JP3462431B2 - Foam composite sheet and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin resin foam composite sheet.

[0002]

2. Description of the Related Art Since the decomposition temperature of a thermal decomposition type chemical foaming agent is considerably high, when a foamed layer is formed on a base material such as paper or woven cloth which is weak against heat, problems such as charring of the base material occur. Therefore, a method of producing a foamed sheet and bonding it to a fibrous base material using an adhesive or the like has been used so far.

[0003]

However, when a sheet is formed by an extrusion method and foamed at the same time, it is difficult to simultaneously control the thickness, width and foaming ratio.

[0004]

The present invention has been made to solve the above problems, and the present invention according to claim 1 is characterized in that 100 parts by weight of an olefin resin is provided on a fibrous base material. On the contrary, 0.5 to 10 parts by weight of the thermal decomposition type chemical foaming agent,
Contains zinc oxide and zinc octylate, and the total zinc content is 0.1
It is 1 to 1 part by weight, and is a foamed composite sheet in which an olefin resin foamed layer having a ratio of the amount of zinc derived from zinc oxide and the amount of zinc derived from zinc octylate of 1: 1 to 30: 1 is laminated.

According to the second aspect of the present invention, based on 100 parts by weight of the olefin resin, 0.5 to 0.5 of the thermal decomposition type chemical foaming agent is used.
10 parts by weight, zinc oxide, mixed zinc octylate, all nitrous
The amount of lead is 0.1 to 1 part by weight, and the amount of zinc derived from zinc oxide
And the ratio of the amount of zinc derived from zinc octylate is 1: 1 to 30: 1
Pelletizing the composition that is not foamed,
It is a method for producing a foamed composite sheet which is crushed, scattered on a fibrous base material, sintered, and then foamed.

According to the third aspect of the present invention, the thermal decomposition type chemical foaming agent is added in an amount of 0.5 to 100 parts by weight of the olefin resin.
10 parts by weight, zinc oxide, mixed zinc octylate, all nitrous
The amount of lead is 0.1 to 1 part by weight, and the amount of zinc derived from zinc oxide
And the ratio of the amount of zinc derived from zinc octylate is 1: 1 to 30: 1
Pelletizing the composition that is not foamed,
This is a method for producing a foamed composite sheet, in which the pellets are molded into a sheet in a non-foamed state by an extrusion method, and at the same time, the pellets are bonded to a fibrous base material and then foamed.

Examples of the olefin resin used in the present invention include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polyethylene such as polyethylene polymerized with a metallocene catalyst, and random polymerized polypropylene. , Polypropylene such as block-polymerized polypropylene and syndiotactic polypropylene; ethylene-based copolymers such as ethylene-vinyl acetate, ethylene-acrylic acid, ethylene-acrylic acid ester, ethylene-methacrylic acid and ethylene-methacrylic acid ester, or a mixture thereof. Etc. Polyethylene polymerized using a metallocene catalyst is preferable from the viewpoints of the shape stability of the foamed cell, the cell shape holding power, and the flexibility.

As the thermal decomposition type chemical foaming agent used in the present invention, azodicarbonamide (ADCA), oxybisbenzenesulfonyl hydrazide (OBSH),
Benzenesulfonyl hydrazide (BSH), p-toluenesulfonyl hydrazide (TSH), diazoaminobenzene (DAB), azobisisobutyronitrile (A
IBN) and the like. These foaming agents can be used alone, a plurality of thermally decomposable chemical foaming agents can be used together, or a thermally decomposable chemical foaming agent and thermally expandable microcapsules can be used together.

The thermal expansion type microcapsules are obtained by enclosing low boiling point hydrocarbons in a shell made of a thermoplastic polymer material. The thermoplastic polymer material forming the shell of the microcapsules includes a polymer mainly composed of a copolymer of vinylidene chloride and acrylonitrile, and a polymer mainly composed of a copolymer of acrylonitrile and (meth) acrylic acid ester. Etc. can be used. Further, examples of the low boiling point hydrocarbon enclosed in the shell of the microcapsule include isobutane, pentane, hexane and the like.

In the present invention, zinc white (zinc oxide) and zinc octylate are added. From the viewpoint of cost, the amount of zinc white added is preferably 1 to 15 parts by weight, and if too small, a large amount of heat is generated during foaming. Is necessary, and the cost becomes expensive when there are too many. The amount of zinc white added is particularly preferably 2 to 5 parts by weight. If the amount of zinc octylate added is too small, a large amount of heat is required at the time of foaming, and if it is too large, the cost is high, so 0.05-5
Part by weight is preferable, and 0.5 to 3 parts by weight is particularly preferable. Further, when the addition amount of zinc white and zinc octylate is converted into the actual zinc amount, the total zinc amount is 0.1 to 1 part by weight, but the total zinc amount is 0.3 to 0.5 part by weight. In that case, pelletization is easily performed, and foaming can be performed with a relatively small amount of heat during foaming, which is also preferable in terms of cost.

