JPH07100368B2 - Method for manufacturing composite sheet material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is particularly applicable to interior decoration materials for construction or interior materials such as vehicles, and particularly to fields requiring water repellency, oil repellency, water resistance and stain resistance. This is a method for producing a composite sheet material having excellent performance and effects.

[Conventional technology]

As a method for imparting water repellency and water resistance to a so-called water-driving interior interior material that conventionally uses a lot of water, (1) a method of forming a matting surface treatment agent layer on the surface layer of a vinyl chloride resin interior material, (2) A method in which a fluorine-based or silicone-based additive is mixed into the surface layer, (3) A soft vinyl chloride resin foamed on a base material (glass non-woven fabric, water-resistant base paper, etc.) with little water-shrinkage as a so-called water-resistant wallpaper A method of forming a layer and laminating and integrating a soft vinyl chloride resin sheet layer or another thermoplastic resin sheet as a skin layer is generally used.

[Problems to be Solved by the Present Invention]

However, in the above method (1), when a matte surface treating agent layer is applied on the surface layer, the water repellent property is remarkably reduced, and when the matte surface treating agent layer is not applied, the plasticizer of the soft vinyl chloride resin layer is Since it bleeds to the surface, it has a temporary water repellent effect, but it is not preferable because it causes defects such as easy attachment of dirt to the surface. In addition, the method (2) can impart water repellent and water resistant effects, but the compatibility with the mixed resin is poor and the agent exudes to the surface of the skin layer, and the above effect is lacking in durability. There is a defect that the surface migration arrangement property of the agent to the surface of the epidermis layer is not sufficient. Further, in the product of the method (3), the product using the soft vinyl chloride sheet for the skin layer is easily soiled, and the thick layer makes the product hard and heavy, resulting in poor workability. There is also a method of laminating a film such as an acrylic resin or a fluorine resin having an antifouling effect on the soft vinyl chloride resin foam layer (intermediate layer) as the above-mentioned skin layer to form a laminate. It has drawbacks such that the skin layer becomes hard, lacks flexibility, and causes problems in construction.

The present invention does not have the above-mentioned drawbacks, has excellent water-repellent, oil-repellent, water-resistant and stain-resistant properties that have a long-lasting effect, and also has good workability. It is intended to provide a method for producing a composite sheet material that realizes the above-mentioned effects, which are excellent as an interior / interior material in the field of

[Means for solving problems]

The present invention laminates a non-foamed or foamed vinyl chloride resin as an intermediate layer on a substrate having water resistance and flame retardancy,
Further, a thermoplastic synthetic resin is used as an extremely thin skin layer on the layer, and 0.1 to 3% by weight of an additive having both excellent surface migration and compatibility with the skin layer is mixed in the synthetic resin. A composite sheet material in which objects are laminated, heated, dried and integrated, wherein the skin layer (a) has a layer thickness of 10 μ to 200 μ, and the surface is a smooth surface or an uneven surface of a drawn pattern,
(B) The graft polymer is a copolymer of an acrylic compound macromonomer and an acrylic fluorine compound or an acrylic silicone compound, and (c) a block polymer is a copolymer of an acrylic compound and an acrylic fluorine compound. A method for manufacturing a composite sheet material.

[Action effect]

 The manufacturing method of the present invention will be described in detail below.

As the base material of the present invention, a base material having water resistance and flame retardancy is particularly used. The reason is that the product manufactured by the present invention is particularly intended to be used in a field where water is frequently used, so that the base material also has water resistance, and in addition, it has flame retardancy for use as an interior material. It is possible to sufficiently exhibit the functionality as a substrate, which is the object of the present invention. As the base material, paper, non-woven fabric, knitted fabric, or the like is used. Is flame-retardant treatment with a flame retardant such as a halogen-containing organic phosphoric acid ester, a thiourea compound, or a guanazine compound in order to impart flame retardancy thereto? , Mixed with non-combustible fibers such as glass fiber, or treated with a water repellent such as fusso-based or silicone-based compound to impart water resistance, or water-resistant polyester-based resin fiber, polyolefin A resin fiber, rayon fiber, or glass fiber may be used alone or mixed, or a mixed knitted fabric may be used.

