JPS63228587A - Foamed polyester resin heating plate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a foamed polyester resin heating plate that can be suitably used as a heating plate for floor, wall heating, snow melting, etc., or as a heating container material. It is.

[r, Y:, Next technology L Ue, this type of heating plate for floor and wall heating has a heating element built in between the L plate and the lower plate, and the heating element is connected to a heating wire. At the same time, this is stored and arranged in a pot temporarily provided below, and this heating wire, I:.

It is known that a metal foil heat-uniforming plate made of aluminum foil or the like is laminated on the 1-, and an L plate is laminated and integrated on the 1-.

The heating element may be a base fabric coated or impregnated with a conductive tI/i material, a fibrous conductor woven into the base fabric to impart conductivity, or a synthetic resin or rubber coated with a conductive material. There are also known products that incorporate this mixed in and coated on the base fabric.

[Problems to be Solved by the Invention] However, in these heating plates since B℃, the upper and lower plates are made of wood, the heating element is housed in a clear space provided in the lower part, and Because they are stacked and assembled, productivity is extremely low, making them unsuitable for sightseeing and resulting in high costs.
It could only be manufactured as a fixed-size heat-generating panel. In addition, since the top and ten boards are made of wood, floors and walls are
When used for long periods as a 6-chamber type, there were also problems with dimensional stability such as shrinkage and deformation.

The present invention was developed in view of the above problems, and has a production capacity of 5 μJ, is easy to manufacture as a durable and arbitrary long heat generating plate, and can be used for long periods of time on floors and walls. An object of the present invention is to provide a foamed polyester resin heating plate that does not undergo deformation even when used for heating or snow melting, and has excellent electrical insulation, corrosion resistance, and water resistance.

Means for Solving Problem L] The structure of the present invention to achieve the above-mentioned objective t1 is to use a highly elastic fiber mat in the form of wrappers, fibers, whiskers, etc. A mixture of fine carbon particles and a binder was attached to a breathable sheet, a pair of electrodes were attached to this, and to this laminate a blowing agent, a curing agent, and a curing accelerator were added to unsaturated polyester. The gist is to uniformly mix a liquid mixture and heat it to foam and harden it.

The high modulus fiber mat used in the present invention is a non-conductive fiber such as a woven or non-woven mat made of synthetic fibers, natural fibers, glass fibers, etc., and has a high rating of 151 times! j'l force.

In the present invention, preferably polyester mltt, polyolefin [l[i, polyamide ffl il! , acrylic fibers, sea fibers, etc.), but polyester fibers are particularly preferred because they have excellent recovery elasticity, and among them, polyester composite fibers with latent crimp properties are preferred.
~ has excellent performance.

This polyester composite fiber mat has two components, for example, 5-sulfoisophthalic acid copolyester and polybutylene terephthalate. The combined ratio is 70/3
0-30/70. A web consisting of 1 g core-sheath 11 composite fibers with a melting point difference of 20 to 40°C is bonded at the entanglement points with a low-fusion polymer, for example: The length is 10 to 200Jz, preferably 2 (1 to 50μ, the number of curls is 25 to 50%, the 8-fold pitch is 10 to 50Jz, and (2) the melting point of the low melting point polymer is composite #iI miscellaneous). 40 = 90°C lower than the gf4 melting point component, the content of matte, fm M is 3 to 30 weight percent, (3) the outer circumference of the mat is] 0 to 40 cm 37 g, and the recovery elastic force is 1.7 of 10 to 50 g1 6, which appeases sex, can be preferably used.

In the present invention, the high modulus fiber mat may be provided with a chewing strength Jt4 consisting of a large number of fibers t1t, such as glass, carbon, ceramics, etc.! un and organic materials such as polyester, polyolefin, polyamide, acrylic, etc. l! ,
These nonwoven fabrics, woven fabrics, etc. are used. Furthermore, these materials can be used in combination, and the arrangement and number of layers of the reinforcing fibers may be arbitrarily selected.

In the present invention, a glass fiber mat is preferred for this reinforcing layer, and the reinforcing layer is preferably a glass fiber mat. ! This is good because it can be made into a heat generating plate with exceptional strength and rigidity.

