JP2013068024A - Fireproof adhesive agent and fireproof structure - Google Patents

Abstract

【Task】
An object of this invention is to provide the adhesive which can obtain the fireproof coating which was more excellent in fireproof performance by using for joining a fireproof coating material and a wooden member.
[Solution]
The fireproof adhesive of the present invention is an adhesive used for joining a wooden member and a fireproof coating material in a fireproof coating of a building, etc., and polyvinyl alcohol in the total amount of the synthetic resin nonvolatile content contained in the adhesive And / or its derivative | guide_body is 1-100 mass%, It is characterized by the above-mentioned. FIG. 1 shows a cross section of a fireproof structure in which a fireproof coating material is joined to a wooden member via a fireproof adhesive.
[Selection] Figure 1

Description

  The present invention relates to a fireproof adhesive used for joining a wood member and a fireproof coating material.

Conventionally, in order to protect structural members such as pillars and beams of buildings or non-structural members from a flame in the event of a fire, a fireproof coating is applied to the pillars and beams.

  The fireproof coating is performed by covering members such as columns and beams with a fireproof coating material. As a method of coating a member with a fire-resistant coating material, a paint-like fire-resistant coating material is applied to the member to form a fire-resistant coating material layer on the surface of the member, or a sheet-like or plate-like fire-resistant coating material is applied to the member. There is a method to stick on the surface. In the method of attaching the fireproof coating material to the surface of the member, an adhesive may be used for joining the fireproof coating material and the member.

  In addition, steel members such as steel frames are mainly used as members to be covered with the fireproof coating material, but it has also been performed to cover a wooden member with a fireproof coating material.

  For example, Patent Document 1 describes “a fire-resistant coated wood obtained by coating a long wooden base material having a rectangular cross section with a foamed fire-resistant layer made of a foamed fire-resistant material”. When forming a foam refractory layer around the outside, the foamed fireproof coating material may be coated on the outside of the wooden substrate, or a layered foamed fireproof coating material may be applied to the outside of the wooden substrate. It may be attached, and it is described that an adhesive layer can be interposed between the wooden substrate and the foamed refractory layer as necessary.

JP, 2011-38317, A (claim, paragraph 0017, etc.)

  When an adhesive is used for joining the fireproof covering material and the wooden member, the fireproof performance may differ depending on the adhesive used, but the adhesive used for the fireproof covering has not been sufficiently studied.

  The present inventor pays attention to the difference in the fire resistance performance of the fireproof coating material depending on the adhesive interposed between the fireproof coating material and the wooden member, and repeatedly studies to obtain an adhesive suitable for the fireproof coating material. Thus, the present inventors have found that a fireproof coating having excellent fire resistance can be obtained by using an adhesive containing polyvinyl alcohol and / or a derivative thereof in a certain ratio.

  An object of this invention is to provide the adhesive which can obtain the fireproof coating which was more excellent in fireproof performance by using for joining a fireproof coating material and a wooden member.

  The invention according to claim 1 is an adhesive used for joining the fireproof covering material and the wooden member, and polyvinyl alcohol and / or a derivative thereof is added to the total amount of the synthetic resin non-volatile content contained in the adhesive. It is an adhesive for fire resistance characterized by containing 100 mass%.

  The invention described in claim 2 is a fire-resistant structure characterized in that a fire-resistant coating material is joined to a wooden member via the fire-resistant adhesive according to claim 1.

  By using the fire-resistant adhesive of the present invention for joining the fire-resistant coating material and the wooden member, a fire-resistant coating having more excellent fire resistance can be obtained.

  Moreover, a fireproof covering material and a wooden member can be joined with a fireproof adhesive to obtain a fireproof structure excellent in fireproof performance.

The fireproof adhesive of the present invention is an adhesive used for joining a wooden member and a fireproof coating material in a fireproof coating of a building or the like.

This fireproof adhesive is characterized by containing 1 to 100% by mass of polyvinyl alcohol and / or its derivative in the total amount of the synthetic resin (nonvolatile content) contained in the adhesive.

Specific examples of the synthetic resin include synthetic resin emulsions and water-soluble polymers.

