JP2000037801A - Dispersion process stampable sheet and expanded molding of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase peeling strength of a skin in a wide range of temperature by sequentially laminating a non-permeable resin layer, an adhering layer composed of a thermoplastic resin having a low melting point and an adhering layer composed of a thermoplastic resin having a lower melting point on a porous material layer composed of a reinforcing fiber and a thermoplastic resin. SOLUTION: An expanded molded by 13 is formed by sequentially laminating a non-permeable resin layer 2, a first adhering resin layer 3 and a second adhering resin layer 4 on a porous material layer 1 having a reinforcing fiber and a thermoplastic resin as main components. At this time, a layer 5 containing considerable amount of thermoplastic resin is preferably laminated on a part where the porous material layer 1 contacts with the non-permeable resin layer 2 (a part indicated by crossing hatched lines), thereby adhering between the non-permeable resin layer 2 and the porous material layer 1 is improved, and a rigidity of the expanded molded body 13 is increased. The first adhering resin layer 3 has a lower melting point than that of the thermoplastic resin composing the porous material layer 1, and the thermoplastic resin having lower melting point than that of the resin composing the resin layer 3 is used for the second adhering resin layer 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an expansion molded article of a dispersion method stampable sheet and a dispersion method stampable sheet. In particular, the present invention relates to an expansion molded article of a dispersion method stampable sheet having excellent skin adhesion even at a temperature of 80 ° C., and a dispersion method stampable sheet suitable for obtaining the same.

[0002]

2. Description of the Related Art A stampable sheet (fiber reinforced thermoplastic resin sheet) is known as a fiber reinforced thermoplastic resin composite material which has high strength and high rigidity while making use of excellent properties in molding of a thermoplastic resin. I have.

[0003] As a typical production method for obtaining this stampable sheet, there is a dispersion method, and this dispersion method is further roughly classified into a dry dispersion method and a wet dispersion method. In the dry dispersion method, a nonwoven fabric-like deposit (web) is formed by dispersing discontinuous fibers and thermoplastic resin particles in a gas phase, and is heated and pressed to be solidified into a sheet, thereby forming a stampable sheet. (See, for example, JP-A No. 2-16).
No. 9632). On the other hand, the wet dispersion method is a method for producing a stampable sheet using a papermaking technique, in which discontinuous fibers and thermoplastic resin particles are dispersed in a liquid phase to form a nonwoven fabric-like deposit (web). Is heated and pressurized to solidify it into a sheet (for example,
9119, JP-A-60-58227, etc.).

[0004] A stampable sheet obtained by this dispersion method (dispersion method stampable sheet) is a sheet-like molding material, which is heated to a melting point of a thermoplastic resin constituting a matrix or higher, and then applied to a desired shape. Is shaped.

As a method for forming this dispersion method stampable sheet, an expansion molding method has been conventionally known (for example, see JP-A-4-33138). This expansion molding method is a molding method utilizing a property unique to the dispersion method stampable sheet, and supplies a heated dispersion method stampable sheet into a mold so that voids remain in the obtained molded article. This is a method of adjusting the clearance of the mold, compressing and cooling and solidifying. This is because, in the dispersion method stampable sheet, the reinforcing fibers are present in a state of being laid open after being fibrillated into single fibers, and when the thermoplastic resin as the matrix is melted, the rigidity of the reinforcing fibers, etc. In order to return to the original state of the web, the property of exhibiting a peculiar phenomenon that the thickness recovers to near the thickness of the web is used.

[0006] A molded product obtained by this expansion molding method is called an expansion molded product. This expanded molded article has a three-dimensional network-like structure in which reinforcing fibers are dispersed in a random direction and entangled, and the intersections of the intersecting reinforcing fibers are bonded with a thermoplastic resin. What to do.

In recent years, the above-mentioned expanded molded articles have been frequently used for applications such as interior materials for ceilings of automobiles. In such applications, it is common to use an expansion molded product as a base material, at least one surface of which is bonded with a nonwoven fabric, leather, or the like as a skin, for example, by being mounted on the ceiling of an automobile. It is. For example, when used as an interior material for a ceiling of an automobile, (1) adhesiveness to the skin bonded to the base material (2) non-breathable (Note: when air flows in the thickness direction of the base material, the skin Therefore, the surface of the skin is prevented from being stained by providing a non-ventilating layer.)

Therefore, a technique satisfying these requirements has been proposed in Japanese Patent Application Laid-Open No. Hei 8-229994.
This technology is manufactured by laminating a three-layer film on the surface of a stampable sheet and heating it. The outermost film acts as an adhesive to the skin, and the middle film acts as a non-ventilating layer. It is. According to this technique, those having satisfactory properties with respect to non-breathability and peel strength of the skin at room temperature can be obtained.

