JPH0622916B2 - Laminated material manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to an automobile ceiling material, a door trim, and a shell.
Sheet back, trunk / lid, trunk surrounding materials, interior materials such as floors, building ceiling materials, wall materials, and deep-moldable rigidity useful as molding materials for decorative containers, and laminated materials with both heat insulation and shielding properties. The present invention relates to a manufacturing method.

[Prior art]

Conventionally, as the above-mentioned interior material for automobiles, materials which can withstand a temperature of 100 ° C. or higher, such as resin felt in which a phenol / aldehyde condensation resin is filled with fibers, foam synthetic resin, polypropylene composite, and cardboard made of polypropylene are used. Among these materials, the resin felt is excellent in rigidity, heat-resisting shape retention, dimensional stability, and shielding property, but has drawbacks of poor molding workability, impact resistance, and lightness.
Further, polypropylene cardboard is excellent in rigidity and lightness, but on the other hand, it is poor in deep drawing and has a directional strength because it uses a corrugated member. Further, a foamed synthetic resin, such as polystyrene, is excellent in lightness, but has a drawback that molding workability and bending resistance are poor, and the appearance (roughness) after molding is difficult. Further, the polypropylene composite has excellent rigidity but has drawbacks in molding workability, impact resistance and dimensional stability. Required performance as interior materials, namely rigidity and appropriate flexibility, lightness, dimensional stability, heat-resisting shape retention,
A material satisfying all of the moldability has not been obtained.

First, the present inventor has provided a first backing material (A) containing the following resin aqueous emulsion (A) and expandable polystyrene particles (B) on the back surface of the rug stock. Aqueous resin emulsion mainly composed of an aqueous dispersion of a resin having a melting point of 80 ° C. or higher (100 parts by weight in solid content) (B). After coating expandable polystyrene particles (10 to 100 parts by weight) with a particle size of 1.5 mm or less, a melting point lower than that of the resin particles of the above-mentioned (A) aqueous emulsion was used as the second backing material on the surface of this first backing material. Having a melting point of 50 to 125
A coating having a heat-adhesive property, which is characterized in that an aqueous emulsion of a resin having a temperature of 0 ° C. is applied, and then dried by heating to dry the emulsion to form a backing layer and foamable polystyrene particles. A method for producing the material has been proposed (Japanese Patent Laid-Open No. 60-59176).

In this method, resin 100 in aqueous emulsion is used.
The amount of expandable polystyrene particles used is 10 parts by weight.
As small as 100 parts by weight, the foam layer does not form a continuous smooth layer, and spherical foam particles project and adhere to the back surface, so the wall thickness of the laying material is not uniform, and other metal, wood, etc. In order to perform uniform attachment to the base material, there is a drawback in that a large amount of an adhesive is used to fill the valley between the protruding foam particles and the original sheet of the rug. Also, the appearance of the back side is poor.

For the purpose of improving the performance of such a laying material, that is, improving the shielding property, improving the heat insulating property and rigidity, improving the appearance property, and improving the crack prevention, the present inventor discloses in Japanese Patent Application No. 61-286927. Base cloth made of material with heat distortion temperature of 150 ° C or higher
On (A), (a). Resin water emulsion 100 parts by weight in solid form (b). Expanding styrenic resin particles with a particle diameter of 1.5 mm or less 150-700 parts by weight of a coating composition of a coating composition is applied, and then the coated banking coating layer has a heat distortion temperature of A base fabric (B) made of a material having a temperature of 150 ° C. or higher is laminated to form a laminate, and the laminate is compressed from one side or both sides of the laminate to form a part of the coating material as the base fabric (B). After impregnating,
The foamable styrene-based resin particles have a softening point or higher, and the foamable styrene resin particles are foamed by heating at a temperature lower than the heat deformation temperature of the base fabrics (A) and (B) and the resin water-based emulsion. Was provided to obtain a laminate having a foam layer between the base fabrics (A, B), thereby providing a method for producing a laminate.

