JP5782571B2 - Environmentally low load phenol foam resin composition with improved heat insulation performance and phenol foam using the same - Google Patents

Description

  The present invention relates to a phenol foam resin composition and a phenol foam using the same, and more specifically, an environmentally low load phenol foam resin composition in which a nucleating agent is added to the phenol resin to improve heat insulation and the phenol foam resin composition. The present invention relates to a technique for providing a used phenol foam heat insulating material.

  A foam type heat insulating material, such as polyisocyanurate foam and polyurethane foam, which can be produced by mixing and reacting polyol, isocyanate, catalyst and foaming agent, etc. Is formed.

Patent Document 1 discloses a technique related to a composite heat insulating material using such a urethane foam foam. The foaming gas is contained in the cell structure of the polyisocyanurate foam, and is diffused to the outside as time passes, so that the inside of the cell is replaced with air. Since air generally has a higher thermal conductivity than the foamed gas, the thermal conductivity of the foam gradually increases with time and the thermal insulation performance decreases.

Also, most of the present foam insulation materials use a large amount of hydrochlorofluorocarbon (HCFC) series foaming agents. Therefore, there is a problem of ozone layer destruction, and it is necessary to develop a phenol foam insulation material manufactured with environmentally low-impact foaming gas to replace the existing insulation material whose insulation performance declines over time. is there.

Korean Published Patent No. 10-1985-0000145

An object of the present invention is to provide a phenol foam resin composition having improved heat insulation performance as compared with existing phenol foam while being environmentally friendly, and a phenol foam using the same.

In order to achieve the above object, a phenol foam resin composition according to the present invention comprises a phenol resin, a hydrocarbon foaming agent, a nucleating agent and an additive, and has a closed cell size of 20 μm or more and 200 μm or less. It can be formed.

The phenol foam according to the present invention has an advantage that it has excellent heat insulation performance compared to a phenol foam formed using an existing phenol foam resin composition by being manufactured with a resin composition containing a nucleating agent. There is.

In addition, the phenol foam resin composition according to the present invention has no danger of global warming using a hydrocarbon-based foaming agent, and the phenol foam produced through this has the advantage that it has a high thermal insulation performance in the long term. There is.

The advantages and features of the present invention and the manner in which they are achieved will become apparent upon reference to the examples described in detail below. However, the present invention is not limited to the embodiments disclosed below, but can be embodied in a variety of different forms. The embodiments are merely intended to make the disclosure of the present invention complete, and to which the present invention belongs. In order to fully inform those skilled in the art of the scope of the invention, the present invention is only defined by the scope of the claims.

Hereinafter, a phenol foam resin composition according to a preferred embodiment of the present invention and a phenol foam using the same will be described in detail.

The phenol foam resin composition according to the present invention includes a phenol resin, a hydrocarbon-based foaming agent, a nucleating agent, and an additive, and can form a foam having a closed cell size of 20 μm to 200 μm. It is characterized by being.

The phenol foam resin composition has a foamable phenol resin as a main component, and the phenol resin may be either a resol type or a novolac type.

Examples of the phenol resin include a resol type phenol resin synthesized with an alkali metal hydroxide or an alkaline earth metal hydroxide. In addition to the resol type phenol resin, a novolak type phenol resin synthesized by an acid catalyst, an ammonia resol type phenol resin synthesized by ammonia, a benzyl ether type phenol resin synthesized by lead naphthenate, or the like can be given. The phenolic resin may be a mixture of different types.

As an example, the resol type phenol resin can be obtained by heating and polymerizing phenol and formalin as raw materials with an alkali catalyst in a temperature range of 40 ° C. to 100 ° C. Moreover, you may add additives, such as a urea, at the time of resole resin polymerization as needed. When adding urea, it is more preferable to mix urea methylolated with an alkali catalyst in advance into the resole resin. Since the resole resin after synthesis usually contains excess water, the amount of water suitable for foaming is adjusted during foaming.

In addition, aliphatic hydrocarbons or high-boiling alicyclic hydrocarbons, or mixtures thereof, diluents for viscosity adjustment such as ethylene glycol and diethylene glycol, and other additives as necessary are added to the phenol resin. You can also.

The phenol foam resin composition according to the present invention contains a nucleating agent. In the foam formed from the phenol foam resin composition containing the nucleating agent, the number of closed cell cells (cells) increases dramatically, the size of the cells becomes small and uniform, and the heat insulation effect is improved. .