However, in the conventional expanded molded article, the adhesive layer provided on the outer surface of the stampable sheet is made of a single layer in order to adhere the stampable sheet and the skin.
Moreover, since the adhesive layer has a low melting point, for example, an adhesive having a melting point of 90 to 110 ° C., the peel strength of the epidermis at room temperature is sufficiently satisfactory.
The peel strength at 0 ° C. was insufficient. Because the temperature inside the car rises to nearly 80 ° C in summer,
The adhesion of the epidermis at high temperatures is also important. Further, when the adhesive layer is a single layer made of an adhesive having a high melting point, for example, an adhesive having a melting point of 120 to 130 ° C., the peel strength of the epidermis is insufficient at both normal temperature and high temperature. Met.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an expandable material having not only room temperature but also excellent peel strength at 80 ° C. as well as room temperature as well as conventional products in terms of bending characteristics and air permeability. An object of the present invention is to provide a molded article and a dispersion method stampable sheet suitable as a material for obtaining the expanded molded article.

[0011]

Means for Solving the Problems In order to achieve the above-mentioned object, as a result of diligent studies, it has been found that the adhesive resin layer is formed of two different melting points.
An expanded molded article having a two-layer structure made of two thermoplastic resins and having a layer made of a low-melting thermoplastic resin disposed on the outer layer has excellent peel strength not only at room temperature but also at 80 ° C. The inventors have found that the present invention can be performed, and arrived at the present invention.

That is, the present invention provides a porous material layer mainly composed of a reinforcing fiber and a thermoplastic resin (r-1), and a non-porous resin layer laminated on at least one surface of the porous material layer. A) and a first adhesiveness made of a thermoplastic resin (rb) having a melting point lower than the melting point of the thermoplastic resin (r-1) laminated on the air-impermeable resin layer (A). A thermoplastic resin (rc) having a melting point lower than the melting point of the thermoplastic resin (rb) above the first adhesive resin layer (B). It is intended to provide an expansion molded article of a dispersion method stampable sheet having a second adhesive resin layer (C) composed of:

The present invention also provides an expansion molded article of a dispersion method stampable sheet having a skin layer on the outer surface of the second adhesive resin layer (C).

Further, the present invention provides a fiber-reinforced thermoplastic resin material in which reinforcing fibers are dispersed in a base made of a thermoplastic resin (r-1) as a material suitable for obtaining the above-mentioned expanded molded article. A non-breathable resin layer (A) laminated on at least one surface of the fiber-reinforced thermoplastic resin material, and a thermoplastic resin (r-1) laminated on the non-breathable resin layer (A). A first adhesive resin layer (B) made of a thermoplastic resin (rb) having a melting point lower than the melting point;
On the upper layer of the adhesive resin layer (B), the thermoplastic resin (r-
thermoplastic resin having a melting point lower than that of b) (r-
The present invention also provides a dispersion method stampable sheet having a second adhesive resin layer (C) comprising (c).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the expanded molded article and the stampable sheet by a dispersion method of the present invention will be described in detail.

The expanded molded article of the present invention comprises a porous material layer, a non-permeable resin layer (A) laminated on at least one surface of the porous material layer, and a non-permeable resin layer (A) on the porous material layer. It has a laminated first adhesive resin layer, and further has a second adhesive resin layer laminated on the first adhesive resin layer.

In the expanded molded article of the present invention, the porous material layer contains reinforcing fibers and a thermoplastic resin (r-1) as main components. As the reinforcing fiber which is a component constituting the porous material layer, either an inorganic fiber or an organic fiber may be used, or a composite fiber thereof may be used. Examples of the inorganic fibers include glass fibers, carbon fibers, and metal fibers such as boron fibers and stainless fibers. Examples of the organic fibers include aramid fibers, polyester fibers, polyamide fibers, and wood fibers. These may be used alone or in combination of two or more. Among these, it is particularly preferable to use glass fiber because a high reinforcing effect can be obtained at low cost.

The fiber length of the reinforcing fiber is preferably from 5 to 30 mm, more preferably from 10 to 26 mm, from the viewpoint of ensuring the reinforcing effect, expandability and shapeability. In addition, the diameter of the reinforcing fiber is preferably from 5 to 30 μm, more preferably from 10 to 25 μm, from the viewpoint of securing the reinforcing effect and the expandability. Further, in order to improve the wettability and adhesion between the reinforcing fiber and the thermoplastic resin, it is preferable to perform a treatment with a silane coupling agent or the like.

The thermoplastic resin (r-1), which is another main component of the porous material layer, is a component constituting a matrix of the porous material layer, and is a polyolefin resin such as polyethylene or polypropylene, polystyrene, or polychlorinated resin. vinyl,
Polyethylene terephthalate, polycarbonate, polyamide, polyacetal, etc., or copolymers such as ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, styrene-butadiene-acrylonitrile copolymer, and thermoplastic elastomers such as EPM, EPDM Can be used alone or in combination of two or more. Among these, polyolefin resins such as polyethylene and polypropylene are preferred because of their excellent strength, rigidity and moldability, and polypropylene is particularly preferred because these properties are balanced and the cost is low. Furthermore, among polypropylene, MF
R (measurement conditions; in accordance with JIS K6758, 210 ° C.,
2.16 kgf) is preferably in the range of 1 to 200 g / 10 minutes from the viewpoint of strength, rigidity and moldability.

