 x 3.18 ujl x 1.6 im). Thermomechanical analysis consists of the top of a weighed sample being slowly heated at a uniform rate of compression. The temperature at which the probe begins to penetrate is determined by the penetration distance vs. The softening point is measured by the intersection of d for the inflection point on the plot of degrees near the temperature. Polymers useful in the products of the present invention may have active thermoforming temperatures above 75°C, but other materials such as about 130°C or about 180'C'!
Lower softening temperature Y: stomach.

The fabric consists of four different textile fabrics, for example the fabric can be woven or non-woven. Of this cloth! '! A desirable property is that it stretches sufficiently in certain directions of its surface to conform to the desired complex shapes imparted by thermoforming. The stolen cloth is the original form of Q Monozozo ￥6
For example, about 10 to 50 degrees of molding without using a support fan.
It consists of a cloth stretched by 1 of C5 and Σ1-11. Natural mata [text is last a! Good σ), the remaining fabric generally has an elongation Y7TS lower than 10, so these have good formability and moldability @ r
Not useful for making B 4F/I7. The X′-tasteful cloth that can be absorbed by such elongation is unbelievable.
Spinning Ajl contact, 1 Ken polyester t゛ snout ilQ piece,
It consists of 6 parts. One pile of cloth for one knife costs 17 tons? Contains polyesters, nylons, and seripropylenes. The fabric may be any reasonable 11 kW. Typically, useful fabrics have a thickness r of 0.05 to i, Qp+i. However, thicker fabrics can also be used. Preferably, this city is 6 and 0.
1 to Q, with a thickness of 4 b wings. Typically, useful fabrics have a density of 0.3 to 10.0 ounces per square yard (10-3
40M/square meter) 4v@, preferably 1.0~
6.0 oz/sq yd (34-203 g/sq m) of basic polymeric dipping cloth is prepared by soaking the fabric in a solution of 100 g/sq. It is possible, for example, to pull the cloth through a vaat of the solution and then through a set of coolants for excess solution. This cloth can be dried to remove excess medium and then glued to one side of the foamed thermoplastic sheet. Is this adhesive a polymer td cloth? This can be accomplished by any hair dye bonded to the foamed thermal sheet. Preferably, the adhesive does not exhibit creep at low temperatures, e.g. below the temperature dependence of the foam. Acrylic adhesives are useful for this purpose.

Rudimentary flexible polymers include polymers that are industrially designated as resins. Preferred are polymers that are compatible with liquids such as water and quaternary alcohols such as methanol, ethanol, M-zolopanol, and the like. The most preferred polymers are those that are soluble in water, such as water and ammonia.

Such resins include acrylic resins, such as styrene-methacrylic composites. Water-ammonia fermentation 1
One such Acrylic A/system it I that is soluble during the night
I)t kt, S, O,, Tohnaon & Son.
, Tonkryl (S
73 t as acrylic scar! I am paid A salary, which is 8
Softening temperature of 9℃? Wataru fro.

Is the 11th layer of 113 the same A? ni 1fll, ・Uchiru. Phenol j'J Il
uχ Preferred acrylic, to be used in place of T1 fat, should be used in place of phenol; When the phenol resin is completely cured, it cannot be molded, and thus the phenol resin cannot be molded. J-shukuminfu must be only partially cured. This must be partially cured until the final molding stage. The preferred use of acrylic resin is to prevent curing7. I'm like a donor and a supporter.
′! ! ! The use of phenolic resins and phenolic resins avoids the release of foreign substances and pollutants. Nobuko! is adhered to one of the surfaces of the foamed thermoplastic '@J. This can be achieved by heat treatment during lamination or by contacting with water which is preferably a moisture content.
It is carried out by agent II.

Such acrylic resins must also exhibit a softening temperature of greater than about 75° C.8 Such high softening temperatures provide stable laminates, particularly for applications where local temperatures are moderately crystallizing.

Combined emulsions are also suitable for the method of the invention and consist of particles of a polymer dispersed in a medium consisting of, for example, water. Preferred emulsions contain up to about 50 Mml of solid polymer.

On the other hand, this emulsion has a lot of j, J! The solid polymer particles D1 may also consist of an i-, ie 80 cut width housing.

Good! The new polymer consists of an acrylic type polymer. Such a bulging body has a temperature higher than 75°C, but for example about 1300°C.
or 1 degree higher than the minimum thermoforming temperature of the foamed thermoplastic sheet at about 18,001 degrees centigrade.

■The method of the present invention using a polymeric emulsion film to produce overlay foam volume has the following points: It is also more economical than other methods.