Specifically, when a nucleating agent is added to the phenol foam resin composition, a polar phenol resin and a non-polar nucleating agent do not mix well, and thus many nuclei are formed during the initial reaction. Therefore, many closed cell cells are generated by the addition of the nucleating agent. At this time, the reactant maintains an emulsion state due to the insolubility of the nucleating agent to reduce the surface tension of the closed cells, and suppresses the closed cells from being mutually bonded during growth. Therefore, small closed cell cells are uniformly present in the phenol foam containing the nucleating agent.

The phenol foam concerning this invention is manufactured using the phenol foam resin composition in which the nucleating agent was contained. Therefore, the phenol foam of the present invention has a large number of small and uniform closed cell cells, and thereby has a heat insulation performance superior to that of the existing phenol foam.

The kind of the nucleating agent used in the present invention is not particularly limited, and a silane-based nucleating agent, a siloxane-based nucleating agent, a perfluoroalkane-based nucleating agent, or the like can be used. More preferably, a silane compound and a siloxane compound having a low surface tension and excellent compatibility with a phenol resin can be used, and one or more of these can be mixed and used. Compounds such as hexamethyldisilazane and dimethoxydimethylsilane can be used as the silane compound, and hexamethyldisiloxane is preferably used as the siloxane compound.

In the phenol foam resin composition according to the present invention, the nucleating agent is preferably contained in an amount of 1 to 5 parts by weight based on 100 parts by weight of the composition. If the nucleating agent is contained in an amount of less than 1 part by weight, the effect due to the use of the nucleating agent becomes insignificant. If the nucleating agent is contained in an amount exceeding 5 parts by weight, the foam density of the phenol foam is reduced.

The phenol foam resin composition according to the present invention is characterized in that a foam having a closed cell size of 20 μm to 200 μm can be formed. The size of the closed cell means the cell diameter. Since the phenol foam resin composition according to the present invention contains a nucleating agent as described above, the foam produced thereby has a feature that the size of the closed cell is 20 μm or more and 200 μm or less. . When the size of the closed cell exceeds 200 μm, there is a problem that the heat insulating performance and long-term durability of the foam are deteriorated. In addition, since there is a problem in that the manufacturing unit price increases dramatically if the size of the closed cell is made small, the present invention takes into consideration the manufacturing unit price and the quality of the product. The thickness is limited to over 20 μm.

Moreover, the phenol foam resin composition concerning this invention contains a hydrocarbon type foaming agent. The foaming agent functions to form a foam structure.

In the present invention, an aliphatic hydrocarbon foaming agent having 1 to 8 carbon atoms is used as the foaming agent. In the past, since freon gas or HCFC (hydro-fluoro-fluoro-carbon) was used as a foaming agent, there was a problem of global warming due to ozone layer destruction. However, in the present invention, by using a hydrocarbon as a blowing agent, it is possible to eliminate the burden on the danger of threatening the environment as compared with the conventional case.

Examples of hydrocarbons that can be used as a blowing agent in the present invention include cyclopentane, isopentane, and isobutane, and it is preferable to select them in consideration of the thermal conductivity and boiling point of the blowing agent.

The foaming agent preferably contains one or more selected from the group consisting of one or more of isopentane, isobutane, and cyclopentane.

By using the hydrocarbon as a blowing agent, the initial thermal conductivity and long-term durability of the phenol foam according to the present invention have the desired physical properties, and the burden on environmental pollution can be eliminated.

The foaming agent is preferably included in an amount of 3% to 15% by weight based on the total weight of the phenol foam resin composition. If the content of the foaming agent is less than 3% by weight, foaming does not occur sufficiently, and heat transfer is performed through the solid surface of the foam, resulting in a decrease in efficiency. On the contrary, when the content of the foaming agent exceeds 15% by weight, a phenomenon that an excessive amount of the foaming agent breaks the cell wall during the curing and expansion process occurs, so that the closed cell rate and the thermal conductivity are deteriorated.

The phenol foam resin composition according to the present invention may further contain a surfactant, a curing agent, a plasticizer, and a neutralizing agent as additives.

In the present invention, the surfactant not only serves to stabilize the interface between a finely dispersed hydrophobic material such as a foaming agent and a hydrophilic material such as a resin, but also stabilizes the cell surface when foaming is performed. Will not be formed. Specific examples include non-ionic surfactants such as polysiloxanes, polyoxyethylene sorbitan fatty acid esters, and castor oil ethylene oxide adducts.