Further, a reinforcing fiber and a thermoplastic resin (r-
In order to improve the adhesiveness of 1), a thermoplastic resin (r-
Modified 1) with an acid such as an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, or various compounds such as an epoxy compound can be used in combination. The modification can be performed by graft copolymerization or the like. For example, polypropylene, maleic acid, maleic anhydride, obtained by graft copolymerization of acrylic acid and the like, those having a modifying group such as an acid anhydride group and a carboxyl group in the molecule are preferable from the viewpoint of improving strength. .

In the expansion molded article of the present invention, the content of the reinforcing fiber and the thermoplastic resin (r-1) in the porous material layer is determined by the expansion molded article having high mechanical strength such as bending strength and bending elastic modulus. From the viewpoint of being obtained, the weight ratio of the reinforcing fiber / thermoplastic resin (r-1) is preferably in the range of 10/90 to 70/30.

The density of the porous material layer is preferably adjusted to 1 to 0. 0, because the density (load resistance) and rigidity of the entire molded product can be increased by adjusting the clearance of the mold in expansion molding. 1 g / cm ³ or less, more preferably 0.8~0.2g / cm ^3.

The expanded molded article of the present invention has a non-breathable resin layer (A) laminated on at least one surface of the porous material layer. The air-impermeable resin layer (A) may be laminated on only one side of the porous material layer, or may be laminated on both sides. The non-breathable resin layer (A) secures the non-breathability of the expanded molded article, and the first adhesive resin layer (B) and the second
Thermoplastic resin (rb) constituting the adhesive resin layer (C)
And (rc) have a role of preventing the porous material layer from being impregnated. In the present invention,
The non-breathable means one having a permeability of 0 cc / cm ² · sec measured according to ASTM-D737.

The resin constituting the air-impermeable resin layer (A) is not particularly limited, and may be any of a thermosetting resin and a thermoplastic resin. In particular, a thermoplastic resin is preferable from the viewpoint of moldability. As the thermoplastic resin, the same resin as used as a main component of the porous material layer can be used. In particular, those which do not melt at the molding temperature at the time of production of the dispersion method stampable sheet or the expansion molded body, and the like, are more preferable, and the thermoplastic resin (r-1) which is the main component of the porous material layer of the expansion molded body is more preferable. Those having a melting point higher than that of ()) are preferred. For example, when the thermoplastic resin (r-1) of the porous material layer is polypropylene, it is preferable that the air-impermeable resin layer is made of polyamide, polyethylene terephthalate, or the like.

In the expanded molded article of the present invention, the thickness of the air-impermeable resin layer is 5 μm in order to secure air-impermeable properties.
More preferably, the thickness is 10 to 50 μm.

The expansion molded article of the present invention comprises a first adhesive resin layer (B) on a non-permeable resin layer (A), and a second adhesive resin layer (C) laminated thereon. And The first adhesive resin layer (B) is made of a thermoplastic resin (rb) having a melting point lower than the melting point of the thermoplastic resin (r-1) constituting the porous material layer.
In particular, this thermoplastic resin (rb) has a melting point of 110 ° C.
The above are preferred, and more preferably 110 to 120
It is in the range of ° C.

The thermoplastic resin (rb) is not particularly limited as long as it has the above-mentioned melting point. For example, compounds such as α-olefins such as ethylene and propylene, and vinyl compounds such as vinyl chloride and vinyl acetate are
Homopolymers or copolymers containing a single species or a combination of two or more species are exemplified. This thermoplastic resin (r-
Specific examples of b) include polyolefin resins such as polyethylene and polypropylene, and copolymers such as ethylene-vinyl chloride copolymer and ethylene-vinyl acetate copolymer. In addition, these thermoplastic resins (rb) can be used alone or in combination of two or more.

Further, the thermoplastic resin (rb) is
MFR (measurement conditions; in accordance with JIS K6758, 190
(C, 2.16 kgf) in the range of 3 to 50 g / 10 min is preferable because of excellent adhesiveness.

Further, in the expansion molded article of the present invention, the first
The thickness of the adhesive resin layer should be 10
μm is preferred, and more preferably in the range of 20 to 100 μm.

Further, the expanded molded article of the present invention is characterized in that
A second adhesive resin layer (C) is further provided above the adhesive resin layer (B). The second adhesive resin layer (C) is made of a thermoplastic resin (rc) having a melting point lower than that of the thermoplastic resin (rb). The second adhesive resin layer (C) is made of a thermoplastic resin (rc) having a melting point lower than the melting point of the thermoplastic resin (rb) constituting the first adhesive resin layer (B). It becomes. In particular, this thermoplastic resin (rc)
In order to ensure adhesiveness, the melting point is preferably 90 ° C or higher, and more preferably 90 to 120 ° C.

The thermoplastic resin (rc) is not particularly limited as long as it has the above-mentioned melting point. Specific examples of the thermoplastic resin (rc) include olefin resins such as polyethylene and polypropylene, and copolymers of these olefins, and those modified with acrylic acid, maleic anhydride, and the like. .
In addition, these thermoplastic resins (rc) can be used alone or in combination of two or more.

Further, the thermoplastic resin (rc) is
MFR (measurement conditions; JIS K678, 190
C., 2.16 kgf) is preferably in the range of 5 to 100 g / 10 min because of excellent adhesion.

