JP2000079622A - Stock roll for polyurethane foam manufacturing process paper, and process paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process paper having improved chemical resistance and water resistance to be used for manufacturing polyurethane foam, and a sheet which is a raw material of the process paper (a pattern paper), i.e., what is called a stock roll for a polyurethane foam manufacturing process paper. SOLUTION: A biaxially drawn laminated sheet with a density of at most 0.8 g/ml provided with a resin layer A contg. a crystalline propylene resin, a cyclopentadiene petroleum resin and an inorg. filler and a resin layer B wherein a crystalline propylene resin is a main ingredient on one face or both faces of the resin layer A is used as a stock roll for a polyurethane foam manufacturing process paper. In addition, a polyurethane foam manufacturing process paper is manufactured by applying emboss molding on the stock roll.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyurethane foam.
The present invention relates to process paper used in the production of a system. More specifically, a sheet used as a raw material of a process paper (pattern) for forming a concave or a projection on a surface of a polyurethane foam for forming a pattern recess or protrusion, a so-called polyurethane foam manufacturing process paper raw material, and embossing the raw material And urethane foam production process paper.

[0002]

2. Description of the Related Art Polyurethane foam production includes a dry production method and a wet production method. In the production, a process paper (pattern) for molding a pattern on the surface of the polyurethane foam and forming a depression or a projection is used. Used. Particularly in the wet production method, there is no suitable one, and a process paper is used in which a polyolefin is laminated on paper and embossed. In this polyurethane foam production, a process paper is coated with a polyurethane resin solution,
The coated process paper is immersed in a mixed solution of dimethylformamide (DMF) and water to solidify the polyurethane resin. At the time of this production, there is a problem that the paper portion of the process paper is severely worn, and the development of a new process paper that does not cause damage is desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a process paper which is free from damage during the production of polyurethane foam. More specifically, it is an object of the present invention to provide a raw material for the process paper (pattern), a so-called raw material for a polyurethane foam manufacturing process paper, and a process paper which is not damaged during polyurethane foam production. That is, the coagulant dimethylformamide (DM
An object of the present invention is to provide a process paper for producing polyurethane foam which has no wear even when immersed in a mixed solution of F) and water, that is, has excellent chemical resistance and water resistance, and a raw material thereof.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a sheet containing a polypropylene resin and having a specific density or less has good embossability. This sheet was used as a raw material for urethane foam production process paper, and embossing was performed on the material to find the desired polyurethane foam production process paper. Thus, the present invention was completed.

[0005] The paper raw material for the polyurethane foam production process of the present invention is as follows. A raw paper for a polyurethane foam production process paper comprising a sheet containing a propylene-based resin and having a density of 0.8 g / cm ³ or less. Biaxial having a resin layer A containing a crystalline propylene-based resin, a dicyclopentadiene-based petroleum resin and an inorganic filler, and a resin layer B containing a crystalline propylene-based resin as a main component on one or both sides of the resin layer A The raw material for a polyurethane foam production process paper according to the above item, comprising a stretched laminated sheet. The raw material for a polyurethane foam production process paper according to the above item, wherein the resin layer B does not contain a dicyclopentadiene-based petroleum resin and / or an inorganic filler. The raw material for polyurethane foam production process paper according to the above item, wherein the resin layer B contains a dicyclopentadiene-based petroleum resin and / or an inorganic filler in a smaller ratio than the resin layer A. The raw material for a polyurethane foam production process paper according to any one of the above items, wherein the thickness of the laminated sheet is 50 μm to 500 μm and the thickness of the resin layer B is 100 μm or less.

[0006] The paper for producing polyurethane foam of the present invention is obtained by embossing the raw material according to any one of the above items.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION A raw material for paper of a polyurethane foam production process of the present invention has a density of 0.8 containing a propylene resin.
It is characterized by a sheet of g / cm ³ or less. Specifically, a sheet containing an inorganic substance or a petroleum resin is biaxially stretched on a propylene-based resin, so that numerous voids are generated inside the stretched sheet, which has an appropriate cushioning property and is further broken. It is a sheet with small elongation. In the biaxial stretching, it is preferable to stretch by heating at least twice in each of the longitudinal and transverse directions. The density of the process paper of the present invention is 0.8
g / cm ³ or less, preferably 0.7 cm ³ or less,
More preferably, it is 0.6 to 0.2 g / cm ³ . If the density exceeds 0.8 g / cm ³ , the workability of embossing is inferior and the productivity deteriorates. The biaxially stretched sheet may be a single layer, but a stretched laminated sheet is more preferred.