In this method, in order to improve the compression moldability of the laminated material, when a water-based emulsion having a glass transition point of 80 ° C. or higher is used as the resin-based water-based emulsion of the component (a), the ceiling material, door trim, rear shell of an automobile, etc. Has high rigidity and is suitable for applications with excellent mold fidelity, but when used as a floor material for automobiles, the rigidity is too high,
It has been found that there is a lack of elasticity when walking on the floor material and that the foam layer can be cracked when the processed laminate is folded.

It was also found that there are points to be improved in terms of fittability according to the irregularities inside the automobile.

In order to reduce the rigidity of the laminated material, improve elasticity, and obtain the fit property, it is sufficient to use a resin water-based emulsion having a low glass transition point, but the heat resistance of the laminated material decreases and the heat of the engine is transmitted indoors. In fact, the room temperature in the car in summer is 60 ℃.
Taking into consideration the situation before and after, it is not preferable to lower the glass transition point of the emulsion resin.

[Specific means for solving problems]

In order to improve the fitting property of the laminated material, the present inventor added a plasticizer of emulsion resin to the coating material of the prior application,
It was found that when a cross-linked resin aqueous emulsion is used, a resin film having a three-dimensional network structure is formed and the heat resistance of the laminated body is not significantly reduced, and a laminated material with improved fitting and walking characteristics can be obtained. It was

Furthermore, as a result of various studies on cross-linking type resin aqueous emulsions, room temperature cross-linking type resin aqueous emulsions (for example, JP-A-57-3850 and 57-3857).
No. 58-96643) was used, it was found that the heat resistance was greatly reduced by the presence of the plasticizer as in the case of using the non-crosslinking resin emulsion, and the heat-crosslinking type resin aqueous emulsion was found. (For example, JP-A-58-677
No. 62, No. 58-69253, No. 58-132051.
No. 59-74166, No. 60-35059, No. 60-212469), it was found that the decrease in heat resistance was small, and the present invention was reached.

That is, the present invention comprises: (a) on a base fabric (A) made of a material having a heat distortion temperature of 150 ° C. or higher. Thermo-crosslinkable resin aqueous emulsion Solid content 100 parts by weight (b). Expandable styrenic resin particles having a particle size of 1.5 mm or less 150 to 700 parts by weight (c). Plasticizer 6 to 30 parts by weight of a backing coating agent is mixed, and then the coated banking layer is coated with a base cloth (B) having a heat distortion temperature of 150 ° C or higher. ) To form a laminated body, and the laminated body is compressed from one side or both sides of this laminated body to impregnate a part of the coating agent into the base fabric (B), and then the expandable styrene resin. By heating at a temperature above the softening point of the resin of the particles and lower than the heat distortion temperature of the materials (A) and (B), the expandable styrenic resin particles are foamed and the heat-crosslinkable resin aqueous emulsion is added. The present invention provides a method for producing a laminated material, which comprises drying and crosslinking to obtain a laminated material having a foam layer between the base fabrics (A, B).

Base cloth (A) The base cloth (A) is a surface layer material, preferably having a cosmetic property, and is made by screen-printing on a non-woven fabric such as tufted carpet, woven fabric, needle punch carpet or synthetic leather, non-woven fabric. It is also possible to use those obtained by backing these base cloths.

As the material of the base cloth, in addition to natural fibers such as wool and silk, nylon, polyethylene terephthalate, polypropylene,
A resin fiber such as polyacrylonitrile is used.

The heat deformation temperature of the materials of the base cloth (A) and the base cloth (B) described later is preferably 40 ° C. or more higher than the softening point of the material resin of the expandable styrenic resin particles of the backing material. By doing so, heat shrinkage during foaming can be prevented.

As the base cloth (A), when a needle punched carpet or spunbonded nonwoven fabric having a bad appearance obtained by using scraps or recycled fibers is used, the present invention is carried out to obtain a laminated material, and then the base cloth is obtained. On the surface of (A), artificial leather or synthetic or printed or embossed synthetic paper, titanium paper, polyvinyl chloride decorative paper, woven cloth, or a composite material of these and urethane foam or the like is laminated to make up the surface.

The basis weight of the base fabric (A) is 50 to 1,000 g / m ² , preferably 80 to 500 g / m ² .

Base cloth (B) The base cloth (B) is used by adhering it to a base material, or is used on both sides in contact with the floor, that is, on the back side of the interior material, so the appearance is not limited and an inexpensive material is preferable.