The reinforcing layer can be provided on the high modulus fiber mat by pasting it with an R-me adhesive or the like, but it can also be provided by overlapping the reinforcing layer on the high modulus m fiber mat during molding. Figure 1 shows that the reinforcing layer is 4.
11 and 2 are reinforcing layers.

Next, we will explain about 1. the features that are frequently used in the present invention.

21st:/1. , is an idea system that adds 1.k to the present invention.
・One example of this is 4°4°1'4), this heating sheet 3 is made of fine carbon particles in the shape of particles, fibers, whiskers, etc. ・1 is mixed with a binder (It!- The mixture is put on the breathable sheet 5.
is a partial enlargement of 1-4, and electrodes 7.7 of 1 are provided on this. That is, the thermal sheet 3 is a breathable sheet 1. (11' + 〆1, : °n minute 1' Pine da 6 made of bamboo?fi
Apply a mixture of 1 haiku sprinkled in the liquid like -・ and dry it, i, 9
A conductive layer is formed thereon.

The ventilation sheet 5 may be made of non-fabric material such as glass fiber, glass fiber, woven fabric such as natural yellow, non-woven fabric or paper, porous film sheet, open cell foam sheet, etc. is used.

The diameter 6 made of the high-density material Ii in which the carbon fine particles 4 are dispersed and mixed is (・Rt l/) z! ! A flexible resin, a thermosetting resin, and a reaction +1 resin are used.As for this resin, the electric layer is heated and used as it is for a long period of time.
J! Resin stable at Jn temperature 3;1! It is desirable that these vA fats are
1f is understood and used, and the first row is acetone, methyl ethyl 1-rugetone, metoluisoptyl lactone, siku I7, renal san, tetoushi dorofuran, 11111! Methyl, ethyl acetate, nee thyl, glycol dimethyl ether, niraoxane, benzene 2; luene, mep lenc t7
Select 41 solvents such as Ride, Ethylene 17 Ride, etc. fJ
<t, can be used.

The fine carbon ha/l mixed in this binder 6 is:
Based on the electrical resistance W of carbon 1 and the same 1 that soft wire piece 4 has, the resistance obtained by the present invention is:!!4 Depending on what kind of electrical resistance value t-t can.

When the carbon fine particles 4 have the same specific resistance, the darkness mixed is small f
'i! , the exothermic temperature decreases. ' 3 ml Usually, the carbon fine particles 4 are mixed 11, and the carbon is 10 to 60 weight 1 part, 5'6 of the state office 4-1 breathable sheet 5, preferably 20
~30% by weight.

Also, the use of binder 6, the river is carbon! 5 to 10% of the R strip 4 and breathable sheet 1-5 can be preferably used.

It is also possible to add a flame retardant to the wood obtained in this way.This flame retardant includes fat group IIb,
Brominated aromatic compounds, phosphorus bromide, Su! Brominated flame retardants such as wood acid soda, zinc bromide, ammonium bromide, ammonium polyphosphate, biphenyl phosphate, F'0C
I3. l'cI,, I+ 31'02, l'011r
Phosphorus flame retardant such as 3, C,% C11Ch, N11-
Chlorinated flame retardants such as CI, 11, 11113. [1,
Boron-based products such as 03, amine-based products such as guanidine, diphenylamine, and isan.

Melamine cyanurate, etc. are used. Such flame retardants are prepared by adding charcoal to a solution of binder 6 dissolved in an organic solvent.
J: @ [It may be added and mixed together with the piece 4, or it may be treated with a flame retardant by soaking the sheet 111 in a flame retardant-containing liquid.

The electrodes 7.7 provided on this single sheet are made of silver! i of R1 etc.
Q conductive paint, or a combination of carbon talli and conductive paint, is used, or copper wire, #4 foil, the pond, etc.
- A dummy metal wire or metal foil can be used. As described above, the heat generating sheet 3 used in the present invention can be made by appropriately selecting the type of carbon fine particles 4 and the amount used. The electrical resistance value of can be freely changed according to [1].

Next, this fully ripened fiber mat is placed on a high elastic fiber mat.
The Jl/conductive 1 & fibers 1 to 30 which are overlapped with the Jl/conductive fibers 1 to 30 are made of non-conductive fibers, such as glass, lass gi fibers, Q/lI of synthetic resin II fibers, or mat-like non-woven fabrics, which are preferred in the present invention. However, glass fiber sheets can be used conveniently.

