JP2000063583A - Olefin-based resin composition and sheet or film made therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefin-based resin composition having an excellent flameproof property and also excellent in calendering processability and foamability, and a sheet or a film composed of the resin composition widely used for the wallpaper of building, interior material of various product such as vehicle or furniture, and the material of other miscellaneous goods. SOLUTION: This olefin-based resin composition contains 100 pts.wt. of a composition containing (A) 20-80 wt.% of an ethylene.α-olefin copolymer having <=0.89 g/cm3 density and 0.5-10 g/10 min melt index and (B) 80-20 wt.% of a metal hydrate and (C) 1-20 pts.wt. of a resin having a vinylic polymer block miscible with an ethylene.α-olefin copolymer. This sheet or film is formed by calender processing the resin composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin resin composition, and more specifically, it is a flame retardant material useful as wallpaper for buildings, interior materials such as vehicles and furniture, and miscellaneous goods such as bags and bags. Olefin resin composition and a sheet or film using the same.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resin has been used as wallpaper for buildings, interior materials for various products such as vehicles and furniture, and bags and bags for reasons of cost, processability, flame retardancy, etc. However, in recent years, a foamed sheet made of an olefin resin composition that can be used as an interior sheet has been proposed in Japanese Patent Laid-Open No. 5-200948. However, since these olefin resin compositions are inferior in processability, particularly calender processability, to vinyl chloride resin, it is not possible to increase the calender speed in processing into a sheet and there is a problem in terms of production efficiency. is there. Also,
In order to meet the market needs, it is necessary to improve the flame retardancy, but adding a large amount of flame retardant further reduces the calendering processability and also reduces the foamability and improves flame retardancy. There is also a problem in that respect.

For example, Japanese Laid-Open Patent Publication No. 7-19860 proposes a polyolefin resin having calendering suitability, but the blending ratio of the flame retardant is small and the flame retardancy is low. Further, Japanese Patent Laid-Open No. 9-12792 discloses that
It has been proposed to use an ethylene / α-olefin copolymer having a narrow molecular weight distribution for the purpose of improving mechanical properties, but it is not intended to improve calendering processability and foamability.

By the way, conventionally, in order to improve the calendering processability of a resin composition, an acrylic processing aid, an organic acid metal salt, an organic fatty acid, a wax and the like are added alone or in admixture of two or more. The method of doing is adopted. However, the olefin resin composition to which such a material is added is improved to some extent around the roll bank, but the tackiness is increased and the ease of taking out the sheet is rather deteriorated.
Furthermore, when such a material is added, the foamability is lowered, and a phenomenon in which an additive or the like is deposited on the surface (bleed, bloom) or the like occurs. Therefore, such a method cannot solve the above problems.

[0005]

From the above, the present invention solves the above-mentioned drawbacks of the olefin resin composition, and the interior materials and bags / bags of various products such as wallpaper for buildings, vehicles and furniture. To provide an olefin resin composition which is widely used as a material for miscellaneous goods such as, and has excellent flame retardancy, calender processability and foamability, and a sheet or film using the same. The purpose is to do.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on additives for improving the processability of olefin resin compositions, and as a result, have found that they have compatibility with ethylene / α-olefin copolymers. It has been found that the above problems can be solved by adding a resin having a certain vinyl-based polymer block, and the present invention has been completed based on this finding. That is, the problem is that (A) density is 0.89 g / cm ³
And the melt index is 0.5 g to 10
(C) the ethylene based on 100 parts by weight of a composition containing 20 to 80% by weight of an ethylene / α-olefin copolymer and 80 to 20% by weight of a metal hydrate (B), which is g / 10 minutes. The problem is solved by an olefin resin composition containing 1 to 20 parts by weight of a resin having a vinyl polymer block, which is compatible with an α-olefin copolymer.

The olefin resin composition of the present invention can maintain the foamability even if the amount of the flame retardant added is increased to improve the flame retardancy. Further, since it is also excellent in calendering workability, it is possible to increase the calendering speed at the time of forming into a sheet shape, and as a result, it is possible to manufacture a flame-retardant sheet or the like with high production efficiency.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to embodiments.

