JPS58162337A - Heat-insulating and thermoplastic synthetic resin foamed laminaed board - 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 The present invention relates to a synthetic resin foam board having a film laminated on at least both surfaces of the board, which has a low thermal conductivity and which changes over time in the thermal conductivity. This invention relates to a thermoplastic synthetic resin foam laminate with high heat insulation performance and a low ratio (deterioration of heat insulation performance).

In general, a thermoplastic synthetic resin foam board with a cell structure rich in closed cells, particularly a styrene resin foam board, is widely used as an excellent heat insulating material that is lightweight and has excellent drawing properties. However, the thermal insulation performance of these thermal conductivity (Kaaj / m-kxr0
When expressed as ℃at Q℃], it is usually 0.020 or more, and the thermal conductivity gradually increases over time (
It is known that insulation performance deteriorates.

The rate of change in insulation performance over time is determined by the environmental conditions over time (
It also depends on temperature and humidity conditions.・On the other hand, the thermal conductivity of a foam is determined by the three elements that propagate heat through the foam (
In other words, it is said that it is determined by the magnitude of conduction, radiation, convection), and is generally known to be related to the foam density, bubble diameter, closed cell ratio, and the type of gas inherent in the bubbles. There is.

JP-A No. 47-9593 describes foaming with a closed-cell structure of low density and small diameter as a method to improve the thermal insulation performance of foams obtained by extrusion foaming at the technological level of foams obtained by the extrusion foaming method. It is proposed to create a body.

However, with this method, the resulting foam has the best thermal conductivity of 0.200 Btu 71n, hr, 'p)
(0,0248Koa/ / FN・hr・℃ equivalent)
However, this method has the disadvantage that the sustainability of the insulation performance over time under conditions where a water vapor pressure difference occurs is not good.

The reason for this is, for example, when the density is 30 Kg/m's, the bubble diameter is 0. ．． When obtaining 610 foam, the density is 23Kg/
#f3, bubbles! When compared with the case of obtaining a foam with a diameter of 0.371111, the latter has approximately four times the number of cells compared to the former.

Unless advanced technology is used to increase the thickness of the cell membrane to metal V2, the closed cell ratio will decrease9, resulting in distortions and scratches on the cell membrane, which will eventually lead to low thermal conductivity and its aging. It is thought that if sustainability is not achieved, K will result. That is,
When forming a foam, it is extremely difficult to increase the number of bubbles and to uniformly grow and fix the bubbles, which naturally leads to technical limitations. On the other hand, in JP-A No. 53-2564, the initial thermal conductivity is 0.0150.1 by making the type of gas inherent in the bubble and its component ratio t-specific. 0.0164 in degrees (KOal/WJ, hr ℃
There is a statement that a foam exhibiting a value of ) was obtained.

However, according to follow-up tests conducted by the present inventors, this foam has extremely poor manufacturing reproducibility, and the foam that was finally obtained has poor dimensional stability and is unable to maintain thermal conductivity under conditions where a water vapor pressure difference occurs. Due to its poor quality, the conclusion was reached that it cannot be used for industrial production or practical use.

At present, this type of foam board does not exist on the market, nor has it ever been put to practical use. , - JP-A No. 56-50935, 1 foaming.

An attempt has been made to improve the heat insulation performance by adding a substance that absorbs heat propagation due to radiation to the resin composition of the body. However, the level of thermal conductivity that was practically achieved with this approach was approximately 0.03 Kaa//m@h
Since the temperature is around r@℃, the result is that the theory-savvy bob cannot be obtained.

That is, II! which has been explained in detail with one or more examples. In addition, the insulation performance of the foam, especially the influence of temperature and humidity, was also considered.The improvement of the insulation performance over time that can withstand the use of the foam, even though the clay can be considered,
It is extremely difficult to find a concrete means to achieve this, which is why it is impossible to find any industrial improvement measures. Therefore, even if there is a demand for a synthetic resin foam board that has a high level of thermal insulation performance during cold and menstrual periods, it has not been possible to provide it.

The present invention was made in view of the current situation, and its purpose is to improve heat insulation without being bound by the conventional technical idea of creating a low-density, small-diameter foam and specifying the blowing agent used. Our goal is to provide foam boards with excellent performance. Therefore, since the foam material can be manufactured using the same stable and efficient manufacturing process as before, most of the mechanical properties of the foam material can be changed and it can be easily manufactured in one state. , we can stably supply foam laminates with excellent heat insulation performance.

In addition, this foam laminate has excellent sustainability of thermal insulation performance over time considering temperature and humidity, making it suitable for underground insulation, tunnel insulation, underfloor insulation, li over insulation, etc. This will lead to the provision of new metal resin insulation materials.

The above object is achieved by using the foam of the present invention, that is, the density of the foam containing 1 L of fluorinated water with a partial pressure of 0.2 atm or more is approximately 52'90 Kg/m's compressive elastic modulus (A8'
rMD-1621) is 30 Kg/az2 or more, the nitrogen permeability (MuaTun-1
434) is 5 cc/Ill day-atm
23℃ or below, water vapor - survival rate (Mu8TM l 96
-63 T) is 69/111 days *day at 25℃
A film whose main body is synthetic resin satisfies the following values:
Through an adhesive resin layer of the same type as the foam board, a heat-sensitive adhesive resin layer, or a two-component curing adhesive resin layer.