The synthetic resin emulsion can be appropriately selected from those generally used for adhesives. For example, vinyl resins such as vinyl acetate, ethylene vinyl acetate, vinyl propionate and vinyl versatate; methyl (meth) acrylate resin, ethyl (meth) acrylate resin, methyl (meth) acrylate resin, (meth) acrylic Acrylic resin such as ethyl acid resin, (meth) acrylic acid butyl resin, (meth) acrylic acid 2-ethylhexyl resin, acrylonitrile resin, methacrylonitrile resin; polyester resin; fluororesin; epoxy resin; polyurethane resin; A vinyl acetate resin; a resin in which a synthetic resin such as a silicone resin is dispersed in water, or a resin in which two or more synthetic resins are copolymerized in water can be used. Two or more synthetic resin emulsions may be mixed and used.

  The water-soluble polymer refers to a water-soluble polymer, generally having a molecular weight of 10,000 or more and having a water-soluble group such as a hydroxyl group, a carboxyl group, a carboxylic acid ester group, or a sulfonic acid group. A molecular compound. Examples thereof include polyvinyl alcohol, starches, water-soluble acrylic resins, water-soluble apolyester resins, water-soluble apolyamide resins, water-soluble apolyurethane resins, and cellulose derivatives (such as methylcellulose, hydroxycellulose, and hydroxypropylcellulose).

The polyvinyl alcohol is represented by the following chemical formula.

In addition, OAc in Chemical formula 1 represents an acetic acid group. M is an integer of 1 or more, and n is an integer of 0 or more.
The derivatives of the polyvinyl alcohol are ethylene-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, modified polyvinyl alcohol such as cation-modified polyvinyl alcohol, hydroxyl groups such as carbonyl group, carboxyl group, alkyl group, and acetate groups. Polyvinyl alcohol having a functional group.

In addition, the value of “m + n” in Chemical Formula 1 is referred to as the polymerization degree, and the value of “(m / (m + n)) × 100” is referred to as the saponification degree.

The degree of polymerization of the polyvinyl alcohol or derivative thereof is preferably 300-3500, more preferably 500-2500. By using a polymer having a degree of polymerization within this range, a fireproof coating having more excellent fireproof performance can be obtained.

The saponification degree of the polyvinyl alcohol or a derivative thereof is preferably 70.0 mol% or more, more preferably 80.0 to 99.0. When the degree of saponification is in this range, a fireproof coating with better fireproof performance can be obtained.

The content of polyvinyl alcohol or a derivative thereof in the total nonvolatile content of the synthetic resin is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, and particularly preferably 10 to 40% by mass. . When the content is in this range, a fireproof coating having excellent fireproof performance can be obtained. When the content is too small, the heat resistance of the fireproof adhesive is not sufficient, and a fireproof coating excellent in fireproof performance cannot be obtained. In addition, when considering the adhesive performance, drying / curing properties, and coating workability of the adhesive, it is preferable to use polyvinyl alcohol or a derivative thereof in combination with other synthetic resins, particularly in combination with a synthetic resin emulsion. Is more preferable.

  The fireproof adhesive may contain pigments, fillers, additives and the like as components other than the synthetic resin as long as the effects of the present invention are not impaired. These may be appropriately selected from those usually used for adhesives.

  The wooden member mainly includes a member that forms a part to be subjected to fireproof coating in a building, specifically, a structural member such as a pillar or a beam, or a wall or a floor, or a non-structural member. It is done.

Moreover, when these structural members and non-structural members are composite members formed of a plurality of materials, the wooden members among the members forming the composite members are also the wooden members, and the fireproof covering material and the wooden material Even when the members are joined to form a composite member, a fireproof adhesive can be used. For example, when laminating wooden plate-like members (single plates) and fire-resistant coating materials alternately like the laminated wood members described in JP2010-242331, for joining the plate-like members and fire-resistant coating materials. The refractory adhesive can be used.

  The fire-resistant coating material is a fire-resistant coated layer such as a plate or sheet having a fire-resistant performance, or a fire-resistant coating layer having a fire-resistant performance by being applied to an object to be coated such as a paint, a coating material, or a spraying material. The material to be formed.