The olefin resin composition of the present invention is
Containing (A) an ethylene / α-olefin copolymer, (B) a metal hydrate, and (C) a resin having a vinyl polymer block compatible with the ethylene / α-olefin copolymer. And further contains other components as required.

(A) Ethylene / α-olefin Copolymer The ethylene / α-olefin copolymer used in the present invention has a density of 0.89 g / cm ³ or less and 0.8
5 to 0.89 g / cm ³ is preferable, and 0.86 to 0.8
8 g / cm ³ is particularly preferred. The density is 0.89 g /
If it exceeds ³ cm ³ , the touch of the molded product may not be sufficient, the molded product may shrink, and curling may occur when laminated on a base material such as a backing paper, which is not preferable. On the other hand, when the density is 0.89 g / cm ³ or less, the above-mentioned defects do not occur and
It is preferable because the roll processing can be performed in a wide temperature range of 120 ° C. or more and 150 ° C. or less, which is lower than the decomposition temperature of the blowing agent. The density is measured according to JIS K7112.

The ethylene / α-olefin copolymer used in the present invention has a melt index (hereinafter referred to as "M
It may be abbreviated as "I". ) Is 0.5 g to 10 g / 1
It is 0 minutes, preferably 1.0 g to 7.0 g / 10 minutes, and particularly preferably 2.0 g to 5.0 g / 10 minutes. If the MI is less than 0.5 g / 10 minutes, roll processability deteriorates, and the roll appearance at normal temperature deteriorates the sheet appearance and the like. Moreover, the foamability is also insufficient. on the other hand,
If the MI exceeds 10 g / 10 minutes, the strength of the sheet obtained by processing may be reduced, or the workability may be reduced due to increased tackiness and neck-in. When the MI is in the above-mentioned preferred range, the above-mentioned defects are not present, and it is easy to control the balance between roll processability and foaming property in a good state, which is preferable. In addition, the measurement of MI is based on JIS K721.
It is measured according to 0.

The ethylene / α-olefin copolymer used in the present invention has a maximum melting peak temperature Tm (° C) by DSC of preferably 60 to 100 ° C, more preferably 60 to 80 ° C. More preferable. When the maximum melting peak temperature by DSC exceeds 100 ° C, it becomes difficult to carry out calendering while suppressing decomposition of the foaming agent. On the other hand, when the maximum melting peak temperature by DSC is less than 60 ° C, the heat resistance tends to be poor. It is preferable for the content to be in the above-mentioned range since the above-mentioned drawbacks are not caused and processing can be performed at a low temperature, so that energy consumed during processing can be saved.

The ethylene / α-olefin copolymer used in the present invention is a copolymer of ethylene and α-olefin, and among them, a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms is used. preferable. For example, ethylene and propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1, decene-1, dodecene-1.
And the like are polymerized by a conventional method. In particular, it is preferable to use an α-olefin having 3 to 8 carbon atoms in terms of monomer cost and polymerization efficiency. These α-olefins may be used alone or in combination of two or more.

The ethylene / α-olefin copolymer is preferably obtained by, for example, a solution polymerization method using a geometrically constrained catalyst (CGC) which is a kind of single-site catalyst (SSC) centering on a metallocene compound. For example, the polymerization temperature is 0 to 250 ° C, and the polymerization pressure is normal pressure to 100M.
It can be obtained by solution polymerization under the polymerization condition of Pa. When the geometrically constrained catalyst is used, the molecular chain structure is not disturbed even when the amount of the comonomer is large and the comonomer can be uniformly introduced in a large amount, as compared with the case where a conventional Ziegler catalyst or the like is used. Further, since the molecular weight distribution width of the copolymer can be narrowed, as a result, the dependency of the melt viscosity on the shear rate and the melt tension are increased,
It is advantageous in that a copolymer having excellent moldability can be obtained.