The t-plane tension at the end of these stacks is approximately 35 dyn/
When immersed for 24 hours in a water-n-butanol mixture adjusted to have a ratio of t:s, #mixture (red) forms a dense layer with a bond shape (m) that does not penetrate for a length of 10 mm from the edge to the laminated interface. Laminated, thermal conductivity (Mu8TMO-518
) is skin 018 Kaal / #1-hr, 'c (
This can be easily achieved by using a thermoplastic synthetic resin foam logging board with thermal insulation properties that satisfies the rate of change in thermal conductivity of 15- or less under the following conditions when a water vapor partial pressure difference is applied: be able to.

Hereinafter, the contents of the present invention will be explained in detail with reference to the drawings.

FIG. 1 is a cross-sectional view showing one example of the foamed laminate of the present invention.

In Figure 1, 1 is a synthetic resin foam board, 2 'e 2'
1 indicates a barrier film mainly made of synthetic resin laminated on at least both surfaces of the foam board; -3, 3'b indicates the presence of an adhesive resin layer interposed between the two; The present invention will now be described in detail.

First, in the present invention, one foam board 1 has a density of approximately 25=90K.
g/m3. It is necessary to use a compressive elastic modulus of 3oKg/3m or more.

The reason for this is that it provides the laminate itself with excellent heat insulation performance and its durability over time, which will be described later, and that it forms the basis for economically and stably supplying the laminate.

In other words, the foam board regulations are based on the current hard thermoplastic resins such as polystyrene, high-impact polystyrene, styrene-acrylonitrile, polymethyl methacrylate, styrene-methyl methacrylate, and styrene-methyl acetoacrylate. This means that there is a foam board that can be manufactured under reasonable foaming conditions using foaming technology. In short, it is a normal foam material that suppresses heat propagation through beasts, gas convection, and conduction through solid parts to within the respective ranges. 25-90Kg/#l”.

Cell diameter is approximately 0.1~0.6■, closed cell ratio is 95III
The above-described foamed board can be easily produced continuously using a very common extrusion foaming method. Therefore, it is light □
It is possible to provide a stable supply of These generally have a wall thickness of 10ff to 150m11F.

Furthermore, when the compressive elastic modulus is less than 30 Kg/l"ll".

It is difficult for the lamination of the films described below to reach the state targeted by the present invention, and as a result, it becomes difficult to impart excellent heat insulation performance and durability to the laminate.

Next, this foam board is filled with fluorinated hydrocarbon at a partial pressure of 1 and 0.
．． The content is 2 atm or more, preferably 0.4 atm or more. This necessity is to impart thermal insulation properties to the laminate itself, and in conjunction with the above-mentioned properties of the foam board, the thermal conductivity of the laminate is 't0.018Kcaj/@-
Provides the basis for making it below hr, °C.

Fluorinated hydrocarbons for this purpose are, for example, trichloromonofluoromethane, dichlorodifluoromethane, monochloro, difluoromethane, dichlorotetrafluoroethane, dichloro, monofluoro, rometabe monochlorotrifluoromethane, trichloro, trifluoromethane, monochlorodifluoroethane. represented by the population. Fluorine-containing carbon, halogenated carbon, and hydrogen carbon having a boiling point of 70° C. or less at normal pressure are used.

This fluorinated expanded hydrogen can be added to the foamed board by bringing it into contact with fluorinated hydrocarbon to impregnate it after the foamed board has been formed, but in general. Since the above-mentioned fluorinated hydrocarbons cannot be used as blowing agents for the foam board, it is advantageous to use them as blowing agents alone or in combination and to contain them in one foam body.

Also, depending on the fluorinated hydrocarbon used, it may make the production of rigid resin foam boards unstable, so in this case, use it together with other blowing agents such as methyl chloride or methylene chloride, and adjust the production conditions. Stabilization is desirable.

In either case, the fluorinated hydrocarbon has a partial pressure of 0.
It is necessary to contain 2 atm, preferably 0.4 atm or more in order for the laminate to exhibit its heat insulation performance, and from the knowledge that it further improves the heat insulation performance and increases the dimensional stability of the laminate. , fluorinated hydrocarbons include dichlorodifluoromethane, dichlorotetrofluoroethane, trichloromonofluoromethane, tM, and their partial pressure t-0.4 atm or more (substantially #
(1 atm or less) is desirable. The density of the foam board is t'30-60Kg/m3, and the cell diameter is t0.1-0. !
sr.

It is desirable to select one with a closed cell ratio of 98 coefficient or higher.

Next, the film shown at 2.2' in Figure 1 has the role of preventing the above-mentioned fluorinated hydrocarbon contained in the foam board from being diluted over a long period of time. This serves to block incoming water vapor over a long period of time, and to protect the surface of the foam board from external stress.

For this purpose, it is generally considered that the thickness does not matter as long as the barrier property is at the required value, but in the present invention, the thickness is 150μ or less, more preferably, It is necessary to maintain barrier properties with a wall thickness of 80μ or less.

The reason for this seems to be related to the state of bonding with the foam board, which will be described later.For example, if the film exceeds 150μ, the bonding state described below will not be stable, resulting in the disadvantage that the sustainability of the heat insulation performance cannot be maintained.

And the nitrogen permeability is 5 (cc/j*”-day
, atm, at23℃) or less and water vapor transmission rate is 6 (y
/m2・day・at 25°C) If at least one of the following values is not satisfied, the present invention refers to excellent heat insulation performance.

and/or sustainability.