You may use several sheets for this shi-1, but it is also possible to use a plurality of sheets in piles.

The foamed polyester resin heat-generating plate of the present invention is manufactured by using a laminate in which the above-mentioned elastic fiber pine 1-1 is laminated with a heat-generating sheet 30 and a heat-generating sheet 30. Figure 3 shows how to manufacture the heat generating plate of the present invention! It is a diagram showing an example of I construction: 6.

In the figure, rpa is a feeding device that continuously feeds out a highly elastic mu1 mat 1, a heat generating sheet 3, and a non-conductive fiber sheet 30.

The impregnation equipment is equipped with a residue tank 8 containing unsaturated polyester with a foaming agent, a curing accelerator, and if necessary a foam stabilizer, a decomposition accelerator, etc., and a liquid tank 9 containing organic peroxide and anhydrous organic acid as curing agents. It is being

Each of the liquids in the liquid tanks 8 and 9 is supplied to a metering pump 10,
11, a predetermined mixture is sent to a mixer 12 and mixed.

Mixed liquid without water! 1vt3 is scattering '81
ti) to uniformly impregnate the laminate at room temperature according to step 4.
The liquid mixture 82 fibrous body 5 is led to a heating tunnel metal 11 for molding.

Heating tunnel gold for molding ■1 is equipped with a cooling section 16 that is cooled with water, and the heating section of the mold H is divided into multiple sections, each of which has an inner surface equipped with a heater 17 that can independently adjust the temperature. It is a chrome plated tunnel shaped thing.

The liquid-impregnated fiber body 15 is cooled to about room temperature at the entrance, enters the heating section, is heated by heating 2; 17, the polyester is foamed, and reaches the final heater 17 to complete curing.

The obtained heat generating plate 18 is pulled out by a pulling device K.

The pulling device includes an endless bell 1I9ai9b made of rubber, for example, with a black square on its surface, and continuously pulls out the heating plate 18 by sandwiching it from above and below.

This withdrawal speed is 4! ! The fiber body 5 is adjusted in the final heater 17 so that curing is just completed. The pulled out heating plate 18 is cut into a desired length by a cutter 20.

(1) In order to prevent heating plate 18 from running on the inner surface of II, and to obtain a heat generating plate with a glossy surface, heat generating plate 18 was placed on the -1; In between, there is an endless bell made of polyester!・21
a, 21b can be provided.

A protective terminal is fixed to the end of the electrode 7.7 of the foamed polyester resin heating plate 18 thus obtained, and a lead wire is connected to this. This can be used as it is for floor and wall heating, and for fa'M.

Here, the unsaturated polyester used in the present invention is a so-called polyester that is produced when an unsaturated acid such as maleic acid or fumaric acid is reacted with glycols.
This polyester is soluble in single U wood such as styrene. This solution is suitable for this! When a curing agent and a curing accelerator are added, an addition polymerization reaction occurs between the polyester and the monomer to grow a thermosetting resin. This resin is called unsaturated polyester.

2. For unsaturated polyesters. The change from the fFI liquid to the resin described in E is carried out in a very short time.

Attempts have been made to utilize this property to produce unsaturated polyester resin foams. However, unsaturated polyesters have very different curing behavior than other resins and are therefore difficult to foam. That is, unsaturated polyester is liquid and fluid, but as the C synthesis reaction progresses, its viscosity increases rapidly and gels. This is because the time is extremely short, and even if a blowing agent is used, it is extremely difficult to decompose the blowing agent within this time.

As a result of intensive research to solve this problem, the inventor of the present invention has found that when foaming unsaturated polyester, ammonium hydrogen carbonate powder is used as a blowing agent, organic peroxide is used as a curing agent, a curing accelerator, and anhydrous organic He invented a method in which a liquid mixture containing an acid and no water is combined and heated to foam and harden.
No. 01 (1985 3717 I+ application), Ma? Patent Application No. 1986-086256 (filed on 14Ll, August 1986), Patent Application No. 1986-193036 (August 19, 1988)
0 applications).