The fire-resistant coating material may be any material that is generally used, and among other fire-resistant coating materials, it is a foamable fire-resistant coating material that exhibits fire resistance performance by forming a fire-resistant heat insulation layer by volume expansion in the event of a fire. It is preferable. The fireproof adhesive is suitable as an adhesive for a foamable fireproof coating material, and can improve the fireproof performance of the foamable fireproof coating material.

  The foamable fireproof coating material is a fireproof coating material that forms a nonflammable porous fireproof heat insulating layer by being foamed and expanded by being heated in a fire. The foamable fireproof coating material may be a sheet or the like or a paint.

  Examples of the foamable fireproof coating material include those containing a carbonizing agent and a flame retardant foaming agent that form a fireproof heat insulating layer by heating when exposed to a flame using a synthetic resin as a binder.

  The synthetic resin is not particularly limited as long as it can maintain the shape of the foamable fireproof coating material until the foamable fireproof coating material is exposed to a fire and foaming starts.

  Examples of the synthetic resin include melamine resin, acrylic resin, alkyd resin, vinyl chloride resin, vinyl acetate resin, urethane resin, epoxy resin, silicone resin, polyester resin, ethylene / vinyl acetate resin, vinyl acetate / versaic acid vinyl ester. Examples thereof include copolymer resins, vinyl acetate / ethylene resins, vinyl acetate / versaic acid / acrylic resins, vinyl acetate / acrylic copolymer resins, acrylic / styrene copolymer resins, and polybutadiene resins. These resins may be used alone, or may be a copolymerized product or a mixture thereof.

  The carbonizing agent is a component that is carbonized by being heated and forms a skeleton of a porous structure of a fireproof heat insulating layer formed by exposing a foamable fireproof coating material to a fire.

  As the carbonizing agent, for example, a polyhydric alcohol such as pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, a substance formed only by carbon, oxygen, hydrogen, such as polysaccharides and expansive graphite may be used. it can.

  The flame retardant foaming agent is decomposed by heating to generate a nonflammable gas, and the carbonized layer formed by the carbonizer is foamed by the nonflammable gas to make the carbonized layer porous. It is an ingredient for.

As the flame retardant foaming agent, for example, phosphates such as ammonium phosphate, ammonium polyphosphate, melamine phosphate, melamine polyphosphate, aluminum polyphosphate, magnesium polyphosphate phosphate are preferably used. A salt (such as ammonium sulfamine) or a borate (such as ammonium borate) can also be used.

  Further, the foamable fireproof coating material can contain a nitrogen-containing foaming agent as a foaming agent other than the flame retardant foaming agent. Nitrogen-containing blowing agents include, for example, dicyandiamide, azodicarbonamide, melamine and trimethylolmelamine, hexamethylolmelamine, derivatives thereof such as hexamethoxymethylmelamine, urea, butylurea, dimethylurea, guanylureaphosphate, aminoguanyl Examples include urea, urea formaldehyde, aminoacetic acid and guanidine.

  In addition, the said foamable fireproof coating material can mix | blend other submaterials in the range which does not impair fireproof performance besides the above-mentioned component. As the auxiliary material, pigments, fillers, additives, and the like that are usually used for fireproof coating materials may be appropriately used.

  Secondary materials include, for example, pyrolytic organic / inorganic foaming agents that generate nonflammable (fire extinguishing) gases such as ammonia and carbon dioxide, titanium oxide, red pepper, yellow lead, iron yellow, titanium yellow, fast yellow, Anthraquinone yellow, benzidine yellow, phthalocyanine green, bitumen, ultramarine blue, phthalon cyanine blue, carbon black and other inorganic and organic pigments, calcium carbonate, aluminum powder, aluminum hydroxide, inorganic fibers, alumina, silica, diatomaceous earth, shirasu balloon, perlite And additives such as fillers such as vermiculite and kaolinite, plasticizers, surfactants, thickeners, antifoaming agents, film-forming aids, and the like.

The fireproof adhesive can be used as follows.
If the fire-resistant coating is molded into a plate or sheet, apply the fire-resistant adhesive to the fire-resistant coating or the wooden member to which the fire-resistant coating is applied, before the fire-resistant adhesive is cured. Next, a fireproof covering material is affixed to the wooden member.