The surfactant is preferably included in an amount of 0.5 to 10% by weight based on the total weight of the phenol foam resin composition. If the surfactant content is less than 0.5% by weight, the compatibility between the raw materials will be reduced, resulting in the formation of phenol foam with large bubbles and low closed cell content. If the content exceeds 5% by weight, the hardness of the phenol foam will be low. Handling of the finished product is not good.

In the present invention, the curing agent serves to cure the phenol resin at a temperature of 100 ° C. or lower. Specific examples include inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphtholsulfonic acid, and phenolsulfonic acid. Of these, benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphtholsulfonic acid and phenolsulfonic acid are preferred. One of these curing agents may be used alone, or two or more thereof may be used in combination.

The curing agent is preferably included in an amount of 5 to 20% by weight based on the total weight of the phenol foam resin composition. If the content of the curing agent is less than 5% by weight, foaming is performed prior to curing, so that the foaming gas escapes and bubbles are not formed well. Not only will the pH be too low.

In the present invention, since the plasticizer imparts flexibility to the cell wall surface, it functions to prevent long-term durability by preventing the wall surface from cracking or deteriorating and preventing the foamed gas in the cell bubble from being replaced with air. Specific examples include triphenyl phosphate, dimethyl terephthalate, dimethyl isophthalate, polyethylene glycol, polyol, and the like.

The plasticizer is preferably included in an amount of 1% to 15% by weight based on the total weight of the phenol foam resin composition. If the content of the additive is less than 1% by weight, the long-term durability is not affected, and if it exceeds 15% by weight, the performance of the phenol foam is deteriorated.

In the present invention, the neutralizing agent serves to increase the pH of the phenol foam resin composition to about 3 to 9.

Generally, since an acidic curing agent is used during the production of phenol foam, the product is acidic, and there is a problem of reliability such as corrosion occurring on the finished plate and the metal bonding surface.

Therefore, in the present invention, the phenol resin cured foam is made neutral by using a neutralizing agent. Examples of the neutralizing agent in the present invention include hydroxides and oxides of metals such as aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, aluminum oxide, and zinc oxide, metal powders such as zinc, calcium carbonate, Metal carbonates such as magnesium carbonate, barium carbonate, and zinc carbonate can be contained. These may be used alone or in combination of two or more. The neutralizing agent is preferably included in an amount of 0.5 to 50% by weight based on the total weight of the phenol foam resin composition.

When the content of the neutralizing agent is less than 0.5% by weight, the phenol foam becomes acidic, and when it exceeds 50% by weight, there is a problem of change in physical properties.

The phenol resin composition according to the present invention can be obtained by foaming and curing the phenol resin composition as described above.

The foaming and curing of the phenolic resin foam can be performed at room temperature or by heating. After the foamable phenolic resin composition is discharged onto the surface material that runs at a constant speed, it is formed into a plate shape between the conveyors in the curing path. A molding method can be adopted.

Specific examples of the phenol foam resin composition and the phenol foam using the same according to the present invention are as follows.

[Production of phenol foam]
Example 1
40 g of additive composed of 200 g of phenol resin and polyoxyethylene sorbitan fatty acid ester (surfactant), ethylbenzenesulfonic acid (curing agent), triphenyl phosphate (plasticizer) and isopentane (foaming agent) as additives A phenol foam resin composition containing 1 part by weight of hexamethyldisilazane (nucleating agent), which is a liquid silane compound, based on 100 parts by weight of the resin composition was prepared.

The phenol foam resin composition was foamed and cured to obtain a phenol foam according to Example 1. When the cross-section of the phenol foam according to Example 1 was observed and the size (diameter) of the closed cell was measured, all of the closed cell satisfied the range of 20 μm to 200 μm.

(Example 2)
Phenol foam was produced under the same conditions as in Example 1 except that 2 parts by weight of dimethoxydimethylsilane was included as a nucleating agent based on 100 parts by weight of the total resin composition. When the cross-section of the phenol foam according to Example 2 was observed and the size (diameter) of the closed cell was measured, all the closed cell satisfied the range of 20 μm to 200 μm.