In the expanded molded article of the present invention, the thickness of the second adhesive resin layer is usually preferably 10 μm or more, more preferably 20 to 20 μm, in order to secure adhesion.
The range is 100 μm.

As shown in FIG. 1, the expansion molded article of the present invention has a non-breathable resin layer (A) 2 as an upper layer on a porous material layer 1 mainly composed of reinforcing fibers and a thermoplastic resin. In addition, a first adhesive resin layer (B) 3 is provided on the non-permeable resin layer (A) 2, and further, the first adhesive resin layer (B) 3
Has a second adhesive resin layer (C) 4 as an upper layer. It is preferable that a layer 5 rich in the thermoplastic resin (r-1) is formed in a portion where the porous material layer 1 is in contact with the air-impermeable resin layer 2 (a portion indicated by a diagonal line crossing in FIG. 1). Thereby, the adhesion between the non-breathable resin layer (A) 2 and the porous material layer 1 is strengthened, and the rigidity of the expanded molded product is increased.

The expanded molded article of the present invention may have a skin layer on the outer surface of the second adhesive resin layer (C). For example, as shown in FIG. 2, an air-impermeable resin layer (A) 2 is provided on an upper layer of a porous material layer 1 mainly composed of a reinforcing fiber and a thermoplastic resin, and the air-impermeable resin layer ( A)
2 has a first adhesive resin layer (B) 3 on an upper layer thereof, and further has a second adhesive resin layer (C) 4 on an upper layer of the first adhesive resin layer (B) 3. It may have a skin layer 6 on the outer surface of the adhesive resin layer (C) 4. In the expansion molded article of the present invention, the skin layer 6 is appropriately disposed according to various purposes such as decoration of the surface of the expansion molded article, provision of cushioning properties, and provision of heat insulation properties. It is preferable that the skin layer 6 has heat resistance so as not to be melted or broken during the production of the expansion molded body. A layer 5 rich in the thermoplastic resin (r-1) is formed in a portion where the porous material layer 1 is in contact with the non-breathable resin layer (A) 2 (a cross-hatched portion in FIG. 2). Preferably. Thereby, the adhesion between the non-breathable resin layer (A) 2 and the porous material layer 1 is strengthened, and the rigidity of the expanded molded product is increased. Further, when the skin layer 6 is bonded, first, the thermoplastic resin (rc) constituting the second adhesive resin layer (C) 4 is melted, and the skin layer 6 is wetted. Then, the skin layer 6 wetted by the thermoplastic resin (rc) has improved wettability with the first adhesive resin layer (B) 3, and the heat constituting the first adhesive resin layer (B) 3 is improved. As the plastic resin (rb) melts, the impregnation into the skin layer 6 is sufficiently promoted. Therefore, it is considered that the peel strength of the skin can be improved not only at room temperature but also at a high temperature (80 ° C.).

Specific examples of the skin material forming the skin layer laminated on the expansion molded article of the present invention include a woven fabric made of natural and synthetic fibers, an organic fiber nonwoven fabric subjected to needle punching and the like, and a raised woven fabric. , Knitted cloth, flocking cloth, etc. (hereinafter abbreviated as “cloth etc.”), or a thermoplastic resin sheet made of polyvinyl chloride (PVC), thermoplastic olefin (TPO), thermoplastic polyester, elastomer, etc. Abbreviated as “sheet or the like”). Further, a resin foam such as polypropylene, polyethylene, polyvinyl chloride, polyurethane, polyamide-based, modified polyolefin-based, urethane-based, or polyolefin-based is applied to the bonding surface of the sheet or the like (with the second adhesive resin layer) such as a cloth or the like. Etc. may be laminated, or a hot melt adhesive may be further applied. In particular, the skin layer is stuck in the second adhesive resin layer or the first adhesive resin layer, or the skin is impregnated with the thermoplastic resin (rb) or (rc), so that the skin layer is bonded to the skin layer. Cloth or the like is particularly preferable as the skin, since the adhesion with the conductive resin layer is improved. In addition, the outer surface (non-bonded surface) of the skin layer may be provided with an uneven pattern such as a grain, printing, or the like, and is not particularly limited.

The method for producing the expansion molded article of the present invention is not particularly limited, and it can be carried out according to an expansion molding method conventionally used for producing an expansion molded article of a dispersion-type stampable sheet. For example, the following methods (a) to (f) are mentioned as preferred methods for producing an expanded molded article having no skin as shown in FIG. (A) A fiber-reinforced thermoplastic resin material in which reinforcing fibers are dispersed in a substrate made of a thermoplastic resin (r-1) in advance, and a non-ventilated layer laminated on at least one surface of the fiber-reinforced thermoplastic resin material Resin layer (A) and the thermoplastic resin (r-1) laminated on the air-impermeable resin layer (A)
Thermoplastic resin having a melting point lower than that of (rb)
And a thermoplastic resin (rc) having a melting point lower than the melting point of the thermoplastic resin (rb) on an upper layer of the first adhesive resin layer (B). A) preparing a dispersion method stampable sheet having a second adhesive resin layer (C) comprising: (a) and expanding the dispersion method stampable sheet.