Therefore, it is a woven or non-woven fabric obtained from natural and resin fibers such as wool, nylon, polyacrylonitrile, polyacetate, polypropylene, etc. rather than woven fabric or artificial leather, needle punched carpet, spunbond or inexpensive regeneration. A product felt is preferably used. Further, these base cloths may be subjected to a packing treatment with a phenol resin, a synthetic resin emulsion or a latex, or may be paper, a glass fiber woven cloth or a lower woven cloth. The fibers may be recycled.

This needle punch carpet is a web obtained by needling a fiber mat made of synthetic fibers and / or natural fibers, and this web is manufactured by a known method for manufacturing a non-woven fabric. That is, 1.2-300 denier, fiber length 25-
A web (fiber mat and / or a fiber mat and / or a fiber obtained by sufficiently mixing and opening 150 mm of fibers and supplying the opened fiber to a web forming device, and stacking cards formed from the mixed fibers so as to have a desired fiber areal weight Further, this web) is temporarily fixed by needling in the vertical direction and interlocking the fibers.

When a part of the fibers (15 to 50% by weight of the mat weight) is replaced with a resin fiber binder having a low melting point of 80 to 160 ° C., the strength of the obtained laminated material is further improved. As such a fiber binder, a short fiber (length 15 to 40 m) of a resin such as polyethylene, polypropylene, linear polyester, low-molecular-weight condensation polyamide or the like is used.

As a raw material of the synthetic fiber constituting the fiber mat, polyethylene terephthalate, polyamide or the like is 40 ° C. or more, preferably 70 ° C. or more higher than the melting point of the thermoplastic resin fiber binder (specifically 200 to 280 ° C.). ) Is used. As the natural fiber, cotton, hemp, wool, etc. are used.

The basis weight of this base cloth (B) is 10 to 2,000 g / cm ₂ ,
Although it depends on the application, it is preferably 10 to 100 g / m ₂ when used for the purpose of simply adhering or protecting the foam layer, and 100 to 1 when the laminated material is provided with cushioning property and thickness. It is used at a rate of 1,000 g / cm ₂ .

(Backing Material) The backing material contains at least a heat-crosslinkable resin aqueous emulsion, expandable styrene resin particles, and a plasticizer. The expandable styrenic resin particles are continuous, and in order to obtain a smooth foam layer, 150 to 100 parts by weight of the resin in the emulsion is added.
It is used in an amount of 700 parts by weight, preferably 200 to 500 parts by weight.

(Expandable Styrenic Resin Particles) Expandable polystyrene includes styrene alone or vinyl monomers such as styrene and α-methylstyrene, vinyltoluene, methylmethacrylate, butylmethacrylate, acrylonitrile, acrylic acid, and maleic anhydride. Suspension polymerization,
It is obtained by impregnating polymer particles obtained with a foaming agent during or after the polymerization, and examples thereof include polystyrene, styrene, α-methylstyrene / acrylonitrile copolymer, and styrene / α-methylstyrene. -Acrylonitrile-methyl methacrylate copolymer, styrene-methyl methacrylate copolymer, and other styrene-based resins (softening point is 100 to 125 ° C) as a raw material having a particle size of 0.1 to 1.
5 mm expandable resin particles (content of blowing agent 2-15% by weight) are used.

(Heat-Crosslinkable Resin Aqueous Emulsion) As a backing material, as a heat-crosslinkable resin aqueous emulsion having a function of locking a fiber mat and an adhesive function of foam particles, a glass transition point of the resin after heat-crosslinking is 80 to 140 ° C. A resin aqueous emulsion is used that gives a resin.

For example, (1) 3 to 10% by weight of a vinyl monomer having a hydroxyl group as a thermal crosslinking group, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, etc. Vinyl monomer 97-90% by weight A copolymer aqueous emulsion obtained by emulsion polymerization of a mixture of vinyl monomers 100 parts by weight (solid content) and 2 to 20 parts by weight of water-soluble aminoplast. .

(2) Obtained by emulsion polymerization of 1 to 10% by weight of N-methylolacrylamide or / and N-methylolamide as a thermal crosslinking group and 99 to 90% by weight of a vinyl monomer mixture of other vinyl monomers. Self-crosslinking resin aqueous emulsion.