  If the fireproof coating material is not a molded body but a material that forms a layer having fireproof performance by applying to the member, such as paint, coating material, spraying material, etc., the fireproof adhesive is previously applied to the wooden member. The fire-resistant coating material is applied onto the fire-resistant adhesive when the fire-resistant adhesive is uncured or after curing.

The method for applying the fire-resistant adhesive to the fire-resistant coating material or the wooden member is not particularly limited, and for example, a painting tool such as a brush, a roller, a spatula, a trowel, an air spray, or an airless spray may be used.

Example 1
As the refractory structure 1, a pillar material having the following specifications was produced. An outline of a cross-sectional view of this fireproof structure is shown in FIG.
As the core material 11 to which the fireproof coating is applied, a wood member (cedar prism) having a square shape with a cross section of 10 cm × 10 cm and a height of 3 m was used.

  After the fire-resistant coating material 13 coated with the fire-resistant adhesive 12 was adhered to the surface of the core material 11, a finishing layer 14 was further formed on the surface of the fire-resistant coating material 13.

In addition, the fireproof adhesive 12 used the thing of the following composition, and the thickness after hardening of the fireproof adhesive 12 was about 0.5 mm.
Acrylic resin emulsion (non-volatile content 50% by mass): 100 parts by mass polyvinyl alcohol (polymerization degree 600, saponification degree 87 mol%): 15 parts by mass Water: 100 parts by mass

As the fireproof covering material 13, a foamable fireproof covering material having the following composition formed into a sheet shape having a thickness of 2 mm was used. This foamable fireproof coating material foams at a temperature of about 250 ° C. to form a heat insulating layer. At this time, the degree of foaming varies depending on the ambient temperature at the time of foaming and the conditions such as the composition and thickness of the finished layer, but expands 10 to 20 times when there is no external restriction.
Pentaerythritol: 100 parts by weight Melamine: 100 parts by weight Vinyl acetate / acrylic resin: 350 parts by weight Ammonium polyphosphate: 450 parts by weight Titanium dioxide: 200 parts by weight

  For the finishing layer 14, a 2 mm thick wood member (cedar veneer) was used. Further, the fireproof adhesive 12 having the above composition was also used for bonding the fireproof covering material 13 and the wood member forming the finish layer 14. The fire-resistant adhesive 12 had a thickness after curing of about 0.5 mm.

(Example 2)
The same fireproof structure as in Example 1 was produced except that a fireproof adhesive 12 different from that in Example 1 was used.

The fireproof adhesive 12 used in Example 2 has the following composition.
Acrylic resin emulsion (non-volatile content 50% by mass): 100 parts by mass polyvinyl alcohol (polymerization degree 600, saponification degree 87 mol%): 6 parts by mass Water: 100 parts by mass

(Example 3)
The same fireproof structure as in Example 1 was produced except that a fireproof adhesive 12 different from that in Example 1 was used.

The fireproof adhesive 12 used in Example 3 has the following composition. Silanol-modified polyvinyl alcohol was used as the polyvinyl alcohol derivative.
Acrylic resin emulsion (nonvolatile content 50% by mass): 100 parts by mass Derivative of polyvinyl alcohol (polymerization degree 600, saponification degree 87 mol%): 30 parts by mass Water: 100 parts by mass

(Comparative Example 1)
The same fireproof structure as in Example 1 was produced except that the following adhesive was used in place of the fireproof adhesive 12 used in Example 1.

The adhesive used in Comparative Example 1 has the following composition.
Acrylic resin emulsion (non-volatile content 50% by mass): 100 parts by mass

(Comparative Example 2)
The same fireproof structure as in Example 1 was produced except that the following epoxy adhesive was used in place of the fireproof adhesive 12 used in Example 1.