The ethylene / α-olefin copolymer having a narrow molecular weight distribution width is preferable because it retains high processability, and Mw / M which is an index showing the uniformity of the molecular weight distribution.
It is preferable that n is 3.0 or less.

The ethylene / α-olefin copolymer used in the present invention may be one synthesized as appropriate by the above-mentioned method or a commercially available product. Examples of suitable commercially available products include ethylene / octene-1 copolymers such as "Engage" (registered trademark) manufactured by DuPont Dow Elastomer Co., Ltd. and "Toughmer H" (registered trademark) manufactured by Mitsui Chemicals, Inc. To be

(B) Metal Hydrate The metal hydrate used in the present invention functions as a flame retardant. Metal hydrates do not contain halogenated compounds, so
It is environmentally preferable to use this. Examples of the metal hydrate that functions as a flame retardant include magnesium hydroxide, aluminum hydroxide, alumina (hydrate), zinc borate, hydrotalcite, dawsonite, calcium aluminate, kaolin clay and the like. Among them, magnesium hydroxide is preferable because it can achieve both foamability and flame retardancy. These metal hydrates may be used alone or in combination of two or more. Moreover, a commercial item can also be used.

The metal hydrate used in the present invention has been surface-treated with a surface treatment agent from the viewpoint of improving the dispersibility of the metal hydrate in the composition and the compatibility with other components. Is preferably used. Examples of the surface treatment agent include higher fatty acids, metal salts of higher fatty acids, and silane coupling agents. In addition, a commercially available surface-treated metal hydrate can also be used. As commercially available products, "Kisma 5A", "Kisma 5B" manufactured by Kyowa Chemical Industry Co., Ltd.,
Suitable examples include magnesium hydroxide such as "Kisuma 5J".

(C) Resin Having Vinyl Polymer Block Compatible with Ethylene / α-Olefin Copolymer (hereinafter sometimes referred to as "(C) Resin") The vinyl polymer block used in the present invention is The resin possessed is compatible with the ethylene / α-olefin copolymer. Therefore, from the viewpoint of maintaining high compatibility with the ethylene / α-olefin copolymer, it is preferable to have, for example, an olefin polymer block or a polymer block of a conjugated diene together with the vinyl polymer block.

Examples of such a resin include a block copolymer having a polymer block of a vinyl monomer and a polymer block of a conjugated diene monomer, and a vinyl monomer polymer and a conjugated diene monomer. Examples thereof include a mixture with a polymer of a polymer, a graft copolymer obtained by graft-copolymerizing a vinyl-based monomer with a polymer chain having an olefin polymerization block, and the like. Among them, styrene as a vinyl-based monomer, using an aromatic vinyl monomer such as α-methylstyrene, a block copolymer using a conjugated diene such as butadiene and / or isoprene as a conjugated diene monomer, or, Mixtures of the respective polymers are preferable from the viewpoints of high compatibility with the ethylene / α-olefin copolymer, improved processability, and improved foamability.

Aromatic vinyl monomers such as styrene and α-methylstyrene, and acrylic acid vinyl monomers such as acrylic acid esters are used as vinyl monomers, and these are used as olefins such as ethylene and propylene. A polymer chain of a polymer or a polymer chain of an olefin such as ethylene and a vinyl-based monomer such as glycidyl methacrylate, ethyl acrylate, and vinyl acetate is graft-copolymerized with an ethylene / α-olefin copolymer. It is highly compatible with the polymer, and is preferable in terms of improving processability and improving foamability.

The block copolymer used as the resin (C) can be produced by a conventionally known method. For example, a living polymer is synthesized by anionically polymerizing a vinyl monomer such as an aromatic vinyl monomer in an organic solvent using an anionic polymerization initiator such as n-butyllithium, followed by butadiene and isoprene. A conjugated diene monomer such as the above is dropped into the system and copolymerized to obtain a diblock copolymer. In some cases, an aromatic vinyl monomer is further dropped into the system to obtain a triblock copolymer. By repeating this operation, a desired block copolymer is obtained.