(B) The fiber reinforced thermoplastic resin material
The non-breathable resin layer (A), the first adhesive resin layer (B) and the second adhesive resin layer (C) of the expansion molded article of the present invention.
And a multilayer film having a plurality of film layers for forming each of the above is laminated so that the film layer forming the air-impermeable resin layer (A) is on the fiber-reinforced thermoplastic resin material side. A method of expanding and forming the laminate for expansion molding after forming the body. (C) After a porous body is formed by expansion-molding a fiber-reinforced thermoplastic resin material in advance, the air-impermeable resin layer (A) of the expansion-molded body of the present invention is formed on the porous body. A multilayer film having a plurality of film layers for forming each of the first adhesive resin layer (B) and the second adhesive resin layer (C) may be formed by forming a non-breathable resin layer (A) into a porous film layer. A method of laminating and bonding to the body side. At this time, in the methods (b) and (c), in order to improve the adhesion between the multilayer film and the porous material layer,
It is preferable to heat the multilayer film. Among these methods, from the viewpoint of productivity, handling, etc.
The method (a) is preferred.

As shown in FIG. 2, preferred methods for producing an expanded molded article having a skin include the following methods (d) to (f). (D) a fiber-reinforced thermoplastic resin material in which reinforcing fibers are dispersed in a base made of a thermoplastic resin in advance, and a non-breathable resin layer (A) laminated on at least one surface of the fiber-reinforced thermoplastic resin material. ) And a dispersion method stampable sheet having a structure having a first adhesive resin layer (B) and a second adhesive resin layer (C) laminated on the air-impermeable resin layer (A). In addition, a method of laminating an epidermis to the stampable sheet by the dispersion method and then performing expansion molding. In this method,
In order to improve the adhesiveness of the skin, it is preferable to preheat the skin. (E) The non-breathable resin layer (A), the first adhesive resin layer (B), and the second adhesive resin layer (C) of the expanded molded article of the present invention are added to the fiber-reinforced thermoplastic resin material, respectively. Is laminated so that the film layer forming the non-breathable resin layer (A) is on the fiber-reinforced thermoplastic resin material side, and further a skin is formed on the upper layer. Lamination and expansion molding.

(F) After a porous body is formed by expansion-molding a fiber-reinforced thermoplastic resin material in advance, the air-impermeable resin layer (A) of the expansion-molded body of the present invention is formed on the porous body. A multilayer film having a plurality of film layers for forming each of the first adhesive resin layer (B) and the second adhesive resin layer (C); and a non-breathable resin layer (A). A method in which a film layer to be formed is laminated so as to be on the porous body side, and an epidermis is bonded on the film layer. In the above methods (e) and (f),
It is preferable to preheat the skin and the multilayer film in order to improve the adhesion between the multilayer film and the porous material layer and the adhesion between the skin and the adhesive resin layer. Among these methods, from the viewpoint of productivity, handling, etc.
The method (d) is preferred.

In the above methods (a) to (f), in the expansion molding, the object to be molded is formed by melting the thermoplastic resin (r-1) constituting the matrix of the porous material layer of the expansion molded body at a temperature higher than or equal to the melting point. Temperature below the decomposition point (for example, thermoplastic resin (r-
When polypropylene is used as 1), 170 to 2
After heating to a temperature in the range of 30 ° C., preferably in the range of 190 to 210 ° C.), it is placed in a molding die, and the height of the die spacer and the clamping height of the press are adjusted and compressed. Can be.

At this time, the temperature of the molding die may be lower than the freezing point of the thermoplastic resin (r-1), and is preferably room temperature to 60 ° C. from the viewpoint of handling properties and productivity. The molding pressure is appropriately adjusted depending on the shape of the product. However, since an excessive pressure may break the reinforcing fiber, it is usually preferably 0.5 to 50 kg / cm ² .

Further, the present invention provides a stampable sheet suitable for producing the above-mentioned expanded molded article, comprising a fiber-reinforced thermoplastic resin material and a non-breathable resin laminated on at least one surface of the fiber-reinforced thermoplastic resin material. Provided is a dispersion method stampable sheet having a layer (A) and a first adhesive resin layer (B) and a second adhesive resin layer (C) laminated on the air-impermeable resin layer (A). Is what you do. In this dispersion method stampable sheet, the air-impermeable resin layer (A), the first adhesive resin layer and the second adhesive resin layer may be laminated on only one surface of the fiber-reinforced thermoplastic resin material. And may be laminated on both sides, and is appropriately selected according to the use of the expanded molded article.

FIG. 3 shows an example of the structure of the dispersion method stampable sheet. The dispersion method stampable sheet 7 shown in FIG. 3 includes a fiber-reinforced thermoplastic resin material 8 in which reinforcing fibers are dispersed in a base made of a thermoplastic resin, and a layer laminated on the fiber-reinforced thermoplastic resin material 8. Non-breathable resin layer (A) 9, and first adhesive resin layer (B) 1 laminated on non-breathable resin layer (A) 9
0 and a second adhesive resin layer (C) 11 laminated on the first adhesive resin layer (B) 10. A layer 12 rich in the thermoplastic resin (r-1) is provided at a portion where the fiber-reinforced thermoplastic resin material 8 is in contact with the air-impermeable resin layer (A) 9 (a portion indicated by a diagonal line crossing in FIG. 3). It is preferably formed. Thereby, the adhesion between the fiber-reinforced thermoplastic resin material 8 and the air-impermeable resin layer (A) 9 is strengthened, and the rigidity of the expansion molded product obtained by expansion molding is increased.