In the present invention, 0.1 to 1 part by weight of total zinc is mixed with 100 parts by weight of olefin resin, and zinc oxide and zinc octylate are used in a ratio of 1: 1 to 30: 1. However, when the proportion of zinc octylate is too low or when only zinc oxide is blended, the decomposition temperature of the foaming agent does not decrease so much, and it is not particularly preferable when a relatively heat-sensitive substrate is used. On the other hand, when the total amount of zinc is 0.1 to 1 part by weight and the amount of zinc octylate is more than the amount of zinc oxide, the decomposition temperature of the foaming agent is too low and pelletization is difficult. Usually, as a zinc-based compound, zinc stearate or the like is used as a foaming aid in addition to zinc oxide and zinc octylate, but when a large amount of zinc stearate is blended,
Since the decomposition temperature of the foaming agent is lowered too much, it becomes difficult to pelletize the resin composition, which is not preferable.

In the olefin resin of the present invention, in addition to the above-mentioned foaming agent and zinc compound, a pigment, a lubricant, a stabilizer, an ultraviolet absorber, a filler, an antibacterial agent, a fungicide, a deodorant, an electrostatic charge. You may add various additives, such as an inhibitor, if needed.

As the filler, calcium carbonate, titanium oxide, aluminum hydroxide, talc and the like can be used.

As the antistatic agent, carbon black,
Inorganic antistatic agents such as graphite, silver and tin oxide, sorbitan antistatic agents such as polyoxyethylene sorbitan monostearate; ether antistatic agents such as polyoxyethylene alkyl ether and polyoxyethylene allyl ether; poly An amine- or amide-based antistatic agent such as oxyethylene alkylamine or polyoxyethylene amide; a fatty acid ester-based antistatic agent such as polyoxyethylene fatty acid ester; an organic-based antistatic agent such as a monoglyceride-based antistatic agent can be used. These antistatic agents can be used alone or in admixture of two or more. Among them, the amine-based antistatic agent has an immediate effect, and the monoglyceride-based antistatic agent hardly causes bleeding. Therefore, it is preferable to use the amine-based antistatic agent and the monoglyceride-based antistatic agent together.

Examples of the fibrous base material include natural animal or vegetable fibers such as cotton, hemp, silk and wool; synthetic fibers such as polyester, polyamide, polyethylene, polypropylene, acrylic and vinylon; rayon, suhu, acetate and the like. Regenerated fiber: paper, woven fabric, non-woven fabric, knitted fabric, or film or sheet containing these fibers, which is made of one or more types of fibers selected from glass fiber, pulp, asbestos, rock wool, etc. it can. If necessary, paper, woven cloth, non-woven cloth, knitted cloth, or a film or sheet containing these fibers and a laminated sheet thereof can be used. Further, these may be mixed or laminated with an inorganic filler, a synthetic resin binder or the like. Further, the present invention is particularly effective when using a fibrous base material that deteriorates at a relatively low temperature (about 160 to 220 ° C.).

The method for producing the composite sheet of the present invention includes:
As an example, the following method can be given. Heating the olefin resin sheet containing the foaming agent produced by an extruder,
A method in which an olefin resin foam sheet is produced by foaming and then laminated with a base material using an adhesive or the like. A method in which an olefin-based resin sheet containing a foaming agent produced by an extruder or the like is laminated by an extrusion laminating method or an adhesive, and heated and foamed. A method in which olefin resin pellets containing a foaming agent are sprinkled on a substrate, sintered, and foamed to produce. A method in which olefin resin pellets containing a foaming agent are pulverized and then dispersed on a substrate, sintered, and foamed to produce. In particular, the method for producing pellets or pulverized products by spraying, sintering, and foaming them on a substrate can take various widths, thicknesses, and expansion ratios of various sheets, and can obtain a wide variety of foamed sheets. Therefore, it is preferable.

The olefin resin foam sheet of the present invention can lower the foaming temperature, so that it can be used for paper, woven fabric,
It is particularly effective when forming a foamed layer on a fibrous base material such as non-woven fabric or knitted fabric, which is relatively weak to heat.

The foamed layer may be either a crosslinked foamed layer or a non-crosslinked foamed layer, but the non-crosslinked foamed layer is preferable because it has better dent recovery and fewer manufacturing steps.

The method for producing a foamed composite sheet made of an olefinic resin according to the present invention comprises: 0.5 to 10 parts by weight of a thermal decomposition type chemical foaming agent; In this method, a composition containing 1 to 1 part by weight is pelletized, crushed, sintered on a fibrous base material, and foamed to form a foamed layer. First, with respect to 100 parts by weight of an olefin resin, 0.5 to 10 parts by weight of a thermal decomposition type chemical foaming agent and 0.1 of zinc derived from a zinc compound are used.
The resin composition containing 1 to 1 part by weight is kneaded to prepare pellets. At this time, it is necessary to perform the operation at a temperature at which the thermal decomposition type chemical foaming agent does not decompose. Next, the prepared pellets are crushed and dispersed on the base material. At this time, it is preferable to make the layer thickness of the ground product uniform using a doctor knife or the like. Then, it is heated in an oven or the like to be sintered, and then foaming is performed at a temperature or higher at which the foaming agent is decomposed.

