JP2000127313A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate made of a cork powder-containing polyolefin- based resin sheet suitable for the interior finishing material of a building, the surfacing material of a notice board or the like. SOLUTION: This laminate is produced by laminating a fibrous layer C through a bonding layer B onto one side of a layer A, which is made of a polyolefin-based resin having a flexural modulus of 200-2,000 kgf/cm2 and includes 15-150 pts.wt. of cork powders having the average particle diameter of 200-5,000 μm and 10-180 pts.wt. of a flame-retarder to 100 pts.wt. of the resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate using a polyolefin resin sheet containing cork powder, which is suitable as an interior material of a building or a surface material of a bulletin board.

[0002]

2. Description of the Related Art Conventionally, building interior materials and bulletin board surface materials for posting notices have excellent surface performance, such as inconspicuous pin holes when a pin is stabbed, and have excellent flame retardancy and durability. In addition, foamed sheets made of vinyl chloride resin are widely used because of their excellent properties and low cost. However, when a vinyl chloride resin foam sheet is incinerated after use, it is necessary to take measures such as using an acid-resistant incinerator, and it takes time and effort to separate and treat the sheet. There was a problem. Further, there is a problem that the plasticizer contained in the sheet blows out and easily contaminates the surface of the sheet and other articles in contact with the sheet.

[0003] Therefore, as substitutes for the foamed sheet made of vinyl chloride resin, polyethylene, polypropylene,
The use of a sheet obtained by foam-forming a polyolefin-based resin such as an EVA resin using a foaming agent has been studied.
However, when a large amount of a flame retardant is added to impart flame retardancy to the sheet, the expansion ratio does not increase, and it is difficult to obtain a thick foam sheet. In particular, when used as a bulletin board surface material, it is necessary to increase the thickness of the sheet, and there has been no satisfactory material.

[0004]

SUMMARY OF THE INVENTION The present invention provides a laminate made of a cork powder-containing polyolefin-based resin sheet which does not require much trouble in disposal after use and has excellent surface performance when used as a bulletin board surface material.

[0005]

The gist of the present invention is that a flexural modulus is 200 kgf / cm ² or more and 2000 kgf / c.
m ² less than the polyolefin resin, and the resin per 100 parts by weight of cork powder having an average particle diameter of 200～5000Myuemu 15 to 150 parts by weight, on one side of the layer (A) containing 10 to 180 parts by weight of a flame retardant And a fibrous layer (C) laminated via an adhesive layer (B).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyolefin resin used for the layer (A) of the laminate of the present invention has a flexural modulus of 200 kgf / cm ² or more and 2000
It is less than kgf / cm ² . This flexural modulus is
The value measured according to JIS K 7203 shall be used.

If the flexural modulus is less than 200 kgf / cm ² , the surface of the layer (A) is likely to have irregularities due to the elasticity of the cork powder during the molding of the layer (A), making molding difficult or noting more than necessary. There is a problem that things are hard to stop. On the other hand, when the flexural modulus is 2000 kgf / cm ² or more, the rigidity of the laminate increases, and there is a problem that it is difficult to perform the bonding work when directly attaching to a wall surface as a bulletin board surface material or the like.

The flexural modulus is 250 to 1500 kgf /
More preferably, it is in the range of cm ² . Examples of the polyolefin-based resin include a polyethylene-based resin, a polypropylene-based resin, a mixture thereof, and a mixture of these and another polymer (polymer blend). Among them, a polypropylene-based resin is preferable.

Examples of the polyethylene resin include a homopolymer of ethylene (homopolymer), a copolymer containing ethylene as a main component (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene). (HDPE) and copolymers such as metallocene-based polyethylene), mixtures thereof, and mixtures of these with other polymers.

Examples of the polypropylene resin include propylene homopolymer, propylene and ethylene or other α-polymer.
-Random copolymers or block copolymers with olefins, propylene graft polymers having a polyolefin copolymer as a backbone polymer, and mixtures thereof, and mixtures of these with other polymers. As the α-olefin copolymerizable with propylene, those having 4 to 12 carbon atoms are preferable. For example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl -1-pentene, 1
-Decene and the like, and one or a mixture of two or more thereof is used. The mixing ratio of ethylene or α-olefin is preferably 5 to 40% by weight based on propylene.

Examples of the polyolefin-based copolymer for the backbone polymer of the graft copolymer with propylene include ethylene-propylene rubber, ethylene-butene rubber, and ethylene-propylene-diene rubber. Other polymers that can provide the above polymer blends include, for example, ethylene-propylene rubber,
Styrene-based thermoplastic elastomers such as styrene-butadiene rubber and styrene-isoprene rubber are exemplified. This styrenic thermoplastic elastomer is preferably hydrogenated. The amount of the other polymer to be mixed is 20 to
It is preferably 80% by weight, particularly preferably 30 to 60% by weight.