The blowing agent used in the present invention is preferably ammonium bicarbonate (15) wood, which has a finely divided particle size h'30
The amount of 7° ammonium bicarbonate, which is preferably less than μ, can be arbitrarily selected depending on the desired foaming ratio of the heating plate, but it ranges from 0.1 to 100 parts of unsaturated polyester. 20 heavy scenes, preferably (], 2・lO
Heavy Jj part is used.

The curing agent used for curing the low fI 8-wa polyester by polycondensation reaction is 11-bar oxide. These include ketone varo A-side yarn ((q4, for example, methyl ethyl lactone peroxide), hydroperoxide type (for M, cumene hydroperoxide),
Diacylpa-oxide type (e.g., benzoyl peroxide), baroxydicarbonate-1 type ((N, diiso-10-pyl peroxide), peroxy ester type (e.g., t-butylperoxyacetate), etc. Organic peroxides can be mentioned, these 2fl1
It is also possible to use a combination of the above.

Curing accelerators used in combination with this curing agent include, for example, cobalt naphthenate, cobalt octoate, manganese naphthenate,
Copper leaf date, zinc naphthenate, lauryl mercaptan, dimethylaniline, triethanolamine, diethylene chloride, pyridine, piperidine, etc. can be used, and two or more of these may be used in combination.

The conditions for this suitable mixing amount are unsaturated polyester + (1
The curing agent is 0.5 to 2.0 parts by weight relative to 070iii parts, and the cutting amount is 0.5 to 2.0 parts by weight. The old -0.5 double foot section is used.

In the present invention, methyl ethyl ketone peroxide can be used as a curing agent, and cobalt naphthenate is preferable for fIP (N31 is used as an agent and 17 is used in combination with ammonium bicarbonate). This is good because it has good molding workability and allows for uniform and fine foaming.

In addition, in the present invention, +ir+ curing agent and curing accelerator]
Anhydrous organic acids can also be used, for example anhydrous lactate or acrylic acid. This mixture (1:, is 0.1 to 3.0'1 per 100 weight Jψ parts of unsaturated polyester.
A portion of R3 is used.

History, in short, foam stabilizer, 1iii! It is also possible to use +9 shavings, colorants, etc. as necessary.

FIG. 4 shows the disassembled side WF4 of the heat generating plate 18 thus obtained.
In the lower part of the heat generating sheet 3, a ll7r thermal layer 1a made of highly foamed resin of the highly elastic fiber mat 1 is formed, and the electrical insulation layer 30 made of a low foamed resin made of the non-conductive fiber sheet 1-30 is formed on the upper part.
a is formed.

I Function of the Invention The foamed polyester resin heating plate of the present invention is made by fixing a mixture of a highly elastic fiber mat 1, carbon fine particles 4, and a binder 6 to an air permeable di-1. electrode 7
．． 7 and a non-conductive fiber sheet 1-3.
This laminate (JL mixture 13, which is made by adding a foaming agent, a curing agent, and a curing accelerator to saturated polyester) is uniformly impregnated with the laminate, heated, foamed, and cured to produce an unsaturated polyester. The mixed liquid substance 13 is easily impregnated into the laminate, and during foaming, the decomposed gas is uniformly dispersed within the laminate, so that a light heating plate with a uniform fine volume can be obtained. Becomes a reinforcing material and provides mechanical strength.
In order to make a heat generating plate with excellent rigidity, a heat insulating layer 1a made of a highly elastic foamed resin of pine I-1 with high elasticity is formed at the bottom of the heat generating sheet 3, and a non-conductive layer is formed on the top. Since the electric insulation X430a made of a low foam resin of "1-30" is formed, it is efficiently heated from the insulation layer 3(]a of the low foam resin. Also, since this can be done first, the large j
j) Suitable for production, -/l It does not require any additional work.

It is also possible to apply a rustic film or paint to the human blood on the heating plate 18 to improve stain resistance and decorative properties.

) Effects of the invention I 1. iQ Description: The heat generating plate of the present invention has a heat generating element between the 1-plate and the 1-plate as follows. Unlike those that are incorporated and made into f-books,
However, since it can be obtained in any length size, it can be easily mass-produced.
5.It does not shrink or deform even after long-term use, and can be used not only for coughing and heating purposes, but also for livestock, gardens, etc.
It can be used in a wide range of areas, even in areas where it was impossible to use it with &e Higashi's products such as ItJ.

Embodiment 5 The present invention will be further explained in Section 911 based on the following embodiments.