Next, a non-foamed body or a foamed body of vinyl chloride resin is laminated and formed as a sheet on the above base material as an intermediate layer. Examples of the polyvinyl chloride resin of the resin composition used for the layer include a homopolymer of vinyl chloride, a copolymer of vinyl chloride and vinyl acetate, a copolymer of vinyl chloride and ethylene monovinyl acetate, and vinyl chloride. It is also possible to use graft copolymers with various monomers, and also mixtures of these copolymers and vinyl chloride homopolymers, and mixtures of vinyl chloride homopolymers with other thermoplastic resins. Further, as these polymers, any polymerization method such as suspension polymerization and emulsion polymerization can be used.

For the non-foamed material of the layer, a plasticizer, a stabilizer, a lubricant,
In addition to kerators, dyes, colorants such as pigments, flame retardants, and the like, fillers and the like are mixed and used. In the case of foam, a chemical foaming agent is mixed with the above non-foamed composition.
As a method for forming the intermediate layer, various methods such as a calendering method, an extrusion method or a coating method can be used for the non-foamed body, but the calendering method is preferable from the viewpoints of mass productivity and production cost. Whichever method is used, it is preferable that the formed thickness of the sheet is about 0.1 to 1 mm, and if 0.1 mm or less, problems in physical strength tend to occur, and if it is 1 mm or more, it is tough and problems in physical strength. But not
Since it is heavy in weight and hard in texture, it causes a problem in construction when used as the interior material.

Further, in the above foam, by using a processing temperature below the decomposition temperature of the foaming agent at the softening temperature of the vinyl chloride resin composition,
A sheet is laminated by any of the above processing methods.
Also in this case, it is preferable to use the calendar method as in the above. Whichever method is used, the applied thickness of the sheet is preferably about 0.1 to 0.4 mm. Then, the above-mentioned sheet layer is heat-foamed using a foaming furnace to obtain a laminate having a thickness of
Form a foam of 0.3 to 3 mm. In this case, if it is 0.3 mm or less and 3 mm or more, the same reason as in the case of the above non-foamed body occurs, which is not preferable.

Alternatively, the foam may be separately manufactured into a foam sheet having a layer thickness of 0.3 to 3 mm, and the foam sheet may be laminated and integrated with the above-mentioned substrate by using a laminating method.

Next, a skin layer having various functions such as water repellent property, water repellent property, oil repellent property and stain resistant property is coated on the above-mentioned intermediate layer in a very thin layer thickness. The thermoplastic synthetic resin composition used for the skin layer of the present invention is a polyacrylic meter resin, a homopolymer or copolymer of a polyurethane resin or the like, or a mixture thereof in the form of a solvent-based paint, which has the above-mentioned various effect performances. The additive which embodies the above is mixed and used. The additive has both excellent surface migration and compatibility with the synthetic resin of the skin layer, and the graft polymer is a macromonomer of an acrylic compound and an acrylic fluorine compound or an acrylic silicone compound. And a block polymer is a copolymer of an acrylic compound and an acrylic fluorine compound. That is, one of the acrylic fluorine compound or acrylic silicone compound in the additive serves as a functional segment having extremely excellent interfacial migration to the synthetic resin of the skin layer,
It imparts excellent water-repellency, oil-repellency, water resistance and stain resistance to the surface of the skin layer, and the macromonomer or acrylic compound of the other acrylic compound in the additive is compatible with the resin which is the skin layer. Plays a role as a compatible segment having a so-called anchor effect with respect to the skin resin layer and is sufficiently compatible, and the effects of both are synergized to produce a product having a long-lasting modification effect, Moreover, the original hardness of the resin composition of the skin layer, tensile strength,
It is possible to obtain those having excellent water repellency, oil repellency, water resistance and stain resistance without changing physical properties such as elongation. Such excellent durability and durability of the modification effect cannot be found in the conventionally used fluorine-based additives and silicone-based additives. The amount of the additive added to the skin layer resin composition is 0.1 to 3% with respect to the resin solid content.
It is preferable that the contact angle between the skin layer and the liquid (water, oil, etc.) is about 100 to 120 °, and the "wetting phenomenon" at the physical interface is reduced by the addition amount within the range. The above various performance effects can be exhibited. In this case, if the content is less than 0.1%, the contact angle becomes 90 ° or less, and the effect of modifying the various performances described above cannot be realized, and even if the content exceeds 3%, the effect is not further improved.