The layer (A) comprises the above polyolefin resin, 15 to 150 parts by weight of cork powder and 10 to 180 parts by weight of a flame retardant per 100 parts by weight of the resin. Cork powder has an average particle size of 200-5000μ
m, preferably 300 to 3000 μm. Fine cork powder having an average particle diameter of less than 200 μm requires time and effort for pulverization, and is liable to be powdered when mixed with a resin component or the like, and may contaminate the periphery. Further, when the average particle diameter of the cork powder exceeds 5000 μm, heat generated by the frictional resistance of the cork powder during molding increases, and foaming due to generation of gas due to decomposition of the cork powder,
Coloring may occur.

The average particle size of the cork powder is such that the integrated value of the weight of each fraction measured by a JIS sieve is 50% of the total.
It is expressed as the particle diameter at the point where In addition, the average particle diameter of the cork powder is within the above specific range,
Further, it is preferable that the cork powder of 70% by weight or more, preferably 80% by weight or more of the whole is in the above range.

When the amount of the cork powder to be added is less than 15 parts by weight based on 100 parts by weight of the polyolefin resin, the cushioning property of the laminate cannot be obtained, and the resistance at the time of sticking or pulling out of a thumbtack or a pin with a needle is large. In addition, the pull-out trace of the needle tip is also notable, which is not preferable. On the other hand, when the added amount of cork powder exceeds 150 parts by weight, the surface of the laminate becomes insufficient in smoothness and the appearance becomes poor, or the mechanical strength is significantly reduced.

More preferably, the amount of cork powder to be added is 25 to 100 parts by weight per 100 parts by weight of the polyolefin resin. The moisture contained in the cork powder is not particularly problematic as long as the cork powder does not significantly absorb moisture, but, for example, when the cork powder has a water content of more than 10% by weight, foaming at the time of molding becomes intense. Problems are more likely.
In such a case, for example, use after reducing the water content in advance by using an oven or a hopper dryer, etc., or prior to mixing with the resin, agitate while heating only the cork powder in the mixing machine to be used to perform the drying process. Then, a method of adding a polyolefin-based resin may be used.

The water content of the cork powder is preferably 3% by weight or less. The cork powder used in the present invention is bark obtained from cork oak, and may be obtained by pulverizing this bark. The bark may include an inner skin and an outer skin in addition to the cork layer. Further, a cork sheet or a cork formed in a block shape may be crushed and recycled as cork particles.

The flame retardant used in the layer (A) includes generally used organic flame retardants and inorganic flame retardants.
Examples of the organic flame retardant include phosphorus-based flame retardants such as polyphosphate ammonium polyphosphate and phosphate ester, and nitrogen-based, halogen-based, and bromine-based flame retardants. Examples of the inorganic flame retardant include boron. Examples include compounds, aluminum hydroxide, magnesium hydroxide, antimony trioxide, sodium antimonate, zirconium compounds, borax, zinc borate, molybdenum trioxide, and composite inorganic substances that are complexes of these compounds. Among them, a non-halogen flame retardant that does not generate harmful halogen gas at the time of fire or incineration after use is preferred.

The addition amount of these flame retardants is 10 to 180 parts by weight based on 100 parts by weight of the polyolefin resin. If the addition amount is less than 10 parts by weight, a sufficient effect of the flame retardancy cannot be obtained, while if the addition amount of the flame retardant is more than 180 parts by weight, the deterioration of the physical properties of the laminate is remarkably deteriorated, and the moldability also deteriorates. Layer (A) contains other synthetic resins and stabilizers, inorganic fillers, lubricants, surfactants, anti-adhesives, pigments, antibacterial agents, etc., in addition to the above components, as long as the object of the present invention is not impaired. You may.

The layer (A) is obtained, for example, by kneading a polyolefin resin pellet, a predetermined amount of the above specific cork powder and a flame retardant with a Banbury mixer, and then forming the mixture into a sheet shape with a heating roll or calender roll. Can be
Alternatively, the above resin, cork powder and flame retardant may be mixed and pelletized using a twin-screw extruder kneader equipped with a hot-cutting device, and formed by an extruder equipped with a T-die.

The molding temperature is preferably in the range of 150 to 200 ° C. In particular, in order to prevent the cork powder from being colored by heat, the molding temperature is preferably 1 to 200 ° C.
More preferably, it is in the range of 60 to 180 ° C. The thickness of the layer (A) thus formed is 0.5 to 10 mm.
Is preferably within the range. When the thickness is less than 0.5 mm, the layer (A) is apt to break during molding.
mm, the molding speed is reduced,
The productivity of the layer (A) tends to be remarkably reduced, and the workability at the time of secondary processing tends to be deteriorated. More preferably, the thickness of the layer (A) is 0.7 to 3 mm.