The fiber reinforced thermoplastic resin material constituting the dispersion method stampable sheet of the present invention may be produced by any of a wet dispersion method and a dry dispersion method. In particular, since a web in which particles of the reinforcing fiber and the thermoplastic resin (r-1) are uniformly dispersed is obtained, the thermoplastic resin is uniformly impregnated between the reinforcing fibers to form a uniform fiber-reinforced thermoplastic resin. From the viewpoint of obtaining a material, those manufactured by a wet dispersion method are preferable. For example, in the case where the fiber-reinforced thermoplastic resin material is manufactured in advance alone, the chopped strand of the reinforcing fiber and the particulate or fibrous thermoplastic resin (r-
1) is dispersed in a foam liquid or a surfactant aqueous solution, and the deposit is dried to obtain a web. This web is composed of a reinforcing fiber and a thermoplastic resin (r-1) or the like, and the thermoplastic resin (r-1) is uniformly dispersed in the reinforcing fiber. Next, the web is heated to a temperature not lower than the melting point of the thermoplastic resin (r-1) and lower than the decomposition point (for example, when polypropylene is used as the thermoplastic resin (r-1), 170
~ 230 ° C, preferably 190-210 ° C),
After the thermoplastic resin (r-1) is melted, a pressure (for example, 3 to 50 kgf / cm ² ) is applied between the cooling boards to obtain a solidified fiber-reinforced thermoplastic resin material.

Further, in the dispersion method stampable sheet of the present invention, the air-impermeable resin layer (A) laminated on at least one surface of the fiber-reinforced thermoplastic resin material, and the first adhesive resin layer (B) and the second adhesive The conductive resin layer (C) is the same as the non-breathable resin layer (A), the first adhesive resin layer (B) and the second adhesive resin layer (C) in the above-mentioned expanded molded article.

The dispersion method stampable sheet of the present invention is not particularly limited as long as it has the above structure, and may be manufactured by any method. Here, the following methods (g) and (h) are preferable methods for producing the dispersion method stampable sheet having the structure shown in FIG. (G) a plurality of non-breathable resin layers (A) and a plurality of first and second adhesive resin layers (B) and (C) on the surface (one or both sides) of the web; A method of laminating a multilayer film having a film layer, heating and melting the thermoplastic resin (r-1), and then applying pressure between cooling boards to solidify. (H) On the fiber-reinforced thermoplastic resin material obtained as described above, a non-breathable resin layer (A), a first adhesive resin layer (B) and a second adhesive resin layer (C) are formed. By laminating a multilayer film having a plurality of film layers for
A method in which the thermoplastic resin (r-1) and / or the multilayer film is heated to melt the thermoplastic resin (r-1), and then, pressure is applied between cooling plates to solidify. Among these two methods, the method (g) is preferable in terms of productivity, handling properties, and the like.

In these methods, the heating temperature is not lower than the melting point and lower than the decomposition point of the thermoplastic resin (r-1) contained in the web or fiber-reinforced thermoplastic resin material (for example, the thermoplastic resin (r-1) In the case where polypropylene is used as), the temperature is in the range of 170 to 230 ° C, preferably
0 to 210 ° C.) and the pressure is, for example, 3 to 5
The range is 0 Kgf / cm ² .

In the production of this dispersion method stampable sheet, the multilayer film used is a non-breathable resin layer (A), a first adhesive resin layer (B) and a second adhesive resin of the expanded molded article of the present invention. It has at least three film layers for forming each of the layers (C). As preferable examples of the multilayer film, a film layer (fc) for forming the second adhesive resin layer (C) made of the thermoplastic resin (rc) and a thermoplastic resin (rb) A) a film layer (fb) for forming a first adhesive resin layer (B) comprising: a) a film layer (fa) for forming a non-breathable resin layer (A); Laminated on the side of thermoplastic resin material or web,
What has at least 4 layers with the film layer (fd) which consists of resin melted at the time of manufacture of a dispersion method stampable sheet is preferred. The resin constituting the film layer (fd) is a thermoplastic resin (r-1) which is a matrix resin of a fiber-reinforced thermoplastic resin material and a thermoplastic resin which constitutes the porous material layer of the expansion molded article of the present invention. The same type as (r-1) is preferable.

The resin constituting the film layer (fd) is heated,
At the time of compression, the web is partially impregnated, and a resin-rich layer (layer 5 or 12 shown in FIGS. 1 to 3) is formed on the inner surface on the side in contact with the resin layer of the fiber-reinforced thermoplastic resin material to form a sandwich structure. The laminated body is formed, and as a result, the expansion molded body and the molded article of the dispersion method stampable sheet of the present invention have an effect of improving the rigidity, adhesion to the non-air permeable resin layer, and non-air permeable property.

The resin constituting the film layer (fd) has good adhesion to the thermoplastic resin (r-1) constituting the web, and the web is partially impregnated during heating and compression. In order to make such a configuration, a fiber-reinforced thermoplastic resin material, a thermoplastic resin (r-1) constituting a porous material
The same type as above and having a higher melt viscosity than the thermoplastic resin (r-1) are preferable.