The laminate of the present invention has been developed by taking economic efficiency into consideration in addition to the above reasons.

2. For the 3' film, a film mainly composed of 1 synthetic resin is used. Specifically, vinylidene chloride film, polyand film, polyester film,
Single items such as vinyl chloride film.

Or, a film with increased barrier properties by applying a metal thin film or a vinylidene chloride resin film mv on the surface of a synthetic resin film such as Iriand film, polyester film, or chlorinated gel, or the surface of such a film with high barrier properties. This is a multi-layer y5ts;mu etc. covered with a polyolefin resin.

The reason for this is: (1) The film subject to this application must have a relatively thin wall thickness of 150JlI or less and satisfy the values of nitrogen permeability and water vapor permeability. Flexibility and toughness are required to play the role of layers, and in addition, in practical use, even when deformation stress is applied to the laminate, it deforms according to this stress and maintains the sustainability of its insulation performance. Therefore, the film 2.2' is a layer of about 50 μm to 2 μm of disdenne chloride resin.

It is preferable to use a vinylidene chloride resin laminated film having an olefin layer attached to its surface.

Next, this fill A 212' is integrally laminated over at least both wide surfaces of the foam board 1 via adhesive resin layers 3 and 3'. If necessary, 7 layers of foam board are laminated.

The reason is that F9rum 2. Alternatively, even if 2' satisfies the requirements of the present invention, it is not possible to achieve excellent heat insulation properties, i and its sustainability with only one surface, and furthermore, 3 and/or 3'. This is because without the presence of the adhesive resin layer, the bonding conditions of the present invention, which will be described later, cannot be satisfied.

However, the presence of a 3.3' adhesive resin layer (a foamed resin layer and/or a heat-sensitive, two-component curing adhesive resin layer) does not necessarily mean that the bonding state a as defined in the present invention is
Therefore, it is necessary to carry out sufficient preliminary experiments with reference to the manufacturing method described later and aiming at the bonded state referred to in the present invention. It is desirable to cover the entire surface of the foam board with the film.

What is the bonded state in the present invention?1. When the laminated end of the laminate is immersed for 24 hours in a mixture of water and n-butanol (usually at a ratio of 1 ooot of water to 579 n-detanol) whose surface tension is adjusted to a target of 55 ayn/on, the above liquid It is necessary that the bonding state is such that the bonding state does not penetrate into the laminated interface for a distance of 10H from the end face.

The reason for this is that a laminate in which the penetration length exceeds 10 ffile is a laminate that satisfies all the specifications of 1 foam board, 1° film 2, 2', and resin layer 3, 3' in the present invention. However, the heat insulation performance and its sustainability as defined in the present invention cannot be achieved.

According to research conducted by the present inventors, this phenomenon is inferred to be caused by gases in the atmosphere that enter the foam board from the interface ends of the laminated layers and gases under aging conditions.

In addition, the infiltration of this gas into the interface area progresses in an unexpectedly short period of time, and the progress is accelerated and one more line is created. Even if we were to conduct an experiment in which a film, etc. was bonded, it would be impossible to confirm the effectiveness of the foam board, such as improving its insulation performance or its sustainability, unless we investigated the bonding conditions mentioned above. be.

In other words, until the indicators of the bonding state described in this application have been determined, it will be extremely difficult to search for conditions for bonding, and the experiment will probably be abandoned when the optimum conditions cannot be found. .

The heat-sensitive adhesive resin used in the laminate of the present invention is:
Ethylene-♂yl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, etc. have a melting point of 60° to 100°C.

Further, the two-component curing adhesive is one such as polyurethane resin, urethane resin, etc., which is a liquid in a separated state and is cured by mixing two parts.

The laminate of the present invention having the above structure has a thermal conductivity of o, o i
Excellent precipitation performance with a lower value of s tear /jjl-hr・℃ or less, and one surface of the plate 't27℃ (target value), the temperature difference between both surfaces of the plate is 1℃ (per plate thickness 1W) The rate of change in thermal conductivity before and after aging for 100 days in an atmosphere with a water vapor partial pressure difference of t 21.5 aHg (target value) (hereinafter abbreviated as rate of change) ], it shows excellent sustainability of thermal insulation performance of 15 or less.

The thermal conductivity value of 0.018 was determined based on the practical limit at which the thickness of the insulation material can be substantially reduced when using this as an insulation material and expecting the same insulation performance as conventional products. It is. Furthermore, the conditions for the rate of change are comparable to those for 6 years in a wet application where a water vapor pressure difference is applied, such as rooftop insulation.

Therefore, laminates that meet the above characteristics can be used for walls of conventional buildings,
In addition to general insulation applications for ceiling floorboards, it exhibits excellent insulation performance for applications such as foundation insulation buried underground, basement insulation, tunnel insulation, rooftop insulation where rainwater collects, external wall insulation, etc. Become.

According to the inventor's experiments, the heat insulation performance of the laminated board obtained by the present invention is as follows.

FIG. 2 is a cross section showing one example of a desirable embodiment of the laminate of the present invention. The difference from FIG. 4′
exists.

The existence of this skin layer 4.4' has the advantage of not only making the above-mentioned bonded state specific in the present invention, but also making the rate of change (gradient) excellent at a level of 10° or less. The layer can be created by quenching or quenching the surface of the foam board, which is still in a flowable state, during the manufacture of the foam board.