The laminate of the present invention is obtained by laminating a fibrous layer (C) on one side of the layer (A) obtained as described above via an adhesive layer (B). The adhesive layer (B) is preferably made of a synthetic resin. Examples of the synthetic resin include a polyurethane-based resin and a polyolefin-based resin.
Particularly, a polyolefin resin is preferable. As the polyolefin-based resin, those mentioned in the layer (A) can be used, and among them, a polyethylene-based resin or a polypropylene-based resin is more preferable.

The adhesive layer (B) includes, in addition to the above synthetic resin,
Other synthetic resins, additives, and the like may be added as needed within a range that does not impair the purpose of the present invention. The thickness of the adhesive layer (B) is preferably in the range of 5 to 50 μm, and if it is less than 5 μm, the adhesive strength to the fibrous layer (C) may not be sufficient, which is not preferable. On the other hand, when the thickness exceeds 50 μm, the laminate becomes too rigid to produce workability, which is not preferable. A more preferred thickness is 10 to 30 μm.

Examples of the fibrous layer (C) include those composed of natural fibers and synthetic fibers.
Paper, woven fabric, non-woven fabric and the like can be mentioned. Among them, paper made of natural fiber is preferable. Paper types include high quality paper for printing, medium quality paper, kraft paper, glassine paper, paperboard,
Examples include Japanese paper, flame-retardant paper, and non-combustible paper. Fiber layer (C)
Is preferably in the range of 5 to 200 g / m ² . When the basis weight is less than 5 g / m ² , wrinkles are apt to be formed during lamination, and when the basis weight is more than 200 g / m ² , rigidity appears when the laminate is formed, which causes a problem in workability and increases costs. It is not preferable. More preferred basis weight is 50-15
0 g / m ² .

In order to form the laminate of the present invention, the layer (A) is formed on the adhesive layer (B) side of the fibrous layer (C) with the adhesive layer (B) formed on one side in advance. The adhesive layer (B) and the fibrous layer (C) may be sequentially laminated on the layer (A). The adhesive layer (C) may be laminated as a film or may be formed and laminated by dissolving in a solvent and coating. The laminate thus obtained can be used as it is as a bulletin board or an interior material of a building. Further, the board may be used as an insulation board or a bulletin board surface material, which is bonded to a wood-based material such as plywood with an adhesive, cut into an appropriate size, and fitted with a frame material.

[0025]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. <Evaluation of flexural modulus of polyolefin resin> JIS
It was measured according to K 7203.

<Evaluation of Sheet> (1) Formability: When a sheet was prepared as shown in Example 1 below, ease of forming and appearance were evaluated. The evaluation criteria are as follows.・ ・ ・: A sheet having a good appearance was produced without any problem. Δ: A sheet could be prepared, but the appearance was inferior. X: The sheet could not be formed.

(2) Surface performance: A plywood having a thickness of 5 mm was used as an underlayer, and the laminate was fixed to the plywood. The board was repeatedly inserted and removed 50 times with a bulletin board pin within a 1 cm diameter circle on the sheet side surface of the laminate. The appearance of the marks was visually evaluated. The evaluation criteria are as follows.・ ・ ・: The resistance of pin sticking is small. Marks of pin holes are not so noticeable. Δ: There is a slight resistance to pin sticking. Pin holes are slightly noticeable. ×: High resistance to pin stab. Pin hole marks are very noticeable.

(3) Adhesive strength (adhesive strength between sheet and fibrous layer): A test piece was cut into a strip having a width of 2 cm and a length of 15 cm, and the adhesive strength of the test piece was measured by an autograph.
Measured at 0 ° peel. The measurement conditions were a temperature of 23 ° C. and a pulling speed of 200 mm / min.

(4) Workability: Using a construction adhesive (JISA6922) specified by the Wall Covering Materials Association, the composition and adhesion of the adhesive were evaluated by constructing a laminate according to the wall covering standard construction method of the Association. In addition, the base material was a legally incombustible gypsum board board wall surface, and the test was performed in which the laminate was installed on the same vertical wall surface as in practical use. At this time, the influence of the curl of the laminate on the workability and the state of adhesion to the wall surface after the adhesion were evaluated visually. The evaluation criteria are as follows.・ ・ ・: Can be attached without any problem in construction. The adhesive strength after construction is also sufficient. Δ: After the application, the sheet slightly floated. Adhesive strength after construction is somewhat insufficient. X: peeled off without being fixed by the adhesive. Almost no adhesive strength.