It has been found that with this method, for example using a combined emulsion film, less than 16 grams of polymer (eg 5-8 grams per square meter) is required. For example, if the fabric is dipped in a polymer solution before being applied to the foam sort, - Xl per square meter of ff1llW material: 8140,! It turns out that a combination of 70 cities will be used.

This fabric was placed on a wet polymer emulsion film of -7
The composite of the combined emulsion film and the foamed thermoplastic/formable sheet may then be optionally calendered to promote the formation of the ff1 combined emulsion film into the fabric. Laminated bedding can be formed by evaporating the solvent at the outer surface of the polymer emulsion.

On the other hand, the polymer emulsion film cut onto the surface of the foamed thermoplastic sheet can be dried before application of the fabric. Apply the cloth to a dry film and roll the product
-4 and the application of pressure. For example, a high surface with a temperature of about 120-150C? It can be pressed into the fabric (coalescing film?) and impregnated and impregnated into the fabric.

Suitable polymer emulsions include: to promote adhesion of the polymer emulsion film to the foamed thermoplastic sheet;
glue? May be contained. Such adhesives are Rohm
2138 Acrylic Adhesive or K from and Haas
It may consist of an acrylic adhesive such as those not available as 958 acrylic adhesive. Such adhesives are described, for example, by S., C1Johnacn & Son.
An acrylic emulsion such as that available as an emulsion with a water ti5 of about 48 acrylic facets having a softening temperature χ of 101''C and an equal weight ratio Can be mixed with.

The following rolling examples illustrate certain embodiments of the laminated structures and methods according to the present invention.

Example ■ This example demonstrates the formation of a formable, ageable laminate structure of the present invention according to the method of the present invention.

The first aqueous acrylic emulsion was prepared by mixing two aqueous acrylic emulsions of 100% of the polymer emulsion. Consisting of isomorphic components: fon
cr1189 Styrenated acrylic Bunshintai (S+C+J
ohnson & son, inc.
son Wax Chemical Products
Division fez et al.). This emulsion has a milky appearance, a sea viscosity of 400-600 centiboids, and a sea viscosity of 8.7 bonds/gal (1,0
11/α3)'s 8th degree.

The second aqueous acrylic emulsion is adhesive K-2153 (Rohm and Haas
(available from the Company). This emulsion has a milk-1T color, G'' + 25 ppm ammonia, and has a mild ammonia Jl' of about 0.5
Contains ppm of formaldehyde. This emulsion has a viscosity ranging from ao, ooo to so, ooo centiboise.

The mixture of the two acrylic polymer emulsions was prepared to a thickness of about 130 mils and a thickness of about 427 mm/cm.
It was applied in a thin film to one surface of a sheet of styrene having a density of 1,000 square feet (205,9/square meter). 8 wires (0,1
/4 having a diameter of 62 inches (in the order of 4, 1)
Approximately 0.75 mil (19X IQ-6m) thick Tefilm was applied with a 68 stainless steel metric rond. Approximately 1.5 pounds/1 of this emulsion film,
00 square feet (7F/-2).

While this film was still wet, a piece of spun-bonded, non-woven polyester cloth was placed on the emulsion coated surface of the polystyrene foam. This polyester cloth is 1
．． It had a base weight tv of 0 oz/sq yd (33,99/m2), but Reemay by au Font
260'F (
W with steam heating plate for temperatures of 127 °C)
ab2Lsh Metal Products.

Wabash hydraulic press, model 50-
2424-2STMA medium polystyrene foam [+'ff
:S. This press is equipped with a pair of scissors that provide a molding gear for forming the foam.

Wet bond; ・One beggar added 30 members in this press, and then pressed about 100″T'(38') in 90 seconds.
Cooled to temperature C). This laminate count is then approximately 15
Two larvae with a thickness of 0 mil (3.8 mm) were produced.

This merry ester fabric was bonded with good adhesion to a polystyrene optical envelope. Is it glued to cloth? When fibers from a nonwoven fabric break away from the fabric and remain adhered to the foam, it can be measured by pulling and delaminating.
Adhesion is considered to be excellent. Do not cut the fibers on the carcinogen.
→If peeling occurs, the adhesion is considered good.

Actually, scary example ■-■ Examples using various nonwoven fabrics! The chest! The γi process was repeated 8 times.

■Is it unreasonable to have the basics of 68 so/m2 of cloth? Lideropyrene.

Adhesion: Good.

111, cloth: 1055'//l! 2 basics i! ;・
Y a non #a melipropylene.

Adhesion: Good.

■、Cloth: 1659 / m2ノ'Ji=R'XkY:
MTR-g2-lyester.

Adhesion: Excellent.

v, ■: 197g/m” 4H foundation contribution # Y @
non-woven polyester.