Hereinafter, the method for manufacturing a laminate of the present invention will be described in detail.

FIG. 3 shows factors showing an example of the manufacturing process of the laminate of the present invention.

In Fig. 3, a foam board 1, which has been foam-molded, is transported (transfer device - path) in the direction of the arrow a, and in the process of transport, an adhesive resin layer of the same type as the foam board and an adhesive resin layer of the same type as the foam board are transferred. 0 (or) a heat-sensitive adhesive resin layer 3.3' is laminated on one side of the film in advance and the main body is a synthetic resin film 2.2't-
1. Pull out the drawer to a length that matches the length of the foam board, and stack it on both sides of the foam board.

The laminate can be completed by pressure welding with heating rolls 5.5'. In addition, when using a two-component curing type or heat-sensitive adhesive for the adhesive resin layer 3 and 3', 1
Adhesive is applied to the surface of the foam board 1 using a conitor or the like, and barrier films 2, 2'? When a two-component curing adhesive is used, heating of the pressure bonding ring is not necessarily required.The bonding means can be selected as appropriate depending on the materials used.

6, 6' Hafilm 2t2' is induced and supplied in a wrinkle-free state. Intermediate roll groups t-, 7, 7' represent film folders.

Points to be noted in particular in the method of manufacturing the laminate of the present invention include: a) For the foam board 1, use a hard foam board with a compressive elastic modulus of 30 Kg/32 or more; b) Among them, select and use a foam board with a closed cell ratio of 95 or more from the range b with a density of about 90 to 25 Kg/WJ3s and a cell diameter of about 0.1 to 0.6 tm.C) Foam board To use a foamed board with a skin layer on the surface 1. d) To laminate the Nifilm 2.2' for a very short period of time, within about 12 hours after the foamed board was manufactured.

e) Films 2 and 2' have a thickness of 150μ or less and a nitrogen permeability of 5 cc/m2-aay-atm, a
t 23℃ or less.

Water vapor transmission rate is 69/m2-1m2-1ay-at 2
Use a film mainly made of synthetic resin that satisfies the temperature of 3°C or less.

f) - The adhesive layer 3.3' interposed between the foam board 1 and the film 2.2' is an adhesive resin layer of the same type as the foam board 1, a heat-sensitive adhesive resin layer, or a two-component curing resin layer. g) The pressing force during pressure lamination is 10 to 25 in terms of the degree of compression of the foam board.
1. The temperature of the foam should be kept at 35° C. or less, h) The temperature control accuracy of the suppression roll should be set to ±2° C. or less. 5.

etc. This type of product is manufactured under conditions that meet at least five criteria, preferably all criteria.

These advantages are combined to provide a laminate that achieves the objective of the present invention.

Below, examples of trends for each item will be explained in detail.

21st! ! (Results of Examples and Comparative Example 1) show the phenomenon tendency of a) above.

According to the results in Table 2, the foam board that more completely satisfies the bonding conditions defined in the present invention has a compressive modulus of elasticity of 30 kg/m.
``From the above, it is clear that it is necessary to use a rigid foam board with a weight of preferably 50 kg/ala or more.Also, this phenomenon is caused by the variation in compression that occurs between the foam board 1 and the film 2.2' during pressure lamination. In fact, for example, in a laminate using a foam board with a compressive modulus of 20 kg/ClI2,
Even if a product satisfies the bonded state defined in the present invention in the testing process, when it is put into practical use, it tends to change to a product that does not meet the bonded state defined in the present invention during the handling process during transportation and installation. However, there is a drawback that the quality cannot be guaranteed.

Table 3 (results of Example Comparative Example 2) shows an example of the phenomenon tendency of b) above.

The target foam board in this case is an extruded polystyrene resin foam board, which is said to be the most economical, but with the current technology, the cell diameter is o, i Ifll, and the density is 25 kg.
/m3 or less, and foams with a density of 66Kg/FM3 and a cell diameter of less than 0.1W, both of which are difficult to stably supply. This phenomenon occurs in the direction of decreasing the foam plate density with a constant cell diameter, and in the direction of decreasing the cell diameter by changing the density.

Both of these represent technical content that cannot be achieved unless the bubble deposit is increased and the bubbles grow homogeneously, indicating that there are difficulties.

When looking at Table 3 with this background in mind.

A foam board that can be used as a material for a laminate that satisfies the purpose of the present invention has a density of 25 to 90 kg/m3 and a cell diameter of 0.1 to 0.6.
It can be seen that using a foam board with a closed cell ratio of 95 or more within the range of txt is the basis for determining the level of insulation performance.

However, the present invention shows that the object can be fully achieved without using a foam plate tube with low density and small cell diameter, which is unstable in production.

Table 4 (results of Example/Comparative Example 3) shows an example of the phenomenon tendency of C) above.

According to the results in Table 84, the foam board with a skin layer has the advantage of expanding the suitability of adhesive resin layer stacking and also of being able to stably obtain a bonded state with a single bond.

What should be noted here is that the bonding state as used in the present invention is an index that does not necessarily correspond to adhesive strength.

Table 5 (results of Example/Comparative Example 4) shows an example of the phenomenon tendency of d) above.

According to the results in Table 5, it can be seen that even if the density and cell diameter are the same, the insulation performance of the laminate changes depending on the time from the manufacture of the first foam board to the attachment of the film.
We understand the necessity of laminating films in a very short period of time.