[0008] In a preferred embodiment of the paper raw material of the polyurethane foam production process of the present invention, the resin layer A containing a crystalline propylene resin, a dicyclopentadiene petroleum resin and an inorganic filler has a crystalline layer on one or both sides. A biaxially stretched laminated sheet having a resin layer B containing a propylene-based resin as a main component is shown. The biaxially stretched laminated sheet has a layer structure of B / A or B / A / B, a total thickness of 50 μm to 500 μm, and a thickness of the B layer of 1 layer.
It is preferably not more than 00 μm. Total thickness is 50
If it is less than μm, the embossability and rigidity are insufficient, and the thickness is 500 μm.
Exceeding the cost increases the product cost and is uneconomical. Also,
When the thickness of the layer B exceeds 100 μm, it is difficult to form the layer by embossing.

The crystalline propylene resin used in the resin layer A and the resin layer B of the raw paper for process paper of the present invention is at least one selected from the group consisting of ethylene and α-olefins having 4 or more carbon atoms. And a mixture of propylene and propylene as a main component, or a crystalline homopolymer of propylene.
Specifically, a crystalline propylene polymer containing 70% by weight or more, preferably 80% by weight or more of a boiling n-heptane insoluble portion, a highly crystalline propylene homopolymer, and a crystalline propylene polymer containing 70% by weight or more of a propylene component Ethylene / propylene block copolymer, random copolymer, crystalline propylene / 1-butene random copolymer, crystalline propylene / 1-hexene random copolymer, crystalline ethylene / propylene / 1-butene random copolymer And a propylene-based copolymer having a crystalline melting point. These polymers can be used alone or as a mixture as long as the embossability is not impaired. It is not necessary to use the same resin as the crystalline propylene-based resin used for the resin layer A and the resin layer B.

As this crystalline polypropylene, JI
SK7210-1976 The melting index (hereinafter M
FR) is preferably 0.5 to 20 g / 10 min.
Those having a range of 5 to 10 g / 10 minutes are preferable.

Examples of the didicyclopentadiene-based petroleum resin used for the resin layer A of the raw sheet of the process paper of the present invention include the following. That is, one or more selected from cyclopentadiene, dicyclopentadiene, alkyl-substituted products and oligomers thereof, and mixtures thereof obtained from steam cracking of petroleum naphtha and the like (hereinafter, referred to as cyclopentadiene-based component) as a main component. A high-molecular-weight, high-softening-point petroleum resin containing at least 50% of a fraction and having a softening point (ring and ball method) in the range of 160 to 200 ° C is exemplified. Further, among the above-mentioned petroleum resins, those containing 50% by weight or more of a cyclopentadiene-based component can be prepared by a conventionally known method, that is, vanadium, nickel,
Using a catalyst such as a metal such as cobalt or an oxide thereof in the presence of a solvent at a temperature of 150-300 ° C., 10
A hydrogenated dicyclopentadiene-based petroleum resin having a softening point (ring and ball method) of 160 to 200 ° C. obtained by hydrogenation under a hydrogen pressure condition of 00 to 15000 kPa can be mentioned.

The inorganic filler used in the resin layer A of the raw paper of the process paper of the present invention has a mean particle size of 0.01 to 30 μm, preferably 0.01 to 10 μm, calcium carbonate, talc,
Known inorganic additives such as titanium oxide and silica which are added to the polypropylene may be used. There is no particular limitation, but the use of calcium carbonate is advantageous in terms of cost. The inorganic filler powder may be used alone or a mixture of a plurality of inorganic filler powders may be used.

The resin layer A of the raw paper of the process paper of the present invention is composed of a dicyclopentadiene resin having a softening point (ring and ball method) of 160 to 200 ° C. and an inorganic filler powder per 100 parts by weight of the crystalline propylene resin. Is preferably 10 to 200 parts by weight. If the total content of the dicyclopentadiene-based resin and the inorganic filler powder is less than 10 parts by weight, the expansion ratio is too low, so that embossing is difficult to see and molding by embossing is insufficient. On the other hand, if the total content exceeds 200 parts by weight, there is a problem that stretching is frequently broken during stretching and the stretchability is extremely poor.

In the present invention, the components contained in the resin layer B may be the same as those in the resin layer A described above. However, in the resin layer B, it is preferable that the dicyclopentadiene-based resin and / or the inorganic filler is not contained, or even if it is contained, it is smaller than the content in the resin layer A. These conditions are suitable for preventing surface roughening due to generation of voids or adjusting smoothness.

In the present invention, in addition to the above-mentioned crystalline propylene resin, dicyclopentadiene resin and inorganic filler, various additives known to be added to polypropylene are added to the resin layers A and B, respectively. Can be contained in a range that does not impair the purpose. As various additives, for example, known phenol-based or phosphorus-based or thioether-based processing stabilizers / antioxidants, higher fatty acids or higher fatty acid salts such as calcium stearate, fatty acid amide-based lubricants, polyethylenes, ethylene-
Examples include various polymers such as propylene rubbers, antistatic agents, pigments, ultraviolet inhibitors, and foaming agents.