Here, the melt viscosity is determined by the heating temperature during the production of the dispersion method stampable sheet and the heating temperature during the expansion molding.
This is the melt viscosity of the resin constituting the film layer (fd). As a method of increasing the melt viscosity, a resin having a high molecular weight is used, another resin is blended (for example, low density polyethylene is blended with polypropylene), or calcium carbonate, titanium oxide,
A method of filling an inorganic filler such as mica, carbon black, and magnesium silicate may be used. In the case where polypropylene is used as the resin constituting the film layer (fd), the polypropylene may be used in an MFR (measurement condition; JIS K6758, 210 ° C., 2.16 ° C.).
kgf) is preferably 20 (g / 10 minutes) or less, more preferably 10 (g / 10 minutes) or less.

The film layer (f-
The thickness of d) is 10 μm or more, more preferably 20 to 1 μm.
It is in the range of 00 μm.

In the production of the dispersion method stampable sheet, the heating temperature of the multilayer film is set so that only the resin constituting the film layer (fb) for forming the air-impermeable resin layer (A) melts. It is preferable to adjust to a temperature that does not occur.

The multilayer film having the four film layers may be produced by any method and is not particularly limited. For example, the film layer (fc), the film layer (fb), the film layer (fa), and the film layer (fd) are manufactured as separate films, respectively, and laminated using an adhesive. It may be manufactured by any method such as a method of manufacturing by laminating four layers by processing, a method of manufacturing a multilayer film by a co-extrusion method using a T die, an inflation die, or the like. In the co-extrusion method, a multilayer film may be manufactured by co-extruding an adhesive resin between the resins forming each film layer, if necessary.

Further, in the expansion molded article or the stampable sheet of the dispersion method of the present invention, the porous material layer, the fiber-reinforced thermoplastic resin material, the air-impermeable resin layer, the first adhesive resin layer, and the second adhesive resin. The layer may contain, if necessary, an additive such as an antioxidant, a light stabilizer, a metal deactivator, a flame retardant, carbon black, or magnesium silicate, or a coloring agent, as long as the object of the present invention is not impaired. And the like.

Further, in the expansion molded article and the dispersion method stampable sheet of the present invention, the form of the porous material and the fiber-reinforced thermoplastic resin material is a plate-like shape according to the shape of the expansion molding or the dispersion method stampable sheet. And a plate-like material formed into an arbitrary shape. The non-breathable resin layer (A), the first adhesive resin layer, and the second adhesive resin layer are each formed by an expansion molded product or a dispersion stampable sheet. Exist in at least one of the plane portions. Further, when the skin, the adhesive resin layer, and the non-breathable resin layer are formed only on one side, a non-woven fabric or a thermoplastic resin is provided on the side opposite to the side on which the skin or the like is laminated to prevent the surface of the reinforcing fibers from being exposed. A resin film or the like may be bonded.

The expanded molded article of the present invention is lightweight and highly rigid, and has excellent skin adhesion and non-breathability. Therefore, it is widely used as an interior material for automobiles such as ceiling materials and door trims. can do.

[0059]

The present invention will be described in more detail with reference to the following examples and comparative examples.

Example 1 Polypropylene particles (homopolypropylene, melting point: 162 ° C., MFR: 65 g / 10 minutes)
50% by weight, 25% by weight of glass fiber A (fiber length: 25 mm, fiber diameter: 13 μm) and 25% by weight of glass fiber B (fiber length: 25 mm, fiber diameter: 17 μm) are mixed in a foam liquid so as to have a ratio of 25% by weight. After dispersion, defoaming, and drying (wet dispersion method), a web having a basis weight of 700 g / m ² was obtained.

On one side of the obtained web, a multilayer film having the structure shown in Table 1 was laminated so that the first layer was on the front side of the web to form a laminate. After heating this laminated body at 210 ° C., the heated laminated body is placed between cooling boards at 25 ° C. and press-molded at a pressure of 3 kgf / cm ² , and the glass fibers and polypropylene are integrally and densely solidified. Then, a dispersion method stampable sheet having a layer composed of a multilayer film on one side was obtained.

Next, this dispersion method stampable sheet was
After heating to 10 ° C., a polyethylene terephthalate nonwoven fabric (heated to 120 ° C.) is laminated on the multilayer film bonding surface, and placed in a mold for expansion molding (temperature: room temperature), with a clearance of 4.3 mm. The mold was closed (pressure: 1 kgf / cm ² ) to obtain a flat expansion molded product. At this time, the density of the porous agent layer of the expanded molded article to which the skin was bonded was about 0.3 g / cm ³ .

The obtained expanded molded article was subjected to the following measurements of skin peel strength, bending test, and air permeability test. Table 2 shows the results.

(Peel peel strength) A peel test piece (T-peel test) having a length of 150 mm and a width of 25 mm was cut out from the expanded molded article, and the skin was peeled off from the porous substrate at a length of 50 mm from the end. The skin and the porous base material are respectively gripped by the chuck, and a tensile speed of 50 mm /
The tensile test was performed in min. Peeling strength, the average value of the tensile load when the skin was peeled from the porous substrate 25mm width
Divided by The test was performed at 23 ° C and 80 ° C. FIG. 4 shows the relationship between the peel strength of the skin and the test temperature during the peel test.