This phenomenon is caused not only by the volatilization of fluorinated hydrocarbons from the foam board immediately after manufacture, but also by the rapid introduction of air into the foam board cells.
There is a phenomenon in which the concentration of fluorinated hydrocarbons is completely diluted, and it is assumed that the latter phenomenon is the decisive factor.

Table 6 (results of Example/Comparative Example 5) shows the necessity of the above e) and just confirms the above guessed results. Namely, 1 the film laminated on the foam board according to the present invention 2
．． The required characteristics of No. 2 are as follows: First, the nitrogen permeability is 5 cc/
jFf''-day-atm at If the temperature is not below 23°C, the insulation performance cannot be maintained at a high level.

Furthermore, the water vapor transmission rate is 6 f/rostrum Cday-atm, a
t Sustainability A cannot be maintained unless the temperature is below 25°C.

Moreover, if this barrier film is not a thin and flexible film of 150 μm or less (preferably 80 μm or less), it will not work. Even if the bonding degree is 1, the bonded state referred to in the present invention cannot be stably obtained and the quality cannot be guaranteed.

Therefore, the film 2.2' used in the present invention needs to be a single product or a composite film mainly made of a synthetic resin that satisfies the above conditions.

Table 7 (results of Example/Comparative Example 6) is an example of results showing the necessity of f) above.

According to the results in Table 7, when the adhesive resin layer is not interposed between the foam board 1 and the film 2゜2', the bonding condition as defined in the present invention is not satisfied; Even in the case where the adhesive resin layer is used, the axial direction in which the heat resistance and aging performance of the laminate changes depends on the type of adhesive resin layer used.

The blister resistance used in the evaluation in Table 7 is the presence or absence of bubbles with a diameter of approximately 1N or more that occur at the laminated interface of the laminate, and the occurrence of this phenomenon deteriorates the sustainability of the thermal insulation performance. It has been confirmed that

Therefore, from the viewpoint of satisfying the bonding state as defined in the present invention and also satisfying the heat-resistant aging performance, < is the adhesive resin layer 3
．． 3' is to use the same type of resin as the foam board.

Table 8 (results of Example Comparative Example 7) shows an example of the phenomenon trend of g) above.

According to the results in Table 8, the suppression conditions that satisfy the bonding condition as defined in the present invention and do not reduce the closed cell ratio of the foam board are as follows: 1.
It can be seen that it is important to keep the degree of compression of the foam board in the range of 5 to 25 degrees. Moreover, this condition is particularly important when laminating a film to a foam board immediately after production.

Table 9 (results of Example/Comparative Example 8) shows an example of the phenomenon tendency of h) above.

According to the results in Table 9, it is clearly seen that the temperature control accuracy of the suppression roll for obtaining a laminate that satisfies the joint condition rt of the present invention and also satisfies the heat-resistant aging performance is within ±2° C. of the set temperature. Moreover, the bonded 1ift as used in the present invention.

It can also be seen that the adhesive strength is an index that is not directly related.

Table 10 (results of Example/Comparative Example 9) shows a comprehensive comparison of the performance of laminate E of the present invention and a comparative product. In addition, since Tables 2 to 9 above are based on local evaluations so that the phenomenon trends of each factor are easy to understand, these representative tI! It also verifies the authenticity of the evaluation by evaluating it in a professional manner.

According to the results in Table 10, it can be seen that the laminate of the present invention exhibits superior effects in terms of heat insulation performance, especially in terms of sustainability of heat insulation performance, compared to any other comparative products.

In general, once a heat insulating material has been installed in a structure, it is often difficult to replace it. Therefore, when it is necessary to guarantee insulation performance over a long period of time, it becomes necessary to use thicker insulation materials that take into account the decrease in performance from the beginning. It is likely that this will have a negative impact on the economy, leading to an overall deterioration in economic performance. Furthermore, when the degree of this performance decline varies widely depending on practical conditions, it is difficult to predict the amount of decline, and as a result, the insulation performance of the structure after aging cannot be guaranteed.

On the other hand, the laminate of the present invention has excellent heat insulation performance as a light meal, and has excellent performance sustainability under practical conditions.
The significance of its use as a heat insulating material is extremely large.

The evaluation method used in the present invention will be described below.

■ Compressive modulus (unit: iKg/aM”) M8TM D
According to -1621.

■ Bubble diameter [Unit; ■] Carry out measurements in accordance with 6402 to J-Eng. 8, and calculate the average bubble diameter by determining how many bubbles are crossed by a straight line of the total thickness length in the thickness direction, at least 10 places at random. conduct,
The average value was taken as the gold bubble diameter.

(2) Closed cell/bubble ratio (unit: 悌) Measured using M8TM D-2856 (air vicnometer method). Samples were randomly taken from at least 10 locations on the foam board, and the average value was taken as the closed cell ratio.

■Nitrogen permeability [unit, -7111"-1la7'at
m at 25"C) Mu8TM D-1434.

(E) 1g of water air permeation 8 (unit + 9 / #l”
-aay-atm at25'O)mu8TMN96
+ 0■ Thermal conductivity according to 63 pieces BY [unit s Ic
e! L/ / jllll-hr*'Q at □ ℃)
The temperature characteristics were measured according to MO-518 and the experimental formula for temperature characteristics was determined, and the value at 0°C was determined.