As a method of preparing the resin composition constituting these resin layers, a method of stirring and mixing the respective components with a usual blender or a mixer can be adopted. In addition, general extruder, gelation mixer (trade name)
Alternatively, the composition may be melt-mixed to obtain a pellet-shaped composition.

The raw paper for process paper of the present invention is prepared by co-extruding the composition prepared as described above to produce a non-stretched laminated sheet, and biaxially stretching the non-stretched sheet in the longitudinal and transverse directions. After stretching by heating more than twice each,
The obtained stretched laminated sheet can be manufactured by embossing with a previously designed engraving roll.

The stretching method is such that a sequential tenter device, a simultaneous tenter stretching device, and an IOP device for forming and stretching a sheet into a tube using a circular die are used. Method can be adopted. Although biaxial stretching causes numerous voids inside the stretched sheet, the density of the stretched sheet is set to 0.8 g / cm.
Less than ^3, preferably 0.6 g / cm ³ or less 0.2 g / cm
³ or more is good. If the density exceeds 0.8 g / cm ³ , the workability of embossing is inferior and the productivity deteriorates.

The process paper for producing polyurethane foam of the present invention can be obtained by embossing the raw material for process paper of the present invention. As the embossing method, a known embossing method such as a heating press method using a metal plate engraved in a desired shape or a heating roll method using an engraved roll is used.

[0020]

EXAMPLES The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited by these Examples. The evaluation methods of the characteristic values used in the following examples and comparative examples are shown below.

(1) Melt flow rate (MFR; g /
10 minutes) Based on the test condition 14 of JIS K7210-1976 (230 ° C, 2.16 kgf). (2) Embossability Using a surf coder SE-30K manufactured by Kosaka Laboratory Co., Ltd., the average surface roughness (R
The average surface roughness (Ra ') of the transferred stretched laminated sheet with respect to a) was measured, and the transfer rate was calculated to evaluate the following. ：: Transfer rate of 20% or more Δ : Transfer rate of less than 20% to transfer rate of 15% or more XX: Transfer rate of less than 15% (3) Water resistance The process paper cut into a square of 5 cm square was immersed in an aqueous solution of (dimethylformamide 18%) at 40 ° C. for 24 hours, washed with water, and rubbed on the surface 10 times with a finger to observe the condition. ：: No surface peeling, etc. ×: Surface peeling or damage was observed.

Example 1 MFR containing 96% of an n-heptane insoluble part was 2 g / l
0.2 parts by weight of phenolic antioxidant BHT (trade name), 0.1 part by weight of calcium stearate, 0.1 part by weight of glycerin monostearate, 100 parts by weight of crystalline polypropylene powder of 0 minute, softening point 40 parts by weight of a dicyclopentadiene-based petroleum resin (hereinafter referred to as DCPD) at 172 ° C. and calcium carbonate (average particle size of 1.5
μm) was charged into a Henschel mixer (trade name) and mixed with stirring. This mixture was melt-kneaded at 240 ° C. using an extruder having a coaxial rotary twin screw,
The extruded product was cooled and cut to obtain a pellet-shaped composition (A). On the other hand, MFR 1.5 g / 10 min, ethylene component 8%, 100 parts by weight of propylene-ethylene block copolymer powder having a block index of 0.8, 0.2 parts by weight of phenolic antioxidant BHT (trade name), 0.1 part by weight of calcium stearate and 0.1 part by weight of glycerin monostearate were charged into a Henschel mixer (trade name) and mixed with stirring. The obtained mixture was melt-kneaded at 240 ° C. using an extruder having a coaxial rotary twin screw, and the extruded product was cooled and cut to obtain a pellet-shaped resin composition (B). Next, using the two kinds of the obtained compositions (A) and (B), two kinds 3
By layer co-extrusion dies, layer configuration B / A / B,
An unstretched polypropylene laminated sheet having a surface layer (B) of 0.6 mm, a core layer (A) of 2.2 mm, and a total thickness of 3.4 mm was produced. Further, the unstretched sheet is 90 mm × 90 m
m, and preheated at a temperature of 156 ° C. for 120 seconds using a pantograph-type biaxial stretching apparatus, and then simultaneously stretched 5.0 times in the machine direction and the transverse direction at the same temperature.
Further, the laminate was heat-treated at the same temperature for 5 seconds while relaxing by 5% to produce a stretched laminated sheet having a density of 0.56 g / cm ³ and a total thickness of about 200 μm, that is, a raw material for a polyurethane foam production process paper. Subsequently, an embossed pattern was transferred to the surface layer of the laminated stretched sheet using a stainless steel plate embossed with a barbed pattern so as to have an average surface roughness of 0.35 μm using a hydraulic molding machine manufactured by Shoji Co., Ltd. Then, embossing was performed to produce urethane foam manufacturing process paper. The embossing conditions are a temperature of 100 ° C. and a pressure of 250.
0 kPa and the time was 3 seconds.