<Example 1> 50 parts by weight of a polypropylene resin (FY4 manufactured by Mitsubishi Chemical Corporation) and a styrene-based thermoplastic elastomer (Dynalon 132 manufactured by Nippon Synthetic Rubber Co., Ltd.)
0P) 50 parts by weight of cork powder having an average particle diameter and amount shown in Table 1 and an ammonium polyphosphate flame retardant (Hostaflam AP422 manufactured by Clariant Japan KK) were mixed with an internal mixer (MS manufactured by Minami-Senju Seisakusho Co., Ltd.). −36
00) at a temperature of 170 ° C. and a rotor rotation speed of 50 rpm
After kneading under the conditions of m and a kneading time of 10 minutes, a sheet was formed at a temperature of 170 ° C. using a roll (manufactured by Ishikawajima-Harima Heavy Industries, Ltd.). Next, on one side of the sheet, a basis weight of 50 g
/ M ² kraft paper (fibrous layer) and 15 μm thick LL
A laminate of DPE films (adhesive layer) was laminated at a speed of 2 m / min with a laminator having a surface temperature of 170 ° C. to produce a laminate. This laminate was evaluated for surface performance and workability. Separately, a sheet was prepared in the same manner as above using a resin composition having the same composition except that cork powder and a flame retardant were not contained, and the flexural modulus of the resin used was measured. The results are summarized in Tables 1 and 2.

<Example 2> A sheet was prepared in the same manner as in Example 1 except that the composition of the sheet was as described in Table 1, and an adhesive layer and a sheet were formed on one surface of the sheet in the same manner as in Example 1. A fibrous layer was provided to produce a laminate. This laminate was evaluated for surface performance and workability. Separately, a sheet was prepared in the same manner as in Example 1 using a resin composition having the same composition except that it did not contain cork powder and a flame retardant,
The flexural modulus of the resin used was measured. The results are summarized in Tables 1 and 2.

Comparative Example 1 A sheet was prepared in the same manner as in Example 1 except that the composition of the sheet was as described in Table 1, and an adhesive layer and a sheet were formed on one surface of the sheet in the same manner as in Example 1. A fibrous layer was provided to produce a laminate. This laminate was evaluated for surface performance and workability. Separately, a sheet was prepared in the same manner as in Example 1 using a resin composition having the same composition except that it did not contain cork powder and a flame retardant,
The flexural modulus of the resin used was measured. The results are summarized in Tables 1 and 2.

Comparative Example 2 A sheet was prepared in the same manner as in Example 1, except that the composition of the sheet was as shown in Table 1. A kraft paper having a basis weight of 50 g / m ² was laminated on one surface of this sheet under the same conditions as in Example 1 to form a laminate. This laminate was evaluated for surface performance and workability. Separately, a sheet was prepared in the same manner as in Example 1 using a resin composition having the same composition except that it did not contain cork powder and a flame retardant, and the flexural modulus of the resin used was measured. The results are summarized in Tables 1 and 2.

Comparative Example 3 A sheet was prepared in the same manner as in Example 1 except that the composition of the sheet was as shown in Table 1. The surface performance and workability of this sheet were evaluated. Separately, a sheet was prepared in the same manner as in Example 1 using a resin composition having the same composition except that it did not contain cork powder and a flame retardant, and the flexural modulus of the resin used was measured.
The results are summarized in Tables 1 and 2.

[0035]

[Table 1]

[0036]

[Table 2] * 1: The winding habit of the laminate is remarkable.

[0037]

The laminate of the present invention does not require much time for disposal after use, and has excellent surface performance when used as a bulletin board surface material or the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/20 B32B 27/20 Z // G09F 7/00 G09F 7/00 D (72) Inventor Miyuki Yamashita F-term (reference) 4F100 AA04H AJ02A AJ02H AK03A AK03G AK07 AK12 AL09 AR00B BA02 CA08 CA08A CA23A CB00 DE01A DE01H DG00B00A DG00B90BDG10 J08GB00BDG10 J00 GB00BDG10 J04 GB00BDG10 J04 GB00BDG10 J04 GB00BDG10 J00 GB00BDG00 J04 GB00BDG10 J00 GB90B00 JDG

Claims (5)

[Claims] 1. A polyolefin resin having a flexural modulus of 200 kgf / cm ² or more and less than 2000 kgf / cm ² , and having an average particle diameter of 20 per 100 parts by weight of the resin.
On one side of the layer (A) containing 15 to 150 parts by weight of a cork powder of 0 to 5000 μm and 10 to 180 parts by weight of a flame retardant,
A laminate in which a fibrous layer (C) is laminated via an adhesive layer (B). 2. The fibrous layer (C) has a basis weight of 5 to 200 g /
The laminate according to claim 1 which is m ^2. 3. The laminate according to claim 1, wherein the fibrous layer (C) is made of paper. 4. The laminate according to claim 1, wherein the adhesive layer (B) is made of a polyolefin resin. 5. A bulletin board surface material comprising the laminate according to any one of claims 1 to 4.