The block copolymer obtained in this way may be hydrogenated to saturate the double bond in the block copolymer, and may be used as the resin (C). Hydrogenation is carried out by a conventionally known method, and for example, there is a method of using a Ziegler catalyst and under a hydrogen pressure higher than normal pressure. The graft copolymer used as the resin (C) can be produced by a conventionally known radical polymerization method or the like.

The resin (C) used in the present invention may be a resin produced by the above method or a commercially available product. Examples of commercially available products include "Clayton G" (Sh
ell), “Septon” (Kuraray), “Tuftec” (Asahi Kasei), “Dynaron” (JSR), “VMX” (Mitsubishi Chemical), “Modiper”
(Nippon Yushi Co., Ltd.), "SB-Polymer" (Kuraray Co., Ltd.)
Etc. are preferably used.

(A) of the olefin resin composition of the present invention
The blending ratio of the component (C) to the component (A) of the olefin resin containing the ethylene / α-olefin copolymer as the main component is 20.
-80% by weight, and 100 parts by weight of the composition containing 80 to 20% by weight of the metal hydrate (B), 1 to 20 parts by weight of the resin having the vinyl polymer block (C).
Preferably, (A) is 30 to 70% by weight and (B) is 70%.
To 30 parts by weight of the composition containing 30% by weight,
2 to 15 parts by weight of (C), more preferably 40 to 60% by weight of (A) and 4 to 10 parts by weight of (C) to 100 parts by weight of a composition containing 60 to 40% by weight of (B). It also contains 10 parts by weight. If the content of the metal hydrate is less than the above range, the flame retardancy becomes insufficient. On the other hand, when the amount exceeds the above range, the calender processability and foamability tend to be deteriorated. Further, if the content of the resin having a vinyl-based polymer block is less than the above range, effects such as improvement of calendering processability are not exhibited, while if it exceeds the above range, further effects cannot be obtained. Not economically favorable.

(A) of the olefin resin composition,
Other components than the component (C) are not particularly limited and can be appropriately selected depending on the application of the olefin resin composition. For example, a neutralizing agent, a dispersant known per se,
Examples include various additives such as antioxidants, light stabilizers, light resistance improvers, antistatic agents, pigments, flame retardants, and foaming agents. Preferable examples of the pigment include titanium oxide and phthalocyanine pigments. Suitable examples of the flame retardant include a polyphosphoric acid carbamate compound, a silicone compound, and a metal oxide. Further, as the antioxidant, polyhydric phenol-based and phosphorus-based antioxidants can be used.

Examples of the foaming agent include azo compounds such as azodicarbonamide (ADCA) and azobisisobutylnitrile (AIBN); sulfonyl hydrazide compounds such as P, P'-oxybisbenzenesulfonyl hydrazide (OBSH). A chemical foaming agent such as a nitroso compound such as dinitrosopentamethylenetetramine (DPT); These may be used alone or in combination of two or more. Among these, in view of stability during processing, azodicarbonamide (ADC
A) is preferred. When the olefin resin composition is used as the material for the wallpaper of the building, it is preferable that the olefin resin composition contains a foaming agent as another component.

(A) in the olefin resin composition
The content of the other components other than the component (C) may be determined as long as the effect of the present invention is not impaired, and can be appropriately determined according to the application of the olefin resin composition. In addition,
When the other component is the foaming agent, the content of the foaming agent in the olefin resin composition is about 2 to 12 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin copolymer. .

The olefin resin composition can be obtained, for example, by mixing the above components using a mixing device, a kneading device or the like known per se. Examples of the mixing device and kneading device include a Banbury mixer and an extruder.

Since the olefin resin composition of the present invention is excellent in calendering property, it can be easily formed into a film by calendering. There are no particular restrictions on the calendering temperature, and the normal processing temperature (120 ° C
~ 150 ° C).

Specifically, first, the olefin resin composition is formed into a sheet or film using a calendering machine (after the surface of the sheet or the like is further subjected to corona treatment or the like, if necessary). With a known adhesive or pressure-sensitive adhesive, laminated on paper such as aluminum hydroxide paper, flame-retardant paper, glass fiber paper, or by directly laminating pellets of an olefin resin composition on the paper by calendering, wallpaper Etc. can be easily manufactured.