Examples 2-4 Polyurethane foam was prepared in the same manner as in Example 1 except that the amounts of DCPD and calcium carbonate were changed as shown in Table 1 below. A process paper was prepared in accordance with the above.

Example 5 Using the same two compositions (A) and (B) as in Example 1, a two-layer, two-layer coextrusion die was used to obtain a layer structure A / B. B) An unstretched polypropylene laminated sheet having a thickness of 0.6 mm, a core layer (A) of 2 mm, and a total thickness of 2.6 mm was produced. Further, the unstretched sheet is 90 mm × 9
After cutting into a square of 0 mm and preheating at a temperature of 154 ° C. for 120 seconds using a pantograph-type biaxial stretching apparatus, the sheet was simultaneously stretched 5 times in the machine direction and the machine direction at the same temperature,
Further, the laminate was heat-treated at the same temperature for 5 seconds while relaxing by 5% to produce a stretched laminated sheet having a density of 0.53 g / cm ³ and a total thickness of about 200 μm, that is, a raw material for a polyurethane foam production process paper. Then, using a hydraulic molding machine manufactured by Shoji Co., Ltd., the embossed pattern was transferred to the surface layer of the laminated stretched sheet by a stainless steel plate embossed with a scabbard, and embossed to give a process paper for urethane foam production. Was prepared. The embossing conditions are 100 ° C,
The pressure was 2500 kPa and the time was 3 seconds.

Comparative Examples 1 and 2 Polyurethane foam production process paper fabric and urethane according to Example 1, except that the addition amounts of DCPD and calcium carbonate, and the total thickness and surface layer thickness were changed as shown in Table 1 below. Process paper for foam production was prepared.

Comparative Example 3 An exfoliated base paper having a basis weight of 130 g was extruded with polypropylene (F3990 manufactured by Chisso Corp.) to a thickness of 30 μm, laminated by lamination, and embossed in the same manner as in Example 1 to produce a urethane foam. Process paper was prepared.

[0027]

According to the present invention, the raw material for paper of the polyurethane foam production process of the present invention is excellent in embossability and water resistance.
It is possible to provide a process paper for producing a polyurethane foam having an accurate mold and pattern without damage or grain during production of the polyurethane foam. Further, the process paper for producing a polyurethane foam of the present invention comprises a coagulant dimethylformamide (DM
F) and there is no wear even when immersed in a mixed solution of water.
Troubles in the process paper in the conventional polyurethane foam production can be solved, and by using this, a polyurethane foam having excellent molding or pattern can be produced.

[0028]

[Table 1] * 1 0.2 parts by weight of antioxidant BHT, 0.1 part by weight of calcium stearate, 0.1 part by weight of glycerin monostearate. * 2 B / A

Continued on front page F term (reference) 4F100 AA00A AA00B AA00C AA00H AK02A AK02B AK02C AK07A AK07B AK07C AK28A AK28B AK28C AL05A AL05B AL05C JA03 BA06 BA10B BA10C BA16 BA13 JA13 CA23ACAB JA13 CA23ACAB JA13 CA23ACAB YY00C 4F212 AA31 AA42 AG20 AJ03 AJ09 UA10 UL07 UN29 UP17 UP18

Claims (6)

[Claims] 1. A density containing a propylene resin of 0.8 g /
Raw material for polyurethane foam production process paper consisting of sheets of cm ³ or less. 2. A resin layer A containing a crystalline propylene-based resin, a dicyclopentadiene-based petroleum resin, and an inorganic filler.
2. A polyurethane foam production process paper according to claim 1, comprising a biaxially stretched laminated sheet having a resin layer B containing a crystalline propylene-based resin as a main component on one or both sides of said resin layer A. . 3. The raw material for a polyurethane foam production process paper according to claim 2, wherein the resin layer B does not contain a dicyclopentadiene-based petroleum resin and / or an inorganic filler. 4. The paper according to claim 2, wherein the resin layer B contains a dicyclopentadiene-based petroleum resin and / or an inorganic filler in a smaller ratio than the resin layer A. Raw material. 5. The thickness of the laminated sheet is 50 μm to 50 μm.
The raw material for a polyurethane foam production process paper according to any one of claims 2, 3 and 4, wherein the thickness of the resin layer B is 0 μm or less and the thickness of the resin layer B is 100 μm or less. 6. A process paper for producing polyurethane foam, wherein the raw material according to claim 1 is embossed.