Adhesion: Excellent.

Although the adhesion of the product of IJII and m is slightly good,
Such 8 to 4 products are acceptable and suitable for non-severe applications.

Example ■ This example demonstrates the thermoformability of a laminate structure of the invention as prepared in Example I.

The laminate structure prepared in Example I was
Comez by Induszries, Inc.
Thermoforming was carried out in a thermoformer, Labmaster model 14X20. This three-dimensional mold is General M
The design was representative of seat buckle covers such as those used on some Ozers automobiles. This thermoformer transports the flat laminate sheet to an infrared heating section and preills the flat laminate sheet to the softening temperature of the sheet material so that the sheet can be easily formed and processed! 710 operated by heating. Place this sheet in the m heating area.
I asked for a second, but is it 260 to 290? (127
Temperatures in the range of ~143-() were reached.

The heated sheet was then placed in an open mold block heated to 70-F (21C). The aged molded laminate had good three-dimensional shape with no signs of delamination and no wrinkling.

The thermoforming process of Example 1 was repeated using the laminate structures prepared in Examples II-V.

W, thermoforming of the laminated sheet prepared in Example ■. The cooled molded laminate had good three-dimensional shape, but
However, the polypropylene fabric partially delaminated from the polystyrene foam.

(2) Thermoforming of the laminated sheet prepared in Example (2). The cooled molded laminate had good three-dimensional definition, but the BoIJ felt pyrene fabric partially delaminated from the polystyrene foam.

■, Thermoforming of the laminated sheet carried out in #XIi #. The cooled molded laminate had a good three-dimensional shape with no signs of delamination and no wrinkling.

Thermoforming of the product I-sheet prepared in Example V. The cooled molded material had a good three-dimensional shape with no signs of peeling or wrinkling.

Although there was some degree of delamination and wrinkling in the thermoformed laminates of Examples 1 and 1, such laminates made of polypropylene fabrics were not suitable for thermoforming molds that were not pulled at deep or sharp angles, for example. It is suitable for applications requiring less severe thermoforming, such as table headliners.

EXAMPLE Natsumoto's actual flow illustrates another method of manufacturing the thermoformable laminate relic of the present invention.

JoncryP61 LV Acrylic B'ftm Fluid (S, C, Johnson & Son) with the following formulation:
A batch of acrylic polymer solution was prepared using a commercially available acrylic polymer solution (commercially available from B.C., Inc.).

Acrylic resin 35 1% by weight 28% aqueous ammonia 7.5% by weight ethylene glycol
1.5-dine propyl alcohol
5.0% by weight water 51.
This acrylic resin component had a softening temperature of 85'C.

The acrylic polymer solution has a 27-fold f! :% acrylic resin concentration with water.

A cloth sheet of g-adhesive polyester nonwoven fabric is immersed in a bath;
A cloth was impregnated with an acrylic polymer solution. Excess solution was removed by passing the cloth through a pair of rubber coated press rolls. This right was then placed in the open at 180'F' (82°C) for 5 minutes to remove the liquid and yield a dry polymer impregnated cloth containing approximately 50 weight all thiacrylic polymer.

Approximately 130 mils (3,3 order) thick and approximately 42 fnd/1
．． Of') 0 million feet) (20!M/10 million meters)
A polystyrene foam sheet having a density of 4.0 to
QWc adhesive E-1958 (Rohm and B
10,000 surfaces were coated with an aqueous acrylic emulsion (manufactured by AAS Co., Ltd.).

This emulsion has a milky white color and a mild acrylic odor. This emulsion has a Type B viscosity in the range of 2,000 to 4,000 centivoids.

A 15M sesquicarbonate catalyst solution (equimolar proportions of sodium bicarbonate and sodium carbonate) was added to the emulsion in an amount of 4 parts per yioo part of emulsion. This catalyst is hot! /168 wire (0,1
having a diameter of 62 inches (4, IW)]/1
68 stainless steel + 11110 mm was applied to the surface of the polystyrene foam and allowed to dry.

A dried polymer impregnated cloth was applied to the surface of the polystyrene foam coated with the dried acrylic emulsion.

Lamination was done in a Wabash hydraulic press by Metal Products, Inc8. The press is held apart by scissors to provide a molding cavity for the polystyrene foam.
0"F (127'C)!! Summer Steam Heat Plate. Heat the laminate in the press for 30 seconds, then heat the plate to a temperature of approximately 100"F (38°C). It was cooled in about 90 seconds. The dry volume W1 groove structure is approximately 150 mils (6,8
It had a thickness of

Example ■ Example M''r:'r: The thermoforming method of Example ■ was repeated using the prepared specimen.The cooled molded laminate had a good three-dimensional shape without wrinkling. I had it.