The method for forming the skin layer is such that the coating composition having the above composition is applied by a general coating method such as a gravure method, a roll coater method, or a rotary screen method, followed by heating and drying to obtain a film thickness of 10 μm. Form a very thin skin layer of ~ 200μ. When the layer thickness is 10μ or less, problems in physical strength tend to occur, and when it is 200μ or more, there is no problem in strength, but the texture is hard and the weight is heavy, which causes an obstacle to workability and is an object of the present invention. I can't get the product. Even if the skin layer is extremely thin as described above, the above-mentioned various performance effects can be sufficiently exhibited by the various properties and effects of the additive additive of the present invention.

The surface of the skin layer may be an ordinary smooth surface at the time of coating, but a roll embossing method which is generally used may be applied to form an uneven pattern on the surface. By doing so, the water repellent property, oil repellent property, and water resistance can be further increased. The reason is that as a result of the orientation of the acrylic fluorine-containing compound or the acrylic silicone compound, which is the surface transferable segment in the additive added to the skin layer, the liquid (water, oil, etc.) contacting the resin surface and the liquid This is because the contact angle with the resin layer is larger than that on a smooth surface, and the so-called physical "wetting phenomenon" is further reduced.

As described in detail above, the composite sheet material obtained according to the present invention has an excellent water repellent property that has a long-lasting effect.
It has oil-repellent, water-resistant and stain-resistant properties, and also has good workability, so that it can exhibit the above-mentioned effects that are excellent as an interior material and other materials in the water-intensive field. is there.

〔Example〕

 The present invention will be specifically described below with reference to various examples.

Example 1 A flame-retardant and water-resistant paper having a water resistance obtained by mixing glass fibers into pulp fibers treated with a halogen-containing organic phosphate ester-based flame retardant for wallpaper lining, and an intermediate layer formed thereon. A polyvinyl chloride resin composition having the following composition is laminated to form an ivory colored layer having a thickness of 0.18 mm using a calendering method, and a gravure printing machine is further formed on the upper surface thereof using a conventional vinyl chloride leather printing paint. After applying a gray cloud pattern print pattern and drying it, gravure printing a skin paint that incorporates a functional additive made of a copolymer of a graft polymer type and an acrylic fuso compound having the following composition as a skin layer Coat the entire surface using a machine and heat dry to form a skin layer having a layer thickness of about 20μ.
A composite sheet material was obtained. Next, each performance test of the obtained product is carried out by the method of the attached sheet, and its water repellent effect and stain resistance effect are as excellent as the attached sheet, and it is also flexible, lightweight, and has good workability and water resistance. Therefore, it was confirmed that the product was excellent as a wall interior material.