(Example 3)
Phenol foam was produced under the same conditions as in Example 1 except that 3 parts by weight of a mixture of hexamethyldisilazane and hexamethyldisiloxane was included as a nucleating agent based on 100 parts by weight of the total resin composition. When the cross-section of the phenol foam according to Example 3 was observed and the size (diameter) of the closed cell was measured, all of the closed cell satisfied the range of 20 μm to 200 μm.

Example 4
Phenol foam was produced under the same conditions as in Example 1, except that hexamethyldisilazane was used instead of dimethoxydimethylsilane as the nucleating agent. When the cross-section of the phenol foam according to Example 4 was observed and the size (diameter) of the closed cell was measured, all the closed cell satisfied the range of 20 μm to 200 μm.

(Example 5)
Phenol foam was produced under the same conditions as in Example 1, except that hexamethyldisiloxane was used instead of dimethoxydimethylsilane as the nucleating agent. When the cross section of the phenol foam according to Example 5 was observed and the size (diameter) of the closed cell was measured, all of the closed cell satisfied the range of 20 μm to 200 μm.

(Comparative Example 1)
A phenol foam was produced under the same conditions as in Example 1, but did not contain the hexamethyldisilazane (nucleating agent). When the cross section of the phenol foam according to Comparative Example 1 was observed and the size (diameter) of the closed cell was measured, all of the closed cell exceeded 200 μm.

[Performance test and evaluation]
Samples of phenol foam produced according to the above Examples 1 to 5 and Comparative Example 1 were put in a constant temperature chamber at 85 ° C., respectively, and maintained for 3 months, while comparing the thermal conductivity with those not subjected to overall heating. Carried out. At this time, an HC-074-200 (manufactured by EKO) thermal conductivity measuring machine was used for the measurement of thermal conductivity. Next, the thermal insulation from 0 to 10 years was predicted by applying an acceleration factor, and the result was converted into thermal conductivity (W / mK) and expressed as shown in Table 1 below.

In Examples 1 to 5, it can be seen that not only the initial thermal conductivity is lower than that of the comparative example, but also the amount of increase with time appears lower than that of the comparative example.

Therefore, it turns out that the phenol foam using the phenol resin composition concerning this invention is excellent in both initial heat insulation performance and long-term durability performance compared with the existing phenol foam. Thereby, since the phenol foam concerning this invention has a high energy load saving rate, it can be used as a highly efficient building finishing material.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments, and the present invention can be manufactured in various different forms, and those who have ordinary knowledge in the technical field to which the present invention belongs can It can be understood that the invention can be implemented in other specific forms without changing the technical idea and essential features of the invention. Therefore, it should be understood that the embodiments described above are illustrative in all aspects and not limiting.

Claims (9)

Including a nucleating agent and an additive which is a silane-based compound including at least one of phenolic resin, hydrocarbon-based blowing agent, hexamethyldisilazane and dimethoxydimethylsilane ,
A phenol foam resin composition for forming a foam having a closed cell size of 20 μm to 200 μm. The nucleating agent is
The phenol foam resin composition according to claim 1, wherein the phenol foam resin composition is contained in an amount of 1 to 5 parts by weight based on 100 parts by weight of the composition. The foaming agent is
2. The phenol foam resin composition according to claim 1, comprising at least one member selected from the group consisting of isopentane, isobutane, and cyclopentane series blowing agents. The composition comprises
The phenol foam resin composition according to claim 1, further comprising a surfactant, a curing agent, a plasticizer, and a neutralizing agent. The surfactant is
5. The phenol foam resin composition according to claim 4 , comprising at least one selected from the group consisting of a polysiloxane-based surfactant, a polyoxyethylene sorbitan fatty acid ester, and a nonionic surfactant. The curing agent is
5. The composition according to claim 4 , comprising at least one selected from the group consisting of sulfuric acid, phosphoric acid, benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphtholsulfonic acid, and phenolsulfonic acid. Phenolic foam resin composition. The plasticizer is
5. The phenol foam resin composition according to claim 4 , comprising at least one selected from the group consisting of triphenyl phosphate, dimethyl terephthalate, dimethyl isophthalate, polyethylene glycol, and polyol. The neutralizing agent is
It contains at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, aluminum oxide, zinc oxide, zinc, calcium carbonate, magnesium carbonate, barium carbonate and zinc carbonate. Item 5. The phenol foam resin composition according to Item 4 . Phenol foam phenolic foam resin composition according to claim 1-8 The foam, which is formed and cured, the size of the closed cells cell characterized in that it is a 20Myuemu～200myuemu.