When the olefin resin composition contains a foaming agent, the laminated sheet or the like obtained as described above can be chemically foamed to produce a foamed sheet.
The foaming ratio in foaming may be appropriately selected according to the application, purpose, etc. of the foamed sheet and cannot be specified unconditionally, but is usually about 2 to 6 times. In particular, when the foamed sheet is used as a wallpaper for a building, the expansion ratio is preferably 3 times or more.

By subjecting the surfaces of various flame-retardant sheets obtained as described above to primer treatment, printing such as gravure printing, and pressing processing, wallpaper having an excellent design and a sharp uneven pattern Etc. can be manufactured.

[0034]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0035]Example 1 (A) Ethylene / α-octene-1 (“ENGAGE
8200 "DuPont Dow Elastomer, MI =
5.0 g / 10 minutes, density = 0.870 g / cm ³, DS
C peak temperature Tm = 68 ° C.) 40 parts by weight
(B) Surface-treated magnesium hydroxide (“Kisuma 5
A) (made by Kyowa Chemical Industry Co., Ltd.) 60 parts by weight, and (C) “die
2 parts by weight of Naron 1320P "(made by JSR)
Kneading at 160 ° C. for 10 minutes using a Lee mixer
After that, it was granulated into pellets. Furthermore, on this pellet
TiO, a colorant₂("Taipaque CR-58"
4 parts by weight of Ishihara Sangyo Co., Ltd., a kicker ("Q
P-222NA ", manufactured by Asahi Denka Co., Ltd.) 1.2 parts by weight
In addition, after kneading at 140 ° C for 5 minutes, the foaming agent
Zodicarbonamide ("Vinihol AC # 3" Eiwa)
Seiko Kogyo Co., Ltd.) 3.2 parts by weight are added and kneading is continued for 5 minutes.
Then, an olefin resin composition was obtained.

Example 2 Dynaron 13 was used as the component (C) in Example 1 above.
An olefin resin composition was obtained in the same manner as in Example 1 except that 4 parts by weight of 20P (manufactured by JSR) was used.

Example 3 In Example 1, the modiper A was used as the component (C).
An olefin resin composition was obtained in the same manner as in Example 1 except that 4 parts by weight of T-317 (manufactured by NOF CORPORATION) was used.

Example 4 An olefin resin composition was prepared in the same manner as in Example 1 except that 4 parts by weight of SB-Polymer SF-55 (manufactured by Kuraray Co., Ltd.) was used as the component (C). Obtained.

Example 5 Dynaron 13 was used as the component (C) in Example 1 above.
An olefin resin composition was obtained in the same manner as in Example 1 except that 10 parts by weight of 20P (manufactured by JSR Corporation) was used.

Comparative Example 1 An olefin resin composition was obtained in the same manner as in Example 1 except that the component (C) was not added.

Comparative Example 2 Calcium stearate which is an organic acid salt in place of the component (C) in Example 1 (manufactured by Nitto Kasei Co., Ltd.)
An olefin resin composition was obtained in the same manner as in Example 1 except that 0.4 part by weight was used.

Comparative Example 3 A wax (“Mitsui High Wax 4202E”, manufactured by Mitsui Chemicals, Inc.) in place of the component (C) in Example 1 was used.
An olefin resin composition was obtained in the same manner as in Example 1 except that 1.2 parts by weight was used.

Examples 1 to 5 thus obtained,
And the olefin resin composition of Comparative Examples 1 to 3 was calendered to obtain a sheet having a thickness of 0.15 mm. At this time, the calendar processability of the olefin resin composition,
The following criteria were evaluated in terms of tackiness, bank rotation, sheet take-off property, and sheet smoothness, and the results are shown in Table 1.