■ The rate of change in thermal conductivity) [unit + IG] Thermal conductivity 2a (at Q℃) before aging, Thermal conductivity tb (at Q℃) at the end of knee song under the conditions shown below
).

[Rate of change in thermal conductivity)) = □x100 (1) The sample preparation method and the calculation method of thermal conductivity a and b were performed as follows.

First, cut out a 453 square YtB plate from the board, further cut out 2CI11 squares at the center from any four sheets, find the average value of the thermal conductivity of these four sheets, set it as t-a, and leave the remaining 45c1
A polyethylene 7 ohm sheet wrapped around the end face of four pieces per corner was aged under the above conditions, then taken out, and a 20C11 square plate was cut from the center of each piece, and the average value of the thermal conductivity of the four pieces was t. -b.

(2) Rate of change in thermal conductivity (B) (Unit 11) Thermal conductivity 1a (atQ°C) before aging and thermal conductivity 1b (atQ°C) after aging under the following conditions were determined by the following formula.

B-a Rate of change in thermal conductivity (B) = -X 100 (H) Conditions [100 days in a dry open environment at 50°C] The sample collection method and calculation method for thermal conductivity a and b are as follows. I went there. First, cut out eight 45 cm square plates from a board, cut out 20 cm square pieces from any four plates, find the average value of the thermal conductivity of these four plates, and set it as fa. ! !
! Four 45 cm square plates were aged under the above conditions and then taken out, 20 cm square plates were cut from the center of each plate, and the average value of the thermal conductivity of the four plates was taken as b.

■ Joining condition [unit: division] 51 square laminate plate cut from the center of the plate, water 1000f
After 24 hours, the laminate was completely submerged in a liquid dissolved in n-butanol 379 at room temperature. After 24 hours, it was taken out and both surfaces of the laminate were observed. The penetration distance measured perpendicularly from the end face is determined by the test, and this operation is repeated for 5 samples, and the average value is shown. still.

It is effective to color the liquid with red ink or the like in order to easily identify the intrusion of the liquid.

[Phase] Bonding condition pass rate (unit: l) Take 506 cuts from the end face of the laminate, and cut 5 from the remaining laminate.
Randomly cut 10 pieces of eIM square board into 9 pieces.

The bonding state t-11J is determined. The number of samples in which the bonded state is less than 101 W is taken as the bonded state pass rate.

G) Adhesive Strength [Unit + IF/25 wrinkles] Test pieces were taken from 10 locations from the same sample, and the average value was taken as the adhesive strength.

◎ Partial pressure of fluorocarbon gas [unit: atmospheric pressure at 24°C] A 50ee' foam is sealed in a 60cc metal container at 24°C.
Heat for 5 hours at a temperature 100°C higher than the melting point of the foam resin to completely melt it, then cool for 24 minutes and record the pressure (a atm) in the container at that time.

If the pressure is lower than atmospheric pressure, mercury is introduced; if it is higher, mercury is released to bring the pressure to atmospheric pressure. Then, the gas inside is collected with a syringe, and the concentration of fluorocarbon gas (bvc31e4) is determined by the gas chromad method, and the fluorocarbon gas content is calculated using the following formula. I asked for pressure.

0 [Freon gas partial pressure] = -X a x - [atmospheric pressure] 5
0 100 The number of measurement points was 10 per foam board, and samples were taken randomly.

Table 1 lists the contents of the foam boards used in Examples and Comparative Examples.

(Hereinafter, remainder f3) Example/Comparative Example-1 Foam board symbol 1. A pre-prepared adhesive resin layer 6.3 is applied to both surfaces of each of the four types of foam board grains II, ■, and ■.
2.7 [In this case, one side of a 40μ thick adhesive resin layer film made of the same type of resin as each foam board 1 is treated with a urethane-based anchoring agent, and Saran latex is applied on top of it. X-509C (commercial product manufactured by Asahi Dow Co., Ltd.) coated with approximately 5 μm of $2 LIC] was self-layered using the wafer shown in Figure 3 to create 60 laminates, each with sample/I61. .2.3.4 numbered.

The main lamination conditions at this time are roll temperature 167℃-175℃.
°C Foam compression degree 15°C, foam temperature approximately 20°C Roll temperature adjustment target value ±2°C or less, foam board feeding speed 18rm
/mim.

From each of the four types of laminates (samples/161 to 4) obtained, 100 samples each having a length of 5 cm and 11 squares were randomly cut out, and the bonding state of the laminates was evaluated using the method described in the text.
The relationship between the percentage of the 6% bonded state according to the present invention and the compression modulus of the foam board is summarized in Table 2.

According to the results in Table 2, the foam board that completely satisfies the bonding conditions defined in the present invention has a compressive modulus of elasticity of 30 kg/c.
It is understood that the rigid foam board must have a weight of at least 50 kg/m", preferably at least 50 kg/m".

(Extra color above) Example/Comparative Example ~ 2 A total of 14 types of foam boards with foam board symbols V ~ ■ were created by the extrusion foaming method, and the opening time of about 2 o'clock and the time of Sekiguchi at about 24 o'clock after each production. Thermal conductivity of the foam board was measured by the method described in the text. Regarding the foam board opened at about 2 o'clock, the partial pressure of the foaming agent (dichlorodifluoromethane) used was measured using the method described in the text, and the results are also summarized in Table 3.