The epoxy adhesive used in Comparative Example 2 has the following composition.
Epoxy resin main component: 100 parts by mass Amine-based curing agent: 40 parts by mass

<Combustion test>
The fireproof structures of Examples 1 to 3 and Comparative Examples 1 and 2 were each cut to a height of 1.2 m and used as test specimens for combustion tests. In each test body, a thermocouple for measuring the surface temperature was embedded in the surface of the core material 11 in advance. The thermocouple was installed so that the measurement position would be the center of the side surface of the prism that is the core 11 (position of height 0.6 m from the bottom surface), and was installed on all the four sides of the prism.
In the combustion test, each specimen was placed in a gas furnace, and 10 cm from the upper and lower ends of each specimen was covered with glass wool having a thickness of 3 cm. After each specimen was installed in the gas furnace, the gas furnace was ignited and the standard heating temperature curve of ISO834 was heated for 30 minutes.

In FIG. 2, the graph which shows the temperature rise of Example 1, the comparative example 1, and the comparative example 2 as a result of a combustion test is shown. In addition, the temperature of each test body shown on a graph is an average value of the temperature measured at the above-mentioned four measurement positions. In addition, “ISO” in the graph indicates a standard heating temperature curve of ISO834.

As a result of the combustion test, in each of the test bodies of Examples 1 to 3, the surface temperature of the core material 11 increased in substantially the same manner, and the temperature after 30 minutes was about 400 ° C. In each test body of 2, the surface temperature of the core material 11 is greatly increased as compared with the test bodies of Examples 1 to 3, and the temperature after 30 minutes of Comparative Example 1 is about 750 ° C. The temperature after 30 minutes was about 670 ° C.

  In the specimens of Comparative Examples 1 and 2, as a phenomenon that was not seen in the specimens of Examples 1 to 3, the phenomenon that the fireproof coating material peels from the core material 11 and the fireproof coating material slides downward can be confirmed. Therefore, it is considered that the surface temperature of the core material 11 has greatly increased.

From this, using a fireproof adhesive containing polyvinyl alcohol and / or derivatives thereof as used in Examples 1 to 3, compared to using the adhesive as used in Comparative Examples 1 and 2, the fireproof performance. An excellent fireproof coating can be formed. Moreover, if it is the fireproof adhesive agent used for Examples 1-3, the effect of the same level will be acquired.

In addition, a combustion test was conducted for the following specifications.
Example 4
The same fireproof structure as in Example 1 was produced except that a fireproof adhesive 12 different from that in Example 1 was used.

The fireproof adhesive 12 used in Example 2 has the following composition.
Acrylic resin emulsion (non-volatile content 50% by mass): 100 parts by mass polyvinyl alcohol (polymerization degree 600, saponification degree 87 mol%): 3 parts by mass Water: 100 parts by mass

As a result of the combustion test, the surface temperature of the core 11 after 30 minutes was about 500 ° C.

(Example 5)
The same fireproof structure as in Example 1 was produced except that a fireproof adhesive 12 different from that in Example 1 was used.

The fireproof adhesive 12 used in Example 2 has the following composition.
Polyvinyl alcohol (polymerization degree 600, saponification degree 87 mol%): 15 parts by mass Water: 100 parts by mass

As a result of the combustion test, the surface temperature of the core 11 after 30 minutes was about 400 ° C.

(Example 6)
A fireproof coating material was further formed on the surface of the fireproof structure having the specifications of Example 1.
First, a fire resistant coating material coated with a fire resistant adhesive was adhered to the surface of the fire resistant structure having the specifications of Example 1, and a finish layer was formed on the surface of the fire resistant coating material. In addition, the thing similar to what was used in Example 1 was used for the wood member which forms this fireproof adhesive, a fireproof coating material, and a finishing layer.

As a result of the combustion test, the surface temperature of the core 11 after 30 minutes was about 320 ° C.
It can be said that the fireproof performance was improved and the increase in the surface temperature of the core material could be suppressed by having two fireproof coating layers.

Sectional view showing the outline of the cross section of the fireproof structure Graph showing the result of the combustion test

Claims (2)

An adhesive used for joining a fireproof covering material and a wooden member, characterized in that 1 to 100% by mass of polyvinyl alcohol and / or a derivative thereof is contained in the total amount of the non-volatile content of the synthetic resin contained in the adhesive. Fireproof adhesive.   A fire-resistant structure, wherein a fire-resistant coating material is joined to a wooden member via the fire-resistant adhesive according to claim 1.

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