According to the manufacturing method of the present invention, the foamed layer can be formed at a relatively low temperature.
It is particularly suitable for producing a foamed composite sheet made of an olefin resin having a low foaming ratio of about 2 to 6 times.

[0021]

[Examples] [Examples 1 to 5] As Examples 1 to 5, pellets were prepared in a non-foamed state according to the composition shown in Table 1, and the pellets were crushed and sintered on paper. After that, foaming was performed to create an olefin resin foamed composite sheet. [Comparative Examples 1 to 6] As Comparative Examples 1 to 6, pellets were prepared according to the formulation shown in Table 2, and the pellets were crushed, sintered on paper and foamed to prepare olefin resin foam composite sheets. . In Comparative Examples 2, 5 and 6 which could not be pelletized, a foamed sheet was prepared by an extrusion method without being pelletized and laminated with paper.

[0022]

[Table 1] * 1 Polyethylene polymerized using a metallocene catalyst Evolution SP0540 manufactured by Mitsui Chemicals * 2 Azodicarbamide (ADCA) Uniform made by Otsuka Chemicals AZ-H25 * 3 Zinc with a zinc content of 10 wt% Zinc manufactured by Kakai Sakai Hana No. 3 * 4 Zinc octylate with a zinc content of 10% by weight Katsuta Kako Co. ABC-1J * 5 Zinc content of 10.7% by weight Zinc stearate by Nippon Oil & Fat Co. Zn-StG * 6 Amine charging Mixture of inhibitor and monoglyceride ELECON SS200FL * 7 manufactured by Dainichi Seika Kogyo KK JR600A * 8 ◎ Uniform foam cells are formed ◯ Almost uniform foam cells are formed △ Part of foam cells Roughness is seen × Foam cells are all over * 9 ◯ Almost no discoloration of the base material is seen × Discoloration of the base material is seen * 0 〇 pelletization may × blowing agent without foaming will decompose, not be obtained neat pellets

[0023]

[Table 2] * 1 to 10 are the same as in Table 1

[0024]

EFFECT OF THE INVENTION The composite foam sheet of the present invention has a thermal decomposition type chemical foaming agent of 0.1 part with respect to 100 parts by weight of an olefin resin.
5 to 10 parts by weight, zinc oxide, zinc octylate are blended,
The total amount of zinc is 0.1 to 1 part by weight, and the ratio of the amount of zinc derived from zinc oxide to the amount of zinc derived from zinc octylate is 1: 1 to 3
By using the olefin resin composition of 0: 1,
The composition can be pelletized and can be foamed at a relatively low temperature. Further, since foaming can be carried out at a relatively low temperature, it is also effective when a substrate which is relatively weak to heat is used.

Further, a composition in which 0.5 to 10 parts by weight of a thermal decomposition type chemical foaming agent, zinc oxide and zinc octylate are mixed with 100 parts by weight of an olefin resin is pelletized in a non-foamed state. A sheet having various widths, thicknesses, and expansion ratios can be obtained by using a manufacturing method in which the powder is crushed, dispersed on a fibrous base material, sintered, and then foamed. Further, a composition in which 0.5 to 10 parts by weight of a thermal decomposition type chemical foaming agent, zinc oxide, and zinc octylate are mixed with 100 parts by weight of an olefin resin is pelletized in a non-foamed state, and the pellets A conventional foamed sheet that is extruded while being foamed by using the method for producing a composite foamed sheet that is formed into a sheet shape by the extrusion method in a non-foamed state, is bonded to a fibrous base material, and is then foamed. It is possible to obtain a foamed sheet having more excellent dimensional stability.

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Claims (3)

(57) [Claims] 1. An olefin resin 10 on a fibrous base material.
0.5 to 10 parts by weight of a pyrolytic chemical foaming agent, zinc oxide and zinc octylate are blended with 0 part by weight, and the total amount of zinc is 0.1 to 1 part by weight. A foamed composite sheet in which an olefin resin foamed layer having a ratio of the amount of zinc and the amount of zinc derived from zinc octylate is 1: 1 to 30: 1 is laminated. 2. A thermal decomposition type chemical foaming agent 0.5 to 10 parts by weight, zinc oxide and zinc octylate are blended with 100 parts by weight of an olefin resin, and the total amount of zinc is 0.1 to 1 part.
And the amount of zinc derived from zinc oxide and zinc octylate.
1 zinc weight ratio come: 30: 1 to pellet der Ru composition in a state that is not foamed, and ground to spread over fibrous base material is foamed from by sintering foamed Composite sheet manufacturing method. 3. A thermal decomposition type chemical foaming agent 0.5 to 10 parts by weight, zinc oxide and zinc octylate are blended with 100 parts by weight of an olefin resin , and the total amount of zinc is 0.1 to 1 part.
And the amount of zinc derived from zinc oxide and zinc octylate.
Almost at the same time, the composition having a conventional zinc content ratio of 1: 1 to 30: 1 is pelletized in a non-foamed state, and the pellet is molded into a sheet in a non-foamed state by an extrusion method. A method for producing a foamed composite sheet, which comprises foaming after bonding with a fibrous base material.