[Composition of vinyl chloride resin in the middle layer]

Polyvinyl chloride resin (= 1100) 100 parts by weight DOP 50 〃 Ca-Ba-Zn stabilizer 2 〃 Titanium white pigment 15 〃 Benzidine yellow pigment 3 〃 Red pigment 1.5 〃 Calcium carbonate 30 〃 Antimony trioxide 5 〃 Kelator 2 〃 [Skin layer coating mixture] Solvent-based acrylic surface treatment coating (solid resin content 15% by weight) 100 parts by weight (additive) Graft polymer of acrylic compound 0.6 parts by weight [Toagosei Chemical Industry Co., Ltd .: Aron GF300] Example 2 The same base material and intermediate layer as in Example 1 were used, and the additive in the composition for skin layer substitution was replaced with a functional additive composed of a copolymer of a graft polymer type and an acrylic silicone compound. Other materials and processing methods are used in Example 1.
A product was obtained in exactly the same manner as. The obtained product was a product having excellent effects as shown in a separate sheet as in Example 1 and having light weight and soft texture and good workability.

[Coating composition for skin layer]

Solvent-based acrylic surface treatment coating (solid resin content 15% by weight) 100 parts by weight (additive) Graft polymer of acrylic compound 0.75 parts by weight [Toagosei Kagaku Kogyo Co., Ltd .: Aron GS30] Example 3 Example As in Example 2, except that the additive in the composition for forming the skin layer was replaced with a functional additive consisting of a copolymer of a block polymer type acrylic fluorine-based compound, the same method of material arrangement as in Example 1 was used. To obtain the product. The obtained product was excellent as in Example 1 as shown in the attached sheet.

[Coating composition for skin layer]

Solvent-based acrylic surface treatment coating (solid resin content 15% by weight) 100 parts by weight (additive) Block compound of acrylic compound 0.5 parts by weight [NOF CORPORATION: MODIPER F210] Example 4 In Example 1 The surface layer surface of the obtained product was heated, and a concavo-convex pattern having a texture pattern was formed using a roll embossing machine to obtain a composite sheet material. As shown in the attached sheet, the obtained product had a water repellent effect superior to that of Example 1.

Example 5 The base material of Example 4 was replaced with a base material which was made by subjecting a polyester nonwoven fabric having a basis weight of 100 g / m ² and having excellent water resistance to a flame-retardant treatment using a halogen-containing organic phosphate ester flame retardant, as a base material. A composite sheet material having a texture-like uneven squeezing pattern on the surface was obtained by using the same material and using the same method except that the thickness of the vinyl chloride resin sheet was set to 0.25 mm. The obtained product had the same excellent effects as in Example 4, and was an excellent product as a vehicle door trim interior material and a building interior material.

Example 6 Containing a vinyl chloride resin foam composition having the following composition as an intermediate foam layer on a non-woven fabric made of glass fiber having a basis weight of 80 g / m ² having water resistance and flame retardancy at a decomposition temperature of a foaming agent or lower. Using a calender at a certain processing temperature of 160 ° C., a white colored layer was laminated to form a sheet having a thickness of 0.15 mm, and then the laminated body was treated at a temperature of 210 ° C. for 3 minutes using a foaming furnace, A foam layer was formed by heat-foaming the sheet layer to a thickness of 1.1 mm, and subsequently a functional additive composed of a copolymer of a graft polymer type having the following composition and an acrylic fuso compound was mixed as a skin layer. The surface coating material was applied to the entire surface by using a gravure printing machine, and heated and dried to laminate and form a surface layer having a layer thickness of about 20μ to obtain a composite sheet material. The obtained product was flexible and lightweight, was excellent in construction, and had excellent water repellent effect and anti-staining effect, and was useful as an interior material for construction.

[Composition composition of intermediate layer vinyl chloride resin foam]

Polyvinyl chloride resin (= 1100) 100 parts by weight DOP 70 〃 Foaming agent (ADCA) 5 〃 Titanium white 20 〃 Ca-Ba-Zn stabilizer 2.5 〃 Calcium carbonate 15 〃 Antimony trioxide 5 〃 Kelator 2 〃 [For skin layer Paint formulation] Solvent-based acrylic surface treatment paint (solid resin content 15% by weight) 100 parts by weight (additive) Graft polymer of acrylic compound 1.8 parts by weight [Toa Gosei Chemical Industry Co., Ltd .: Aron GF300] Comparative example 1 A composite sheet material was obtained in the same manner as in Example 1, except that the additives in the skin layer composition were not added.
The obtained product had no water repellent effect and stain resistant effect.