(3) A mixture of 100 parts by weight (solid content) of the resin aqueous emulsion of (2) above and 2 to 20 parts by weight of a water-soluble aminoplast.

(4) A mixture of the above (1) and (2) and emulsion.

Etc. are mentioned as a typical thing.

Other vinyl monomers include (i) 2-ethylhexyl acrylate and n-acrylic acid.
Butyl, ethyl acrylate, isopropyl acrylate,
A monomer selected from 2-ethylhexyl methacrylate, n-propyl acrylate, n-butyl methacrylate, vinylidene chloride, ethylene and butadiene 20% by weight or more (ii) vinyl acetate, ethyl methacrylate, vinyl chloride,
Monomers selected from n-propyl methacrylate, styrene, acrylonitrile, methyl methacrylate, acrylamide, methacrylamide 80% by weight or less (iii) acrylic acid, itaconic acid, methacrylic acid, maleic acid, fumaric acid and these acids Α, β-unsaturated carboxylic acid selected from anhydrides 0 to 5% by weight.

Is used.

The resin solid concentration of the aqueous emulsion is usually 20 to 60% by weight, and the diameter of the dispersed resin particles is 10 μ (micron) or less, preferably 0.05 to 1.0 μ.

In order to give the obtained non-woven fabric a feeling of weight, it is possible to add an inorganic filler or pigment such as calcium carbonate, iron oxide, ferrite, barium sulfate or the like to the emulsion.

The film forming temperature of the aqueous resin emulsion before crosslinking is lower than the foaming temperature of the expandable styrene resin particles,
Further, it is more preferable that the temperature is lower than the softening point of the expandable resin particles in order to make the foam layer continuous and smooth, and also to make the foaming smooth. The foam particles are bonded together by the emulsion resin acting as an adhesive to form a continuous foam layer.

The heat-crosslinkable resin aqueous emulsion is used as a base fabric for the expandable resin particles, in addition to acting as an adhesive agent for the foam particles.
Acts as a carrier when applied to (A). or,
It also acts as an adhesive between the base fabrics (A) and (B) and the foam layer, and imparts rigidity to the base fabric.

(Plasticizer) As a plasticizer that plasticizes the emulsion resin and imparts elasticity to the foam layer of the laminated material, dioctyl phthalate,
Dibutyl phthalate, epoxidized linseed oil, dibutyl benzyl phthalate, chlorinated paraffin, resin type plasticizer [BASF's Plastolite DS-3060 (trade name)], phosphorus-based plasticizer and the like can be used.

The plasticizer is used in a proportion of 6 to 30 parts by weight based on 100 parts by weight of the resin solid content in the heat-crosslinkable resin aqueous emulsion.

If it is less than 6 parts by weight, the plasticizing effect is poor, and the effect of improving the fit property and elasticity of the laminated material is not sufficient. On the contrary, if it exceeds 30 parts by weight, the rigidity and heat resistance of the laminated material are excessively lowered.

The backing material for the base fabric (A) or (B) is applied by spraying, dipping, brushing, a form coater, a roll or the like. The coating amount of backing material is 100-1700g / m ²
(Solid content), preferably 300 to 1300 g / m ² . The coating is preferably a foam coating method. In particular, when the heat-crosslinkable resin emulsion is foamed 3 to 7 times, the coating workability, coating amount, and thickness can be easily adjusted.

Laminated material manufacturing method Laminated material, on the surface of the base fabric (A) or (B), the above-mentioned heat-crosslinkable resin aqueous emulsion (a), expandable resin particles (b) and a plasticizer.
Apply the backing coating containing (c) and then the base cloth.
(B) or the base fabric (A) is loaded on the surface of this coating agent to obtain a laminate, and a squeezing roll from one side or both sides of this laminate,
The base fabric (A) by pressing with a press or the like, impregnation of the emulsion resin to (B), and then the laminate having a melting point of the expandable resin particles or higher, the base fabric (A), (B ), The foamable resin particles are foamed by heating at a temperature lower than the heat deformation temperature of the material, and drying is performed to dissipate the water in the resin aqueous emulsion, and the base cloth is applied to the front and back surfaces of the foam layer (E). A laminated material (S) in which (A) and the base cloth (B) are integrally bonded is manufactured (see FIG. 1). At this time, a method may be used in which water is removed at a temperature at which the expandable resin particles do not foam, for example, at about 90 ° C., and then the temperature is raised to the foaming temperature for foaming.