(Bending test) From the expanded molded article, a length of 150
mm, a test piece with a width of 50 mm, and a span of 100 m
m, a three-point bending test in which a load was applied from the skin side at a crosshead speed of 50 mm / min, and the maximum load and the elastic gradient were measured. The measurement temperature is 23 ° C. (Air permeability test) The air permeability was evaluated based on ASTM-D737.

(Examples 2 to 21 and Comparative Examples 1 to 3) In each of the examples, as shown in Table 1, except that the types of the multilayer film and the skin were changed, an expanded molded article was produced in the same manner as in Example 1. It was manufactured and subjected to the measurement of the peel strength of the skin, a bending test, and a breathability test. The results are shown in Table 2, and the relationship between the peel strength of the skin and the test temperature during the peel test is shown in FIG.

Examples 1 to 21 and Comparative Examples 1 to 3
Observing the cross section of the dispersion method stampable sheet and the expanded molded article obtained by the above with a microscope (200 ×), the dispersion method stampable sheet has the structure shown in FIG. 3 in all Examples and Comparative Examples, The expanded molded article had the structure shown in FIG. In all the examples and comparative examples, the air permeability of the obtained expanded molded article was 0 cc /
cm ² · sec and was non-breathable.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[0071]

From the results shown in Table 2, the expanded molded article having two adhesive resins having different melting points as the adhesive resin layer, and having the low-melting adhesive resin layer disposed on the outer layer, shows that the skin at 80 ° C. It can be seen that the adhesiveness to the skin at 23 ° C., the bending characteristics, and the air permeability at 23 ° C. are all equal to or higher than those of the related art.

[0073]

The expanded molded article of the present invention exhibits bending properties, air permeability, and adhesion of the skin at room temperature that are equal to or better than those of the conventional product, and has excellent skin adhesion even at 80 ° C. It is. Therefore, the expanded molded article of the present invention is useful because it can be applied to a wide range of fields such as automotive interior materials such as ceiling materials and door trim materials, home electric appliances, and building materials that require high skin adhesion at high temperatures. Further, the dispersion method stampable sheet of the present invention is suitable for obtaining the above-mentioned expanded molded article.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of an expansion molded article of the present invention.

FIG. 2 is a schematic sectional view showing another example of the expansion molded body of the present invention.

FIG. 3 is a schematic cross-sectional view showing one example of the dispersion method stampable sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Porous material layer 2 Non-breathable resin layer (A) 3 First adhesive resin layer (B) 4 Second adhesive resin layer (C) 5 Layer rich in thermoplastic resin 6 Skin layer 7 Dispersible method stampable sheet Reference Signs List 8 fiber-reinforced thermoplastic resin material 9 non-breathable resin layer (A) 10 first adhesive resin layer (B) 11 second adhesive resin layer (C) 12 layer rich in thermoplastic resin 13 expansion molded body

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Yukio Nagashima 1 Kawasaki-cho, Chuo-ku, Chiba City, Chiba Prefecture Inside the Technical Research Institute of Kawasaki Steel Co., Ltd. (72) Eiichi Sumita 1 Kawasaki-cho, Chuo-ku, Chiba City, Chiba Prefecture Address: Kawasaki Steel Engineering Co., Ltd. F term in the company (reference) 4F100 AG00 AK01A AK07 AK41 AK63 AR00B AR00C AT00E BA04 BA05 BA07 BA10A BA10B BA10D BA10E BA13 CA23A CB00 DG01A DG15E DJ00A GB90 JA04D JA04G JB16A JB16D JB02J04K

Claims (3)

[Claims] 1. A reinforcing fiber and a thermoplastic resin (r-1)
A porous material layer having, as a main component, a non-breathable resin layer (A) laminated on at least one surface of the porous material layer, and the thermal laminate laminated on the non-breathable resin layer (A). A first adhesive resin layer (B) made of a thermoplastic resin (rb) having a melting point lower than the melting point of the plastic resin (r-1),
Further, a second adhesive resin layer made of a thermoplastic resin (rc) having a melting point lower than that of the thermoplastic resin (rb) is formed on the first adhesive resin layer (B). An expanded molded article of the stampable sheet by a dispersion method having C). 2. The expanded molded article of a stampable sheet by a dispersion method according to claim 1, wherein a skin layer is provided on an outer surface of the second adhesive resin layer (C). 3. A fiber-reinforced thermoplastic resin material in which reinforcing fibers are dispersed in a substrate made of a thermoplastic resin (r-1), and a non-ventilated layer laminated on at least one surface of the fiber-reinforced thermoplastic resin material. Resin layer (A) and the thermoplastic resin (r-1) laminated on the air-impermeable resin layer (A)
Thermoplastic resin having a melting point lower than that of (rb)
And a thermoplastic resin (rc) having a melting point lower than the melting point of the thermoplastic resin (rb) on an upper layer of the first adhesive resin layer (B). And a second adhesive resin layer (C).