Comparative Example 2 Using the same method as in Example 1 except that the additives in the skin layer composition were replaced with commercially available fusso type additives,
A composite sheet material was obtained using the same compounding amount. The product obtained had a water-repellent effect and a stain-proofing effect immediately after the production, but when the product was washed with a detergent, the additive was washed off and the water-repellent effect was extremely lowered as shown in Table 1. It disappeared and was not durable due to the effect of surface modification.

Comparative Example 3 Using the same method as in the case of the example, only the additive in the skin layer composition was replaced with a commercially available silicone additive, and a composite material was obtained using the same amount. The obtained product had a water-repellent effect and a stain-proofing effect immediately after the production, but when this was washed with a detergent, the additive was washed off and the water-repellent effect was extremely reduced and disappeared as shown in Appendix 1. However, it did not have durability due to the surface modification effect.

Table 1 shows a comparison of the composite sheet materials obtained in Examples 1 to 3 as described above.

[Test method]

[1] [Water-repellency and oil-repellency test] (a) (Water-repellency test) Room temperature using a goniometer
The degree of "wetting" between water at 25 ° C and the surface of the skin layers of Examples 1 to 3 was measured, and the contact angle θ with water was measured to obtain a value for evaluation of water repellency.

(B) (Responsiveness test) Room temperature using a goniometer
The contact angle θ of the skin layer surface of Example 1 to Comparative Example 3 with respect to n-decane at 25 ° C. was measured to obtain a value for evaluation of oil repellency.

[2] [Staining resistance test] A 5% water slurry of activated carbon was dropped on the surface of the skin layer of Examples 1 to 3 and air-dried for one day, and then washed with water using a brush. It was displayed in three stages.

◯: No activated carbon remains.

△: A little bit of 〃 is attached and it becomes a little black.

×: 〃 adheres and turns black.

[3] [Durability Test] (a) (Detergent Cleaning Test) After dipping the skin layer surface of Examples 1 to Comparative Example 3 in a 1% aqueous solution of Mama Lemon (manufactured by Lion Corporation, trade name) at 30 ° C. for 5 hours, After sufficiently washing with water and air-drying for 1 day, the water repellency was measured by the same method as above, and the evaluation value was obtained.

(B) (Weather resistance test) After irradiating the surface of the skin layers of Examples 1 to 3 with ultraviolet rays using a QUV tester at a temperature of 60 ° C for 4 hours, a cycle of humidity 100% × 40 ° C for 4 hours for 330 hours After repeated tests, the water repellency of the surface was measured by the same method as above, and the evaluation value was obtained.

Claims (4)

[Claims] 1. A non-foamed or foamed vinyl chloride resin is laminated as an intermediate layer on a base material having water resistance and flame retardancy, and a thermoplastic synthetic resin as an extremely thin skin layer is further formed on the layer. In addition, 0.1 to 3% by weight of an additive having both excellent surface migration property and compatibility with the skin layer is mixed in the synthetic resin, and the mixture is laminated by heating and drying. A method for manufacturing a characteristic composite sheet material. 2. The method for producing a composite sheet material according to claim 1, wherein the skin layer has a layer thickness of 10 to 200 μm and the surface is a smooth surface or an uneven surface having a drawing pattern. . 3. The production of a composite sheet material according to claim 1, wherein the additive is a graft polymer of a macromonomer of an acrylic compound and an acrylic fluorine compound or an acrylic silicone compound. Method. 4. The method for producing a composite sheet material according to claim 1, wherein the additive is a block polymer of an acrylic compound and an acrylic fluorine compound.