When expandable polystyrene particles (Tg 104 ° C.) are used and the base fabric is made of polyester (melting point is about 240 ° C.) or polypropylene (melting point is 164 ° C.), the drying temperature is set to 110 to 140 ° C.

The heating and drying of the coated emulsion and the foaming of the expandable resin particles can be performed by any method.
For example, a heating cylinder, an infrared heater, a hot air dryer, a saxion dryer and the like can be used, but it is preferable to use a hot air dryer. By this heating, a part or all of the thermally crosslinkable resin is simultaneously crosslinked.

By this heating, the expandable resin particles expand about 2 to 50 times,
Foam particles having a particle diameter of 0.5 to 4.5 mm or a part thereof are fused together to form a foam sheet. Of course, the foam particles also form a continuous foam (E) due to the resin film of emulsion.

This foam layer imparts heat insulating properties, moldability, rigidity, and barrier properties to the laminated material.

(Effect) The laminated material of the present invention is a laminated material having significantly improved rigidity, heat insulating property and shielding property due to the presence of such a continuous foam layer.

Further, by heating the laminated material to a temperature at which the foam softens and melts and at a temperature at which the crosslinkable resin crosslinks, and press-molding the laminated material, the laminated material can be shaped into a desired shape and thickness.

In addition, since both sides of the foam layer are covered with the base cloth, the sound of the foam layer rubbing does not occur and the durability of the foam layer when broken is improved. Furthermore, it has excellent suitability for bonding with other materials.

Furthermore, when manufacturing laminated materials, the backing coating agent is the base cloth.
As shown in (A) and (B), it is compressed and forms a smooth foam layer because it is compressed.

Further, the thermally crosslinkable resin of the binder is crosslinked by heating and drying the emulsion during the production of the laminated material, or by heating during press molding of the laminated material, so that the heat resistance of the foam layer is less deteriorated.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example of Production of Needle Punched Carpets Nonwoven Fabric for Base Fabric (A) Example 1 A plain type needle punched carpet (80% polyester fiber) made of polyester fiber and polypropylene fiber 20 g / m ² was used for screen printing on this surface.

Example 2 Toray Industries, Inc. artificial leather Exeine (trade name) was used (heat resistance of 160 ° C. or higher).

Example 3 A tufted carpet obtained by subjecting a polyester non-woven fabric to a nylon base and subjecting it to nylon pile was used (basis weight: 450 g /
m ² ).

Example 4 A plain type, needle punch carpet made of polyester fiber (basis weight of 300 g / m ² ) was charged with Mitsubishi Yuka Bertesier's resin aqueous emulsion 209 DN (trade name; 50% solid content, MFT 20 ° C.). 100 g / m ² (dry solid content) backing treated was used.

Non-woven fabric for base fabric (B) Example 5 A fiber mat (150 g / m ² ) in which 15 denier, polyester fiber scraps having a fiber length of about 100 mm and polypropylene (melting point 164 ° C.) fibers were randomly stacked was used.
Needle punch carpet (80% polyester fiber) with a thickness of about 1 mm was needled at a rate of 50 per 1 parallel inch using a needle of -32-3 RB, heated to 200 ° C and cooled and pressed. Obtained.

Resin water-based emulsion (1) ANARONAL S-886; Mitsubishi Yuka Verdeishiyu Co., Ltd. thermal cross-linking type styrene-acrylic acid ester-based polymer water-based emulsion (film forming temperature 20 ° C., Tg of cross-linking resin about 110 ° C., solid (2) Analonal YJ-1100D: Non-crosslinking type styrene-acrylic acid ester-based copolymer aqueous emulsion (T) manufactured by Mitsubishi Yuka Verdeshiyu Co., Ltd.
(55 g, solid content concentration 46% by weight) (3) Production example of room temperature crosslinked resin aqueous emulsion A reaction vessel equipped with a temperature controller, anchor type stirrer, reflux condenser, supply container, thermometer and nitrogen inlet pipe. The following raw materials were charged therein.