<Adhesiveness> The adhesiveness was evaluated according to the following criteria, based on the ease of taking out the sheet from the roll. ◎ ・ ・ ・ Easy to take out without sticking. ○: A little sticky, but easy to take out. Δ: It adheres slightly, but there is no problem in taking it out. X: Sticky and cannot be taken out. <Regarding the area around the bank> Regarding the area around the bank, the state of the bank surface and the movement of the bank were visually observed, and evaluated according to the following criteria. ○: The bank surface is in good condition and rotates smoothly. △: The condition of the bank surface is a little rough and the area around the bank is slightly defective. ×: The bank surface is rough and the rotation is poor. <About sheet take-up property> The sheet take-up property was evaluated according to the following criteria by visually observing the occurrence of necking (necking) during roll processing. ○: Necking is small and the sheet width is uniform. Δ: Necking slightly, but there is no problem in practical use. X: Necking is large and the sheet width is not uniform. <Smoothness> The smoothness was evaluated according to the following criteria by visually observing the appearance of the sheet surface. ◯: Smoothness is good. Δ: The smoothness is slightly inferior, but there is no problem in appearance. X: Very bad and practically problematic.

Further, this sheet was laminated on flame-retardant paper and then foamed at 220 ° C. for 45 seconds in a gear oven to obtain a foamed sheet. The foamability at this time was evaluated in terms of magnification and cell state, and the results are shown in Table 1.

<Regarding Cell State> The state of the bubble structure of the sheet (cell state) was visually observed and evaluated according to the following criteria. ◯: The cells are fine, uniform and good. B: The cell is in a slightly defective state, but there is no problem in practical use. C: Large cells with unevenness, which is not preferable.

[0047]

[Table 1]

From the evaluation results in Table 1, "Dinalon" which is compatible with the ethylene / α-olefin copolymer (preferably ethylene / octene-1 copolymer) with the resin,
It has been proved that the olefin resin composition to which a polymer having a vinyl polymer block such as "MODIPER" or "SB-polymer" and a polymer having an olefin polymer block is added has improved calendering processability and foamability.

[0049]

The olefin resin composition of the present invention is added with a resin having a vinyl polymer block and an olefin polymer block which are compatible with ethylene / α-olefin. Even if a large amount of flame retardant is added, it has good foamability and good calenderability. Therefore, as compared with the conventional olefin resin composition, the usefulness as a wallpaper for buildings, an interior material for various products such as vehicles and furniture, and a material for other miscellaneous goods is remarkably good.

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Claims (8)

[Claims] 1. (A) The density is 0.89 g / cm ³ or less, and the melt index is 0.5 g to 10 g / 1.
20 minutes of ethylene / α-olefin copolymer which is 0 minutes
80% by weight, and (B) 80 to 20% by weight of a metal hydrate to 100 parts by weight of a composition containing, (C) the ethylene.
An olefin resin composition containing 1 to 20 parts by weight of a resin having a vinyl polymer block, which is compatible with an α-olefin copolymer. 2. A resin having a vinyl polymer block, which is compatible with the ethylene / α-olefin copolymer (C), is a block copolymer of an aromatic vinyl monomer and a conjugated diene monomer, Alternatively, the olefin resin composition according to claim 1, which is a mixture of a polymer of an aromatic vinyl monomer and a polymer of a conjugated diene monomer. 3. The olefin resin composition according to claim 2, wherein the aromatic vinyl monomer is styrene and the conjugated diene monomer is butadiene and / or isoprene. 4. The olefin resin composition according to claim 2 or 3, wherein the block copolymer is hydrogenated. 5. A resin having a vinyl polymer block, which is compatible with the ethylene / α-olefin copolymer (C), is obtained by graft-copolymerizing a vinyl monomer on a polymer chain having an olefin polymer block. The olefin resin composition according to claim 1, wherein the olefin resin composition is a graft copolymer. 6. The olefin resin composition according to claim 5, wherein the vinyl monomer is aromatic vinyl or acrylic acid ester. 7. The olefin resin composition according to any one of claims 1 to 6, wherein the metal hydrate (B) is magnesium hydroxide. 8. Any one of claims 1 to 7
A sheet or film formed by calendering using the olefin resin composition according to the item.