In this experimental example, the foam boards with symbols V, II, and XW are:
When trying to obtain a foam board with the target density and cell diameter, the closed cell ratio deteriorated in the foam board. Also symbol) a[[
% This is the obtained foam board.

According to the results in Table 115, it can be seen that the insulation performance of the obtained foam board deteriorates within one day if left as is.

Further, the foam board that can be used as a material for the laminate of the present invention is prepared in a state where the partial pressure of the fluorinated hydrocarbon is maintained at at least 0.2 atmospheres,
In other words, it is understood that a foam board with a closed cell ratio of 95 or more and that has not been aged for a long time should be selected to ensure the desired heat insulation performance.

However, the results in Table 3 show that the density is 9/z at 25-90.
3 Among foam boards with a cell diameter of 0.1 to 0.6 and a closed cell ratio of 95 or more, which are sufficiently stably supplied, there is a foam board with excellent heat insulation performance that can be used as a material for the laminate of the present invention. It shows the possibility that it exists. In addition, the investigation of this possibility will improve the insulation performance of conventional foam boards by making them lower density and smaller diameter cells, or
This is the basis of a measure to improve the insulation performance, which is different from the technical idea that was attempted to be achieved by specifying the gas contained within the foam board cells.

(Extra colors below) Maki 3 Table Examples/Comparative Examples ~ 3 Foam boards with foam board symbols XX and XXI (The difference between these two is
60 sets (30 sets + 30 sets) of Φ-sun layers present and absent on both surfaces of the foam board were prepared, and for one of the 30 sets, the samples of Example and Comparative Example 1 were prepared. *
The conditions of 1-1 were repeatedly reproduced. (This sample /i6
3) On the other hand, for the other 30 groups,
An epoxy two-component curing adhesive resin (manufactured by Nippon Ciba Geyser Co., Ltd., resin LY553, curing agent HY956, commercially available) was applied to the surface of the foam board using a plowing agent of about 5097, and then a chloride coating of 20 μm was applied to the important person. Vinylidene-based biaxially stretched films (manufactured by Asahi Dow Co., Ltd., trade name: Saran Film) are stacked together and laminated using a compression roll with a surface temperature of 20°C to compress the foam board to a compression rate of 154I. Afterwards, adhesive resin is applied indoors. was cured to form a laminate (this sample will be referred to as 3-2.3-3).

Obtained sample A63-1.3-2, /l63-3.3-
Regarding the laminate of No. 4, the static bonding pass rate and adhesive strength were evaluated by the method described in the text, and the results are shown in Table 4.

According to the results in Table 4, it is shown that the bonding state referred to in the present invention does not necessarily have the same tendency as the general adhesive strength. Furthermore, the presence or absence of a skin layer on the surface of the foam board does not limit the applicability of the adhesive resin layer, but is an extremely important factor in stably providing the bonded state referred to in the present invention.

It is shown that.

Table 4 Examples/Comparative Examples ~・4 Symbol! The timing for laminating the barrier film 2.2' using the foam board was 1 hour after manufacturing the foam board (sample/164-1).
), 5th hour (sample *4-2), 122nd hour sample/l
The experiments under the conditions of Example Comparative Example ~ 1 and Sample/I61-1 were repeated except that the four-water mK was changed for sample A4-4) and sample A4-4) at the 155th hour.

The four sections of laminates obtained were evaluated for bonding state and thermal conductivity using the methods described in the text, and the results are summarized in Table 5.

According to the results in Table 115, even when the same foam board material is used to laminate barrier films that meet the bonding conditions defined in the present invention, the thermal conductivity of the resulting laminate changes depending on the lamination period, and the present invention Table 5 shows that in order to obtain the thermal conductivity targeted by the invention, it is necessary to complete the lamination of the barrier film 2.2' within a shorter period of time, within 12 hours after production. EXAMPLE/COMPARATIVE EXAMPLE-5 Using a foam board with foam board symbol XX (one hour after manufacture), the same experiment as in Example/Comparative Example-1 Sample Rotation 1-1 was repeated. At this time, the barrier film 2.2' was laminated by changing the layer and VIP composition shown in Table 1N6 "Film composition column used" and laminating conditions so that the bonding condition of the present invention was satisfied. Completed the board. (sample/l6
5-1 to 5-9).

Thermal conductivity of the laminate plate was determined using the method described in the text.
The rate of change (A), rate of change (B), and bonding condition pass rate were evaluated, and Table 116 was compiled in correspondence with the nitrogen permeation and water vapor permeability of each film that had been evaluated and evaluated in advance.

According to the results in Table 6, in order to provide the obtained laminate with excellent thermal insulation performance and its sustainability, the film 2.2' must have a thermal transmittance of at least 5 cc/ml day-at-least.
m at 24℃ or less, water vapor transmission rate 69/m”a
It is necessary to satisfy the characteristics of a7"atm at 24℃ or less, but this barrier film has a
Unless the film is mainly composed of a thin, flexible synthetic resin of 0μ or less, preferably 80μ or less, the bonded state referred to in the present invention can be stably obtained even if the film is laminated to increase the degree of adhesion. It can be seen that there is a drawback that it is not possible to guarantee the quality.

(y% lower total margin Example/Comparative Example-6 Vinylidene chloride barrier resin layer 2 on both surfaces of foam board 1
．． 2, using the foam board with symbol ■ (with skin layer), laminates with the layer configurations shown in Table 7, ``Laminated Structure Column'' were created (Samples 46-1 to 6-6). do).