Water 200 parts 35% aqueous solution of sodium salt of sulfuric acid half ester of p-nonylphenol (anionic emulsifier) reacted with 20 mol of ethylene oxide 5 parts p-Nonylphenol reacted with 25 mol of ethylene oxide (nonionic emulsifier) 20% solution of 20 parts.

The following mixtures were used as feed I.

Water 200 parts 35% solution of the anionic emulsifier 25 parts Styrene 240 parts Acrylic acid 2-ethylhexyl ester 215 parts Acrylic acid 10 parts Acrolein 25 parts Acrylamide 10 parts As feed II, potassium persulfate 2.5 in 85 parts water 2.5 Parts of the solution were prepared.

After replacing the inside of the reactor with nitrogen gas, feed
Of 10% was added and the mixture was heated to 90 ° C. Then 10% of feed II was injected into the reactor, then the remaining feeds I and II were fed into the reactor in parallel over a period of 3 to 3.5 hours. After keeping the temperature at 90 ° C. for 1.5 hours after the feeding, the reactor was cooled to room temperature. The pH of the dispersion was adjusted to 7 to 8 with aqueous ammonia, 8 parts of adipic dihydrazide was added, and the mixture was stirred for about 1 hour.

Thus, a room temperature crosslinkable resin aqueous emulsion having a solid content of 50% was obtained.

(4) Production Example of Aqueous Emulsion of Heat-Crosslinking Resin Styrene 47.5 parts by weight Butyl acrylate 40 parts by weight Ethylene glycol monomethacrylate 10 parts by weight Acrylamide 1.5 parts by weight Acrylic acid 1.0 parts by weight The vinyl monomer mixture described above (3 Emulsion polymerization according to the production example of), solid content of 50% by weight, viscosity (2800 cps,
A thermally crosslinked resin aqueous emulsion having a pH of 8.0 and MET of 25 ° C. was obtained.

(5) Production example of heat-crosslinkable resin emulsion Methyl methacrylate 45 parts by weight Butyl acrylate 47.5 parts by weight N-methylolacrylamide 5 parts by weight Acrylic acid 2.5 parts by weight Using the above vinyl monomer mixture, the production example (3 5.) Emulsion polymerization is carried out according to the procedure (1), solid content is 50% by weight, and pH is 6.
A heat-crosslinkable resin aqueous emulsion having an MFT of 20 ° C. was obtained.

Example 1 Needle punch carpet obtained in Example 1 (Basis weight: 200 g
/ M ² ) on the side opposite to the printed side, (a). 200 parts by weight of acronal S-886 (b). Expandable polystyrene particles having an average particle size of 0.33 mm (containing 5.5% by weight of butane) 400 parts by weight (c). A backing coating agent consisting of 20 parts by weight of dibutyl benzyl phthalate was applied so that the solid content was 700 g / m ^2, and the needle punch carpet obtained in Example 5 was immediately laminated as a base fabric (B). Then, the nonwoven fabric layers on both sides were impregnated with the emulsion by pressing with a roll from both sides. The needle punched carpet laminate impregnated with emulsion was heated from the side of the needle punched carpet obtained in Example 5 with hot air at 130 ° C. for 15 minutes to remove the water content and expand the expandable polystyrene particles. A laminated material was produced in which a layer of continuous polystyrene foam particles having a density of about 0.14 g / cm ³ and a particle size of 1.0 mm or less was sandwiched.

The thickness of the laminated base fabric (Example 1) was about 2 mm, the thickness of the foam layer was about 5 mm, and the thickness of the base fabric (Example 4) was about 1 mm.

Further, this laminated material is heated in a far infrared ray furnace at 180 ° C. for 60 seconds to sufficiently soften the resin of the backing material and the polystyrene foam and crosslink the resin of S-886, and then 20 kg using a cooling press die. A carpet for an automobile interior floor was manufactured by molding at a pressure of / cm ² for 1 minute.

Comparative Example 1 In Example 1, a resin emulsion was used between the upper and lower non-woven fabrics, but expandable polystyrene particles were not used (not used), and the laying material (finishing wall thickness: about 3 mm, A layer: 2 mm, B: A layer 1 mm) was obtained and further molded to obtain an automobile interior carpet.