The heating plate of the present invention is manufactured using the manufacturing apparatus shown in FIG. 3; 1. -5 Elastic fiber ma/so 1
・】(Saints rk, made by high elasticity non-woven fabric + 14-20
cm'.

Rebound elastic force...30g) Glass on both sides! Electrodes were applied to a roll provided with Mat 2 (manufactured by Asahi Glass Fiber Co., Ltd., Condensed Strand) and a sheet body provided with a conductive layer by immersing it in a solution of charcoal Heat generating sheet 3 equipped with
Using a roll equipped with a L7-ru and a glass fiber sear 1-30 (manufactured by Asahi Glass Fiber Co., Ltd., Continuous Sus 1-land) with W/crn 2), a laminate drawn from the roll was coated with unsaturated polyester. (G1 21
(Manufactured by Bika Corporation, Ubika 7595) 100 parts by weight, 3 parts + iL of ammonium bicarbonate powder with a particle size of 10μ or less, 6% cobal naphthenate l-0, 2 parts M, and silica.
Con-oil (manufactured by Toray Silicon Co., Ltd., Toray Silicon S)
l+-190) 0.5 weight'' 5 parts, internal type II agent (manufactured by DuPont Far East Co., Ltd., Zerec NE) 0.
Liquid tank 8 containing 5 parts J1F and 1 part by weight of stearic acid and methyl ethyl peroxide (manufactured by Nippon Jushi Co., Ltd.).

2 parts by weight of acetic anhydride is added to the Vermec N becomes about 60%,
It was impregnated with sea urchin. This liquid-impregnated fiber body 15 is pulled into a heating tunnel mold H for molding (total length 1.150 mm).
g+m x 150mm x height 12mm)
And then.

The temperature of each heater 17N, '5 -) is 70~8
Adjust to 0'C, heat, foam and final heating 31
The heat generating plate 1 obtained by pulling at a speed at which curing is completed in step 7
8 was sandwiched between the drawing belts 19δ and 19b of a drawing device K (pulling strength: 2T), and was continuously drawn out at a speed until curing was completed by the final heater 17. Then cut it to a length of 1.8m with a cutter 20, and the cross section is 150 x 12
The foamed polyester resin heating plate of the present invention having a layer length of 1.81 cm is available.

A protective terminal is fixed to the end of the electrode of this heating plate,
When a lead wire was connected to this and electricity was applied 1 lll, the surface temperature of the heating plate reached about 80° C., which was a preferable heating.

[Brief explanation of drawings]

No. 11'4 is an exploded perspective view of the external appearance of the high-strength fiber mat used in the invention, and No. 21 (a) is a top view of the heat-generating sheet 1-, and Fig. 2 (1) is a partially enlarged view of In. . No. 3121
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing an embodiment of manufacturing equipment for manufacturing a photothermal plate of the present invention. FIG. 4 is an exploded perspective view of the heat plate obtained by the present invention.

Claims (1)

[Claims] 1) A heat-generating sheet in which a mixture of fine carbon particles in the form of powder, whiskers, etc., mixed with a binder is fixed to a breathable sheet on a highly elastic fiber mat, and a pair of electrodes are provided on the sheet. Then, non-conductive fiber sheets are stacked, the laminate is uniformly impregnated with a liquid mixture of unsaturated polyester, a foaming agent, a curing agent, and a curing accelerator, and heated to foam and harden. Features a foamed polyester resin heating board. 2) The foamed polyester resin heating plate according to claim 1, wherein the breathable sheet is a woven fabric, a nonwoven fabric, paper, or a microporous film. 3) Power consumption of heat generating sheet is 0.05 to 0.15 W/c
The foamed polyester resin heating plate according to claims 1 and 2, wherein the heating plate is m^2. 4) The foamed polyester resin heating plate according to any one of claims 1 to 3, wherein the non-conductive fiber sheet is a glass fiber mat. 5) The foamed polyester resin heating plate according to claims 1 to 4, wherein the foaming agent is ammonium hydrogen carbonate. 6) The foamed polyester resin heating plate according to any one of claims 1 to 5, wherein the curing agent is an organic peroxide. 7) The foamed polyester resin heating plate according to claims 1 to 6, wherein the curing accelerator is cobalt naphthenate.