The obtained laminate was evaluated for the pass rate of the bonded state and the blister resistance at 50°C and 70°C using the method described in the text, and the results are summarized in Table 147.

According to the results in Table 7, in order to satisfy the bonding condition referred to in the present invention, it is necessary to have an adhesive resin layer between the foam board and the film, and the laminate of the present invention also has blister resistance. From one point, it is shown that it is necessary to use the same type of adhesive resin as the foam board, a heat-sensitive adhesive resin, or a two-component curing adhesive resin layer for the adhesive resin/If 3, 3'.

In order to easily and economically achieve the above bonding state and blister resistance, the same type of resin as the foam board is used for the adhesive resin layer, and this is laminated on the barrier resin surface in advance. It is more effective to bond this to the foam board with the adhesive resin layer side facing the foam board.

(Hereinafter, Order f3) Example/Comparative Example-7 After manufacturing the foam board symbol XX, a genuine foam board was wrapped around it, and the same experiment as Example/Comparative Example 1 Sample J461-1 was repeated. The temperature was set to 45°C, 35°C, and 25°C, and the compression degree of the foam board was 5°, 10°, respectively.
A total of 12 sections of laminates were prepared by applying a pressure of 20% and 309G (Samples 7-1 to 7-12).

The obtained laminates were evaluated for bonding pass rate and closed cell ratio using the method described in the text, and the results are summarized in Table 8.

According to the results in Table 118, from the viewpoint of obtaining a laminate that completely satisfies the bonding conditions of the present invention and maintains a closed cell ratio of 95 or higher, the foam board temperature should be 35°C or less, and the pressing force should be the same as the foam board compression. It has been shown that it is necessary to select conditions in the range of 10 to 25 degrees.

(Leaving space below) Table 8 Example/Comparative Example-8 In repeating the same experiment as Example/Comparative Example 1, Sample, %1-1, the temperature of the suppression roll was set to the target value of 163°C, 165°C.
The temperature was changed to five levels: ℃, 167℃, and 171℃. Temperature control should be as accurate as possible (actual measurement accuracy, target value ±0)
．． Within 2℃), a total of 5 sections of laminate (sample layer 8-1) were prepared.
-ra-5) were created.

The obtained laminate was evaluated for first bonding strength, bonding condition, and blister resistance using the method described in the text, and the results were evaluated in the ninth section.
It is summarized in the table.

According to the results in Table 9, the suitability of the press lamination temperature from the viewpoint of obtaining a laminate that meets the purpose of the present invention is within the range of 4°C at most, that is, in the case of the experiment in Table 9, it is 167°C ± 2°C. It can be seen that pressure lamination must be carried out at a temperature control degree of (target value ±2° C. or less).

(Hereinafter, remainder f3) tX9 Table Examples/Comparative Examples ~ 9 From Examples 1 to 8 of the present invention, Sample/166-4
．． A laminate of 4-3.5-1.6-2.3-3.5-7.8-5 was selected, and the foam shown in JP-A-53-2564-1625 was selected as a reference product. Board and JP-A-4
Publication No. 7-9593, Table 2, Test 7g63 was reproduced (sample layers were each 9-1, 9-2),
The bonding state, thermal conductivity, thermal conductivity change rate A, thermal conductivity change rate B, and blister resistance were evaluated using the methods described in the text, and the characteristics of the foam board used and the barrier properties of the film used were evaluated. Table 10 summarizes the corresponding results. .

According to the results in Table 10, it can be seen that the laminate of the present invention exhibits excellent heat insulation performance, particularly excellent sustainability of heat insulation performance.

In particular, the performance indicated by the rate of change A is known to correspond to the results of products aged for about 6 years in practical applications where water vapor partial pressure differences occur, so its practicality is extremely large.

(hereinafter referred to as "Yo fa")

[Brief explanation of drawings]

Figures 1 and 2 are cross-sectional views of the laminate according to the present invention;
The figure is a sectional view of the main part of the first stage of manufacturing a laminate according to the present invention. Patent applicant Asahi Dow Co., Ltd. 232-

Claims (1)

[Claims] Contains a fluorinated hydrocarbon with a partial pressure of 0.2 atmospheres or more, has a density of approximately 25-90 Kg/#', and has a compressive modulus (A8TMD-
1621) is 30 Kg/m or more on at least both surfaces of the thermoplastic synthetic resin foam board, with a thickness of 150 μ or less and a nitrogen permeability (Musrmn-1434) of 5 oa/m.
jl-da7 atm at 25℃ or less, water vapor permeability (M8TE M196-65) is 6e/jN"-
A film mainly made of synthetic resin that satisfies the value of fly at 25° C. or less is applied via an adhesive resin layer of the same type as the foam board, a heat-sensitive layer adhesive resin layer, or a two-component curing adhesive resin layer. The surface tension of these laminated end faces is approximately 55 dyn/
2 to a water-n-butanol mixture adjusted to cM.
When immersed for 4 hours, # mixed solution was laminated densely with a bonding state that did not penetrate 10sIl from the end face to the laminated interface, and the thermal conductivity (according to M8! MO-518) was 0. .018 Kcajl/m-hr, °C (4
10°C) or less, or less, thermally insulating thermoplastic synthetic resin foam laminates with a rate of change in thermal conductivity of 15 cm or less under the conditions listed below when a water vapor partial pressure difference is applied.