Comparative Example 2 A carpet for interior decoration of an automobile interior floor was obtained in the same manner as in Example 1 except that a coating agent which did not contain dibutylbenzyl phthalate as the component (C) of the plasticizer was used as the backing coating agent.

Comparative Example 3 As a backing coating agent, instead of the heat-crosslinking type resin aqueous emulsion S-886 of the component (a), a coating agent using the resin aqueous emulsion of Example-4 containing no aminoblast was used. In the same manner as in Example 1, an automobile interior interior carpet was obtained.

Comparative Example 4 Example 1 was repeated except that as the backing coating agent, a coating agent using the room temperature crosslinkable resin emulsion described in (3) above was used in place of the heat-crosslinking type resin aqueous emulsion of component (a).
In the same manner as described above, a carpet for automobile interior interior was obtained.

Comparative Example 5 As a backing coating agent, ACRONAL YJ-110
A carpet for automobile interior and interior was obtained in the same manner as in Example 1 except that 200 parts by weight of 0D, 400 parts of styropol and a mixture coating agent were used.

Example 2 As a backing coating agent, instead of the heat-crosslinking type resin aqueous emulsion S-886 as the component (a), a coating agent using the self-heat-crosslinking resin aqueous emulsion (5) was used. In the same manner as in Example 1, a carpet for an automobile interior floor was obtained.

Example 3 A water-soluble melamine resin “MD-101” manufactured by Sumitomo Chemical Co., Ltd. was added to 100 parts of the water-soluble emulsion of the heat-crosslinking resin of Production Example 4.
A carpet for an automobile interior floor was obtained in the same manner as in Example 1 except that 10 parts of (trade name) was used as the component (a).

Example 4 To 100 parts of the heat-crosslinkable resin aqueous emulsion of Production Example 4,
Sumitomo Chemical Co., Ltd. water-soluble melamine resin "MD-10"
A carpet for an automobile interior floor was obtained in the same manner as in Example 1 except that 1 "6 parts was used as the component (a).

In addition, the following method is used to evaluate the laminated carpet for a car interior floor.

Three-point bending strength A test piece (length 150 mm, width 50 mm) is supported with a span of 100 mm, and a deformation load is applied vertically to the sample piece at a rate of 50 mm / min at the center point of the sample using an Instron type tester. The maximum bending resistance value when loaded was measured.

Non-Water Permeability According to the water permeability test of JIS A-6910.

The head is set to 250 mm and it is judged after 12 hours.

×: Water penetrated on the back surface and did not remain.

Δ: Water bleeding is recognized on the back surface.

○: Water bleeding is not recognized on the back surface.

Adhesion strength test piece (length 150 mm, width 30 mm) The peel strength of the foam layer and the base fabric (A) is measured at a speed of 50 mm / min using an Instron type tester.

Rigid When a car interior carpet is bent at 90 degrees ○: The carpet is hard and has a large bending resistance, and it folds △: The carpet is hard, but it bends without breaking and fits on the floor of the car.

×: There is no resistance to bending the car pet, and it fits gently to the floor of the car.

Heat resistance Carpets for automobile interior floors obtained by press molding at 85 ° C
Then, the degree of deformation of the carpet when stored for 48 hours is evaluated according to the following criteria.

⊚: No deformation.

○: Some deformation.

Δ: Large deformation.

X: Marked deformation.

After winding the elastic carpet with a winding diameter of 50 mmφ and removing the load to return it to its original shape ◯: Wrap without breaking and return to the original shape.

Δ: Can be wound without breaking, but the return is bad.

X: When wound.

Type fidelity ◎: good.

○: Some deformation.

X: Large return after press molding.

Examples 5-6 Bending strength, water impermeability, mold fidelity, as in Examples, except that the artificial leather of Example 2 and the tufted carpet of Example 3 were used in place of the first needle punched carpet. A laminated material excellent in fit property and heat resistance was obtained.

The artificial leather was pressed from both sides of the laminate.