The thermoformable laminate structures of the present invention are useful for producing molded thermoplastic foam products.

Such molded thermoplastic foam products are useful in loads where thermal and acoustic insulation are desirable properties. This laminate provides three-dimensional stiffness over a wide temperature range.

The thermoformable laminate structure is particularly useful in automotive headliner applications where the laminate aids in noise attenuation within the vehicle. A particularly useful headliner uses two sheets of laminate prepared in accordance with the present invention to
A third polymeric foam, such as 250 mil (6,35 in.
) Thick, flexible ether, polyurethane foam can be manufactured as an inner cover. This three-part composite was prepared by using an adhesive on the surface of the laminate sheet to adhere to the soft fiber core.
'u can. An acrylic emulsion adhesive cloth is placed on the surface of the composite to provide thermoformability of the composite. One surface of the composite vinyl-rich soft foam covering for aesthetic interior surfaces can be covered with leather. The automotive headliner is under pending US patent application No. 5ER1AL/16553.
．． 594, is published on j.

Although particular embodiments of the invention have been described, it will be apparent to those skilled in the art that modifications thereof may be made without departing from the spirit and scope of the invention. Therefore,
4! ? This is a hypothetical assumption that changes may be made within the scope of the claims (or within the overall concept of the invention).

Claims (16)

[Claims] (1) (a) a sheet of thermoplastic foam, the sheet having first and second surfaces; and (b) the coating is a polymer-impregnated fabric, the polymer impregnated at about 75°C.
A moisture-resistant, moldable, thermoformable laminate structure comprising a coating adhered to one of the surfaces having a higher softening temperature. (2) The laminate according to item 1 above, wherein the polymer is an acrylic resin. (3) The sheet of thermoplastic foam is made of expanded polystyrene,
The laminate structure according to item 2 above, which is selected from the group consisting of expanded styrene-maleic anhydride copolymer and expanded polyethylene. (4) The laminated structure according to item 1 above, wherein the cloth is a nonwoven fabric. (5) The laminate structure according to item 2 above, wherein the acrylic polymer is a styrene-methacrylic acid copolymer. (6) (a) applying a polymer emulsion film to the surface of a sheet of thermoplastic foam; (b) drying the emulsion film by evaporation of the emulsion liquid; (c) applying a cloth to the dry emulsion film; d)
impregnating the fabric with the film polymer by applying heat and pressure to the surface of the fabric, thereby causing the film polymer to become plastic and impregnating the fabric; (e) and removing the heat and pressure from the fabric surface; having a polymer-impregnated fabric adhered to at least one side of a sheet of thermoplastic foam, comprising adhering the fabric to the sheet of plastic foam film by removing and allowing the polymer to cool and solidify; A method of forming a moldable, thermoformable laminate structure. (7) The method according to item 6 above, wherein the thermoplastic foam sheet is made of polystyrene or a copolymer of polystyrene. (8) The method of item 7, wherein the polymer emulsion comprises an acrylic polymer having a softening temperature higher than 75°C. (9) The method of claim 8, wherein the polymer emulsion film is applied to the sheet in an amount of 5 to 8 g liquid/square meter. (10) (a) applying a polymer emulsion film to the surface of a sheet of thermoplastic foam; (b) applying a fabric to the emulsion film and impregnating the fabric with the polymer; and (c) applying heat and pressure. adding to at least one side of the sheet of thermoplastic foam, thereby making the emulsion solids plastic, and bonding the fabric to the sheet by removing heat and pressure and allowing the polymer to cool and solidify. A method of making a formable, thermoformable laminate structure having an adhered polymer-impregnated fabric. (11) The method of item 10 above, wherein the polymer emulsion film is dried before applying heat and pressure. (12) The method according to item 10 above, wherein the thermoplastic foam sheet is made of polystyrene. (13) The method of claim 12, wherein the polymer emulsion film comprises an acrylic polymer emulsion, and the polymer has a softening temperature greater than 75°C. 14. The method of claim 13, wherein the polymer emulsion film is applied to the surface of the thermoplastic foam sheet in an amount of 5 to 8 grams of liquid per square meter of thermoplastic foam. (15) a) providing a sheet of thermoplastic foam having first and second surfaces; b) impregnating the fabric with a polymer dissolved in a solvent, the polymer having a softening temperature greater than 75°C; c) drying the polymer-impregnated fabric, and d) adhering the polymer-impregnated fabric to a thermoplastic foam to form a laminate structure. (16) The method of paragraph 15, wherein the polymer-impregnated fabric is adhesively bonded to the first and second surfaces of the sheet of thermoplastic foam.