Examples 7 to 8 In Example 1, the mixing ratio of acrodonal S-886 and expandable polystyrene particles (EPS) was 100 parts to 200 parts (Example 7) and 100 parts to 70 in terms of solid content ratio.
A laminated material having the physical properties shown in Table 2 was obtained in the same manner except that the content was 0 part (Example 8).

Example 9 As a resin aqueous emulsion, acronal "S-88" is used.
6S "200 parts by weight, 10 parts by weight of dioctyl phthalate as a plasticizer, the non-woven fabric for the base fabric (A) obtained in Example 4, and the under felt 1000 g of a phenol used for vehicles as the non-woven fabric for the base fabric (B) / M ² as expandable resin, expandable styrene / α-methylstyrene copolymer particles, Mitsubishi Yuka Verdeitshie Co., Ltd. Heat Pole (T
g About 115 ° C., 200 parts by weight of particles having a particle size of 0.5 mm or less, and 100 parts by weight of particles having a particle size of 1.0 mm (applied as a foam layer at 300 g / m ² ) A floor carpet (thickness of foam layer was 1.5 mm) was obtained in the same manner as in Example 1 and molding. The bending strength was 0.13 kg / 5 cm width, but the moldability, heat resistance, adhesion with both non-woven fabrics, and walkability were good.

Example 10 A floor carpet molded in the same manner as in Example 9 except that the coating amount of the coating composition comprising Acronal S-886S and expandable styrene / α-methylstyrene copolymer particles was changed to 700 g / m ^2. (The thickness of the foam layer is about 5 mm).

The bending strength of the carpet was 0.17 kg / 5 cm width.

Example 11 In Example 1, the drying temperature was 95 ° C. for 20 minutes,
After removing water, the mixture was heated at 130 ° C. for 50 seconds in a hot air oven to carry out foaming treatment.

As a result, a foam layer having a thickness of about 5 mm was obtained as in Example 1. No difference was found in moldability, water impermeability, rigidity, etc.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a plan view showing a manufacturing process of a laminated material.

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Claims (8)

[Claims] 1. A base fabric (A) made of a material having a heat distortion temperature of 150 ° C. or higher, (a). Thermo-crosslinkable resin aqueous emulsion Solid content 100 parts by weight (b). Expandable styrenic resin particles having a particle diameter of 1.5 mm or less 150 to 700 parts by weight (c). Plasticizer 6 to 30 parts by weight of a backing coating agent is mixed, and then the coated banking layer is coated with a base cloth (B) having a heat distortion temperature of 150 ° C or higher. ) To form a laminated body, and the laminated body is compressed from one side or both sides of this laminated body to impregnate a part of the coating agent into the base fabric (B), and then the expandable styrene resin. At least the softening point of the resin of the particles, the base cloth (A), by heating at a temperature lower than the heat distortion temperature of the material of (B) foaming of the expandable styrenic resin particles and the heat-crosslinkable resin aqueous A method for producing a laminated material, which comprises drying and crosslinking the emulsion to obtain a laminated material having a foam layer between the base fabrics (A, B). 2. The method according to claim 1, wherein the base fabric (A) is selected from tufted carpet, non-woven fabric and woven fabric. 3. The heat-crosslinkable resin aqueous emulsion is a resin emulsion containing hydroxyl groups and / or carboxyl groups and / or glycidyl groups and water-soluble aminoplast blended therein. The manufacturing method according to item 1. 4. The method according to claim 1, wherein the water-based thermally crosslinkable emulsion is an emulsion of a resin containing a methylol group. 5. The method according to claim 1, wherein the thermally crosslinkable resin aqueous emulsion is a resin emulsion containing a methylol group and water-soluble aminoplast. 6. An aqueous emulsion of a thermally crosslinkable resin is an emulsion of a mixture of copolymer particles containing a hydroxyl group and copolymer particles containing a methylol group. The manufacturing method described. 7. The thickness of the laminated base fabric (A) is 0.5 to 10 m.
m, the foam layer has a wall thickness of 1.0 to 20 mm, and the base fabric (B) has a wall thickness of 0.1 to 10 mm. Method. 8. The basis weight of the base fabric (A) is 50 to 1,000 g / m 2.
^2. The manufacturing method according to claim 1, wherein the basis weight (B) is 10 to 2,000 g / m ² .